3.252 5.

Review Editors Choice

The Role of Carbonate Formation

during CO2 Hydrogenation over
MgO-Supported Catalysts: A
Review on Methane and Methanol
Synthesis

Kamonrat Suksumrit, Sascha Kleiber and Susanne Lux

Special Issue
Advances in Carbon Capture and Utilization
Edited by
Dr. Linda Ansone-Bertina and Prof. Dr. Maris Klavins

https://doi.org/10.3390/en16072973
 energies
Review
The Role of Carbonate Formation during CO2 Hydrogenation
over MgO-Supported Catalysts: A Review on Methane and
Methanol Synthesis
Kamonrat Suksumrit , Sascha Kleiber and Susanne Lux *

Institute of Chemical Engineering and Environmental Technology, Graz University of Technology,

NAWI Graz, Inffeldgasse 25C, 8010 Graz, Austria
* Correspondence: [email protected]

Abstract: Methane and methanol are promising products for CO2 hydrogenation for carbon capture
and utilization concepts. In the search for effective, robust, easy-to-manufacture and stable catalysts,
supported metal-based catalysts have proven advantageous. Whereas nickel for methane synthesis
and copper for methanol synthesis stand out as efficient and cost-effective catalytically active metals,
the best choice of support material is still a matter of ongoing debate. This review discusses the
potential of the alkaline earth metal oxide MgO as support material for CO2 hydrogenation catalysts.
Due to its basicity, it gives access to bifunctional catalysts as it shows pronounced CO2 adsorption
capacity. Whereas carbonate formation seems to be beneficial in CO2 methanation, it may even have
an adverse effect in methanol synthesis from CO2 .

Keywords: CO2 hydrogenation; carbonate; methanation; methanol synthesis

1. Introduction
The utilization of carbon dioxide (CO2 ) from industrial waste sources is highly pro-
Citation: Suksumrit, K.; Kleiber, S.;
Lux, S. The Role of Carbonate
moted, aiming at mitigation of greenhouse gas emissions while exploiting industrial ex-
Formation during CO2
haust gas streams. Fossil resources like coal, oil and gas have been used as main fuels for
Hydrogenation over MgO-Supported transportation and as feedstock material in the chemical, power and energy sector for a
Catalysts: A Review on Methane and long time. Their use is regarded as being the main driver for climate change due to their
Methanol Synthesis. Energies 2023, 16, high CO2 emissions. In 2021, 36.3 Gt of CO2 were emitted from energy combustion and
2973. https://doi.org/10.3390/ industrial processes, which was the highest annual level ever reached [1]. This value means
en16072973 that the average annual CO2 concentration in the atmosphere was 50% higher than that at
the time when the industrial revolution began. In order to limit the global temperature rise
Academic Editors: Maris Klavins and
to 1.5 K in line with the Paris Agreement, global leaders approved diverse goals to achieve
Linda Ansone-Bertina
a renewable and sustainable future. Together with the option of long-term storage (carbon
Received: 5 March 2023 capture and storage, CCS) of anthropogenic CO2 emissions, the utilization of CO2 makes
Revised: 20 March 2023 an important contribution to achieving these climate goals. The technologies associated are
Accepted: 22 March 2023 referred to as carbon capture and utilization (CCU) technologies. Among them, catalytic
Published: 24 March 2023 CO2 hydrogenation with sustainably derived hydrogen (H2 ) adopts a leading role, with
methane (CH4 ) and methanol (CH3 OH) being potential hydrogenation products. Methane
and methanol production via CO2 hydrogenation could make an important contribution to
Copyright: © 2023 by the authors.
future sustainable energy supply by chemically storing renewably derived hydrogen while
Licensee MDPI, Basel, Switzerland.
processing abundant, locally available industrial carbon sources.
This article is an open access article CO2 hydrogenation to methane, the so-called Sabatier reaction or CO2 methanation,
distributed under the terms and has already been discovered in 1913 by Paul Sabatier. It combines the endothermic reversed
conditions of the Creative Commons water–gas shift reaction (RWGS, Equation (1)) with the exothermic methanation of CO
Attribution (CC BY) license (https:// (Equation (2)) in one process step. Overall, CO2 hydrogenation to methane (Equation (3)) is
creativecommons.org/licenses/by/ thermodynamically favored (∆R G0 298 K = −130.8 kJ mol−1 ) but kinetically hindered. This
4.0/). makes the use of catalysts inevitable [2]. The reaction is generally carried out over nickel-,

Energies 2023, 16, 2973. https://doi.org/10.3390/en16072973 https://www.mdpi.com/journal/energies

Energies 2023, 16, 2973 2 of 29

rhodium- or ruthenium-based catalysts [3]. Among them, supported nickel-based catalysts

stand out by showing excellent catalytic performance and low cost, and have thus received
great attention in recent years.

CO2 + H2 ⇋ CO + H2 O ∆R H0 298 K = 41.0 kJ mol−1 (1)

CO + 3 H2 ⇋ CH4 + H2 O ∆R H0 298 K = −206 kJ mol−1 (2)

CO2 + 4 H2 ⇋ CH4 + 2 H2 O ∆R H0 298 K = −164.9 kJ mol−1 (3)

Whereas direct CO2 hydrogenation to methane is thermodynamically favored,
methanol synthesis from CO2 (Equation (4)) suffers from unfavorable chemical thermo-
dynamics (∆R G0 298 K = 3.5 kJ mol −1 ); it requires stringent reaction conditions with high
pressure to achieve sufficient CO2 conversion. Low temperatures would be desirable
with regard to the thermodynamic equilibrium but are not feasible from a kinetic point
of view. Among others, copper-based catalysts are used for methanol synthesis [4,5]. In
this respect, water inhibition is reported to become an issue, especially at lower temper-
atures (<473 K). It is mentioned that a few kPa of water partial pressure are sufficient
to eliminate the majority of the catalytic activity of copper-based catalysts. However,
water formation is unavoidable during direct hydrogenation of CO2 to methanol [6].

CO2 + 3 H2 ⇋ CH3 OH + H2 O ∆R H0 298 K = −49.4 kJ mol−1 (4)

Thus, different process concepts are currently under investigation. Whereas methanol
synthesis from syngas (CO/CO2 /H2 ) over Cu/ZnO/Al2 O3 catalysts is an elaborate, major
industrial process, the best concept for methanol synthesis from CO2 is controversial. While
some researchers claim that a two-step process where the CO2 /H2 feed is first partially
shifted toward CO/CO2 /H2 and subsequently, after the formed water has been removed,
converted to methanol is beneficial [6–8], direct CO2 hydrogenation to methanol also has
its advantages due to the simplified execution of the synthesis in one process step.
In this context, the design of tailor-made supported metal-based catalysts that are
robust, highly active and selective for CO2 hydrogenation toward the respective reaction
product is crucial. In catalysis with metal-based heterogeneous catalysts, not only the
catalytically active metal species but also the carrier (support) material and the presence
of potential promoters play a crucial role. To develop catalysts with high catalytic activity
and product selectivity, the composition of the catalyst needs to be fine-tuned. Thus,
the properties of the catalytically active metal species, their interactions with the carrier
material and their individual role in the course of the reaction need to be known. While Ni
for the synthesis of methane and Cu for the synthesis of methanol have emerged as suitable
catalytically active materials, the role of the carrier material is still a subject of stimulated
research and discussion [9,10]. Until now, several aspects remain controversial. This limits
rational catalyst design.
Basic oxides, among them magnesium oxide (MgO), are regarded as promising
carrier materials for a series of reactions, such as dry reforming, dehydrohalogenation,
decomposition of CCl4 , oxidative coupling of methane, hydrodesulfurization, methane
dimerization, water–gas shift reaction [11,12] and also CO2 hydrogenation to methane
and methanol [13–15]. MgO as a catalyst carrier material modifies the electronic state
of the overall catalytic performance by electron transfer between the native catalytically
active species and MgO as support. This influence is dedicated to the alteration of
acid-base properties. However, the chemical composition of MgO, the preparation
method and the preparation conditions are important factors that affect its surface
and supporting properties as a catalyst carrier material. MgO with a high surface area
and a nanocrystalline structure has encouraging applications. As a carrier material for
CO2 hydrogenation catalysts, MgO offers an abundant source with the advantage of
Energies 2023, 16, 2973 3 of 29

easy recycling of spent catalysts when the CO2 hydrogenation step is integrated into a
compound process, for instance, in metal production, since MgO is an important slag
former in the converter [14]. Whereas for methane synthesis, spent Ni/MgO catalysts
can easily be recycled in a steel converter after their lifetime; for methanol synthesis,
spent Cu/MgO catalysts can be recycled in a copper converter.
Apart from its role as a carrier material, the use of MgO is also propagated for CO2
adsorption as it readily adsorbs CO2 under the formation of carbonate. Thus, it has to
be assumed that carbonate formation also has a decisive influence on the activity and
selectivity of MgO-supported catalysts in CO2 hydrogenation. The purpose of this paper is
to elucidate the role of carbonate formation during CO2 hydrogenation to methane and
methanol over Ni- and Cu-based catalysts on MgO carrier material with the aim of giving
access to tailor-made, customized catalyst design.

2. Magnesium Oxide—Occurrence, Production and Properties

2.1. Occurrence of MgO
Magnesium oxide, also known as magnesia, rarely naturally occurs as mineral MgO. In
these rare cases, MgO is found as periclase, a cubic form of MgO that occurs in metamorphic
rocks and dolomites [16]. However, in nature, it often forms a solid solution with wüstite
(FeO), referred to as ferropericlase and magnesiowüstite, forming 20 vol% of the lower
mantle of the earth. Occurring sites can be serpentine rocks and volcanic ejecta, and it
can also be found in contact metamorphic limestone and dolomite. The reason why it
generally does not form rocks or salt deposits is that it is readily converted to magnesium
hydroxide (Mg(OH)2 ) by water vapor in the atmosphere [17]. The atomic stacking of
MgO is characterized by a B1 cubic crystalline structure (space group Fm3m) known as
the rock-salt (NaCl) structure. Its lattice parameter is about 4.21 Å at ambient conditions.
Oxygen and magnesium atoms that are held together by ionic bonding make up its atomic
structure that spreads by half the diagonal of the cube [18].

2.2. Production of MgO

MgO may be produced by two routes, beginning either with magnesium in sea water
(wet process route) or with magnesite (MgCO3 ) ore (dry process route). The wet magnesia
process from magnesium chloride (MgCl2 ) involves high-temperature hydrolysis and
magnesium hydroxide precipitation. It is implemented in large scale in the United States
and in England. With 600 m3 of seawater, one ton of MgO can be produced by addition
of calcium hydroxide (Ca(OH)2 ) as a precipitating agent. Magnesium brines are another
source for MgO production via the wet process route. They arise as byproduct in salt
production from natural brines, mining or salt deposits. Magnesium brines mainly consist
of MgCl2 and small amounts of MgSO4 and alkali chlorides, making sulfate removal
essential for the precipitation of Mg(OH)2 . MgO production from brines benefits from low
amounts of bicarbonate and boron, which facilitate the complex removal process that is
required for MgO production when seawater is used [17]. Use of the wet process route is
in decline because it requires three times as much energy as the dry process route from
magnesite ore. Therefore, the main process for producing magnesia is thermal processing
of mined natural magnesite, a still energy-intensive process that was developed in Austria
over 100 years ago [17]. It involves the firing of natural magnesite in a multiple hearth
furnace, a shaft kiln or a rotary sintering kiln. The endothermic chemical reaction depends
on high firing temperatures. The process starts at temperatures of around 823–1073 K,
where magnesite is de-acidified, and CO2 is released, yielding caustic calcined magnesia
causter as the reaction product. To produce sintered magnesia, causter is further processed
at 1873–2473 K. The temperatures, along with the duration of the treatment, control the
product quality, such as a high density and a well-crystallized final product [19].
Sommerbauer et al. (2016) suggested reductive calcination for the conversion of
mineral magnesite to magnesium oxide. In a hydrogen atmosphere at ambient pressure
Energies 2023, 16, 2973 4 of 29

and overpressure, methane, CO2 and CO are formed in the product gas without additional
catalysts [20].

2.3. Properties of MgO

MgO as an alkaline earth metal oxide is a typical solid base. It has the lowest basic
strength among the alkaline earth metal oxides: MgO < CaO < SrO < BaO. The surface
areas increase in the reverse order with MgO giving access to high surface area materials
(MgO > CaO > SrO > BaO) [21]. The generation, characterization and properties of the basic
MgO sites were studied by Di Cosimo et al. (2014) [22]. The MgO samples showed surface
sites of strong (low coordination O2− anions), medium (oxygen in Mg2+ -O2− pairs) and
weak (OH− groups) basicity. Increasing calcination temperature drastically decreased the
density of strong basic sites and to a lesser extent that of weak OH− groups. The density of
medium-strength basic sites was only slightly decreased. Wu and Goodman (1992) found
that thermally generated defect sites on the surface exhibit a stronger basic character [23].
MgO may be a reactive substance, for instance, readily forming Mg(OH)2 in the pres-
ence of water or MgCO3 through adsorption of CO2 , while under certain circumstances, it
may be extremely temperature resistant. Its reactivity strongly depends on the temperature
of the calcination process, meaning treatment at different temperatures produces MgO of
different reactivity. Depending on the calcination temperature, MgO is classified into three
grades—caustic, sintered and fused MgO:
(i) Caustic MgO is formed when the solid minerals Mg(OH)2 or MgCO3 are slightly
heated above their decomposition temperature. Caustic MgO can be divided into two
types: light-burned and hard-burned MgO. Light-burned MgO, generally known as
caustic calcined MgO, is formed at calcination temperatures of 1143–1273 K and is
the most reactive form of MgO. Hard-burned MgO, which is calcined at temperatures
of 1823–1923 K, has limited reactivity. The reactivity of caustic MgO decreases with
increasing calcination temperature.
(ii) Sintered or dead-burned MgO, also known as magnesia clinker, is produced at
calcination temperatures of 1673–2273 K. It is an unreactive form of MgO with a
high heat capacity and a high thermal conductivity, thus, generally being used as
refractory material.
(iii) Fused MgO is generally produced from naturally occurring MgCO3 in electric arc
furnaces at 1273–1673 K (‘dead burned’) or by melting caustic magnesia. Fused
magnesia is a crystalline substance with a melting point of 3073 K. When it is heated
up to the melting point, no phase change takes place. Its tendency to undergo
hydration is much lower than that of sintered or caustic calcined MgO, which makes
it essentially stable toward the atmosphere. In a reducing atmosphere, the stability
of fused magnesia is limited to 1973 K. Because it combines high electrical resistance
and high thermal conductivity, it is mainly used as an insulating material [17].
Making use of the property of high temperature resistance, 87% of total MgO produced
is used for refractory products: 65% in the steel industry, 15% in the cement industry and 7%
for other refractory applications, such as non-ferrous metal or glass processing. Since global
steel production is still increasing, the demand for magnesia-containing refractory products
is also growing [19]. Other fields of application of MgO include the pharmaceutical sector,
for instance, as antacid or dental filling, the food sector with use as an additive or anticaking
agent, for example, and the agricultural industry as fertilizer or supplement for animal
feed [17]. Moreover, MgO is used as a carrier material and catalyst support in the chemical
industry [11].

3. CO2 Adsorption Behavior on MgO

3.1. Carbonate Formation—Thermodynamic Considerations
Metal oxides (Men O) readily react with CO2 forming metal carbonates (Men CO3 )
(Equation (5)). This reaction is known as carbonation. In the reverse reaction, known as
calcination, CO2 is liberated from the metal carbonate at elevated temperatures, thereby
Energies 2023, 16, 2973 5 of 29

regenerating the oxide. This reversible CO2 chemisorption process is exploited in CO2
capture technologies. Suitable oxides to capture CO2 are selected based on their CO2
capture capacity, adsorption rate, thermal stability, regeneration heat, costs and structural
properties [24].
Men O CO22 ⇋ Men CO3
O++ CO (5)
The carbonation of metal oxides is exothermic with the extent of exothermics depend-
ing on the metal species. In the context of CO2 capture, it is noted that a highly exothermic
metal oxide carbonation generally requires a large regeneration temperature for the oxide,
entailing a high energy demand [24]. However, this characteristic renders metal carbonates
to be suitable materials for thermochemical energy storage (TCES) processes [25–27]. The
goal of TCES is to utilize waste heat through (thermal) energy storage by means of reversible
chemical reactions, thereby enabling to balance the discrepancies between energy avail-
ability and demand. In TCES based on metal oxides/metal carbonates, the endothermic
decomposition reaction (calcination/decarbonation of the metal carbonate) charges the stor-
age material, whereas by recombination of the former decomposition products, namely the
metal oxide and CO2 , the exothermic reaction (carbonation) discharges the stored energy
and restores the material. In general, one cycle consists of three steps: charging, storing and
discharging [25]. Up to date, mainly CaCO3 , PbCO3 and SrCO3 have been considered for
TCES, predominantly for applications at medium or high temperatures [28,29]. Müller et al.
(2019) showed that, in the presence of moisture, carbonate formation from CaO, MnO, ZnO,
CoO and PbO can even be accomplished at temperatures below 373 K with an elevated CO2
pressure as the driving force. The selected metal oxides were treated with CO2 pressures
of 1–55 bar (298 K) and 110 bar (333 K) [30]. Carbonation/decarbonation of MgO is also
propagated for thermochemical energy storage. Shkatulov et al. (2022) investigated MgO
promoted with the eutectic ternary mixture LiNO3 -NaNO3 -KNO3 for thermochemical stor-
age of medium temperature heat [31]. Zhang et al. (2021) used MgO composites promoted
with alkali metal nitrates [32]. In addition, MgO/Mg(OH)2 is currently getting attention
as another potential system for TCES. Flegkas et al. (2019) investigated this system in
tt tt
fluidized bed reactors and conducted an economical study [33].
The temperature dependency of the standard free enthalpies of reaction ∆R G0 of
carbonate formation from alkaline earth metal oxides (a) and transition-metal oxides (b) for
Δ
temperatures between 300 and 1200 K at ambient pressure is depicted in Figure 1. Among
the alkaline earth metal oxides, MgO has the highest ∆R G0 values. The standard free
enthalpies of the reaction of transition-metal oxide carbonation are even further above. This
Δ
means that, compared to CaO, BaO and SrO, MgO is more stable at comparably ‘lower’
temperatures. Above 670 K, carbonate formation from MgO is thermodynamically not
favored any more with the chemical equilibrium lying on the educts’ side. Above 1073 K,
MgO cannot react with CO2 at all, whereas BaO is still completely converted to its carbonate
at this temperature. Thus, MgO is characterized by the fact that CO2 can be released from
MgCO3 at comparably low temperatures, which renders it the most promising candidate
for the carrier material in CO2 hydrogenation.
The phase transformation behavior of MgO in CO2 atmosphere is depicted in Figure 2.
The solid phases at equilibrium were predicted as a function of the temperature and
the feed CO2 (n0,CO2 /(n0,CO2 + n0,MgO )), where n0 denotes the number of moles of the
feed component.

3.2. Mechanism of CO2 Adsorption on MgO

The adsorption of CO2 on MgO-based adsorbents occurs via the formation of carbonate
species from acidic gaseous CO2 on basic Mg2+ -O2− sites. Carbonate species may occur in
the form of monodentate carbonate, bidentate carbonate and bicarbonate [12,34,35]. These
are assigned to weak, medium and strong basic adsorption sites, respectively (Figure 3).
Energies 2023, 16, 2973 6 of 29

0
Figure 1. Standard free enthalpies of reaction ∆R G for carbonate formation from metal oxides be-
Figure 1. Standard free enthalpies of reaction ΔRG0 for carbonate formation from me
tween 300 and 1200 K at ambient pressure: calculated with HSC Chemistry 8; MeO + CO2 ⇋ MeCO3 ;
tween 300 and 1200 K at ambient pressure: calculated with HSC Chemistry 8; MeO + C
(a) alkaline-earth-metal oxides and (b) transition-metal oxides.
(a) alkaline-earth-metal oxides and (b) transition-metal oxides.

The phase transformation behavior of MgO in CO2 atmosphere is depic

2. The solid phases at equilibrium were predicted as a function of the tempera
feed CO2 (𝑛0,CO2 /(𝑛0,CO2 + 𝑛0,MgO )), where n0 denotes the number of moles of t
ponent.
Energies 2023, 16, 2973 7 of 29

Figure 2. Equilibrium solid phase diagram of the system MgO–CO2: solid phase fields were pre
dicted as a function of the temperature and the feed hydrogen mole fraction; gaseous products ar
not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies).

3.2. Mechanism of CO2 Adsorption on MgO

The adsorption of CO2 on MgO-based adsorbents occurs via the formation of car
bonate species from acidic gaseous CO2 on basic Mg2+-O2− sites. Carbonate species ma
occur in the form of monodentate carbonate, bidentate carbonate and bicarbonat
Figure
Figure 2.2.Equilibrium
Equilibrium soliddiagram
solid phase phase ofdiagram
the systemof the system
MgO–CO MgO–CO
2 : solid phase 2: solid
fields were phase field
predicted
[12,34,35]. These are assignedandto weak, mediummoleand strong gaseous
basic adsorption aresites, respec
dicted
as as a function
a function of the temperature
of the temperature the and the feedfraction;
feed hydrogen hydrogen mole fraction;
products gaseous p
not
tively (Figure 3).
shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies).
not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies).

3.2. Mechanism of CO2 Adsorption on MgO

The adsorption of CO2 on MgO-based adsorbents occurs via the formati
bonate species from acidic gaseous CO2 on basic Mg2+-O2− sites. Carbonate sp
occur in the form of monodentate carbonate, bidentate carbonate and b
[12,34,35]. These are assigned to weak, medium and strong basic adsorption sit
tively (Figure 3).
Figure3.3.Formation
Figure Formationofofthe carbonate
the species
carbonate monodentate
species carbonate,
monodentate bidentate
carbonate, carbonate
bidentate and and b
carbonate
bicarbonate during adsorption of CO on MgO-based adsorbents (adapted from [36]).
carbonate during adsorption of CO2 on MgO-based adsorbents (adapted from [36]).
2

In the adsorption process, the number of basic sites is a key factor. Each adsorption
In themedium
site—weak, adsorption process, the
and strong—is number
classified of basic
according sites
to the is a key temperature
desorption factor. Eachthat
adsorptio
site—weak, medium and strong—is classified according to the
is required. The desorption temperature of weak basic sites is lower than 473 K, the des-desorption temperatur
that is temperature
orption required. The desorption
of medium basictemperature
site lies betweenof weak
473 and basic
573 sites
K, and is the
lower than 473 K, th
desorption
desorptionof
temperature temperature
strong basic of medium
sites is higherbasic
thansite
573 lies between
K [36]. 473 and
The strong 573 that
bonding K, and the desorp
occurs
between CO and Mg 2+ and/or O2− is responsible for the formation of bidentate and mon-
tion temperature
2 of strong basic sites is higher than 573 K [36]. The strong bonding tha
odentate carbonateCO
occurs between with desorption temperatures > 573 K, while the interaction of hydroxyl
2 and Mg2+ and/or O2− is responsible for the formation of bidentate an
groups (OH− ) entails the formation of bicarbonate at desorption temperatures < 373 K [36].
monodentate carbonate with desorption temperatures >573 K, while the interaction of hy
It was concluded that the strength of the basic sites in MgO depends on the number of
droxyl3.groups
Figure Formation (OHof −) entails the formation of bicarbonate at desorption temperature
themetal
carbonate species
coordinated electronegative ions. Thus, thismonodentate
can be enhanced carbonate,
with a high bidentate
surface carbon
<373
carbonateK [36]. It
during was concluded
adsorption of that
CO 2the
on strength
MgO-based
2
area that facilitates an abundant number of O sites [37,38].
− of the basic
adsorbents sites in MgO
(adapted depends
from on th
[36]).
number
Yanagisawa et al. (1995) performed IR studies of CO2 adsorption on MgO powder a hig
of coordinated electronegative metal ions. Thus, this can be enhanced with
surface
from In area
the
which that
they facilitates
adsorption
attributed thean
process,abundant
band number
the number
observed of basic
of O2− sites
to be monodentate [37,38].
sites is a key
carbonate factor.
species. Ab Each a
Yanagisawa
initio molecular et al. studies
modeling (1995) showed
performed IR studies
monodentate ofleast
as the CO2stable
adsorption
carbonate onspecies,
MgO powde
site—weak,
being
medium and strong—is classified be according to the desorption tem
fromunstable
which they at temperatures
attributedbelow 373 K,observed
the band while it could observed at a temperature
to be monodentate of
carbonate species. A
that
773 Kis[39].
required. The desorption temperature of weak basic sites is lower than
desorption temperature of medium basic site lies between 473 and 573 K, and th
tion temperature of strong basic sites is higher than 573 K [36]. The strong bon
occurs between CO2 and Mg2+ and/or O2− is responsible for the formation of bid
monodentate carbonate with desorption temperatures >573 K, while the interac
−
Energies 2023, 16, 2973 8 of 29

Huang et al. (2019) simulated a model for CO2 methanation on MgO (110) surfaces by
three different pathways: (i) CO2 direct dissociation, (ii) a pathway via formate formation,
and (iii) a carboxyl pathway. For CO2 adsorption on the MgO surface, they found that
CO2 preferably adsorbs at the O-top site with an adsorption energy of −2.49 eV form-
ing a carbonate (CO3 2− ) structure that promotes activity and causes the strong basicity
of MgO. The mechanism of CO2 methanation on MgO was illustrated by the reverse
water–gas shift reaction followed by CO hydrogenation (RWGS + CO-hydro pathway):
CO2 *→ COOH*→ CO*→ HCO*→ H2 CO*→ H2 COH*→ CH2 *→ CH3 *→ CH4 *→ CH4 .
In addition, they found that the MgO support is beneficial for OH removal which is
responsible for hydration and water formation during CO2 methanation [40].
Kim et al. (2010) studied the CO2 methanation on MgO surfaces by using Kohn–Sham
DFT calculations with a plane-wave VASP code and extensively discussed the effect of CO2
adsorption on MgO. The computational results showed monodentate carbonate formation
on a MgO (110) surface over Pd-MgO/SiO2 catalysts. They reported that the carbonate
draws electrons from nearby Mg atoms resulting in electron polarization of Mg atoms and a
subsequent local anisotropic surface disordering of MgO (110) [41]. These findings confirm
that not only stable species but also species with a lower stability (low-coordinated surface
atoms, side edges, kinks) account for the activity of MgO [42–44]. In addition, Kim et al.
(2010) suggested a mechanism for CO2 methanation on MgO surfaces that consisted of
9 steps: (i) CO2 adsorption on the MgO surface, (ii) hydrogen adsorption with CO2 and
the formation of COOH on the MgO surface, (iii) COOH hydrogenation with a hydrogen
atom and water formation as byproduct, (iv) hydrogen reaction with CO to form COH,
(v) water formation as byproduct, (vi) hydrogen adsorption on MgO to form CH on the
MgO surface, (vii) formation of CH* and transformation to CH2 , (viii) hydrogen adsorption
and the conversion of CH2 to CH3 , and (ix) hydrogen adsorption resulting in the conversion
of CH3 to CH4 [41].

3.3. CO2 Adsorption Studies on MgO

CO2 adsorption on MgO is extensively studied. Due to their abundant availability
in nature (e.g., from magnesite ore), low cost and tunable physicochemical properties,
MgO-based adsorbents are currently discussed as high-potential candidates for CO2 cap-
ture [36]. Thus, the CO2 adsorption performance of different types of MgO-based materials
is well described in the literature over a wide range of temperatures. Compared to other
metal-oxide-based adsorbents such as CaCO3 or Li2 CO3 , the application of MgO-based ad-
sorbents is beneficial due to a comparably low regeneration temperature during desorption
(<773 K). Their application is also promising in the intermediate temperature region of
473–673 K [34,45].
In general, potential CO2 adsorbents should feature a high surface area, large pore
size and large pore volume, leading to a high number of active sites for adsorption. In
addition to excellent morphologies, low diffusion resistance between CO2 and the adsorbent
and a high surface basicity are crucial for a high CO2 uptake. Large emphasis is put on
enhancing the adsorption performance of MgO-based adsorbents, their morphological
properties and stability during repeated adsorption/regeneration cycles to foster industrial
application. Measures include modification of the preparation method, variation of the
type of magnesium precursor used and the addition of promoters, for instance, other metal
oxides [36].
It is well known that different preparation methods and different preparation pa-
rameters for a respective preparation method result in different structural, morphological
and textural properties. Preparation methods for MgO-based adsorbents include sol-gel,
hydrothermal, flame aerogel, precipitation, calcination, urea hydrolysis and extrusion–
spheronization methods, with various attempts to synthesize MgO-based adsorbents with
a high surface area [36].
Apart from experimental studies, theoretical investigation of the MgO surface is
of great interest as valuable information can be gained about the mechanism of catalysis.
Energies 2023, 16, 2973 9 of 29

Computational studies enable differences in the properties of the bulk and surface defects to
be identified and favorable positions for chemisorption to be found. Historically, it started
with semi-empirical calculations followed by extensive ab initio calculations. Causa et al.
(1987), for instance, studied the MgO (110) surface and CO adsorption thereon. They found
that the fully ionic character of the chemical bond of bulk MgO and its (100) surface is also
maintained at the (110) surface in spite of some redistribution of the electronic charge [46].
Usseinov et al. (2019) also highlighted the importance of understanding the atomistic
interaction between defects and the active surface of solid adsorbents [47]. Kantorovich
et al. (2000) provided an extensive review on MgO (001) surfaces implementing electronic
structure methods based on density functional theory (DFT). They compared a perfect
MgO (001) surface to surface irregularities such as steps and corners, as well as to point
surface defects. Their theoretical results were also compared with experimental data [48].

3.3.1. Composite Promoters in MgO-Based Adsorbents

Introducing promoters such as alkali metal nitrates or carbonates (molten salt), metal
oxides, and amines to MgO has a significant impact on MgO-based adsorbents, enhancing
the CO2 uptake capacity and the performance stability. The introduction of promoters
helps provide smooth mass transfer and improves the characteristics and properties of
MgO as an adsorbent, facilitating CO2 adsorption. For instance, MgO composites exhibit
increased basicity on the surface. This may be dedicated to the generation of oxygen
vacancies and, thus, a reduction of the crystallite size. To modify MgO-based adsorbents
with composite promoters in order to achieve a high CO2 uptake capacity, several factors
need to be considered during the preparation procedure. These are the selection of the
composite promoter, the amount of promoter introduced, and the calcination temperature.
Care has to be taken as an excessive amount of the composite promoter reduces the surface
area, the pore volume, and the theoretical adsorption capacity of MgO. Therefore, an
optimum ratio/percentage of the introduced promoter needs to be found.
For instance, Yu et al. (2018) reported that the CO2 uptake of MgO-CeO2 is higher
compared to MgO-Al2 O3 . Furthermore, MgO-CeO2 prepared by urea coprecipitation
showed pronounced cyclic stability. The introduction of CeO2 increases the basicity of
the MgO phase, which is a key factor for outstanding CO2 uptake capacity, although
MgO-Al2 O3 has a higher surface area and smaller MgO crystallites [49]. It is reported that
an excessive amount of composite promoters has a negative effect on the pore volume,
surface area, and adsorption capacity [50,51]. Therefore, to find the optimum molar ratio of
promoters is an ongoing task. Jin et al. (2019) reported the highest CO2 uptake capacity and
surface area for a molar ratio of Ce/Mg of 0.05, when MgO-CeO2 was prepared via a sol-gel
combustion method at a decomposition temperature of 373 K. The addition of excess cerium
significantly decreased the CO2 uptake capacity [50]. Gao et al. (2019) investigated molten
salts MNO3 /NO2 (M = Li, Na and K) as promoters. They found that NaNO3 /NO2 /MgO
(10 mol% of NaNO3 ), prepared by wet impregnation, enhanced the CO2 uptake capacity
at 625 K, and allowed multiple CO2 sorption–desorption cycles. However, the loading of
25% of NaNO3 reduced the CO2 uptake at various temperatures (550–650 K) [52]. Similarly,
excessive amounts of FeO in FeO/MgO composite adsorbents negatively affected the CO2
uptake capacity. With FeO/MgO mass ratios higher than 3%, decreasing CO2 uptake
capacity was reported [53]. It can be concluded that excessive amounts of metal/non-metal
composites with MgO leads to low CO2 uptake capacities because of reduced adsorbent
surface areas.

3.3.2. Effect of the Adsorption Temperature

The CO2 adsorption capacity decreases with increasing temperature due to the exother-
mic character of the adsorption process. Pure, pristine MgO suffers from poor CO2 adsorp-
tion performance due to a low surface area and slow adsorption kinetics [54]. Moreover,
even though desorption temperatures for MgO-based adsorbents are low compared to
CaCO3 , thermal stability becomes an issue at elevated temperatures as sintering occurs,
Energies 2023, 16, 2973 10 of 29

which reduces the surface area and deteriorates the CO2 adsorption performance and
recyclability of the adsorbent [55,56].
Ito (1982) studied the initial sintering behavior of MgO that was freely dispersed
in CO2 and discussed the effect on surface area diminution and crystallite growth. The
sintering rate at 1123 K was found to be directly proportional to the CO2 pressure in a
pressure range of 0.67–93.1 kPa. Sintering measurements in 18 O-enriched CO2 revealed
that most of the anions migrate only on the surface during sintering. It was concluded
that sintering is enhanced by increased surface migration of O2− -ions being the slower
moving ions, caused by repeated adsorption–desorption cycles of CO2 molecules regarded
as anion-exchange mechanism [57].
Ho et al. (2017) studied the CO2 uptake capacity of MgO at various temperatures
from 303 to 623 K. Their results confirmed that increasing temperature decreases the
CO2 uptake capacity [58]. Vu et al. (2016) investigated the CO2 sorption behavior of
a mesoporous MgO/Na2 CO3 /NaNO3 composite material in a temperature range of
623–723 K for its use in power plants. The simulated gas feed contained 10 vol% CO2 in
N2 . Increasing temperature resulted in an increase of the CO2 uptake capacity (48.7 to
51.6 wt%) at temperatures between 548 and 598 K. In a temperature range of 623–648 K, the
CO2 uptake capacity decreased from 43.2 to 33.9 wt%. The lowest CO2 uptake capacity was
found to be 12.8 wt% at 673 K [59]. Hiremath et al. (2017) found the highest CO2 uptake
capacity of composite xMgO-TiO2 adsorbents at 473 K and encountered a decreasing value
when the temperature reached 573 K and 673 K [60]. Tuan and Lee (2018) prepared MgO
adsorbents by the precipitation method and found that the CO2 uptake capacity decreased
for temperatures higher than 423 K [61]. On the contrary, Ho et al. (2017) [58] and Gao et al.
(2018) [62] reported of good CO2 uptake capacities at temperatures of 303 K and 624 K using
leaf-like, lamellar-shaped MgO. Chen et al. (2016) synthesized mesoporous MgO/carbon
spheres by solid-state grinding synthesis and investigated the effect of temperature on
the CO2 uptake [63]. The highest CO2 uptake capacity was obtained at 273 K. From these
studies it is evident that both the adsorption temperature and the morphological structure
of MgO affect the adsorption efficiency.
The adsorption temperature also has an effect on the formation of carbonate species.
Park and McFarland (2009) reported that unidentate and bidentate carbonates form at room
temperature on MgO adsorbents, with the unidentate carbonate changing to bidentate
carbonate at a higher temperature of 513 K [64]. Both carbonate species disappear at 973 K.
Fukuda and Tanabe (1973) studied the behavior of MgO as a support material by infrared
(IR) spectroscopy analysis. They reported unidentate and bidentate carbonate formation
on MgO after CO2 adsorption at room temperature. The results showed that the formation
of bidentate carbonate increased with increasing outgassing temperature and decreased
with increasing MgO loading [65].

3.4. CO2 Adsorption in the Presence of Water

For many CO2 capture technologies, the presence of water in the off gas is an issue
due to lowering of the CO2 uptake capacity of the adsorbents. Normally, the emitted gases
from coal-fired power plants contain water vapor in a range of 20–30% together with other
components and 15–60% CO2 [66]. Water inhibition of metal-based heterogeneous catalysts
may also become an issue [6]. Thus, the presence of water and its impact have a crucial
role, both in CO2 capture and catalysis.
Regarding a deteriorating effect of water on CO2 adsorption, for MgO-based adsor-
bents, the contrary applies. This serves as the main argument for practical application:
the presence of water has a beneficial effect on the CO2 uptake capacity. For instance,
Vu et al. (2016) reported that the CO2 uptake capacity of wet gas mixtures containing 2.5%
H2 O and 10% CO2 in nitrogen is higher than that of the corresponding dry gas mixture
in a temperature range of 548–627 K [59]. In addition, an 80% conversion of MgO into
MgCO3 was reported in the presence of 10% H2 O at 623 K [67]. Ding et al. (2016) found that
the CO2 uptake capacity of MgO increased from 0.82 to 3.42 mol kg−1 when the relative
 Al–CO3 layered double hydroxide (LDH) [69].
The presence of water influences the reaction between M
readily reacts with water to Mg(OH)2 (Equation (6)). During th
Energies 2023, 16, 2973 CO2, both the initial adsorbent MgO and Mg(OH)2 are 11 of capabl
29

and Sorescu (2010) showed that the sorption temperature is low

perature, andfrom
humidity increased thus,
30 to carbonation ofRam
70%, respectively [68]. Mg(OH) 2 (Equation
Reddy et al. (2008) also showed(7)) dom
the beneficial effect of water vapor that leads to more effective CO2 adsorption when using
temperature
Mg–Al–CO3 layeredisdouble higher than
hydroxide the[69].
(LDH) transition temperature, carbon
The presence of water influences the reaction between MgO and CO2 . Reactive MgO
MgO + H O ⇋ Mg(OH)
readily reacts with water to Mg(OH)2 (Equation (6)). During the carbonation
2 process with 2
CO2 , both the initial adsorbent MgO and Mg(OH)2 are capable of forming MgCO3 . Duan
and Sorescu (2010) showed that the sorption temperature is lower than the transition tem-
Mg(OH) + CO ⇋ MgCO + H2O
perature, and thus, carbonation of Mg(OH)2 (Equation (7)) dominates.
2 2When the sorption
temperature is higher than the transition temperature, carbonation of MgO occurs [70].
3

Figure 4 depictsMgO theO++standard

H 2 O ⇋ Me
CO Mg(OH)
2 free
2 enthalpies of reaction (6) Δ
with MgO (Equation Mg(OH) (5), MgO
2 ++ CO
O CO 2 ⇋ Me
MgCO+ CO
2 3 + H22O⇋ MgCO3) and(7) Mg(O
reaction
Figure 4of H2Othewith
depicts MgO
standard (Equation
free enthalpies (6))∆in
of reaction R G afor
0
temperature
the reaction of ran
+ CO ⇋
CO2 with MgO (Equation (5), MgO + CO2 MgCO3 ) and Mg(OH)2 (Equation (7)), and
O Me
ent pressure.
of H2 O It can be(Equation
seen that(6)) in aabove 600range
K, the
of 300reaction
to 1200 K at of CO
2

the reaction with MgO temperature

dynamically
ambient pressure. Itfavored
can be seen over MgO
that above 600 K,carbonation.
the reaction of CO2 with Mg(OH)2 is
thermodynamically favored over MgO carbonation.

tt tt

tt tt
Δ
tt tt
Δ
Δ
Δ
Δ

Figure 4. Standard free enthalpies of reaction ∆ R G 0 for the reaction of CO 2 with

Figure 4. Standard free enthalpies of reaction Δ G for the reaction o
MgO (MgO O + COCO22 ⇋ Me
MgCO 3 ) and Mg(OH) 2 (Mg(OH) 2O++ CO CO22 ⇋ Me R 30 + H 2 O), and the
MgCO
reaction of H 2 O with MgO (MgO + H 2 O
O + CO ⇋ Mg(OH) 2 ) in a temperature range of 300 to 1200 K
Me
⇋ MgCO ) and Mg(OH) (Mg(OH) + CO ⇋ MgCO + H O), and t
2
3 2 2 2 3 2
at ambient pressure; calculated with HSC Chemistry 8.
(MgO + H O ⇋ Mg(OH) ) in a temperature range of 300 to 1200 K a
2 2
When water vapor is present at low system temperatures, CO2 is released from
with
MgCOHSC Chemistry 8.
3 , and Mg(OH)2 is formed instead of MgO during regeneration. Fagerlund et al.

When water vapor is present at low system temperatu

MgCO3, and Mg(OH)2 is formed instead of MgO during reg
Energies 2023, 16, 2973 12 of 29

forming MgCO
(2012) proposed 3. It can thus
a mechanism for MgO becarbonation
concluded that
in the waterof vapor
presence givesWhen
water vapor. access to
chemisorption
MgO is surrounded interactions
by water, CObetween
3
2 − and HMgO
+
and CO
ions form. [71]. ions
Free2 Mg 2+
However, for
then react MgO-ba
with
CO 2− forming MgCO . It can thus be concluded that water vapor gives access to im-
bents, a high water content in the sorbent system requires high energy due to th
3 3
proved chemisorption interactions between MgO and CO2 [71]. However, for MgO-based
heat. For MgO
adsorbents, a highaswater
a catalyst
contentsupport, water
in the sorbent mayrequires
system have ahigh
negative
energyimpact on the ca
due to the
active
sensiblemetal species.
heat. For MgO as a catalyst support, water may have a negative impact on the
Wu and
catalytically Goodman
active (1992) showed that water dissociates heterolytically on
metal species.
Wu and Goodman (1992) showed that water dissociates heterolytically on MgO sur-
faces [23].
faces [23].
Thephase
The phase transformation
transformation behavior behavior of MgO
of MgO and MgCO3and withMgCO 3 with
water are water
depicted in are d
Figure
Figures 5 and6,Figure
5 and 6, respectively.
respectively.

Figure
Figure 5.5.Equilibrium
Equilibrium soliddiagram
solid phase phase ofdiagram
the systemof the system
MgO–H 2 O: solid MgO–H 2O:
phase fields solid
were phase field
predicted
as a function of the temperature and the feed hydrogen mole fraction; gaseous products
dicted as a function of the temperature and the feed hydrogen mole fraction; gaseous p are not shown;
data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies). The solid phases at equilib-
not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies). The s
rium were predicted as a function of the temperature and the feed H2 O (n0,H2 O /(n0,H2 O + n0,MgO )),
at equilibrium were predicted as a function of the temperature and the feed H2O (𝑛0,H
where n0 denotes the number of moles of the feed component.
𝑛0,MgO )), where n0 denotes the number of moles of the feed component.
 Figure 5. Equilibrium solid phase diagram of the system MgO–H2O: solid phase field
dicted as a function of the temperature and the feed hydrogen mole fraction; gaseous p
not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies). The s
Energies 2023, 16, 2973 at equilibrium were predicted as a function of the temperature and the feed
13 of H
29 2O (𝑛0,H
𝑛0,MgO )), where n0 denotes the number of moles of the feed component.

Figure
Figure 6.6. Equilibrium
Equilibrium solid
solid phasephase diagram
diagram of theMgCO
of the system system3 –HMgCO 3–H
2 O: solid 2O: fields
phase solidwere
phase field
predicted as a function of the temperature and the feed hydrogen mole fraction; gaseous prod-
dicted as a function of the temperature and the feed hydrogen mole fraction; gaseous p
ucts are not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies).
not shown; data calculated with FactSage 8.0™ (Thermfact and GTT-Technologies). The s
The solid phases at equilibrium were predicted as a function of the temperature and the feed
atH equilibrium were predicted as a function of the temperature and the feed H2O (𝑛0,H
2 O (n0,H2 O /(n0,H2 O + n0,MgCO3 )), where n0 denotes the number of moles of the feed component.
𝑛0,MgCO3 )), where n0 denotes the number of moles of the feed component.
4. Hydrogenation of MgCO3
Baldauf-Sommerbauer et al. (2016) discussed the conversion of mineral magnesite to
MgO, methane, CO2 and CO in a hydrogen atmosphere at ambient pressure and overpres-
sure without additional catalysts. This process was termed reductive calcination. It was
reported that low temperature and elevated pressure facilitate CH4 formation, whereas
CO formation is enhanced at moderate to high temperature and low pressure. Methane
is formed directly without any additional catalyst from mineral magnesite. It was stated
that such reductively calcined MgO acts as a highly active reverse water–gas shift catalyst.
This was confirmed by CO formation from gaseous CO2 and H2 at catalytically active,
reductively calcined MgO. The reduction of CO to methane was not catalyzed by the
reductively calcined MgO [20].
In another study from Baldauf-Sommerbauer et al. (2017), the reductive calcination of
magnesite and dolomite to CO and methane was suggested as a means to reuse CO2 and
produce value-added carbonaceous products in mineral processing. More than 70% of the
CO2 emitted during the reductive calcination of the magnesite phase of a mixed magne-
site/dolomite (1:1 mol/mol) sample could be converted to CO at moderate temperature
without the admixture of catalysts [72].
Figure 7 depicts the phase transformation behavior of MgCO3 with H2 .
 of magnesite and dolomite to CO and methane was suggested as a means to r
and produce value-added carbonaceous products in mineral processing. More
of the CO2 emitted during the reductive calcination of the magnesite phase of
magnesite/dolomite (1:1 mol/mol) sample could be converted to CO at moderate
Energies 2023, 16, 2973 ature without the admixture of catalysts [72]. 14 of 29

Figure 7 depicts the phase transformation behavior of MgCO3 with H2.

Figure 7. Equilibrium solid phase diagram of the system MgCO3 –H2 : solid phase fields were
Figure 7. Equilibrium solid phase diagram of the system MgCO3–H2: solid phase fields
predicted as a function of the temperature and the feed hydrogen mole fraction; gaseous prod-
ucts are as
dicted nota function
shown; dataof the temperature
calculated and the
with FactSage feed
8.0™ hydrogen
(Thermfact andmole fraction; gaseous pr
GTT-Technologies).
not solid
The shown; dataatcalculated
phases equilibriumwith
wereFactSage
predicted 8.0™ (Thermfact
as a function of theand GTT-Technologies).
temperature and the feed The so
at equilibrium were predicted as a function of the temperature and the feed H2 (𝑛0
H2 (n0,H2 /(n0,H2 + n0,MgCO3 )), where n0 denotes the number of moles of the feed component.
𝑛0,MgCO )), where n0 denotes the number of moles of the feed component.
3
5. Methane Synthesis over MgO-Supported Catalysts
For methane synthesis via CO2 hydrogenation, a large number of studies has been
5. Methane Synthesis over MgO-Supported Catalysts
conducted based on noble metal catalysts such as Ru [73,74], Rh [75–78] and Pd [79–81] that
describeForthemethane synthesis
high catalytic via excellent
activity and CO2 hydrogenation,
stability of theseacatalysts.
large number
However,of thestudies
high price of noble metal catalysts is a limiting factor for industrial
conducted based on noble metal catalysts such as Ru [73,74], Rh [75–78] and P application. Non-noble,
transition-metal catalysts such as Ni-based catalysts are a promising alternative; not only
that
as they describe
are more the high catalytic
cost-effective compared activity
to nobleand
metalexcellent
catalystsstability of these
but also because catalysts. H
of their
the high catalytic
improved price ofactivity
nobleatmetal catalysts isIn
low temperatures. a CO
limiting factor for
2 methanation, lowindustrial
temperatures applicati
noble,
are transition-metal
favorable catalysts
for high equilibrium such asAsNi-based
conversions. a drawback, catalysts
Ni-based are a promising
catalysts often al
suffer from deactivation due to the sintering of Ni particles, formation
not only as they are more cost-effective compared to noble metal catalysts but also of mobile nickel
sub-carbonyls or formation of carbon deposits [82].
of their improved
In addition to the catalytic
catalyticallyactivity at low
active metal temperatures.
species, In CO
CO2 methanation 2 methanation, low
catalysts gener-
atures
ally areoffavorable
consist metal oxidesfor high equilibrium
as carrier materials. These conversions.
may also act asAs a drawback,
adsorbents. Ni-based
Thus, the
support material provides a crucial factor that affects both the adsorption properties of the
reactants and the catalytic activity of the catalyst. In general, a high surface area is required.
Common support materials for Ni-based methanation catalysts include Al2 O3 , SiO2 , TiO2 ,
CeO2 and ZrO2, in addition to MgO [40]. MgO has the decisive advantage that it reduces
catalyst deactivation such as sintering and carbon formation [41,83,84]. Therefore, several
researchers have studied the use of MgO as a carrier material for Ni-based methanation
catalysts, mainly in combination with other carrier materials and promoters.

5.1. Experimental Studies for CO2 Methanation over Ni/MgO Catalysts

In the literature, Ni/MgO catalysts were successfully used for CO2 methanation.
Table 1 gives a compilation of the experimental studies that include Ni-based catalysts on
MgO carrier material for CO2 methanation.
Energies 2023, 16, 2973 15 of 29

Table 1. Experimental studies using Ni-based catalysts on MgO carrier material for CO2 methanation.

Catalyst Preparation Operation Performance Comments Ref.

Composition Method Conditions
Ni/MgO wet T = 533–648 K XCO2 = 87% [13]
(wNi = 0–27 wt%) impregnation GHSV = YCH4 = 99%
3.7 m3 kg−1 h−1
v(H2 ):v(CO2 ):v(N2 ) =
4:1:5
Ni/MgO wetimpregnation T = 603 K XCO2 = 70% [15]
(wNi = 11 and 17 wt%) GHSV = YCH4 = 99 %
1.24–5 m3 kg−1 h−1
NiO/MgO sonochemicalmethod T = 673 K, GHSV = XCO2 = 85% [85]
(with and without 47.76 h−1 YCH4 = 98%
impregnation with 2% (XCO2 = 90% (Co), 86%
Co, Cu, Fe) (Cu), 89% (Fe)
YCH4 = 99% (Co), 94%
(Cu), 96% (Fe))
Ni/MgO-CNTs 1 precipitation T = 473–713 K X(CO+CO2) = ~100% [86]
GHSV = 40 m3 kg−1 YCH4 = ~100%
h−1
v(H2 ):v(CO):v(N2 ):v(CO2 )
= 75:15:5:5
Ni/MgO citric acid T = 553 K XCO2 = 62–85% space–time yield of [87]
(wNi = 30–90 wt%) complex method v(CO2 ):v(H2 ) = 1:8 SCH4 = 99–100% CH4 : 8.7–28.2 min−1
Ni/MgO coprecipitation T = 553 K XCO2 = 32% space–time yield of [87]
(wNi = 70 w%t) v(CO2 ):v(H2 ) = 1:8 SCH4 = 68% CH4 : 2.7 min−1
Mg-Al-CO3 LDH 2 coprecipitation T = 473–573 K CO2 sorption: 2.72% [69]
catalyst v(CO2 ):v(O2 ):v(N2 ) = (dry sorption), 3.14%
14:4:82 (wet condition, 12%
water)
Ni/MgO DFT calculations [40]
Ni(111), MgO (110)
1 carbon nanotubes, 2 layered double hydroxide.

Takezawa et al. (1986) studied 13% Ni/MgO catalysts for CO2 methanation that were
prepared by impregnation at various preparation conditions (calcination at 673 K, 773 K,
803 K, 873 K, and 973 K with air for 3 h and reduction at 773 K, 803 K, and 873 K with hy-
drogen at 50 mL min−1 for 13 h). The results showed that at a high calcination temperature
(973 K), the Ni(II) ions are highly dispersed in the MgO carrier and become less reducible.
In addition, the activity and selectivity of the Ni/MgO catalysts decrease considerably
with increasing calcination temperature (973 K). The study presented a methane selectivity
of 98% for calcination at 773 K and reduction at 873 K, a feed flow rate of 100 mL min−1
(CO2 :H2 = 5:95), a pressure of 1 atm and a reaction temperature of 480 K [88].
Bette et al. (2016) studied the catalytic effect of 59 wt% nickel on (Mg,Al)Ox which they
derived from a (Ni,Mg,Al)-hydrotalcite-like precursor on CO2 methanation in a fixed-bed
tubular quartz reactor. The catalyst was calcined at 873 K in air, and metallic Ni parti-
cles supported on a spinel-type (Mg,Al)Ox matrix were obtained through reduction at
1173 K in a mixed flow of 10% H2 in N2 . The reaction temperature was varied be-
tween 523 and 623 K at ambient pressure with a WHSV (weight hourly space velocity) of
1100 mL gcat −1 min−1 (H2 :CO2 :Ar:N2 = 18.5:4.6:12.8:64.1). The results showed a maximum
CO2 conversion of 72–76% at reaction temperatures of 603–623 K. At a reaction temperature
of 528 K, the catalyst provided good long-term stability under methanation conditions
for up to 50 h on stream with a stable CO2 conversion of 17–23 % and a CH4 yield of
17–19 % [89].
Guo et al. (2014) studied the catalytic behavior of 10 wt% Ni/SiO2 that was
modified with 1–4 wt% MgO prepared by co-impregnation and calcination at 723 K for
3 h and a cool down to room temperature by mixed 50% H2 in N2 . The methanation
Energies 2023, 16, 2973 16 of 29

reaction was carried out in a fixed-bed continuous flow quartz reactor in a temperature
range of 473–773 K at atmospheric pressure and a feed flow rate of 50 mL min −1
(CO2 : H2 : N2 = 1:4:3). They found that modification with MgO increases the dispersion
of Ni species and also suppresses sintering and oxidation of metallic Ni. Furthermore,
catalyst (10 wt% Ni/SiO2 ) modification with MgO in a quantity of as low as 1 wt%
features pronounced catalytic activity and stability at 623 K for 50 h with 66.5% CO2
conversion and 96.8% methane selectivity [83].
Nakayama et al. (1997) investigated Ni/MgO catalysts (10, 30, 50, 70 and 90% Ni)
by using citric acid and calcination in air at 773 K for 3 h followed by reduction in pure
H2 at 773 K for 2 h. A fixed-bed flow reactor was used for hydrogenation of CO2 with
a feed flow rate of 180 mL min−1 (with varied feed ratio of CO2 :H2 = 1:4 and 1:8) and
a temperature of 553 K at atmospheric pressure. The CO2 conversion at 553 K with 30,
50, 70 and 90% Ni-catalysts were 62%, 79%, 85% and 79%, respectively, and the methane
selectivity ranged at 99–100% for all catalysts with ≥30 wt% Ni. It was suggested that
aggregation of metallic Ni particles was depressed by MgO that was dispersed in the Ni
particles during the reduction of the NiO-MgO solid solution [87].
Varun et al. (2020) prepared NiO/MgO nanocomposite catalysts for CO2 hydro-
genation via four preparation methods. The preparation methods included sonochemical,
co-precipitation, impregnation, and solution combustion methods. The reaction tempera-
ture was 448–723 K at atmospheric pressure. The catalysts prepared by the sonochemical
route gave the best catalytic performance with respect to CO2 conversion and methane
selectivity. They reported the highest CO2 conversion of 85% with 98% methane selectivity
at 673 K with NiO/MgO catalysts and concluded that the MgO carrier promotes CO2
adsorption, which provides more interaction time for H2 and CO2 that enables methane to
be formed at low temperature. They also impregnated NiO/MgO catalysts with 2% Co,
Cu and Fe, whereby impregnation with Co resulted in a significantly reduced activation
energy for CO2 hydrogenation to methane [85].
Baldauf-Sommerbauer et al. (2018) tested two catalysts with a Ni loading of 11 and
17 wt% on MgO. The catalysts were prepared by wet impregnation and resulted in a
Ni/MgO solid solution with a cubic lattice. They performed experiments with a controlled
increase of the catalyst temperature to 773 K (due to the exothermicity of the reaction) and
compared them to steady-state experiments. The two experimental procedures yielded
comparable results in terms of CO2 conversion and methane selectivity. It was shown that
at a moderate reaction temperature of 598 K and a feed composition of H2 :CO2 :N2 = 4:1:5 at
a flow rate of 250 mLSTP min−1 , CO2 conversion and methane selectivity were near the ther-
modynamic equilibrium. With reactor operation for several days at a reaction temperature
of 603 K, the long-term stability of Ni/MgO (17 wt% Ni) catalysts was proven [15]. Loder
et al. (2020) extended this study and investigated the effect of Ni loading (0 to 27 wt%)
and MgO quality on the rate of methanation in a temperature range of 533–648 K. To
investigate the effect of matrix elements, a mixed MgO/CaO carrier material was tested
with 21 wt% nickel loading. The reaction kinetics of CO2 methanation was modeled with a
Langmuir–Hinshelwood approach describing a bifunctional character of the catalyst. Both
studies show that Ni/MgO catalysts act as robust, active and highly selective catalysts for
CO2 methanation, with a CO2 conversion of 87% and a methane selectivity of 99% [13].

5.2. Reaction Mechanism for CO2 Methanation

In the literature, the reaction mechanism for CO2 hydrogenation to methane is gener-
ally classified according to the initial CO2 hydrogenation step in three typical pathways:
(i) CO2 direct dissociation pathway, meaning CO2 direct dissociation into CO*, (ii) formate
pathway, meaning C-terminal hydrogenation of CO2 to HCOO* species, and (iii) carboxyl
pathway, meaning O-terminal hydrogenation of CO2 to COOH* species [90,91].
However, regardless of the pathway, initial adsorption and activation of the reactants,
CO2 and H2 are the decisive steps for the reaction. Several researchers have discussed the
importance of synergistic interactions at the metal/metal oxide interface of the catalyst.
Energies 2023, 16, 2973 17 of 29

Moreover, Ni/MgO catalysts have proven to exhibit bifunctional catalytic activity during
CO2 hydrogenation to methane; while Ni provides the adsorbent capacity for hydrogen,
MgO activates CO2 through chemisorption. For Ni/MgO catalysts the crucial role of
carbonate formation via CO2 adsorption has also been pointed out [40].
To elucidate the roles of Ni and MgO and any support effects on the reaction mech-
anism of CO2 hydrogenation to methane, Huang et al. (2019) [40] performed DFT calcu-
lations. They investigated CO2 hydrogenation on pure Ni (111), hydrogen-assisted MgO
(110) and Ni/MgO catalysts. From their calculations, they confirmed that in Ni/MgO
catalysts Ni is the catalytically active site, and MgO takes over the role as promoter for CO2
hydrogenation to methane. Ni is not only responsible for the dissociation of H2 to H atoms
but also provides the active site for CO2 hydrogenation. Huang et al. also reported strong
metal–support interactions between Ni and MgO in Ni/MgO catalysts compared to pure
Ni surfaces. This distinctly improves the Ni reducibility of the Ni/MgO surface, leading to
the fact that the terminal C of CO2 gains more electrons from the Ni/MgO surface. Thus,
on the Ni/MgO surface, the formate pathway via H2 COO* intermediates is promoted. This
differs from the methane formation on Ni (111), which follows the formate pathway via
HCOOH* intermediates. Moreover, H-spillover and strong OH adsorption on the MgO
carrier favor OH removal and H2 O formation during CO2 hydrogenation. Huang et al.
also pointed out that on the MgO (110) surface, CO2 preferentially adsorbs at the O-top
site of MgO by carbonate formation. On Ni/MgO, the CO2 molecules are adsorbed at the
interface of Ni/MgO and those C atoms form Ni–C bonds with a Ni atom [40].
Loder et al. (2020) studied the reaction mechanism of so-called bifunctional Ni/MgO
catalysts for CO2 methanation in a temperature range of 533–648 K and atmospheric
pressure. To describe the reaction kinetics, a Langmuir–Hinshelwood reaction model
was developed that considers CO2 and H2 adsorption on the catalyst [13]. This sup-
ports the bifunctional catalytic activity of Ni/MgO catalysts. The postulated reaction
model was based on five steps: (i) dissociation of H2 and adsorption on Ni (Equation (8)),
(ii) adsorption of CO2 on the Ni-MgO interface, whereby adsorbed CO2 is attached to two
active Mg sites and one active nickel site, as shown by Huang et al. (2019) (Equation (9)),
(iii) reaction of adsorbed CO2 with adsorbed hydrogen (Equation (10)) to produce methane
and the byproduct H2 O (Equation (11)), (iv) desorption of the reaction product methane
(Equation (12)), and (v) desorption of the byproduct water (Equation (13)). In the literature,
the adsorption of hydrogen on Ni is described as the rate-controlling step for Ni-based
catalysts [92]. As with bifunctional Ni/MgO catalysts, hydrogen (on Ni) and CO2 (on the
Ni-MgO interface) are adsorbed; the availability of active nickel sites is decisive. Hence,
species adsorption on Ni in general was assumed to be rate-controlling by Loder et al. (2020).
As their basic aim was to develop a simple rate law with adequate accuracy, hydrogen and
CO2 adsorption were combined, and it was assumed that both were rate-controlling. As
postulated by Huang et al. (2019), it was assumed that methane is adsorbed on one nickel
site and water on one magnesium site [13].

H2 + 2 Ni ⇋ 2 HNi (8)

CO2 + 2 Mg + Ni ⇋ CO2 (Mg)2 Ni (9)

H2 + CO2 + 2 Mg + 3 Ni ⇋ 2 HNi + CO2 (Mg)2 Ni (10)

CO2 (Mg)2 Ni + 8 HNi ⇋ CH4 Ni + 2 H2 OMg + 8Ni (11)

CH4 Ni ⇋ CH4 + Ni (12)

H2 OMg ⇋ H2 O + Mg (13)
Energies 2023, 16, 2973 18 of 29

Several researchers have mentioned carbonate formation as an intermediate step

during CO2 methanation over Ni-based catalysts on various carrier materials. Pan et al.
(2014) investigated Ni-based catalysts on Ce0.5 Zr0.5 O2 and γ-Al2 O3 using in situ FTIR
spectroscopy. They found similar reaction pathways for both carrier materials, which only
differed in the reactive basic sites, and concluded that CO2 adsorption on medium basic
sites (Ni/Ce0.5 Zr0.5 O2 ) results in monodentate carbonates, while CO2 adsorption on strong
basic sites (Ni/γ-Al2 O3 ) does not participate in the reaction. It was proposed that medium
basic sites enhance the catalytic activity toward CO2 methanation as monodentate formate
derived from monodentate carbonate on medium basic sites can be hydrogenated more
quickly than bidentate formate derived from hydrogen carbonate. CO2 adsorbed on strong
basic sites cannot desorb from the surface until high reaction temperatures and, thus, will
not participate in methane formation at lower temperatures [93].
Moreover, Park and McFarland (2009) described the beneficial effect of carbonate
formation during CO2 methanation over Pd-based catalysts. They prepared bifunctional
Pd–Mg/SiO2 catalysts using the properties of Pd to dissociate molecular hydrogen to
hydrogen atoms, which are subsequently transferred and converted with activated surface
carbonate species. The carbonate species are formed by the reaction of CO2 with the
Mg-containing oxide. It was reported that with carbonate-forming catalyst combinations,
meaning MgO-containing catalysts, a high selectivity to methane and a corresponding
higher H2 conversion was observed due to stabilization of the intermediate carbonate
MeO2 –CO and, thus, inhibition of CO desorption [64].
Westermann et al. (2015) studied the catalytic effect of 5–14% Ni on NiUSY and re-
ported that increasing Ni content increases the CO2 conversion (44.9–72.6%) and methane
selectivity (60–95%). The mechanism of CO2 hydrogenation on impregnated NiUSY cat-
alysts (5–14%Ni) was also investigated over various temperatures. They stated that
the occurrence of CO arises from formate (T ≤ 473 K). Methane formation is found
when the system’s energy becomes high enough for CO hydrogenation or dissociation
(473 ≤ T ≤ 573 K). The C-O dissociation step is the rate-determining step following
HCOO− (ads) → CO(ads) → CH4 (g). High CO concentrations are formed on the surface
and limit CO hydrogenation and dissociation (573 ≤ T ≤ 623 K). At 573 K, the maximum
CO concentration is reached, which limits formate dissociation regarding a Langmuir–
Hinshelwood mechanism. As methane concentrations increase along with increasing
temperature, it can be assumed that formate can be directly hydrogenated to methane. Due
to the vacancy of new active sites, formate is hydrogenated to methane. In addition, CO
is obtainable for hydrogenation and dissociation with decreasing CO concentration and
increasing methane concentration (T ≥ 623 K). Methane formation is limited by thermo-
dynamics and the rate-determining step (dissociation/hydrogenation of CO). From the
studies at different temperatures, Westermann et al. (2015) also proposed a mechanism
with NiUSY catalysts, in which initiation occurs via two options: (i) CO2 adsorbs onto
exchangeable cations or (ii) monodentate onto EFAL/Ni species. Then, dissociated hy-
drogen reacts to monodentate formate, which is adsorbed onto Ni (T = 423 K). At 573 K,
formate dissociates to carbonyl and methane with a low rate of methane formation. An
increase in Ni loading results in an increase in adsorption sites, generating more adsorbed
formate species. From the study of zeolites, it was concluded that carbonate is not likely to
be directly hydrogenated to methane but mainly via formate formation and dissociation to
carbonyls [94].
In addition to Ni-based catalysts on MgO, Kim et al. (2010) suggested a reaction
mechanism for CO2 methanation over MgO-supported Pd-based catalysts (Pd-MgO/SiO2 )
elucidating the decisive role of carbonate formation. The Pd-MgO/SiO2 catalysts were
prepared by a reverse microemulsion (ME) method. The reaction mechanism depicts
the role of Pd and MgO in CO2 methanation and shows that MgO enables magnesium
carbonate formation on the surface. This step adopts a critical role in CO2 methanation.
Pd can dissociate hydrogen molecules that are responsible for consecutive magnesium
carbonate hydrogenation to methane. This mechanism focuses on the following steps on
Energies 2023, 16, 2973 19 of 29

MgO surfaces: (i) CO2 adsorption occurs on the MgO surface and exposes carbonate on
MgO to hydrogen atoms. The oxygen species of carbonate are then hydrogenated with two
hydrogen molecules whereby water is formed. (ii) The residual C on the MgO surface is
hydrogenated with hydrogen to form methane [41].
The formation of carbonate species during CO2 methanation was also reported by
Arellano-Treviño et al. (2019). They investigated the effect of different metal loading on
MgO carrier material for three different catalysts including Ni-based catalysts (5% Ru, 0.5%
Rh, 10% Ni). They also used Na2 O, CaO, and K2 O as carrier material. The methanation
reaction with 5% Ru_10% MgO/Al2 O3 catalysts was performed in a packed-bed reactor at
a temperature of 593 K and atmospheric pressure. The feed flow rate was 30 mL min−1
(CO2 /N2 = 10:90) plus 30 mL min−1 (H2 :N2 = 15:85). With MgO/Al2 O as the carrier
material, 91% CO2 conversion was achieved showing that MgO/Al2 O3 is a suitable carrier
material for low-temperature methanation (T < 423 K). This may be dedicated to the
fact that bicarbonate and bidentate carbonate (bonds between CO2 and MgO/Al2 O3 ) can
be active at low temperatures with both carbonate sites increasing the catalyst activity.
However, infrared studies of the Ni catalysts showed that also inactive carbonate species
were formed on the Ni surface that resulted in unreacted adsorbed CO2 [95].
Baldauf-Sommerbauer et al. (2016) reported methane formation through hydrogena-
tion of mineral magnesite in a fixed-bed tubular reactor with a flow rate of 500 mL min−1
(H2 : N2 = 9:1) in a temperature range of 748 K, 763 K and 778 K, and a pressure of
0.3–1.2 MPa. It was shown that with increasing MgCO3 conversion, the methane yield
increased from 4.9 to 36.6% at 748 K, from which it was assumed that the dissociation of
carbonates has a positive effect on methane formation [20]. This is in accordance with the
findings and conclusion of Arellano-Treviño et al. [95].
Interestingly, carbonate formation was also mentioned for Ni-based catalysts on SiO2
carrier material, whereby it must be noted at this point that SiO2 normally reacts acidically.
Xu et al. (2021) studied CO2 methanation over Ni/SiO2 catalysts that were prepared by a
combustion-impregnation method and reported 66.9% CO2 conversion and 94.1% selec-
tivity to methane at 593 K. These results were superior than CO2 conversion and methane
selectivity with Ni/SiO2 catalysts that were prepared by the conventional impregnation
method. They proposed a reaction pathway in which CO2 adsorption occurs on the support
sites that are located close to the metal–support interface enabling carbonate, hydroxy-
carbonate or carbonyl formation. Xu et al. interestingly described basic sites of Ni/SiO2
catalysts that were classified as weak basic sites (bicarbonate) at 323–573 K, medium basic
sites (bidentate) at 473–673 K and strong basic sites (monodentate carbonate) at 673–1073
K. They stated that more medium basic sites which were beneficial for the CO2 activation
could be created by the combustion-impregnation method. The carbonate species were
then hydrogenated to yield methane [96].
To conclude, the above-mentioned publications elucidate the crucial role of a ba-
sic support material enabling carbonate formation through CO2 adsorption during CO2
methanation over Ni-based catalysts. Following the reaction mechanism postulated by
Park and McFarland (2009) for a highly dispersed Pd–Mg/SiO2 catalyst, a similar reaction
mechanism is conceivable for CO2 methanation over Ni/MgO catalysts (Figure 8). The
mechanism is based on the following steps [64]:
(i) CO2 is stabilized by MgO via CO intermediates forming carbonate at the surface. The
carbonate formation has a critical role in CO2 methanation. CO dissociation may be
rate-determining.
(ii) The carbonate is sequentially hydrogenated producing a carboxy group and water
as byproduct.
(iii) The carboxy group reacts with MgO to form MgCOO and is sequentially hydrogenated
forming MgCOOH, whereas one molecule of water is generated.
(iv) Hydrogenation with three hydrogen atoms on the MgO surface forming
MgOC—MgOCH—MgOCH2 —MgOCH3 , respectively.
(v) MgOCH3 is hydrogenated with a hydrogen atom to form MgO and methane.
 ated forming MgCOOH, whereas one molecule of water is ge
(v) Hydrogenation with three hydrogen atoms on the MgO sur
MgOCH—MgOCH2—MgOCH3, respectively.
Energies 2023, 16, 2973 20 of 29
(vi) MgOCH3 is hydrogenated with a hydrogen atom to form Mg

Figure 8. A potential bifunctional mechanism for Ni–MgO whereby spillover of atomic hydrogen
from Ni in contact with MgCO3 sequentially hydrogenates carbon until the product methane desorbs
(adapted from Pd-Mg/SiO2 catalysts from [64]).

6. Methanol Synthesis over MgO-Supported Catalysts

Various catalysts for methanol synthesis from CO2 have been developed and in-
tensively investigated over the last decades. Analogous to CO2 methanation, the main
influencing factors for the catalytic activity, stability and selectivity of the catalysts are the
process conditions for the reaction, the preparation method of the catalyst, the choice of
the catalytically active material, the catalyst carrier material, and the use of promoters.
The target of optimum process conditions, such as temperature, pressure, feed gas compo-
sition and flow rate, the amount of catalyst, and continuous or batch operation mode is
controlled by the thermodynamics and the kinetics of the reaction. The choice of carrier
material, additional promoters, and the preparation method affect catalyst parameters
such as particle size, surface area, distribution of the catalytically active metal, acidity
and basicity of the carrier material, and temperature and pressure stability of the catalyst.
In general, catalysts for methanol synthesis by CO2 hydrogenation can be categorized as
follows: Cu-based catalysts, noble metal-based catalysts (Pd, Pt), oxygen-deficient catalysts
(In2 O3 ), and bimetallic catalysts (Ni-Ga, Au-Ag) [97,98].
Cu-based catalysts have attracted research interest over the past years, and they are
already industrially applied, mainly with the carrier material Al2 O3 and the promoter ZnO.
However, the bottleneck of Cu/ZnO/Al2 O3 catalysts is their deactivation behavior and the
relatively low selectivity for methanol because of byproduct formation [99–101].
Energies 2023, 16, 2973 21 of 29

In Cu-catalyzed synthesis of methanol by CO2 hydrogenation, the nature of the carrier

material has a pronounced effect on the reaction mechanism [102]. The catalytic activity
linearly correlates with the metallic Cu0 surface [103,104], indicating that the reaction takes
place at the metallic Cu0 surface [6]. Several studies have shown that the admixture of
MgO as an additional promoter increases CuO dispersion, the metallic Cu0 BET surface
area and the active basic sites for improved CO2 and also H2 adsorption [6,41,105–110].

6.1. Experimental Studies for CO2 Hydrogenation to Methanol over Cu-Based Catalysts with MgO
In the literature, various studies are presented with Cu-based catalysts using MgO ei-
ther as a carrier material or as promoter (Table 2). However, compared to CO2 methanation,
the use of MgO as a sole carrier material is rarely suggested.
To hinder agglomeration and increase the surface area of Cu-based catalysts, alkaline
earth metal oxides are mentioned as attractive materials for promoters and catalyst support
material [111,112]. Dasireddy et al. (2018) evaluated the effect of alkaline earth metal
oxides (MgO, CaO, SrO and BaO) on Cu/Al2 O3 catalysts in methanol synthesis by CO2
hydrogenation and compared the results with commercially available Cu/ZnO/Al2 O3
catalysts. They reported that according to their electronegativity, the basicity of the catalysts
increased in the order of Zn < Mg < Ca < Sr < Ba. The introduction of alkaline earth metal
oxides enhanced the interaction between Al2 O3 and CuO, which resulted in a weaker
reducibility of CuO. The Cu+ :Cu0 ratio and Cu0 surface area were higher in all alkaline-
earth-metal-containing catalysts, compared to the Cu/ZnO/Al2 O3 catalyst, and increased
in the order of Ba < Ca < Zn < Sr < Mg. A higher Cu+ :Cu0 ratio as well as a higher Cu0
surface area were stated as significant factors for the enhanced CO2 conversion. Moreover,
all catalysts showed an enhanced activity in methanol synthesis with increasing GHSV.
Best results were obtained with the Cu/MgO/Al2 O3 catalyst, which showed an increased
number of active sites for CO2 and H2 adsorption. The catalytic performance exceeded
even the commercially available HFRI20 and LURGI catalysts [113].
Ren et al. (2015) investigated the promoting effect of ZnO, ZrO2 and MgO on a
Cu/γ-Al2 O3 catalyst. The introduction of the metal oxides increased the Cu0 dispersion,
the Cu0 surface area and decreased the Cu0 particle size. While the promotional effect of
individually added ZnO and ZrO2 on CO2 hydrogenation to methanol was marginal, the
simultaneous addition of both oxides increased the CO2 conversion and methanol selectiv-
ity significantly. Even better results were achieved with the Cu/ZnO/ZrO2 /MgO/γ-Al2 O3
catalyst. The optimal ratio of Mg:Zr was observed to be 1:9. A significant increase in STY
(space–time yield) was observed for increasing GHSV. The optimal activation temperature
of the catalyst was reported to be the hydrogenation temperature. Though lower activation
temperatures form smaller Cu0 particles and a higher Cu0 surface area, particles seem to
agglomerate if the reaction temperature exceeds the activation temperature [105].
Chatterjee et al. (2019) investigated support interactions in Cu-based catalysts and
reported of (strong) metal–support interactions (SMSI). They noted that Cu-supported
MgO behaves very much like Cu/Al2 O3 and Cu/Ga2 O3 [9]. Baseline experiments with
pure Cu were in accordance with experimental results from Fichtl et al. (2014) [114],
but the results with Cu/MgO were contrary to the ones from Fichtl et al. However,
it was speculated that the differences were caused by the preparation methods, which
elucidates the critical role of the catalyst preparation method and conditions, and the
calcination temperature.
A comprehensive review of Cu-based CO2 hydrogenation to methanol giving insights
from experimental work and theoretical analysis was presented by Niu et al. (2022). They
investigated structural and surface properties of Cu-based catalysts for methanol synthe-
sis. A stronger inverse kinetic isotope effect of H/D substitution for methanol synthesis
compared to CO formation was observed, suggesting that methanol synthesis and CO
formation do not share a common intermediate, which indicates that CO2 hydrogenation
to methanol is not a combination of the RWGS reaction and CO hydrogenation. CO2 acts
as dominant carbon source on Cu0 surfaces, while CO is the dominant carbon source on
Energies 2023, 16, 2973 22 of 29

Cu+ . The reaction rate of CO2 hydrogenation was reported to be faster than that of CO
hydrogenation. H2 dissociation was described to proceed on the Cu surface, while CO2
adsorption is more favored to occur on the support or the interface [115].
Liu et al. (2016) investigated MgO promotion of Cu/TiO2 catalysts. MgO promotion
resulted in a larger specific surface area of TiO2 and increased Cu dispersion. However, an
excess of MgO covered the surface of TiO2 and thereby decreased Cu dispersion [108].
Cu-based catalysts are not only the most commonly used catalysts in methanol syn-
thesis from CO2 but are also good candidates for the water–gas shift reaction and the
reverse water–gas shift reaction. Thus, there is still a lively debate about the dominant
carbon source for methanol synthesis; CO or CO2 . It is well known that both CO and CO2
can undergo hydrogenation to methanol, and thus, Robbins et al. (1991) suggested that
the dominant carbon source depends on the valence state of the surface Cu. CO2 acts as
the dominant carbon source on the Cu0 surface, while CO is the dominant carbon source
on the Cu+ surface. In addition, it was found that the reaction rate of CO2 hydrogena-
tion was faster than that of CO [104]. These findings were confirmed by Nielsen et al.
(2020) [6], suggesting that methanol is mainly generated via CO2 hydrogenation from the
CO/CO2 /H2 mixtures.
Cao et al. (2021) gave in his study further insights on CO and CO2 hydrogenation for
methanol synthesis and described the key role of adsorbate–adsorbate interactions on Cu
and the highly active MgO-Cu interface. They investigated two questions: (i) which of
the CO or CO2 hydrogenation routes dominates the methanol synthesis rate, and (ii) what
makes irreducible, inert oxides such as MgO efficient promoters for the CO hydrogenation
process. The MgO/Cu interface was reported to act as a highly active site proposing a
novel lattice oxygen-involved reaction mechanism at the interface for methanol formation.
Moreover, formate coverage effects and hydrogen bond formation can significantly lower
the activation barrier of the CO2 hydrogenation [116].
Yang et al. (2005) performed a mechanistic study of a novel low-temperature methanol
synthesis route on Cu/MgO catalysts from syngas using ethanol as a promoter [110].
The role of the oxide component in the development of Cu-based composite catalysts
for methanol synthesis from CO, CO/CO2 mixtures and CO2 was discussed by Zander et al.
(2013). It was found that ZnO acts as a geometrical spacer between the Cu nanoparticles
and helps to increase and stabilize the Cu dispersion. Thus, ZnO was reported to have two
functions in the final catalyst: (i) as nanoparticles, ZnO acts as a physical spacer between the
Cu particles, stabilizing the porous microstructure; and (ii) as a thin layer at the surface of
the Cu particles, ZnO is an essential ingredient for the active site, and its presence has been
shown to affect the adsorption properties. Cu/MgO catalysts showed a slightly smaller BET
surface area with smaller crystallites but a 20% higher Cu surface area. It was stated that
MgO is an intrinsically better geometrical spacer compared to ZnO as, even at a non-ideal
ratio (80:20), Cu particles could be obtained that, with an average size below 10 nm, were
similarly small as those found in state-of-the-art Cu/ZnO/Al2 O3 catalysts. Thus, it was
concluded that the structurally promoting role of ZnO had been successfully replaced by
MgO. However, in the hydrogenation of pure CO2 , Cu/ZnO showed a much higher activity
than Cu/MgO, showing clearly that the methanol synthesis rate was not only a function
of the exposed Cu surface area. The low activity of Cu/MgO in CO2 hydrogenation was
explained by the absence of the synergetic SMSI effect as MgO is an irreducible oxide that
does not show the necessary SMSI in the relevant temperature regime. The addition of 5%
ZnO to Cu/MgO increased the BET surface area, the Cu-specific surface area and crystallite
size, and also promoted methanol synthesis significantly without promoting the reverse
water–gas shift reaction [109].
Kleiber et al. (2022) proposed Cu/MgO catalysts in a novel process concept for direct
reduction of siderite ore combined with catalytic CO/CO2 hydrogenation to methanol [14].
In their first study (Kleiber et al. (2021) [117]), preliminary results of the activity of a
38 wt% Cu/MgO catalyst in a semi-continuous tank reactor were presented emphasizing
that the catalyst support material MgO was calcined at a low calcining temperature of
Energies 2023, 16, 2973 23 of 29

823 K. For the chosen calcining conditions, MgO is highly active with respect to CO2 adsorp-
tion. Good catalytic activity in CO2 hydrogenation and a high selectivity for methanol were
shown for the Cu/MgO catalyst. In repeated cycles with continuous product condensation
followed by reactant re-dosing, an overall relative CO2 conversion of 76% and methanol
selectivity of 59% were obtained. The maximum methanol selectivity in a single cycle was
88%. However, the long-term stability of the Cu-MgO catalyst was not investigated in this
preliminary study.

Table 2. Experimental studies using Cu-based catalysts on MgO carrier material for CO2 hydrogena-
tion to methanol.

Catalyst Preparation Operation Performance Comments Ref.

Composition Method Conditions
CuO/MgO impregnation T = 573 K XCO2 = 23–29% Semi-continuous [117]
(wCu = 38 wt%) p = 50 bar YCH3OH ~ 28% operation
v(CO2 ):v(H2 ) = 1:3 (after 53 h)
SCH3OH ~ 88% (after
53 h)
XCO2 = 76%
SCH3OH = 59%
Cu/MgO DFT calculations T = 500–600 K - [116]
PH2 = 30 bar, PCO2 =
PCO = 10 bar
Cu/MgO precipitation T = 523 K YCH3OH = ~20% [6]
(wCu = 50 wt%) p = 50 bar,
H2 /CO2 /inert = 68/3/29
Cu/MgO/Al2 O3 co-precipitation T = 523 K XCO2,2000h−1 = ~3% [113]
Cu:MgO:Al2 O3 = p = 20 bar CH3 OH2000h−1 = 0.80
50:30:20 n(H2 ): n(CO2 ) = 3:1 molCH3OH kg−1 h−1
GHSV = 2000 h−1 and CH3 OH6000h−1 = 1.48
6000 h−1 molCH3OH kg−1 h−1
TOFCH3OH = 11.9 ×
10−4 s−1
Cu-ZnO-ZrO2 - impregnation T = 523 K, XCO2 = 12.1% mCuO/MgO = [105]
MgO/Al2 O3 p = 20 bar, SCH3OH = 36.0% 5g
n(H2 ): n(CO2 ) = 3:1, SCH4 = 2.4% Cu:Zn:Zr:Mg = 2: 1:
GHSV = 1400 h−1 SCO = 61.61% 0.9: 0.1
STY (31.0 g kgCat −1
h−1 )

6.2. Reaction Mechanism for CO2 Hydrogenation to Methanol over Cu-Based Catalysts
Detailed investigations of the reaction mechanisms of CO2 hydrogenation to methanol
are available in the literature (e.g., for Cu/ZnO/Al2O3 [118], Cu/Al2O3 [119], Cu/MgO [116],
CuO/CeO2/ZrO2 [120]). The so-called formate pathway is a potential pathway for methanol
synthesis from CO2:

CO2 * → HCOO* → HCOOH* → CH3 O2 * → CH2 O* → CH3 O* → CH3 OH*

Tabatabaei et al. (2006) reported that CO2 adsorption on Cu/ZnO catalysts forms a
formate species (HCO2 − ) that is displaced by monodentate at an anion vacancy. Moreover,
bidentate formate was found on Zn-terminated ZnO surfaces at 530 K [121]. Similarly, Shido
and Iwasawa (1993) also reported bidentate formate formation on ZnO [122]. Furthermore,
Nielsen et al. (2020), who studied the mechanism of CO and CO2 hydrogenation to
methanol on bifunctional Cu-based catalysts, described that the bifunctional catalysts
combine the effect of copper and basic oxide with (i) basic oxide sites that activate CO as
formate at the metal/oxide interface, and (ii) metal-assisted hydrogenation of the interfacial
formate species. The results for the CO/H2 feed showed formate and methoxide formation
at 523 K and methanol formation at 423 K over Cu/MgO catalyst. The majority of formate
Energies 2023, 16, 2973 24 of 29

species on MgO were less reactive and more stable, which is pronounced for methanol
production, and less displaced by carbonate [6].
Regarding the formate pathway, carbonate formation has also been considered and
critically discussed for Cu-based catalysts. With Cu/MgO catalysts for CO2 /CO/H2 feed
streams, the presence of CO2 was reported to create carbonate and bicarbonate species (the
formate species react at the metal/oxide interface and are displaced by carbonate) and,
thus, deteriorates methanol production.
Nielsen et al. (2020) concluded that the presence of CO2 in mixed CO/CO2 feed
streams has a negative effect for basic oxide sites and, thus, the bifunctional interaction
results in a deactivation effect of CO2 on Cu/MgO catalysts due to carbonate blocking [6].
This agrees well with the findings of Cao et al. (2021) who discussed the adsorbate–
adsorbent interaction through microkinetic modeling. They described formate formation
at the surface that was poisoned and reduced the accessible sites for other intermediates,
leading to low methanol synthesis rates [116].
To conclude, the above-mentioned, sometimes contradictory, findings discussed above
point out that carbonate formation has a decisive role when MgO is used as support
material for metal-based catalysts. However, carbonate formation does not always have a
positive effect. It may also result in blocking and, for CO2 hydrogenation, limits methanol
formation. Following the reaction mechanism postulated by Nielsen et al. (2020) [6] for
CO2 and CO hydrogenation
supported to methanol
Cu catalysts, the reaction over
mechanism Cu/MgO
depicted catalysts,
in Figure indicating
9 is conceivable for CO2the dea
ing effect
and COof CO 2. It is suggested
hydrogenation that
to methanol with
over CO2,catalysts,
Cu/MgO the basic magnesium
indicating sites are block
the deactivating
inactive carbonate
effect of CO2 . Itspecies.
is suggested that with CO2, the basic magnesium sites are blocked as
inactive carbonate species.

Figure 9. Potential mechanism of methanol synthesis from CO and CO via formate and methoxide
Figure 9. Potential mechanism of methanol synthesis from
2
CO2 and CO via formate and met
over a Cu/MgO catalyst (adapted from [6]).
over a Cu/MgO catalyst (adapted from [6]).
7. Conclusions
In this review, the role of MgO as support material for Ni-based catalysts for methane
7. Conclusions
synthesis and Cu-based catalysts for methanol synthesis was discussed. Due to its basicity,
In this review, the role of MgO as support material for Ni-based catalysts for me
synthesis and Cu-based catalysts for methanol synthesis was discussed. Due to its
ity, the alkaline earth metal oxide MgO shows pronounced CO2 adsorption capacit
ing access to bifunctional catalysts via carbonate formation and, thus, CO2 activation
Energies 2023, 16, 2973 25 of 29

the alkaline earth metal oxide MgO shows pronounced CO2 adsorption capacity giving
access to bifunctional catalysts via carbonate formation and, thus, CO2 activation. This has
been intensively described for CO2 methanation. A similar advantageous role would also
be conceivable for methanol synthesis from CO2 . However, a disadvantageous effect is
described in the literature. It can be assumed that carbonate formation and, thus, strongly
bound CO2 is somehow deactivating the catalyst for methanol synthesis. Be that as it
may, the results in the literature are not totally consistent. It can be assumed that the type
of catalyst preparation and the preparation conditions are also decisive for the role of
carbonate formation in methanol synthesis and therefore greater attention should be paid
to the calcination temperature in future studies.

Author Contributions: Conceptualization, S.L.; methodology, S.L.; data curation, K.S., S.K. and
S.L.; writing—original draft preparation, K.S., S.K. and S.L.; writing—review and editing, S.L.;
visualization, K.S.; supervision, S.L.; project administration, S.L. All authors have read and agreed to
the published version of the manuscript.
Funding: Supported by TU Graz Open Access Publishing Fund.
Data Availability Statement: The data presented in this study are available in the cited references.
Acknowledgments: The authors gratefully acknowledge the support from the NAWI Graz program.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.

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