5.

5 Methanol Chemistry
Edward Kunkes and Malte Behrens*

Fritz-Haber-Institut der Max-Planck-Gesellschaft, Department of Inorganic Chemistry

Faradayweg 4-6, 14195 Berlin, Germany

*[email protected]

5.5.1 Why Methanol?

One major problem of regenerative energy from wind and solar power is its naturally fluctuating abundance, which
does not necessarily match the current energy demand (see chapter 1). A very powerful and versatile energy storage
strategy is to store excess energy as bond energy in products of a chemical reaction. These products can be
sustainable synthetic fuels in the transportation sector, and be available to compensate in times of low wind or
sunlight irradiation in the energy sector. Moreover, the products can be used as a carbon source for the chemical
industry. Methanol is a very promising candidate for such an energy storage molecule.

Methanol, CH3OH, is the smallest alcohol and liquid at ambient temperature. Currently existing gasoline distribution
and storage infrastructure like pipelines, road tankers and filling stations would require little modification to operate
with methanol [1-2]. Methanol is a versatile fuel as it can be used directly in combustion engines or as feed for fuel
cells (see chapter 3.4), either for a direct methanol fuel cells (DMFCs), or as on-board hydrogen storage for
downstream proton exchange membrane fuel cells (PEMFCs). In the latter case, hydrogen has to be liberated from
methanol. This is possible at relatively mild conditions by steam reforming of methanol (see section 5.5.7). Direct
combustion of methanol in motor engines is attractive due to its good combustion properties. Methanol has a high
octane number (RON=133), comparable to currently available gasoline blends. The emissions of NOx and
hydrocarbons (not of CO and formaldehyde) are lower compared to gasoline, while the thermal efficiency and the
motor power are higher by ca. 15 and 10%, respectively [3]. It has to be noted, however, that the energy density of
methanol is only ca. 50% of that of gasoline, leading to an increased volume-based consumption. Today, up to 3%
methanol is used as a blend in gasoline (M3). Pure methanol (M100) or mixtures of methanol and gasoline (e.g.
M85, 85% methanol, 15% gasoline) have been proved feasible in large-scale practical studies [1-2, 4-5] with several
hundred cars in the USA and Germany. In the 1960s, gasoline has been completely replaced by methanol in the Indy
Car Racing circuit in the USA for safety reasons; in contrast to gasoline methanol fires can be extinguished with
water. Methanol-containing fuels (MW50, 50% methanol, 50% water) have also been used as a synthetic fuel for
temporarily increased performance of aircrafts during the Second World War.

Methanol is particularly interesting, because it can be produced by hydrogenation of the greenhouse gas CO2 (see
section 5.5.5). Thus, anthropogenic CO2, e.g. from industrial exhaust or coal power plants, could be used for its
manufacture. The amount of CO2 emitted upon methanol combustion is then equal to the amount consumed during
its production. Such CO2 recycling via methanol has been proposed by Olah et al. [2] as a carbon-neutral “methanol
economy”.

Another promising aspect of the use of methanol in energy applications is that its synthesis already is a large-scale
industrial process (see section 5.5.3). Thus, regarding a further up-scaling of methanol production, which is
necessary for energy-related application, a mature technology and long-lasting experience already exist. This is an
important advantage compared to completely new approaches that have to be developed from scratch like renewable
hydrogen or biofuels. Today, methanol is an important platform molecule in chemical industry. It is further
upgraded into other chemical intermediates like formaldehyde or acetic acid. Zeolite catalyzed methanol to olefins
(MTO) and methanol to gasoline (MTG) processes, developed by Mobil, open a pathway for direct conversion of
methanol into fuels and chemicals currently derived exclusively from petroleum. However, these are only expected
to become economically viable in the case of high petroleum prices. Among the direct products of methanol
conversion methyl-tert-butyl-ether (MTBE) and dimethylether (DME) are of relevance for the energy applications.
MTBE is used as an octane-booster to improve the anti-knocking properties of gasoline, but recently has been
banned by some states due to environmental concerns. DME has been proposed as a potential substitute for Diesel
fuel.

Methanol production today is not a sustainable process, but is part of a petrochemical route for conversion of fossil
carbon into chemicals and fuels (see section 5.5.3). It has to be emphasized that a one-to-one up-scaling of existing
industrial methanol synthesis capacities for fuel production is not useful. This is mainly because the current
industrial process has not been developed and optimized under the boundary conditions of conversion of
anthropogenic CO2, but rather for synthesis gas feeds derived from fossil sources such as natural gas or coal. The
switch to an efficient large-scale methanol synthesis with a neutral CO2-footprint is still a major scientific and
engineering challenge and further research and catalyst and process optimization is urgently needed to realize the
idea of a sustainable “methanol economy”.

Obviously, the other reactant for methanol production by CO2 hydrogenation is hydrogen. Thus, all considerations
on the use of methanol as sustainable fuel are only useful, if a regenerative source of hydrogen is available. The
electrolysis of water (see chapter 3) through renewably derived electricity such as hydro- or wind power, or
alternatively gasification of biomass (see chapter 2) may serve as such a source [2]. Hence, the primary chemical
energy storage has to happen in form of hydrogen production. The further conversion of hydrogen into methanol is
associated with a gain in volumetric and a loss in gravimetric energy density, but also with a much easier handling
of the energy carrier. This does not only imply distribution and storage without pressurized or cryogenic containers,
but also safety issues. However, it should not be concealed that methanol itself is toxic and flammable, with risks
and safety measures for every-day use, that are comparable to those of gasoline [2].

This chapter focuses on the catalytic aspects of methanol chemistry and covers thermodynamic, kinetic, chemical
engineering and materials science aspects. It provides brief introductions into these topics with the aim of
establishing an overview of the state-of-the-art of methanol chemistry with only a snapshot of the relevant literature.
It highlights what the authors think are the most relevant aspects and future challenges for energy-related catalytic
reactions of methanol. It is not meant to provide a complete literature overview on methanol synthesis and
reforming.

5.5.2 Introduction to methanol synthesis and steam reforming

The current primary feed stock for industrial methanol synthesis is synthesis gas – a mixture of CO, CO2 and
hydrogen derived from the reforming of natural gas or other hydrocarbons [2]. The inter-conversion of carbon
oxides and methanol, central to methanol synthesis and steam reforming, is defined by three equilibrium equations
below.

  3 
     ∆ 49.8 / (1)

  2 
  ∆ 91.0 / (2)

   
    ∆ 41.2 / (3)

Methanol synthesis from CO2 (equation 1) and CO (equation 2) is mildly exothermic and results in volumetric
contraction. Methanol steam reforming (MSR) refers to the inverse of reaction 1 and the inverse of reaction 2 is
conventionally referred to as methanol decomposition – an undesired side reaction to MSR. The slightly
endothermic reverse water-gas shift (rWGS) reaction (equation 3) occurs as a side reaction to methanol synthesis
and MSR. According to Le Chatelier’s principle, high pressures and low temperatures would favor methanol
synthesis; whereas the opposite set of conditions would favor MSR and methanol decomposition. It should be noted
that any two of the three reactions are linearly independent and therefore sufficient in describing the compositions of
equilibrated mixtures.

A precise quantitative description of the methanol synthesis equilibrium must account for the non-ideal
non behaviors of
the gas species, in particular those of water and methanol. Skrzypek et al. show that the Soave-Redlich-Kwong
Soave
equation gives good agreement ment with experiment [6]. Although non-idealities
idealities lead to higher methanol yields
compared to those expected from ideal gas behavior [7], non-corrected corrected equilibrium calculations suffice in
qualitatively illustrating the equilibrium behavior as a function of conditions. Figure 1 A. and B. shows the ideal gas
methanol and CO yields respectively for a 3:1 H2:CO2 feed mixture. The methanol yield displays a positive
dependence on pressure and an inverse dependence on temperature, whereas the rWGS yield shows weak pressure
dependence and increase with increasing temperature. The addition of CO to the feed mixture has a positive effect
on the equilibrium yield of methanol, as will be discussed iin detail in section 5.5.5.

Figure 1.. Equilibrium Methanol and CO yields from 3:1 H2:CO2 mixture

The current “low pressure” synthesis process (see section 5.5.3) yields methanol with greater than 99% selectivity
on a CO free basis. The equilibrium constants (p
(per CO2 molecule reacted) for the formation of common byproducts
o
at 250 C are shown in Figure
igure 2. The high methanol selectivity is fairly astonishing, considering that the formation of
ethers, ketones, and alkane impurities found in industrial methanol is mo morere thermodynamically favored than is the
formation of methanol. Similarly, coke – another thermodynamically favored product and common cause of catalyst
deactivation is never observed [8].. This observation unambiguously states that the aforementioned products are
kinetically inaccessible on the used Cu/Zn
Cu/ZnO-based catalyst that will be described in more detail in section 5.5.5.
From these thermodynamic considerations the need for more active CO2 hydrogenation catalyst yst becomes apparent.
-5 -6
Even
ven at temperatures associated with the low pressure process, K2 lies between 10 and 10 allowing for a single
pass methanol yield of 15-25% and thus necessitating the implementation of costly recycling loops.

Figure 2. The equilibrium constant of formation methanol synthesis byproducts from 3:1 H2:CO2 mixtures at 250°C
MSR is also carried out on active methanol synthesis catalysts at similar temperatures (see section 5.5.7), but unlike
methanol synthesis, it is not subject to thermodynamic constraints. Thermodynamic considerations play a lesser role
in MSR, as the inverse of reactions 1 and 2 can be considered irreversible at atmospheric pressure. However, lower
temperature operation would thermodynamically hinder CO formation via methanol decomposition and rWGS. A
low CO content is desired for MSR-PEMFC combinations (see section 5.5.7). To that end, the development of
catalysts active at lower temperatures still remains the central goal of methanol catalysis research.

5.5.3 Today’s industrial methanol synthesis

As mentioned in section 5.5.1, unlike hydrogen and other potentially renewable fuels, methanol would be a mature
starting point for portable energy applications. The first internal combustion engines relied exclusively on alcohol,
namely bio-derived ethanol, as a fuel [2]. The advent of economically competitive petroleum distillates in half 20th
century lead to the nearly complete replacement of alcohol fuels, but rising petroleum prices have spurred new
interest in alcohols as fuels [9]. However, economically feasible production of bio-ethanol (see chapter 2) remains
relegated to regions with sufficient agricultural capacity and it may interfere with food production. In contrast to
ethanol, methanol can be obtained economically from diverse feedstocks, including the reforming of natural gas and
coal as well as agricultural residues and municipal waste [2, 5].

In 2009 worldwide production of methanol was around 40 million metric tons. Although this amount represents only
0.01 % of the worldwide gasoline production, it is nearly equivalent to the total biodiesel and bioethanol production
[10]. From this number it is clear that a large-scale replacement of gasoline by methanol as fuel requires an
enormous increase of the world-wide methanol synthesis capacities. Today, chemical intermediates dominate
methanol consumption. Formaldehyde – a platform molecule for the synthesis of polymer resins is responsible for
nearly half of the total demand. Acetic acid, MTBE and methyl methacrylate (MMA) – a monomer, constitute
another 25% [7, 11]. Direct fuel and additive usage accounts for 15% of demand, but is expected to rise.

Until the commercialization of the first heterogeneous catalytic process for methanol synthesis by BASF in the
1920’s, methanol was produced exclusively from the dry distillation of wood. The BASF process utilized sulfur-
containing coal or coke derived synthesis gas and ZnO/Cr2O3 catalyst operating at 300-450 °C [12]. High pressures
(100- 300 bar) were required to counteract these thermodynamically unfavorable temperatures. Although the
superior activity of Cu-based methanol synthesis catalysts was reported shortly thereafter [13], only the advent of
natural-gas derived sulfur free synthesis gas allowed for feasible industrial application. The commercialization of
more active Cu/ZnO/Al2O3 based catalysts (see section 5.5.5) by ICI in the 1960’s lead to the application of milder
reaction conditions; 240-260°C and 50-100 bar – in a “low pressure” process [14]. Since its inception, this process
has been optimized to yield methanol with a >99% selectivity and 75% energy efficiency, and has thus become the
exclusive means of methanol production [2]. Catalysts based on supported palladium and other noble metals have
also been shown to yield methanol at current process conditions, but due to their price, these materials remain only
of academic interest.

Methanol synthesis plants utilizing the low pressure process currently operate at capacities of 2×105 to 2×106 metric
tons per year [14]. Such installations are comprised of a synthesis gas production unit, the actual methanol synthesis
reactor, and a separation and purification section. The production and purification of synthesis gas accounts for 50-
80% of the total cost of methanol production, with the remaining cost associated with the actual synthesis and
purification of methanol [2, 7]. Although a variety of carbonaceous feedstocks can be transformed into synthesis
gas, the steam reforming of natural gas (equation 4) is by far the most common option, especially for large plants [2,
14-15].

      
 
 (4)

Gas mixtures with a modulus value M (equation 5) around 2 satisfy the stoichiometric requirements.
 (5)

Countries with large domestic coal reserves, such as China and South Africa rely primarily on coal gasification to
produce synthesis gas. This synthesis gas is hydrogen deficient ((M < 2) and must undergo a further water-gas
water shift
step to yield a CO2 rich mixture [2].. Methanol synthesis from CO2 and CO2-rich rich mixtures provides special catalyst
and reactor design challenges, which wiwill be further discussed in more detail.

Industrial methanol synthesis is carried out in fixed bed flow reactors, which are designed to achieve effective
removal or dissipation of the heat generated during this exothermic reaction. The original adiabatic quench
q reactor
developed by ICI consists of a single catalyst bed, with cold syngas injected at several points along the axial
direction of the bed. The Kellogg and Haldor
Haldor-Topsøe reactor designs consist of a series of catalyst beds with inter-
inter
stage cooling of the products. A qausi--isothermal
isothermal reactor developed by LURGI consists of several tubular catalyst
beds surrounded by an outer shell of boiling water [7].. The pressure in the shell is used to control
contro the reaction
temperature. The ICI and LURGI configurations account for approximately 60% and 30% of global methanol
production respectively. Crude methanol leaving the reactor contains volatile impurities such dissolved gases, light
hydrocarbons, esters and ketones (Figure
igure 2), that are removed in an initial stripping step. Less volatile impurities
such as water and heavier alkanes (C8+) are removed as bottoms in subsequent distillation steps [2, 7, 14]. A
simplified schematic of a methanol synthesis plant is shown in Figure 3.

Figure 3.. A simplified schematic of a methanol synthesis plant. A) Gasifier B) Compressor C) Methanol Reactor D) Flash drum
E) Light
Light-Ends column F) Methanol column

Low pressure methanol synthesis relies almost exclusively on catalysts ba based

sed on copper, zinc oxide and alumina.
The catalysts are produced by ICI (now Johnson Matthay)
Matthay), Südchemie, Haldor Topsøe, BASF and other chemical
enterprises and contain 50-70
70 atomic % CuO, 2020-50% ZnO and 5-20% Al2O3. Instead of alumina, also Chromium
oxide and rare earth th oxides have also been used. TThe
he mixed oxide catalysts are usually shipped as 4-6 4 mm
60-100 m2/g. The catalysts are activated in situ with dilute hydrogen,
cylindrical pellets with BET surface area of 60
often derived from off-gases from synthesis
ynthesis gas production. The activation procedure takes place at 190-230°C,
190
completely reducing copper oxide to metallic crystallites interspersed by a ZnO
ZnO-Al2O3 matrix. More details on the
preparation and properties of Cu/ZnO-based
based methanol synthesis catalysts
lysts will be given in a section 5.5.6.

Typical Cu/ZnO/Al2O3 catalyst life times are about 2 years, with one third of the total activity loss occurring during
the first 1000 hours of operation. The loss of activity with time is compensated by increasing the reaction
temperature. Deactivation occurs through loss of copper dispersion during particle growth or poisoning by
impurities. High partial pressures of water, associated with CO2 rich gas mixtures, have also been shown to
accelerate particle growth.. However, the complete removal of CO2 leads to an even faster deactivation
activation by dispersion
loss [16]. Sulfur is a potent poison for Cu catalysts, however sulfur poisoning is seldom a problem as syngas feeds
are desulfarized to less than 0.5 ppm. The ZnO catalyst component provides some protection against sulfur
poisoning by scavenging sulfur irreversibly as ZnS, and thereby preserving a large fraction of catalyst activity even
at sulfur loading of a several percent [7, 16].

5.5.4 The reaction mechanism of methanol synthesis

Gas feeds for industrial methanol synthesis usually contain both CO and CO2. Which carbon oxide serves as the
primary source for methanol formation, has been arguably the most important question pertaining to the reaction
mechanism. Early work by Klier and co-workers assumed that CO was the primary source, and that the active site
consisted of Cu+ species dissolved in ZnO. However, Klier’s model predicted a zero rate of methanol production in
the absence of CO2, and it was assumed that CO2 and water prevented over-reduction of Cu and thus helped
maintain a population of active Cu+ species [17-18]. In the 1980’s experiments conducted by Razovskii and later by
Chinchen et al. involving the use of 14CO or 14CO2 tracers in methanol synthesis from CO2/CO/H2 mixtures over
commercial catalysts proved conclusively that CO2 was the primary methanol source [19-20]. Chinchen et al.
measured the radioactivity of reaction products at the outlet of a reactor operating with a 14CO2/12CO feed. As shown
in Figure 4, at lower space velocities, scrambling of carbon isotopes between CO and CO2 through WGS resulted in
the incorporation of both isotopes into methanol. At high space velocities, where the rate of scrambling is negligible
and conversion is low, methanol retained the specific radioactivity of the 14CO2, indicating that only carbon from
CO2 was incorporated. Chinchen et al. showed that even when present at very low concentrations (100 ppm), CO2
was the primary carbon source for methanol.

14
Figure 4. Effect of Space velocity on C distribution in Methanol synthesis products from [19]

In situ spectroscopic studies have identified a variety of species such as formate, dioxymethylene, carbonate and
methoxide to co-exist under methanol synthesis conditions on Cu/ZnO-based catalysts [21-22]. FTIR studies of Cu
Zn based catalysts under H2/CO2 identified the presence of formate bound to both Cu and ZnO, whereas methoxyl
was found on ZnO only. Carbonates were found to form via CO2 adsorption on ZnO [23] and partially oxidized Cu
[22], and were quickly converted into formate via Cu activated hydrogen. Upon exposure to CO mixtures, only zinc-
bound formate was observed [21]. The hydrogenation of these formates to methoxyl is thought to be rate
determining in methanol synthesis. However, this hydrogenation may not be direct, as – even in the presence of
hydrogen – the rate of methanol synthesis on Cu/SiO2 from formate was negligible compared to the rates of formate
decomposition into CO2 and H2 [24]. The presence of water and/or hydroxyl groups was found to be critical for
methanol formation [25]. However, the absence of direct coverage by reducible oxygen species, (and therefore of
Cu+) was confirmed by CO pulse experiments on catalysts in the working state [26].
Surface science studies on Cu single crystals also identify formate an abundant surface species, but report a wide
range of activities for methanol synthesis. The intrinsic reaction rates reported by Szanyi and Goodman for the
hydrogenation of CO/CO2 mixtures on Cu(100) were four orders of magnitude below those reported for high surface
area Cu Zn catalysts [27-28]. Rasmussen et al. report rates 2-3 orders of magnitude higher than those reported by
Zanyi and Goodman for Cu(100), but using CO2/H2 mixtures. Yoshihara et al. report rates comparable to those on
high surface area catalysts on polycrystalline copper [29], and even three times higher rates on the more open
Cu(110) surface [30]. Yoshihara and Rasmussen both confirm the absence of oxygen on the Cu surface, assume
metallic Cu to be the active phase [30-31]. Furthermore, ZnO is assumed to maintain metallic Cu in a form that
more closely resembles an open surface, thereby acting as a promoter [30]. Direct deposition of up to 0.19 ML of Zn
on a polycrystalline Cu surface has been shown increase CO2 hydrogenation activity by a factor of six, thus
suggesting a more direct role for ZnO [32].

The structure sensitivity of the rWGS reaction, that accompanies methanol synthesis, was even more pronounced,
with Cu(110) being an order of magnitude more active than polycrystalline Cu. Furthermore, kinetic studies of CO2
hydrogenation on Cu/ZnO catalysts yielded a temperature-dependnet non-zero CO selectivity at the limit of zero
CO2 conversion [21, 30, 33]. These findings suggest that both reactions do not share a common intermediate.
Whereas methanol formation is associated with formate hydrogenation, the rate of the rWGS reaction is controlled
by direct dissociation of CO2, a direct “redox” process that is more favorable on open surfaces [30].

Theoretical studies confirm the importance of formate as a surface intermediate, and its sequential hydrogenation as
being rate determining. A highly simplified version of the mechanism proposed by Askgaard et al. for methanol
synthesis from CO2 on Cu(111) is given below [34], where step 3-6 may each represent a series of reaction events.
The formation of formate from CO2 with hydrogen is a fast process, and CO2 is thought to bind directly to adsorbed
hydrogen in an Eley-Rideal step [35], instead of forming carbonate by binding to surface oxygen species [36].
Asgaard et al. propose that the hydrogenation of H2COO* is rate limiting, whereas Yang et al., Hu et al. and
Grabow and Mavrikakis, identify the hydrogenation of HCOO* and CH3O* respectively as rate determining [35-
37]. The presence of adsorbed Zn may promote methanol synthesis on Cu(111) by stabilizing formate and associated
transition states [38]. Zhao et al. show that methanol cannot be formed directly though formate hydrogenation on
Cu(111), but is instead formed by a hydrogen transfer reaction requiring the presence of water [39]. According to
Grabow and Mavrikakis, the main role of CO in promoting the hydrogenation of CO2 is the removal of site-blocking
OH species via rWGS, although the direct hydrogenation of CO is said to account for 1/3 of the methanol produced
under industrial conditions [36].

  2  2  (1)

   2      (2)

  2 
    (3)

    
  (4)


  3 
     2  (5)


   
   2  (6)

5.5.5 Methanol synthesis from CO2 – Thermodynamic and kinetic considerations

Methanol synthesis from waste CO2 streams has potential to contribute to the limitation of worldwide CO2
emissions, and to serve as an alternative carbon source to fossil fuels, if a renewable source of hydrogen is available
(see section 5.5.1). The main obstacle to methanol synthesis from CO2 rich streams is thermodynamics. The
equilibrium yield of methanol from 25% CO/CO2 rest H2 mixtures of varying CO/CO2 ratio is shown in Figure 7.
For pure CO, a one-pass
pass methanol yield of nearly 55% can be obtained at 525 K, while pure CO2 would only yield
18%. Besides the addition of CO, this his equilibrium limitation can be overcome by operating at lower temperatures-
temperatures
an option that requires more active catalyst
catalysts,
s, or by implementing higher recycle ratios, or product extraction-
extraction an
option that
at requires higher capital investment [7].

Figure 7. Equilibrium yield of methanol at 50 bar from 3:1 CO:CO2/H2 mixtures as a function of CO2/CO ratio

The feasibility of methanol synthesis from CO2 can be achieved by circumventing the thermodynamic
thermod limitations
through innovative reactor design. These design considerations involve efficient product removal without excessive
recycling of feed gases. One strategy involves a liquid pha
phase reactor using a high-boiling
boiling hydrocarbon oil solvent.
The methanol and water can be separated from the solvent upon cooling, whereby the solvent is recycled back into
the reactor. The use of alkane and alcohol solvents under supercritical conditions has also been proposed. Liquid
phase methanol synthesis has the advantage of higher capacities and better temperature control. However diffusion
limitations may be encountered with solvent present in the pores of the catalyst. Furthermore, catalysts that are
stabile in the solvent environment must be developed. Other strategies involve a series of gas-phase
gas reactors with
inter-stage
stage absorption of methanol and water by a polar liquid solvent, or a in
in-situ
situ desorption with a solid such as
alumina [7, 40].

Although CO2 has been shown to undergo hydrogenation faster than CO, kinetic limitations would arise in a process
operatingg at high conversions, as in industrial applications. Several investigators have shown that a maximum in
methanol production with CO2/CO ratio occurs at CO2 concentrations of 2-5 5 mol% of total carbon [18, 33, 41]. Klier
et al. ascribed this behavior to active Cu+ sites being created by oxidation at low CO2 concentrations, and surface
poisoning by strongly bound CO2 at higher concentrations, thus resulting in an activity maximum [18]. Further
investigations have shown that such a maximum in the synthesis rate is only exhibited at high reactant conversions,
thus indicating that product inhibition play
plays an important role [33, 41-43]. Shibzada et al. have studied the effect of
methanol synthesis rate versus CO2/CO ratio in an integral internal recycle reactor compared to a differentially
operated down flow micro reactor. Their results (F (Figure 8)) show that a maximum exists at 2% CO2 in the integral
reactor,
tor, while in the differential reactor (operated at < 0.3% methanol yield) at almost linear relationship between
the methanol synthesis rate and CO2 concentration was observed. These investigators have correlated the methanol
synthesis rate at integral conditions
ditions with the concentration of water in the product stream during CO2 hydrogenation.
Furthermore, they have shown that co co-feeding
feeding of water to a differential reactor in concentrations similar to those
formed during integral operation results a 10 10-fold decrease of the methanol synthesis rate [33].. These
The results show
conclusively that water acts to inhibit methanol synthesis from CO2, and that the promotional effects of CO at
integral conversion arises from its ability to “scavenge” excess water via WGS [22, 44].
 Figure 8. Methanol synthesis at differential and integral conditions at 250°C and 50 bar from [33]

Indirect evidence for the inhibitory role of water in methanol synthesis can be drawn from a simple experiment
involving the variation of space velocities. In Figure 9A, the methanol synthesis and rWGS rates as a function of
space velocity for two Cu/ZnO based catalysts are shown. The more active catalyst is derived from a zincian
malachite (MA) precursor [45] (see section 5.5.6) and promoted with Al2O3. It possesses a Cu surface area of 30
m2/g, while the less active catalyst is derived from a hydrotalcite (HT) precursor [46] and possesses a smaller Cu
surface area (7 m2/g). In both catalysts the rate of rWGS shows little variation with increasing space velocity,
whereas the rate of methanol synthesis increases dramatically. The concentration of the rea reactants
ctants does not vary
significantly throughout this space velocity range as the maximum CO2 conversion is not higher than 14% for the
MA catalyst. However the concentrations of water and methanol decrease by a factor of 3 when increasing the space
velocity from 10 to 80 mmol/gcatmin, as a result of product dilution. In the absence of external mass transport
limitations these results imply product inhibition of methanol synthesis. The rWGS reaction does not seem to be
product inhibited. Furthermore the rWGS rrate ate seems to remain constant even as the concentration of methanol
decreases at higher space velocities, also due to product dilution. The lack of correlation between methanol partial
pressure and CO production rate implies that CO does not form from metha
methanol.
nol. Although methanol decomposition
(K = 200 at 230 °C)) is more thermodynamically favorable than rWGS (K = 0.01 at 230 °C)) at these conditions, the
former has been shown to be kinetically unfavorable on Cu [47].

Figure 9. The variation of CO and methanol production rates with space velocity (A) and methanol synthesis rates on
promoted CuZn based catalysts derived from hydrotalcite and Malachite precursors (B). Reaction conditions: 200 mg catalyst
30 bar, 230 °C K 3:1 H2:CO2
When comparing the intrinsic methanol synthesis activity of both catalysts (TOF per surface Cu site measured with
N2O-RFC) at the space velocity of 20 mol/gcatmin, the HT catalysts (0.54 min-1) appears twice as active as the MA
catalyst (0.24 min-1). Although both catalysts are exposed to nearly the same reactant concentration, the MA catalyst
operates at 11% CO2 conversion and is exposed to 3.5 times as much reaction-inhibiting water as the HT catalyst (X
= 3.3%). If both catalysts are tested at the same CO2 conversion (5-6%), they show a similar intrinsic activity (TOF
ca. 0.35 min-1). These results suggest that the interpretation of catalytic activity data for the hydrogenation of CO2 is
a strong function of the measurement conditions, and therefore great caution must be taken when comparing and
interpreting reactivity data for different materials. It is noted that for methanol synthesis from CO-containing feed
gases, these considerations less important, as water is scavenged by CO.

The selectivity to methanol is another important consideration in CO2 hydrogenation. Methanol synthesis and rWGS
are independent reaction channels on Cu-based catalysts (see sections 5.5.2, 5.5.4). On Cu based catalysts the
apparent activation energies are reported around 120 kJ/mol and 70 kJ/mol for rWGS and methanol synthesis
respectively [24, 48-49]. As a result of this difference, selectivity towards methanol decreases with increasing
temperature. The selectivity to methanol also increases with total reaction pressure, as the total pressure increases
the rate of methanol synthesis, but does only weakly affect the rate of rWGS [50] (Figure 1B). How the properties of
Cu/ZnO-based catalysts can be tailored in order to favor methanol synthesis over rWGS is a key question for
catalyst development for CO2 hydrogenation. Recently Liao et al. showed that methanol selectivity can be controlled
by the shape of ZnO crystallites in catalysts consisting of physical mixtures of Cu and ZnO crystallites [51]. They
suggest that a stronger Cu-ZnO interaction observed for plate-like crystallites showing the polar (002) face as
opposed to non polar rod-like crystallites is responsible for higher methanol selectivity. These results suggest that
tuning the so-called synergy between Cu and ZnO (see section 5.5.6) is a promising approach to improve the
selectivity of Cu towards methanol synthesis. The undesired rWGS is known to be more structure sensitive than
methanol synthesis on copper. Therefore, another selectivity control strategy may involve controlling Cu particle
size and shape [27]. Another approach is the use of promoters. Arena et al. have suggested that adding promoters
such as ZrO2 which increase the hydrophobicity of the catalyst surface would lead to better activity in CO2
hydrogenation [48, 52] due to less product inhibition by water. Oxides such as Al2O3, Cr2O3, Ga2O3 or ZrO2 are
known to promote methanol synthesis [53]. They may improve Cu dispersion and stability [8], but also the intrinsic
catalytic properties of the exposed Cu surface [54]. The latter is probably related to an adjustment of the properties
of the ZnO crystallites and related to modified interactions between Cu and ZnO. A clear picture of the nature of the
promoting effect of different oxides and their influence on the selectivity in CO2 hydrogenation is still lacking.

When studying the effect of promoters on the methanol synthesis activity of differently promoted catalysts, again
great caution is needed for a reliable comparison of performance data. An example is shown in Figure 9B. The
intrinsic methanol synthesis activities for a series of MA derived catalysts and a series of HT derived catalysts with
difference promoters are plotted as a function of Cu surface area and compared to an unpromoted binary MA
derived catalyst (MA-bin). The activity was measured at the either the same space velocity or the same CO2
conversion. When considering activities measured at the same space velocity, all HT based catalysts appear
intrinsically more active than the MA derived ones. All promoted MA-based catalysts show the same intrinsic
activity as MA-bin under these conditions. One might thus presume that the promoting effect is limited to
improvement of the Cu dispersion within this series of samples. However, isoconversion activities of both promoted
series fall in the same range (0.3-0.35 min-1) and are significantly greater than that of the unpromoted sample (0.25
min-1), showing clearly that the presence of the promoters also improves the intrinsic activities of the MA-derived
catalysts.
5.5.6 Cu/ZnO-based methanol synthesis catalysts1
Commercial Cu/ZnO/Al2O3 methanol synthesis catalysts are often mistaken as supported systems, but neither ZnO
nor Al2O3 represent classical extended oxidic supports. This is apparent, when considering the typical composition
of modern Cu/ZnO/(Al2O3) catalysts, which is characterized by a molar Cu:Zn ratio close to 70:30, while the
amount of Al2O3 typically is significantly lower than that of ZnO. This Cu-rich composition manifests itself in a
peculiar microstructure of the industrial Cu/ZnO/Al2O3 catalyst (Figure 5) [56], which is composed of spherical Cu
nanoparticles of a size of ca. 10 nm (Figure 5B,C) and often even smaller ZnO nanoparticles arranged in an
alternating fashion. Thus, porous aggregates are formed (Figure 5A) in which the oxide particles act as spacers
between Cu particles (Figure 5B [56]). The presence of inter-particle pores as seen in the HRTEM image (Figure
5B) allows some access to the “inner surface” of larger Cu/ZnO aggregates (Figure 5A).

a) b)

c)
100 110 111
} Disordered
ZnO xoverlayer

Twin boundaries

Figure 5: (High resolution) TEM images of a Cu/ZnO/Al2O3 methanol synthesis catalyst consisting of porous aggregates (A) of
metallic Cu and ZnO nanoparticles (B [56]) showing details of the surface faceting, decoration and defect structure (C [57]),
which is discussed in detail in the text.

This unique microstructure can be described as an intermediate stage between a supported catalyst and a bulk
metallic sponge or skeletal Raney-type catalyst. It enables a reasonably high dispersion of Cu and exposure of many
Cu-ZnO interfaces at a high total Cu content. The specific Cu surface area (SACu) of methanol catalysts can be
determined by reactive N2O titration [58-59], which causes surface oxidation of the Cu particles and allows
calculation of SACu from the amount of evolved N2. The SACu of state-of-the-art methanol synthesis catalysts
measured by this method amounts to 25-35 m2g-1. If reliable data of the average Cu particle size are available, e.g.
by sufficient TEM observations [56], the degree of oxide coverage of the Cu particles, i.e. the average ratio of
interface area to surface area, can be calculated [60]. For industrial Cu/ZnO/Al2O3 catalysts, this value is around

1
Part of this section is based on work previously published in ref. [55].
35%. The favorable microstructure and the proper balance of Cu dispersion and loading in this type of
Cu/ZnO/(Al2O3) catalysts leads to a large SACu, which is probably the most important property of a methanol
synthesis catalyst.

The SACu has been observed to scale linearly with the activity for sample families with a similar preparation history
[54]. However, between these families considerably different intrinsic activities, i.e. activities normalized by SACu,
can be found [60]. Thus, in agreement with the structure sensitivity of methanol synthesis over Cu [30], different
“qualities” of Cu surfaces can be prepared, which vary in the activity of their active sites and/or in the concentration
of these sites. Differences in instrinsic activity of the exposed SACu can be related to defects and disorder in the Cu
nanoparticles and to the role of ZnO. Clearly, one role of ZnO that is apparent from Figure 2B is to act as spacer and
stabilizer avoiding direct contact of the Cu particles and preventing them from sintering [61]. But it is generally
agreed that the role of ZnO in Cu-based methanol synthesis catalysts exceeds the function of a mere physical
stabilizer. In addition to this geometrical function, a so-called Cu-ZnO synergy is described in literature for
methanol synthesis [7, 62-63]. The nature of this synergy and the contribution of ZnO to the active site of methanol
synthesis are strongly debated and several models have been proposed, e.g., Cu+ ions in the ZnO matrix [64], ZnO
segregated on Cu+ [65], electron-rich Cu at the Cu-ZnO heterojunction [66], CuZn surface alloy formation [67] or
Cu metal supported on ZnO [22]. Strong metal-oxide-interactions (SMSI) between Cu and ZnO were observed at
highly reducing conditions [68-69] and it was suggested that partially reduced ZnOx migrates onto the surface of the
Cu particles under methanol synthesis conditions [70]. On a supported Cu/ZnO model catalyst, reversible
wetting/de-wetting was observed as the reduction potential of the gas phase was varied [71], an observation not
made on Cu/SiO2.

Another contribution to variations of intrinsic activity is the different amount of defects and disorder in the metallic
Cu phase. This disorder can manifest itself in form of lattice strain detectable, e.g., by line profile analysis of XRD
peaks [72], 63Cu-NMR lines [73], or as an increased disorder parameter (Debye-Waller-factor) derived from
extended X-ray absorption fine structure (EXAFS) spectroscopy [74]. Strained copper has been shown theoretically
[75] and experimentally [76] to have different adsorptive properties compared to unstrained surfaces. Strain, i.e.
local variation in the lattice parameter, is known to shift the centre of the d-band and alter the interactions of metal
surface and absorbate [77]. The origin of strain and defects in Cu/ZnO is probably related to the crystallization of
kinetically trapped non-ideal Cu in close interfacial contact to the oxide during catalyst activation at mild conditions.
A correlation of the concentration of planar defects in the Cu particles with the catalytic activity in methanol
synthesis was observed in a series of industrial Cu/ZnO/Al2O3 catalysts by Kasatkin et al. [56]. Planar defects like
stacking faults and twin boundaries can also be observed by HRTEM and are marked with arrows in Figure 5C [57].

Recently, experimental and theoretical evidence for a model of the active site of industrial methanol synthesis that
combines the role of ZnO and defects in Cu has been presented [57]. Planar defects have been shown to lead to
changes in surface faceting of the Cu nanoparticles (Figure 5C) associated with formation of steps and kinks that
were assumed to represent high energy surface sites of special catalytic activity. For a series of Cu/ZnO-based
catalyst a linear correlation of the defect concentration with the intrinsic activity of the exposed Cu surface was
observed. In addition, (partial) surface decoration of Cu with ZnOx by SMSI have been confirmed by HRTEM
(Figure 5C) and in-situ XPS. The high catalytic activity of surface steps containing Zn was supported by DFT
calculations. Thus the active site of industrial methanol synthesis could be identified as a complex surface ensemble
requiring a high energy site due to defects in Cu and the presence of Zn in the close vicinity due to in-situ
adjustment of Zn surface decoration. It is noted again that a successful methanol synthesis catalyst also requires
large total SACu; the aforementioned results may offer new options for a knowledge-based fine-tuning of the
intrinsic activity of the Cu surface in Cu/ZnO materials with already optimized Cu dispersion.

In the technical catalyst, these three requirements – large SACu, defective Cu nanoparticles and many reactive
interfaces to ZnO – are elegantly realized by the nanoparticulate and porous Cu/ZnO arrangement shown in Figure
5. Preparation of this microstructure requires a homogeneous and maximized intermixing of the Cu and Zn species
in order to stabilize the alternating arrangement of small Cu and ZnO nanoparticles. Thus, the main goal of catalyst
synthesis is to carry over and maintain the perfectly homogeneous cation distribution in the starting mixed solutions
to a maximum extent to the final catalyst [78]. Different methods of Cu/ZnO catalyst preparation can be found in
literature [79], but this preparation is most successfully achieved by co-precipitation, which is by far the most
important and technically applied technique. Figure 6A gives a schematic overview of the multistep synthesis route
of Cu/ZnO catalysts introduced by ICI in the 1960s [61, 80]. It comprises co-precipitation [78] and ageing [73, 81]
of a mixed Cu,Zn,(Al) hydroxy-carbonate precursor material, thermal decomposition yielding an intimate mixture of
the oxides and finally activation of the catalyst by reduction of the Cu component [82]. The synthesis parameters of
this route have been studied in many academic and industrial groups and a high degree of optimization could be
achieved over the last decades by mostly empirical fine-tuning of the conditions [78, 83-85]. The delicate
nanoparticulate and porous microstructure of the industrial methanol synthesis catalyst (see above) can only be
obtained if the optimized parameters are strictly obeyed during synthesis. Especially the synthesis conditions during
the early co-precipitation and ageing steps turned out to be crucial for the catalytic properties of the resulting
methanol synthesis catalyst. This phenomenon, sometimes termed the “chemical memory” of the Cu/ZnO system
[86], indicates the critical role of the preparation history of this catalyst system [72, 84, 87]. Baltes et al. [84]
elaborated a quantitative basis of the chemical memory in a systematic study and reported dramatic difference in
SACu and catalytic activity for Cu/ZnO/Al2O3 catalysts of the same composition as pH or temperature of the co-
precipitation step was varied (Figure 6B).

A) B)

Figure 6: A) Simplified geometrical model [45, 88] for the preparation of industrial Cu/ZnO catalysts comprising subsequent
meso- and nano-structuring of the material from [55]. In a first microstructure directing step (meso-structuring) the Cu,Zn co-
precipitate crystallizes in form of thin needles of the zincian malachite precursor, (Cu,Zn)2(OH)CO3. In a second step, the
individual needles are decomposed and de-mix into CuO and ZnO. The effectiveness of this nano-structuring step depends
critically on a high Zn-content in the precursor, which in zincian malachite is limited to Cu:Zn ca. 70:30 due to solid state
chemical constrains [74]. Finally, inter-dispersed CuO/ZnO is reduced to yield active Cu/ZnO. B) Chemical memory:
Dependence of catalytic activity in methanol synthesis on the conditions of the co-precipitation and ageing steps from [84].

5.5.7 Methanol steam reforming (MSR)2

Methanol is a promising candidate for a hydrogen storage molecule to be used for decentralized (on-board)
hydrogen generation in combination with downstream PEMFCs. It has a high H:C ratio of 4:1 and no C-C bond,
which has to be broken. MSR is the preferred way to liberate hydrogen from methanol as it generates a high
hydrogen concentration in the product stream, runs at relatively low temperatures of 200 – 300 °C, and unlike
methanol decomposition does not directly produce CO, which acts as a poison for the downstream PEMFC anode
catalyst. MSR was first described in 1921 by Christiansen [89] and research on its application for hydrogen

2
This section is based on the work previously published in ref. [55].
production has a long history [90]. The recently renewed interest was triggered by the development of fuel cell
technology requiring clean and preferably renewable hydrogen. A number of general overview articles and reviews
are available addressing the role of MSR in this context [11, 90-95]. In areas, where steam reforming of natural gas
is not an option, MSR is also applied in the methanol-to-hydrogen (MTH) process to produce hydrogen in relatively
small-sized units.

MSR is an endothermic reaction (see section 5.5.2) and requires external heating. It is sometimes used in
combination with exothermic partial oxidation of methanol (autothermal reforming or oxidative steam reforming)
[96-97] or combustion of methanol [93] in order to generate the necessary heat. The endothermicity of MSR is much
weaker compared to steam reforming of other hydrocarbons or higher alcohols [93] and reformer units can be
relatively small enabling the onboard combination with PEMFCs. A comparison between methanol and other
molecules as reactants for onboard hydrogen production can be found in the comprehensive review by Palo et al.
[11]. The detrimental role of CO in the effluent for the downstream PEMFC is to be emphasized. CO chemisorbs
irreversibly on Pt-based fuel cell catalysts and causes irreversible site blocking. Its concentration has to be below ca.
20 ppm in order to prevent poisoning, which is usually not achieved in the reformer outlet gas. Thus, in technical
applications, a gas purification step has to be introduced between reformer and fuel cell. The CO concentration in
the gas stream can lowered by means of WGS reaction, preferential oxidation (PROX) or using Pd membranes,
which in all cases complicates the setup and generates costs [98]. Generally, a low selectivity to CO – in addition to
high activity and stability – is, thus, a major and particular requirement for a successful MSR catalyst to be used for
onboard hydrogen production. Methanol reforming catalysts should be particularly stable towards abrupt changes of
the conditions of reforming, i.e. work reliably in transient situations like on-off operations as well as in steady state
to produce sufficient amounts of hydrogen on demand.

Commercial industrial Cu/ZnO-based catalyst for methanol synthesis (see section 5.5.6) or WGS are also active in
MSR. Cu/ZnO/Al2O3 catalysts or the unpromoted binary Cu/ZnO model system were thus employed in many
studies of MSR [55]. While preparation and composition of the industrial Cu/ZnO/Al2O3 catalysts have been
adjusted for application of methanol synthesis and WGS, modifications of the Cu/ZnO/X system turned out to
improve the properties for use in MSR. In particular, choosing another second oxide phase X like rare earths [99] or
ZrO2 [100-104], or employing new catalyst precursors like layered double hydroxides [105-108], or even changing
to ZnO-free samples and using ZrO2 and/or CeO2 [109-113] for preparation of Cu-based catalysts was reported to
lead to interesting MSR performance.

Several studies are available addressing the mechanism and kinetics of the MSR reaction over Cu based catalysts
[114-120]. There is agreement nowadays that CO2 is a direct product of the MSR reaction and not of a sequence of
methanol decomposition and WGS reactions. The main source of CO is the rWGS reaction taking place as a
secondary reaction after MSR. Frank et al. [120] presented a comprehensive microkinetic analysis of the MSR
reaction based on the work of Peppley et al. [116]. They investigated several Cu-based catalysts with various oxide
components showing considerably different activities. Similar activation energies support the idea that the surface
chemistry is independent of the oxide material (with the exception of Cu/Cr2O3/Fe2O3, which behaved differently).
Dehydrogenation of methoxy groups is the rate limiting step and by means of DRIFTS experiments methoxy and
formate species were found as the dominating species at the surface. Two distinct kinds of active sites were
considered, one for the adsorption and desorption of oxygenates and one for hydrogen. Two reaction pathways of
the methoxyl intermediate are discussed via dioxomethylene/formate, intermediates of the reverse methanol
synthesis reaction, or methyl formate. Recent theoretical studies favor the former pathway [121-122].

There are many similarities between methanol synthesis and MSR [117]. This is often accounted for by the concept
of microscopic reversibility, as MSR formally is the reverse reaction of methanol synthesis from CO2 (see section
5.5.2). It has to be considered, however, that the different reactant gas mixtures used for MSR and methanol
synthesis will affect the surface state of the catalyst, which consequently will be different under highly reducing
methanol synthesis conditions compared to the less reducing MSR feed. Thus, unlike forward and reverse reactions
at equilibrium, methanol synthesis and MSR probably may take place over practically different catalytic surfaces.
This general limit of the application of the concept of microscopic reversibility has been pointed out by Spencer for
WGS and rWGS [123] and is valid accordingly also for methanol synthesis and MSR [8]. One may conclude that an
optimized methanol synthesis catalyst, for which the fine tuning of preparation and operation conditions is far more
advanced, will also be active in MSR due to its generally large SACu and represents a powerful reference system, but
it does not necessarily represent the optimal catalyst for this reaction [8]. Finding Cu/ZnO/X systems with a
composition and microstructure optimized for the MSR reaction is thus the major current challenge in development
of a MSR catalyst for energy applications. In this context it is interesting to note that the Cu-ZnO synergy (see
section 5.5.6) does not seem to be an as critical factor in case of MSR compared to methanol synthesis [124] or this
synergistic effect is not as strictly limited to ZnO. Highly active Cu-based MSR catalysts can also be prepared in
absence of ZnO, e.g. as Cu/ZrO2.

The question to what is the active site of Cu-based catalysts in MSR is still unclear and debated in literature. Similar
to the methanol synthesis reaction, either metallic Cu0 sites, oxidized Cu+ sites dispersed on the oxide component or
at the Cu-oxide interface or a combination of both kinds of sites are discussed to contribute to the active ensembles
at the Cu surface. Furthermore, the oxidic surface of the refractory component may take part in the catalytic reaction
and provide adsorption sites for the oxygenate-bonded species [125], whereas hydrogen is probably adsorbed at the
metallic Cu surface. Similar to methanol synthesis, factors intrinsic to the Cu phase also contribute to the MSR
activity in addition to SACu. There are two major views discussed in literature relating these intrinsic factors either to
the variable oxidation state of Cu, in particular to the in situ adjustment of the Cu0/Cu+ ratio at the catalyst’s surface
[101, 106, 126-132], or to the defect structure and varying amount of disorder in metallic Cu depending on the
microstructure and preparation history of the catalyst [73-74, 133-134].

Drawbacks of Cu-based MSR catalysts are related to its pyrophoricity and low stability with time on stream and
against changing conditions like redox- or heating cylces. In methanol synthesis, which is operated at a similar
temperature like MSR, modern Cu/ZnO/Al2O3 catalysts can deliver stable performance over years on stream. The
same catalyst may tend to deactivate more rapidly under MSR conditions suggesting a critical role of the gas phase
composition on the deactivation behavior, most probably of water in the feed. In addition to thermal sintering
induced by mobility of Cu, steam-induced segregation or re-crystallization of the ZnO component will have a
detrimental effect on the porosity of the Cu/ZnO aggregates and cause a loss of SACu. Löffler et al. [135]
investigated the stability of several commercial WGS catalysts in the MSR reaction and fitted their data using a
sintering model. Cu/ZnO/Al2O3 formulations were found to be most active compared to other catalyst compositions,
but were also most prone to deactivation by sintering. In their analysis of catalyst deactivation of a commercial
Cu/ZnO/Al2O3 catalyst during MSR, Thurgood et al. [136] revealed in addition to the loss of surface area, a
decrease in intrinsic activity with time on stream. The other major problem of Cu-based MSR catalysts is the
formation of CO during MSR, typically in the low %-range. Agrell et al. [137] reported that the problem of CO
formation over Cu/ZnO/Al2O3 catalysts can be attenuated by increasing the steam-to-methanol ratio or by the
addition of oxygen or air (oxidative MSR). Also decreasing the contact time and lowering of the reaction
temperature leads to lower CO selectivity, but has a negative effect on the overall efficiency. Thus, probably the best
way to make a Cu-based MSR catalyst less selective to CO is to make it more active at lower temperatures.

Pt- and Pd-based intermetallic catalysts have been suggested as an alternative for Cu [55, 138]. In particular the
ordered compound PdZn shows interesting MSR activity and CO2 selectivity, which are higher compared to non-
alloyed pure Pd – a methanol decomposition catalyst. This observation has triggered a lot of research activity in the
recent years [139-142]. With regard to application, these and other new catalysts have to prove their competitiveness
in comparison with the traditional Cu/ZnO system. Unfortunately, firm comparisons with Cu-based catalysts and
studies of pyrophoricity and stability against changes in operating conditions are not always available. In general, all
on-board MSR applications always have to compete with the alternatives of more mature methanol combustion
engines and technically simpler DMFCs.
5.5.8 Challenges and perspectives in catalyst and process development for energy-related
application of methanol
The thermodynamics of methanol synthesis and MSR necessitate process operation at lower temperatures.
Therefore, the development of catalysts that function at low temperatures will remain the goal of methanol catalysis
research for the foreseeable future. Although most researchers agree that copper-based catalysts will remain the
industry standard, numerous possibilities exist for the improvement of the activity, selectivity and stability of these
materials through the incorporation of promoters, more efficient exploitation of the Cu-ZnO synergy and
implementation of new synthesis strategies. Therefore, a deeper understanding of the active sites for methanol
synthesis, MSR and rWGS on Cu-based catalysts is desirable and essential to further knowledge-based catalyst
development. Here, combined effort from the fields of theory, material science, model catalysis and reaction kinetics
is needed. Several studies have exhaustively characterized model systems, whose structure does not represent the
unique interspersed structure of industrial CuZnO catalysts. Although these studies shed some light on the general
nature of the Cu-Zn interaction, they cannot provide sufficient insight into what makes the current state of the
industry catalyst active, and how it could be improved. With that in mind, complementary in situ structural und
surface studies on working industrial catalysts would be beneficial to validate the conclusions drawn from model
studies and promise further progress in the understanding and optimization of methanol catalysts.

In contrast to traditional methanol synthesis, where selectivity to CO formation is not a major issue, diminishing the
rate of rWGS is critical to the efficient methanol synthesis from CO2 as well as MSR. In that respect properties such
as particle size, interaction with oxide matrix, and identity of exposed Cu crystal planes should be investigated in
more detail with respect to CO selectivity. Furthermore, targeted synthesis strategies can be developed to take these
factors into account and in the end allow for tailoring the CO2 and CO reaction channels on Cu surfaces. Due to the
relatively harsh reaction conditions that hinder application of some in situ techniques and the entangled reaction
network of relevant C1 conversions, the contribution from theory to mechanistic understanding is critical. Because
such studies should be consolidated with experimental data carefully determined under relevant conditions, also here
a stronger focus on the “real” multi-component functional catalyst is needed. Although it has been conclusively
established that CO2 is the source of methanol on CuZnO, a very recent detailed theoretical study on Cu surfaces
suggest that CO may not only promote CO2 hydrogenation but also directly contribute to methanol formation [36].
Since this study does not take into account Zn promotion, it is difficult to extrapolate their conclusions to the
industrial system. One solution to this discrepancy would be to construct models based on input from
characterization studies of industrial materials. As a second option, experimentalists could approach the current
models and validate them by determining the methanol carbon source on Cu particles dispersed on inert supports
(irreducible Carbon, Silica, Alumina). Both approaches would yield significant insight into the role of ZnO, Cu as
well as the respective synthesis gas components in the H2/CO2/CO/CH3OH/H2O reaction network.

Future wide-spread use of anthropogenic CO2 in combination with renewable hydrogen as well as the
implementation of coal, biomass and other non-conventional sources of synthesis gas will lead to sub-optimal
synthesis gas compositions. Efficient incorporation of these synthesis gas mixtures into the current methanol
synthesis infrastructure will necessitate the re-development of catalysts to perform stably under high concentrations
of CO2, water and impurities. To that end, advanced characterization methods must be implemented to discriminate
between surface area loss by sintering, loss of active sites by defect annealing and poisoning by impurities. The
freely available data basis of Cu/ZnO catalyst deactivation is still relatively sparse and more investigations are
needed to draw firm conclusions on the role of different deactivation mechanisms. Additionally, current high-
throughput testing methods for methanol synthesis catalysts would need to be modified to take product inhibition
from water into account. Deeper understanding of the performance of a catalyst at industrially relevant integral
conditions can be gained through activity measurements at differential conditions in the presence and absence of
water, as performed by Sahibzada et al. [33]. In this manner the catalyst’s intrinsic activity can be de-convoluted
from its susceptibility to inhibition, thus allowing both properties to be optimized independently.
In summary, as one among other energy storage strategies, methanol has great potential as a sustainable synthetic
fuel and seems particularly promising for the transportation sector. The industrial methanol synthesis process with
Cu/ZnO-based catalysts represents a good starting point for implementation of methanol chemistry in a future
energy scenario. However, the thermodynamic constraints of CO2 hydrogenation require further research. The key
remains the development of catalysts with better low temperature activity. Despite the long-lasting experience with
the industrial processes, methanol chemistry is scientifically not yet mature. Elaboration of a firm scientific basis for
effective catalyst design by resolving the open questions to the mechanism and nature of the active sites of the
relevant reactions is a major challenge for the future.

1. Moffat, S.M., Methanol Powered Science, 1991. 251: p. 515-515.

2. Olah, G.A., A. Goeppert, and G.K.S. Prakash, Beyond oil and gas : the methanol economy. 2006, Weinheim an der Bergstrasse,
Germany: Wiley-VCH. xiv, 290 p.
3. Aldrich, B., ABC's of AFV's: A Guide to Alternative Fuel Vehicles. 1995: Diane Pub.
4. Methanol: the clear alternative for transportation. 2011, www.methanol.org.
5. Reed, T.B. and R.M. Lerner, Methanol - Versatile Fuel for Immediate Use. Science, 1973. 182(4119): p. 1299-1304.
6. Skrzypek, J., et al., Thermodynamics and kinetics of low pressure methanol synthesis. The Chemical Engineering Journal, 1995. 58: p.
101-108.
7. Hansen, J.B. and P.E.H. Nielsen, Methanol Synthesis, in Handbook of Heterogenous Catalysis, Ert, et al., Editors. 2008, Weily-VCH
8. Twigg, M.V. and M.S. Spencer, Deactivation of copper metal catalysts for methanol decomposition, methanol steam reforming and
methanol synthesis. Topics in Catalysis, 2003. 22(3-4): p. 191-203.
9. Bernton, H., W. Kovarik, and S. Sklar, A History of Power Alcohol. 2010, Lincoln, NE: Bison Press. xiv, 290 p.
10. Statistical Review of World Energy, B. Global, Editor. 2011.
11. Palo, D.R., R.A. Dagle, and J.D. Holladay, Methanol steam reforming for hydrogen production. Chemical Reviews, 2007. 107(10): p.
3992-4021.
12. Stiles, A., Methanol, Past, Present, and Speculution on the Future. AIChE Journal, 1977. 23(3): p. 362-275.
13. Lewis, W.K. and P.K. Frolich, Synthesis of Methanol from Carbon Monoxide and Hydrogen. Industrial and Engineering Chemistry,
1928. 20(285).
14. Weissermel, K. and H.-J. Arpe, Industrial organic chemistry. 4th completely rev. ed. 2003, Weinheim: Wiley-VCH. xix, 491 p., 20
folded leaves of plates.
15. Fiedler, E., et al., Methanol in Ullmann's Engcylopedia of Industrial Chemistry. 2011, Weily-VCH Weihneim.
16. Kung, H.H., Deactivation of Methanol Synthesis Catalysts - a Review. Catalysis Today, 1992. 11(4): p. 443-453.
17. Kung, H.H., Methanol Synthesis. Catalysis Reviews, 1980. 22(2): p. 235-259.
18. Klier, K., et al., Catalytic Synthesis of Methanol from CO/H2 iV. The Effect of Carbon Dioxide. Journal of Catalysis, 1981. 74: p. 343-
360.
19. Chinchen, G.C., et al., Mechanism of Methanol Synthesis from Co2/Co/H2 Mixtures over Copper/Zinc Oxide/Alumina Catalysts - Use
of C-14-Labeled Reactants. Applied Catalysis, 1987. 30(2): p. 333-338.
20. Rozovskii, A.Y., Kinetika i Kataliz, 1980. 21: p. 87.
21. Fujita, S., et al., Mechanism of the Formation of Precursors for the Cu/Zno Methanol Synthesis Catalysts by a Coprecipitation
Method. Catalysis Letters, 1995. 34(1-2): p. 85-92.
22. Waugh, K.C., Methanol Synthesis. Catalysis Today, 1992. 15(1): p. 51-75.
23. Saussey, J., J.C. Lavalley, and C.J. Bovet, Chem. Soc. Faraday Trans., 1982. 87: p. 1457.
24. Yang, Y., et al., Isotope effects in methanol synthesis and the reactivity of copper formates on a Cu/SiO(2) catalyst. Catalysis Letters,
2008. 125(3-4): p. 201-208.
25. Yang, Y., et al., (Non)formation of Methanol by Direct Hydrogenation of Formate on Copper Catalysts. Journal of Physical
Chemistry C, 2010. 114(40): p. 17205-17211.
26. Muhler, M., et al., On the Role of Adsorbed Atomic Oxygen and Co2 in Copper-Based Methanol Synthesis Catalysts. Catalysis Letters,
1994. 25(1-2): p. 1-10.
27. Nakamura, J., J.M. Campbell, and C.T. Campbell, Kinetics and Mechanism of the Water-Gas Shift Reaction Catalyzed by the Clean
and Cs-Promoted Cu(110) Surface - a Comparison with Cu(111). Journal of the Chemical Society-Faraday Transactions, 1990.
86(15): p. 2725-2734.
28. Szanyi, J. and D.W. Goodman, Methanol Synthesis on a Cu(100) Catalyst. Catalysis Letters, 1991. 10(5-6): p. 383-390.
29. Yoshihara, J., et al., Methanol Synthesis and Reverse Water-Gas Shift Kinetics over Clean Polycrystalline Copper. Catalysis Letters,
1995. 31(4): p. 313-324.
30. Yoshihara, J. and C.T. Campbell, Methanol synthesis and reverse water-gas shift kinetics over Cu(110) model catalysts: Structural
sensitivity. Journal of Catalysis, 1996. 161(2): p. 776-782.
31. Rasmussen, P.B., et al., Methanol Synthesis on Cu(100) from a Binary Gas-Mixture of Co2 and H2. Catalysis Letters, 1994. 26(3-4):
p. 373-381.
32. Nakamura, J., et al., Methanol Synthesis over a Zn-Deposited Copper Model Catalyst. Catalysis Letters, 1995. 31(4): p. 325-331.
33. Sahibzada, M., I.S. Metcalfe, and D. Chadwick, Methanol synthesis from CO/CO2/H-2 over Cu/ZnO/Al2O3 at differential and finite
conversions. Journal of Catalysis, 1998. 174(2): p. 111-118.
34. Askgaard, T.S., et al., A Kinetic-Model of Methanol Synthesis. Journal of Catalysis, 1995. 156(2): p. 229-242.
35. Yang, Y.X., et al., Fundamental studies of methanol synthesis from CO(2) hydrogenation on Cu(111), Cu clusters, and
Cu/ZnO(000(1)over-bar). Physical Chemistry Chemical Physics, 2010. 12(33): p. 9909-9917.
36. Grabow, L.C. and M. Mavrikakis, Mechanism of Methanol Synthesis on Cu through CO(2) and CO Hydrogenation. Acs Catalysis,
2011. 1(4): p. 365-384.
37. Hu, Z.M., K. Takahashi, and H. Nakatsuji, Mechanism of the hydrogenation of CO(2) to methanol on a Cu(100) surface: dipped
adcluster model study. Surface Science, 1999. 442(1): p. 90-106.
38. Morikawa, Y., K. Iwata, and K. Terakura, Theoretical study of hydrogenation process of formate on clean and Zn deposited Cu(1 1 1)
surfaces. Applied Surface Science, 2001. 170: p. 11-15.
39. Zhao, Y.F., et al., Insight into methanol synthesis from CO(2) hydrogenation on Cu(111): Complex reaction network and the effects of
H(2)O. Journal of Catalysis, 2011. 281(2): p. 199-211.
40. Saito, M., R&D activities in Japan on methanol synthesis from CO2 and H2. Catalysis Surveys from Japan, 1998. 2: p. 175-184.
41. Lee, J.S., et al., A Comparative-Study of Methanol Synthesis from Co2/H-2 and Co/H-2 over a Cu/Zno/Al2o3 Catalyst. Journal of
Catalysis, 1993. 144(2): p. 414-424.
42. Chanchlani, K.G., R.R. Hudgins, and P.L. Silveston, Methanol Synthesis from H-2, Co, and Co2 over Cu/Zno Catalysts. Journal of
Catalysis, 1992. 136(1): p. 59-75.
43. Liu, G., et al., The Rate of Methanol Production on a Copper-Zinc Oxide Catalyst - the Dependence on the Feed Composition. Journal
of Catalysis, 1984. 90(1): p. 139-146.
44. Bart, J.C. and R.P.A. Sneeden, Catalysis Today, 1987. 2: p. 1.
45. Behrens, M., Meso- and nano-structuring of industrial Cu/ZnO/(Al(2)O(3)) catalysts. Journal of Catalysis, 2009. 267(1): p. 24-29.
46. Behrens, M., et al., Phase-Pure Cu,Zn,Al Hydrotalcite-like Materials as Precursors for Copper rich Cu/ZnO/Al2O3 Catalysts.
Chemistry of Materials, 2009. 22(2): p. 386-397.
47. Greeley, J. and M. Mavrikakis, Methanol decomposition on Cu(111): A DFT study. Journal of Catalysis, 2002. 208(2): p. 291-300.
48. Arena, F., et al., Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to
CH3OH. Applied Catalysis A., 2008. 350: p. 16-23.
49. Słoczynski, J., et al., Effect of metal oxide additives on the activity and stability of Cu/ZnO/ZrO2 catalysts in the synthesis of methanol
from CO2 and H2. Applied Catalysis A., 2006. 310: p. 127-137.
50. An, X., et al., Methanol Synthesis from CO2 Hydrogenation with a Cu/Zn/Al/Zr Fibrous Catalyst*. Chinese Journal of Chemical
Engineering,, 2009. 17(1): p. 88-94.
51. Liao, F., et al., Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials Interface in Selective
Hydrogenation of CO2 to CH3OH. Angewandte Chemie International Edition, 2011. 50: p. 2162-2165.
52. Arena, F., et al., Synthesis, characterization and activity pattern of Cu-ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to
methanol. Journal of Catalysis, 2007. 249(2): p. 185-194.
53. Saito, M., et al., Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and
hydrogen. Applied Catalysis a-General, 1996. 138(2): p. 311-318.
54. Kurtz, M., et al., New synthetic routes to more active Cu/ZnO catalysts used for methanol synthesis. Catalysis Letters, 2004. 92(1-2):
p. 49-52.
55. Behrens, M., Methanol Steam Reforming, in Catalysis for alternative energy generation (eds: L. Guczi, A. Erdohelyi), M. Armbruster,
Editor. 2012, Springer.
56. Kasatkin, I., et al., Role of lattice strain and defects in copper particles on the activity of Cu/ZnO/Al2O3 catalysts for methanol
synthesis. Angewandte Chemie-International Edition, 2007. 46(38): p. 7324-7327.
57. Behrens, M., et al., Methanol Synthesis over Cu/ZnO/Al2O3: The Active Site in Industrial Catalysis. Science.
58. Chinchen, G.C., et al., The Measurement of Copper Surface-Areas by Reactive Frontal Chromatography. Journal of Catalysis, 1987.
103(1): p. 79-86.
59. Hinrichsen, O., T. Genger, and M. Muhler, Chemisorption of N2O and H-2 for the surface determination of copper catalysts.
Chemical Engineering & Technology, 2000. 23(11): p. 956-959.
60. Behrens, M., et al., The Potential of Microstructural Optimization in Metal/Oxide Catalysts: Higher Intrinsic Activity of Copper by
Partial Embedding of Copper Nanoparticles. Chemcatchem, 2010. 2(7): p. 816-818.
61. Spencer, M.S., The role of zinc oxide in Cu ZnO catalysts for methanol synthesis and the water-gas shift reaction. Topics in Catalysis,
1999. 8(3-4): p. 259-266.
62. Burch, R., R.J. Chappell, and S.E. Golunski, Synergy between Copper and Zinc-Oxide during Methanol Synthesis - Transfer of
Activating Species. Journal of the Chemical Society-Faraday Transactions I, 1989. 85: p. 3569-3578.
63. Kanai, Y., et al., The synergy between Cu and ZnO in methanol synthesis catalysts. Catalysis Letters, 1996. 38(3-4): p. 157-163.
64. Klier, K., Methanol Synthesis. Advances in Catalysis, 1982. 31: p. 243-313.
65. Jansen, W.P.A., et al., Dynamic behavior of the surface structure of Cu/ZnO/SiO2 catalysis. Journal of Catalysis, 2002. 210(1): p.
229-236.
66. Frost, J.C., Junction Effect Interactions in Methanol Synthesis Catalysts. Nature, 1988. 334(6183): p. 577-580.
67. Nakamura, J., Y. Choi, and T. Fujitani, On the issue of the active site and the role of ZnO in Cu/ZnO methanol synthesis catalysts.
Topics in Catalysis, 2003. 22(3-4): p. 277-285.
68. Topsoe, N.Y. and H. Topsoe, On the nature of surface structural changes in Cu ZnO methanol synthesis catalysts. Topics in Catalysis,
1999. 8(3-4): p. 267-270.
69. d'Alnoncourt, R.N., et al., The influence of strongly reducing conditions on strong metal-support interactions in Cu/ZnO catalysts
used for methanol synthesis. Physical Chemistry Chemical Physics, 2006. 8(13): p. 1525-1538.
70. Grunwaldt, J.D., et al., In situ investigations of structural changes in Cu/ZnO catalysts. Journal of Catalysis, 2000. 194(2): p. 452-460.
71. Hansen, P.L., et al., Atom-resolved imaging of dynamic shape changes in supported copper nanocrystals. Science, 2002. 295(5562): p.
2053-2055.
72. Kurr, P., et al., Microstructural characterization of Cu/ZnO/Al2O3 catalysts for methanol steam reforming - A comparative study.
Applied Catalysis a-General, 2008. 348(2): p. 153-164.
73. Kniep, B.L., et al., Rational design of nanostructured copper-zinc oxide catalysts for the steam reforming of methanol. Angewandte
Chemie-International Edition, 2004. 43(1): p. 112-115.
74. Gunter, M.M., et al., Redox behavior of copper oxide/zinc oxide catalysts in the steam reforming of methanol studied by in situ X-ray
diffraction and absorption spectroscopy. Journal of Catalysis, 2001. 203(1): p. 133-149.
75. Sakong, S. and A. Gross, Dissociative adsorption of hydrogen on strained Cu surfaces. Surface Science, 2003. 525(1-3): p. 107-118.
76. Girgsdies, F., et al., Strained thin copper films as model catalysts in the materials gap. Catalysis Letters, 2005. 102(1-2): p. 91-97.
77. Hammer, B. and J.K. Norskov, Electronic factors determining the reactivity of metal surfaces. Surface Science, 1995. 343(3): p. 211-
220.
78. Behrens, M., et al., Understanding the complexity of a catalyst synthesis: Co-precipitation of mixed Cu,Zn,Al hydroxycarbonate
precursors for Cu/ZnO/Al(2)O(3) catalysts investigated by titration experiments. Applied Catalysis a-General, 2011. 392(1-2): p. 93-
102.
79. Schimpf, S., Methanol Catalysts, in Synthesis of Solid Catalysts (ed: de Jong, K. P.), M. Muhler, Editor. 2009, Wiley VCH:
Weinheim. p. 329.
80. Waller, D., et al., Copper-zinc oxide catalysts. Activity in relation to precursor structure and morphology. Faraday Discussions of the
Chemical Society, 1989. 87: p. 107-120.
81. Whittle, D.M., et al., Co-precipitated copper zinc oxide catalysts for ambient temperature carbon monoxide oxidation: effect of
precipitate ageing on catalyst activity. Physical Chemistry Chemical Physics, 2002. 4(23): p. 5915-5920.
82. Fierro, G., et al., Study of the reducibility of copper in CuO-ZnO catalysts by temperature-programmed reduction. Applied Catalysis
a-General, 1996. 137(2): p. 327-348.
83. Gunter, M.M., et al., Implication of the microstructure of binary Cu/ZnO catalysts for their catalytic activity in methanol synthesis.
Catalysis Letters, 2001. 71(1-2): p. 37-44.
84. Baltes, C., S. Vukojevic, and F. Schuth, Correlations between synthesis, precursor, and catalyst structure and activity of a large set of
CuO/ZnO/Al2O3 catalysts for methanol synthesis. Journal of Catalysis, 2008. 258(2): p. 334-344.
85. Li, J.L. and T. Inui, Characterization of precursors of methanol synthesis catalysts, copper zinc aluminum oxides, precipitated at
different pHs and temperatures. Applied Catalysis a-General, 1996. 137(1): p. 105-117.
86. Bems, B., et al., Relations between synthesis and microstructural properties of copper/zinc hydroxycarbonates. Chemistry-a European
Journal, 2003. 9(9): p. 2039-2052.
87. Shen, G.C., S.I. Fujita, and N. Takezawa, Preparation of Precursors for the Cu/Zno Methanol Synthesis Catalysts by Coprecipitation
Methods - Effects of the Preparation Conditions Upon the Structures of the Precursors. Journal of Catalysis, 1992. 138(2): p. 754-758.
88. Behrens, M., et al., Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via
formate precursors. Chemical Communications, 2011. 47(6): p. 1701-1703.
89. Christiansen, J.A., A reaction between methyl alcohol and water and some related reactions. Journal of the American Chemical
Society, 1921. 43: p. 1670-1672.
90. Prigent, M., On board hydrogen generation for fuel cell powered electric cars - A review of various available techniques. Revue De L
Institut Francais Du Petrole, 1997. 52(3): p. 349-360.
91. Navarro, R.M., M.A. Pena, and J.L.G. Fierro, Hydrogen production reactions from carbon feedstocks: Fossils fuels and biomass.
Chemical Reviews, 2007. 107(10): p. 3952-3991.
92. Sa, S., et al., Catalysts for methanol steam reforming-A review. Applied Catalysis B-Environmental, 2010. 99(1-2): p. 43-57.
93. de Wild, P.J. and M.J.F.M. Verhaak, Catalytic production of hydrogen from methanol. Catalysis Today, 2000. 60(1-2): p. 3-10.
94. Joensen, F. and J.R. Rostrup-Nielsen, Conversion of hydrocarbons and alcohols for fuel cells. Journal of Power Sources, 2002.
105(2): p. 195-201.
95. Cheekatamarla, P.K. and C.M. Finnerty, Reforming catalysts for hydrogen generation in fuel cell applications. Journal of Power
Sources, 2006. 160(1): p. 490-499.
96. Velu, S., K. Suzuki, and T. Osaki, Oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts; a new and efficient
method for the production of CO-free hydrogen for fuel cells. Chemical Communications, 1999(23): p. 2341-2342.
97. Lattner, J.R. and M.P. Harold, Autothermal reforming of methanol: Experiments and modeling. Catalysis Today, 2007. 120(1): p. 78-
89.
98. Park, E.D., D. Lee, and H.C. Lee, Recent progress in selective CO removal in a H(2)-rich stream. Catalysis Today, 2009. 139(4): p.
280-290.
99. Tsai, M.C., et al., Promotion of a copper-zinc catalyst with rare earth for the steam reforming of methanol at low temperatures.
Journal of Catalysis, 2011. 279(2): p. 241-245.
100. Breen, J.P. and J.R.H. Ross, Methanol reforming for fuel-cell applications: development of zirconia-containing Cu-Zn-Al catalysts.
Catalysis Today, 1999. 51(3-4): p. 521-533.
101. Agrell, J., et al., Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3. Journal of Catalysis,
2003. 219(2): p. 389-403.
102. Matsumura, Y. and H. Ishibe, High temperature steam reforming of methanol over Cu/ZnO/ZrO(2) catalysts. Applied Catalysis B-
Environmental, 2009. 91(1-2): p. 524-532.
103. Jones, S.D. and H.E. Hagelin-Weaver, Steam reforming of methanol over CeO(2)- and ZrO(2)-promoted Cu-ZnO catalysts supported
on nanoparticle Al(2)O(3). Applied Catalysis B-Environmental, 2009. 90(1-2): p. 195-204.
104. Velu, S. and K. Suzuki, Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl oxide
catalysts: effect of substitution of zirconium and cerium on the catalytic performance. Topics in Catalysis, 2003. 22(3-4): p. 235-244.
105. Velu, S., et al., Oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts for the selective production of hydrogen for
fuel cells: Catalyst characterization and performance evaluation. Journal of Catalysis, 2000. 194(2): p. 373-384.
106. Costantino, U., et al., Cu-Zn-Al hydrotalcites as precursors of catalysts for the production of hydrogen from methanol. Solid State
Ionics, 2005. 176(39-40): p. 2917-2922.
107. Turco, M., et al., Production of hydrogen from oxidative steam reforming of methanol - I. Preparation and characterization of
Cu/ZnO/Al2O3 catalysts from a hydrotalcite-like LDH precursor. Journal of Catalysis, 2004. 228(1): p. 43-55.
108. Turco, M., et al., Production of hydrogen from oxidative steam reforming of methanol - II. Catalytic activity and reaction mechanism
on Cu/ZnO/Al2O3 hydrotalcite-derived catalysts. Journal of Catalysis, 2004. 228(1): p. 56-65.
109. Ritzkopf, I., et al., Decreased CO production in methanol steam reforming over Cu/ZrO2 catalysts prepared by the microemulsion
technique. Applied Catalysis a-General, 2006. 302(2): p. 215-223.
110. Purnama, H., et al., Activity and selectivity of a nanostructured CuO/ZrO2 catalyst in the steam reforming of methanol. Catalysis
Letters, 2004. 94(1-2): p. 61-68.
111. Liu, Y.Y., et al., Highly active copper/ceria catalysts for steam reforming of methanol. Applied Catalysis a-General, 2002. 223(1-2):
p. 137-145.
112. Szizybalski, A., et al., In situ investigations of structure-activity relationships of a Cu/ZrO2 catalyst for the steam reforming of
methanol. Journal of Catalysis, 2005. 233(2): p. 297-307.
113. Mastalir, A., et al., Steam reforming of methanol over Cu/ZrO2/CeO2 catalysts: a kinetic study. Journal of Catalysis, 2005. 230(2): p.
464-475.
114. Jiang, C.J., et al., Kinetic Mechanism for the Reaction between Methanol and Water over a Cu-Zno-Al2o3 Catalyst. Applied Catalysis
a-General, 1993. 97(2): p. 145-158.
115. Takezawa, N. and N. Iwasa, Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and
group VIII metals. Catalysis Today, 1997. 36(1): p. 45-56.
116. Peppley, B.A., et al., Methanol-steam reforming on Cu/ZnO/Al2O3 catalysts. Part 2. A comprehensive kinetic model. Applied
Catalysis a-General, 1999. 179(1-2): p. 31-49.
117. Rozovskii, A.Y. and G.I. Lin, Fundamentals of methanol synthesis and decomposition. Topics in Catalysis, 2003. 22(3-4): p. 137-150.
118. Lee, J.K., J.B. Ko, and D.H. Kim, Methanol steam reforming over Cu/ZnO/Al2O3 catalyst: kinetics and effectiveness factor. Applied
Catalysis a-General, 2004. 278(1): p. 25-35.
119. Peppley, B.A., et al., Methanol-steam reforming on Cu/ZnO/Al2O3. Part 1: The reaction network. Applied Catalysis a-General, 1999.
179(1-2): p. 21-29.
120. Frank, B., et al., Steam reforming of methanol over copper-containing catalysts: Influence of support material on microkinetics.
Journal of Catalysis, 2007. 246(1): p. 177-192.
121. Lin, S., et al., Pathways for methanol steam reforming involving adsorbed formaldehyde and hydroxyl intermediates on Cu(111):
density functional theory studies. Physical Chemistry Chemical Physics, 2011. 13(20): p. 9622-9631.
122. Lin, S., D.Q. Xie, and H. Guo, Methyl Formate Pathway in Methanol Steam Reforming on Copper: Density Functional Calculations.
Acs Catalysis, 2011. 1(10): p. 1263-1271.
123. Spencer, M.S., On the Activation-Energies of the Forward and Reverse Water-Gas Shift Reaction. Catalysis Letters, 1995. 32(1-2): p.
9-13.
124. Saito, M., et al., Effects of ZnO contained in supported Cu-based catalysts on their activities for several reactions. Catalysis Letters,
2002. 83(1-2): p. 1-4.
125. Noei, H., et al., The identification of hydroxyl groups on ZnO nanoparticles by infrared spectroscopy. Physical Chemistry Chemical
Physics, 2008. 10(47): p. 7092-7097.
126. Goodby, B.E. and J.E. Pemberton, Xps Characterization of a Commercial Cu/Zno/Al2o3 Catalyst - Effects of Oxidation, Reduction,
and the Steam Reformation of Methanol. Applied Spectroscopy, 1988. 42(5): p. 754-760.
127. Raimondi, F., et al., Structural changes of model Cu/ZnO catalysts during exposure to methanol reforming conditions. Surface
Science, 2003. 532: p. 383-389.
128. Raimondi, F., J. Wambach, and A. Wokaun, Structural properties of Cu/ZnO/Si methanol reforming catalysts: Influence of the
composition of the reactant mixture and of the Cu island size. Physical Chemistry Chemical Physics, 2003. 5(18): p. 4015-4024.
129. Reitz, T.L., et al., Time-resolved XANES investigation of CuO/ZnO in the oxidative methanol reforming reaction. Journal of Catalysis,
2001. 199(2): p. 193-201.
130. Busca, G., et al., Methanol steam reforming over ex-hydrotalcite Cu-Zn-Al catalysts. Applied Catalysis a-General, 2006. 310: p. 70-
78.
131. Busca, G., et al., Hydrogen from alcohols: IR and flow reactor studies. Catalysis Today, 2009. 143(1-2): p. 2-8.
132. Vargas, M.A.L., et al., An IR study of methanol steam reforming over ex-hydrotalcite Cu-Zn-Al catalysts. Journal of Molecular
Catalysis a-Chemical, 2007. 266(1-2): p. 188-197.
133. Zhang, X.R., et al., A unique microwave effect on the microstructural modification of Cu/ZnO/Al2O3 catalysts for steam reforming of
methanol. Chemical Communications, 2005(32): p. 4104-4106.
134. Wang, L.C., et al., Production of hydrogen by steam reforming of methanol over Cu/ZnO catalysts prepared via a practical soft
reactive grinding route based on dry oxalate-precursor synthesis. Journal of Catalysis, 2007. 246(1): p. 193-204.
135. Loffler, D.G., S.D. McDermott, and C.N. Renn, Activity and durability of water-gas shift catalysts used for the steam reforming of
methanol. Journal of Power Sources, 2003. 114(1): p. 15-20.
136. Thurgood, C.P., et al., Deactivation of Cu/ZnO/Al2O3 catalyst: evolution of site concentrations with time. Topics in Catalysis, 2003.
22(3-4): p. 253-259.
137. Agrell, J., H. Birgersson, and M. Boutonnet, Steam reforming of methanol over a Cu/ZnO/Al2O3 catalyst: a kinetic analysis and
strategies for suppression of CO formation. Journal of Power Sources, 2002. 106(1-2): p. 249-257.
138. Iwasa, N., S. Masuda, and N. Takezawa, Steam Reforming of Methanol over Ni, Co, Pd and Pt Supported on Zno. Reaction Kinetics
and Catalysis Letters, 1995. 55(2): p. 349-353.
139. Penner, S., et al., Growth and structural stability of well-ordered PdZn alloy nanoparticles. Journal of Catalysis, 2006. 241(1): p. 14-
19.
140. Karim, A., T. Conant, and A. Datye, The role of PdZn alloy formation and particle size on the selectivity for steam reforming of
methanol. Journal of Catalysis, 2006. 243(2): p. 420-427.
141. Liu, S.T., et al., Hydrogen production by oxidative methanol reforming on Pd/ZnO: Catalyst preparation and supporting materials.
Catalysis Today, 2007. 129(3-4): p. 287-292.
142. Fottinger, K., et al., Dynamic Structure of a Working Methanol Steam Reforming Catalyst: In Situ Quick-EXAFS on Pd/ZnO
Nanoparticles. Journal of Physical Chemistry Letters, 2011. 2(5): p. 428-433.
143. Grunwaldt, J.D., et al., In Situ Investigations of Structural Changes in Cu/ZnO Catalysts. Journal of Catalysis, 2000. 194: p. 452-460.