Supporting Information

Efficient Conversion of Syngas to Ethanol by Tandem

Catalysis

Songyue Hana, b, Dong Fana, Nan Chena, b, Wenhao Cuia, b, Linhai Hea, b, Peng Tian*, a and Zhongmin

Liu*, a

a National Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National

Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences,

Dalian 116023, China.

b University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing 100049,

China.

*Corresponding authors: [email protected]; [email protected]

S1
EXPERIMENTAL SECTION

Catalyst preparation

STAGE 1:

CuZnAlOx (Cu/Zn=2/1 in mole, Al2O3 content: 11 wt%) was commercial catalyst purchased from

Yanchang Zhongke (Dalian) Energy Technology Co., Ltd.

H-ZSM-5 (SiO2/Al2O3=50 in mole) was purchased from Nankai University Catalyst Co., Ltd.

γ-Al2O3 was prepared by calcining AlOOH at 823 K for 6 h.

The composite catalyst was prepared by powder mixing of CuZnAlOx and γ-Al2O3 (or H-ZSM-5) with

different mass ratios in an agate mortar for 10 min, pressing the tablet under the pressure of 30 MPa and

granulating to 40-60 mesh. The obtained catalysts were denoted as CuZnAlOx/γ-Al2O3 and CuZnAlOx/H-

ZSM5.
STAGE 2:

SAPO-34, H-Y, H-ZSM-5(A), H-MCM-22 and H-ZSM-35 were supplied by Group 1202 in DICP.

Mordenite was hydrothermally synthesized from the starting gel with molar ratios of SiO2: 0.025 Al2O3:

0.20 TEAOH: 0.12 Na2O: 0.02 CTAB: 20 H2O. A typical synthesis procedure was as follows. NaOH and

NaAlO2 were dissolved in tetraethyl ammonium hydroxide (TEAOH) solution to prepare a clear solution.

Then, colloidal silica and hexadecyl trimethyl ammonium bromide (CTAB) were added into the above

solution under vigorous stirring. After aging at RT for 0.5 h, seeds (3 wt.% relative to SiO2) were added.

The final mixture was stirred for another 2 h and then transferred into a stainless-steel autoclave for

hydrothermal crystallization at 170 °C for 48 h under rotation at 60 rpm. The product was recovered by

centrifugation, washed with deionized water, dried at 120 °C and calcined at 550 °C for 5 h to remove the

organics. The obtained sample was exchanged with 1.0 mol/L NH4NO3 aqueous solution at 80 °C for 3 h

S2
and repeated 3 times. The final sample was recovered by centrifugation, washed with deionized water,

dried at 120 °C, and calcined in dry air at 550 °C for 5 h to obtain proton form mordenite (denoted as H-

MOR).

Py-HMOR was obtained by post-treatment of H-MOR. H-MOR (40-60 mesh) was heated at 673 K for

2 h in a fixed bed reactor to remove the adsorbed water. After cooling to 573 K, pyridine vapor carried

by N2 (30 mL/min) was passed thorough the H-MOR. After treatment for 1h, the sample was flushed with

N2 (60 mL/min) for 1 h.

CuZn-HMOR was obtained by ion exchange method. Cu(NO3)2·3H2O (2.42g, purity 99%) and

Zn(NO3)2·6H2O (2.97g, purity 99%) were dissolved in 100 mL water. The solution was stirred using a

magnetic stir bar and heated to 333 K. NH4+-MOR was then added (solid/liquid=1 g/20 mL). After stirring

for 3 h, the resulting powder was recovered by vacuum filtration, washed with deionized water, dried at

333 K and calcined at 823K for 4 h under dry air. For Co-HMOR preparation, Co(NO3)2·6H2O (2.91g,

purity 99%) was used in replace for Cu(NO3)2·3H2O and Zn(NO3)2·6H2O. Other conditions were the same

as CuZn-HMOR.
STAGE 3:

Pt/Al2O3 was prepared by incipient wetness impregnation method. In details, α-Al2O3 was obtained by

calcining pseudo-boehmite at 1473 K for 10 h. 0.79g of HPtCl6 dissolved in 3 mL of water was added

dropwise to 6 g of α-Al2O3 and mixed well. After being placed in oven at 120°C overnight, the sample

was calcined in air at 673 K for 4 h.

Cu/SiO2 was prepared by urea-assisted method. In details, Cu(NO3)2·3H2O (6.81g, purity 99%) was

dissolved in 100 mL of diluted ammonia water solution. Subsequently, 16.2 g of Ludox AS-40 (40 wt%)

colloidal silica was added with a burette under stirring, which was followed by the addition of 3.0 g of

urea. The mixture was vigorously stirred and aged at 90 °C for 4 h. The resulting pale blue precipitate
S3
was isolated by filtration, washed with deionized water and ethanol, dried under vacuum at 120 °C

overnight, and then calcined in air at 350 °C for 4 h.

CuaZnbAlOx catalysts with different Cu/Zn molar ratios used in the third stage were prepared by co-

precipitation method. Take Cu1Zn2AlOx as an example, Cu(NO3)2·3H2O (3.63g, purity 99%),

Zn(NO3)2·6H2O (8.92g, purity 99%) and Al(NO3)3·9H2O (1.88 g, purity 99%) were dissolved in 50 mL

deionized water. Then, the mixed aqueous solution and Na2CO3 solution (1.0 mol mL-1) were

simultaneously added to a glass beaker containing 100 mL deionized water under vigorous stirring at 343

K. The pH value of the aqueous solution was kept at 7.0. The obtained precipitate was aged for 30min.

Then, the solid product was recovered by filtration, followed by washing thoroughly with deionized

water. The product was dried overnight at 373 K and calcined in air at 623 K for 5 h.

Catalyst characterization

The crystallinity of catalyst samples was obtained on an X-ray diffractometer (XRD) of PANalytical

X’Pert PRO using Cu Kα radiation (λ = 0.15418 nm) with a scanning angle (2θ) range of 5°-80°, a tube

voltage of 40 kV, and a current of 40 mA. The composition of catalyst samples were determined by

Philips Magix-601 X-ray fluorescence (XRF).

Transmission electron microscope (TEM) images and selected area electron diffraction (SAED)

patterns were obtained with a JEOL 2000 electron microscope operating at 200 kV. The reduced catalysts

for TEM measurement were prepared by treating them with 30 mL/min of 10%H2/90%N2 at 553 K for 3

h under normal atmospheric pressure. The morphology of zeolites was measured by Hitachi SU8020

scanning electron microscope (SEM).

S4
 Textural properties of the samples were estimated from nitrogen adsorption-desorption isotherms

measured by Micromeritics ASAP 2020 instrument. All samples were outgassed at 573K for 3 h to

remove physically adsorbed impurities before the measurement.

Temperature programmed desorption of ammonia (NH3-TPD) analysis was performed on

Micromeritics Autochem II 2920 equipped with a thermal conductivity detector (TCD). Prior to the

measurement, the sample (100 mg, 40-60 mesh) was pretreated at 723 K for 1 h under a He flow. After

saturated with NH3 at 373 K, the desorption process was operated from 373 to 973 K.

The reduction properties of the samples were measured by hydrogen temperature-programmed

reduction (H2-TPR), and the tests were performed on a Micromeritics AutoChem II 2920 apparatus. In a

typical procedure, 100 mg of catalyst (40-60 mesh) was placed in a quartz U-tube, treated with Ar at 573

K for 1 h and cooled to 323 K. Then H2 (30 mL/min) was passed through the catalyst bed, and the

temperature was raised from 323 K to 873 K for reduction.

A Bruker Tensor 27 spectrometer (MCT detector) was used for the measurement of fourier transform

infrared spectra (FTIR). The samples were pressed self-supported wafers and placed into the in situ quartz

cell. Subsequently, the wafers were dehydrated at 673 K in a vacuum for 30 min to remove the physisobed

water. After cooling to room temperature, the spectra were collected by a MCT detector in the range of

4000–400 cm−1 with a resolution of 4 cm−1.

The coke deposition amount on the spent catalyst was analyzed by thermogravimetric analysis (TGA,

TA Q-600 analyzer) with a heating rate of 10 K/min from room temperature to 1200 K under air flow.

The organics remained in the spent zeolites after reaction were analyzed by GC-MS. The spent catalyst

(0.1g) was first dissolved in 20% HF solution (1mL). The soluble organics in the mixture was extracted

S5
with CH2Cl2 (1mL, containing 10 ppm C2Cl6 internal standard), and then analyzed with a GC-MS (Agilent

7890B) equipped with HP-5 capillary column.

In-situ Diffuse Reflectance Infrared Fourier Transform (DRIFT) Spectra

In situ DRIFT experiments were performed on a Bruker Tensor 27 device, which was equipped with

Diffuse reflector and MCT detector. The spectra were collected at a resolution of 4 cm−1.

(1) The influence of water on the Bronsted acid sites of molecular sieves at 473-543 K

KBr was first loaded in the diffuse reflection infrared cell. The spectra were collected every 10 K from

473 K to 543 K as backgrounds. 50 mg of Py-HMOR was placed in the in-situ cell and calcined in N2 at

573 K for 1 h. After cooling to the set temperature, N2 was switched to N2/H2O (passing 30 mL/min N2

through a water bath at 298 K) and the spectra were collected at the same temperature.

(2)The influence of water on the formation of methoxyl groups at 473 K and 543 K

50 mg of Py-HMOR was loaded in the in-situ cell. The sample was calcined in a N2 flow at 573 K for

1 h, and the spectra were collected at 543 K and 473 K as backgrounds.

The catalyst was treated with 20 mL/min of N2/DME (5% DME, 95% N2) under the conditions of 543

K and 2 MPa. The spectra were collected at 5 min interval until the spectra did not change. After that, 20

mL/min of N2 was introduced for purging, and the spectra were collected to observe the formation of

methoxy groups. In the control experiment, 20 mL/min of N2/DME (5% DME, 95% N2) and N2/H2O

(passing 30 mL/min of N2 through a water bath at 298 K) were co-fed to treat the catalyst at 543 K and 2

MPa, and the rest of the process was the same as the above. The experiments were also carried out at 473

K, with the same operating procedures as the above except for the temperature.

S6
S7
Catalytic testing

The reaction unit consists of two fixed-bed stainless steel reactors connected in series (Scheme S1).

The temperature of each reactor can be individually controlled. The pressure of both reactors was the

same, which was controlled by outlet pressure backup valve. When all the catalysts were packed in one

reactor, the second reactor was used. In a typical procedure, we assembled the three stage catalysts into

the second reactor by separating them by quartz wool (3 mm in height). Before the reaction, the catalysts

(about 0.5 g) were activated with 30 mL/min of 10%H2/90%N2 at 553 K for 3 h under designed pressure.

Afterwards, the reactor was lowered to the reaction temperature, and then the feed gas (31.7% CO, 63.3%

H2, 5.0% Ar) of 35 mL/min was switched into the reactor and carried out the reaction under the

predesigned condition.

During the reaction, all pipelines were heated by heating belts to ensure that all products were in the

gas phase. On-line analysis was performed using an Agilent 7890B GC, equipped with an HP-PLOT/Q

capillary column and a TDX-1 packed column, connected to FID detector and TCD detector respectively.

The TCD detector was responsible for the detection of CO, CO2 and Ar. The FID was responsible for the

detection of oxygenates (DME, methanol, methyl acetate, ethanol, acetic acid, acetone, etc.) and

hydrocarbons. Methane is the reference bridge between TCD and FID results. CO conversion and product

selectivity were calculated using molar carbon bases. The organic product selectivity was calculated by

excluding CO2. The detailed calculation formulas are shown in the following:

COinlet  COoutlet
Conv CO = 100%
COinlet
CO 2 ,goutlet
Sel CO 2 = 100%
COinlet  COoutlet
Product X goutlet
Sel Product X = n
100%
 n gC H
1
n m O x，outlet

S8
 COinlet: the mole of CO in the reactor inlet.

COoutlet: the mole of CO in the reactor outlet.

CO2, outlet: the mole of CO2 in the reactor outlet

Product X outlet: the mole of C atoms in organic product X.

n

 n gC H
1
n m O x，outlet : the total C moles in all organic species. n is the number of C atoms in the organic

products (including hydrocarbons).

Scheme S1 Process flow diagram of the tandem catalysis system for syngas-to-ethanol reaction.

S9
Figure S1. (a) XRD patterns of CuZnAlOx, γ-Al2O3, H-ZSM-5 and their powder mixtures. (b) TEM

images of the reduced CuZnAlOx /γ-Al2O3 with particle size distribution (1) and lattice fringe analysis

(2).

S10
Figure S2. Effect of reaction temperature (a), space velocity (b) and pressures (c) on product distribution

on CuZnAlOx/γ-Al2O3. Reaction conditions: (a) H2/CO = 2; P = 2.0 MPa; GHSV = 10000 mL g-1 h-1. (b)

H2/CO = 2; P = 2.0 MPa; T = 543 K. (c) H2/CO = 2; T = 543 K; GHSV = 20000 mL g-1 h-1. The data were

obtained in steady state.

S11
Figure S3. CO equilibrium conversions of STM and STD at different temperatures. Simulation

calculation conditions: H2/CO = 2; P = 2 MPa. Data were calculated by HSC 9.0 chemistry software.

S12
Figure S4. Stability of syngas to DME reaction over (a) CuZnAlOx/H-ZSM-5 and (b) CuZnAlOx/γ-Al2O3.

Reaction conditions: T = 543 K, P = 2.0 MPa, H2/CO = 2, GHSV = 10000 mL g-1 h-1.

S13
Figure S5. XRD patterns (top) and SEM images (down) of the zeolites. (a) SAPO-34, (b) H-USY, (c) H-

MCM-22, (d) H-ZSM-5(A), (e) H-ZSM-35.

S14
Figure S6. N2 adsorption-desorption isotherms of different zeolites.

Figure S7. NH3-TPD profiles of the zeolites. All the figures have the same scale of Y axis.

S15
Figure S8. Catalytic performance of CuZnAlOx/γ-Al2O3 │ zeolite. Reaction conditions: T = 543 K;

H2/CO = 2; P = 2.0 MPa; F = 35 mL min−1; weight of CuZnAlOx /γ-Al2O3 and zeolite: 0.10 g and 0.20 g;

time on steam = 5 h. The selectivity of organics was calculated on a molar carbon basis (CO2 free).

S16
Figure S9. XRD patterns (a) and NH3-TPD profiles (b) of the metal-modified H-MOR. (c) Catalytic

performance of CuZnAlOx/γ-Al2O3│Me-HMOR. Reaction conditions: T = 543 K, P = 2.0 MPa, H2/CO

= 2, F = 35mL min-1, weight of CuZnAlOx/γ-Al2O3 and zeolite: 0.10 g and 0.20 g; time on steam = 5 h.

The selectivity of organics was calculated on a molar carbon basis (CO2 free).

S17
Figure S10. Effect of the second-stage reactor temperature on product distribution in the dual-bed system.

Reaction conditions: T (upper bed, CuZnAlOx/γ-Al2O3) = 543 K, T (lower bed, Py-HMOR) = 473-543

K, P = 2.0 MPa, H2/CO = 2, and F = 35 mL min-1. Weight of CuZnAlOx/γ-Al2O3 and Py-HMOR: 0.10 g

and 0.20 g.

S18
Figure S11. (a) XRD patterns and (b) H2-TPR profiles of the third-stage catalysts. (c) XRD patterns of

the reduced Cu4Zn1AlOx and Cu1Zn2AlOx. (d) TEM images of the reduced Cu4Zn1AlOx with particle size

distribution (1) and lattice fringe analysis (2). (e) TEM images of the reduced Cu1Zn2AlOx with particle

size distribution (1) and lattice fringe analysis (2).

S19
Figure S12. Catalytic performance of CuZnAlOx/γ-Al2O3 │ Py-HMOR │ CuaZnbAlOx. Reaction

conditions: T = 543 K, P = 2.0 MPa, H2/CO = 2, and F = 35 mL min-1, weight of CuZnAlOx/γ-Al2O3, Py-

HMOR and CuaZnbAlOx: 0.10 g, 0.20 g and 0.20 g.

S20
Figure S13. Pyridine-adsorbed FT-IR spectrum of Cu1Zn2AlOx.

S21
Figure S14. Characterization of MOR catalysts. (a) TG curves of the fresh and spent catalysts. (b) GC-

MS chromatograms of organic materials retained in spent catalysts. The spent catalyst was taken out after

50 h reaction under conditions of H2/CO = 2, P = 2.0 MPa and F = 35 mL min−1 (CuZnAlOx/γ-Al2O3 and

zeolites: 0.10g and 0.20g).

S22
 3CO+3H2=CH3OCH3+CO2 (1)
CO+ 2H2 = CH3OH (2)
CH3OCH3 + CO = CH3COOCH3 (3)
CH3OH + CO = CH3COOH (4)
CH3COOCH3 + 2H2 = CH3OH + CH3CH2OH (5)
CH3OH+CO = CH3COOH (6)
CH3CH2OH + CH3COOH = CH3COOCH2CH3 (7)

Figure S15. Gibbs free energy (ΔrG) changes for the reactions in the tandem system of syngas to ethanol.

S23
Figure S16. Equilibrium calculation of syngas to DME following temperature change. (a) Raw simulated

data. (b) Changes in CO conversion and product selectivity at different temperatures calculated from raw

data. Simulation calculation conditions: H2/CO = 2; P = 2 MPa. Data was calculated by HSC 9.0 chemistry

software.

Figure S17. Equilibrium calculation of the effect of pressure change on syngas to DME reaction. (a) Raw

simulated data. (b) Changes in CO conversion and product selectivity at different pressures calculated

S24
from raw data. Simulation calculation conditions: H2/CO = 2; T = 543 K; P = 0-5 MPa. Data was

calculated by HSC 9.0 chemistry software.

Figure S18. Morphology and XRD patterns of the spent catalysts after 120h reaction. (a) XRD of Py-

HMOR (b) SEM images of Py-HMOR. (c) TEM images of CuZnAlOx /γ-Al2O3 with particle size

S25
distribution (1) and lattice fringe analysis (2), (d) TEM images of Cu1Zn2AlOx with particle size

distribution (1) and lattice fringe analysis (2).

S26
Figure S19. Effect of H2O and CH3OH on MA and AA formation over CuZnAlOx/γ-Al2O3│Py-HMOR.

Left: T = 473 K, P = 2.0 MPa, H2/CO = 2, F = 35 mL min-1, weight of CuZnAlOx/γ-Al2O3 and Py-

HMOR: 0.10 g and 0.20 g. Right: Only Py-HMOR catalyst (0.20 g) was used. Simulated feed gas from

the first-stage effluents but without H2O/CH3OH (22.7% CO, 60.1% H2, 6.3% Ar, 5.7% DME, 5.2% CO2)

was used to replace the effluents from CuZnAlOx-γ-Al2O3. Other conditions were the same as the Left.

S27
Figure S20. Comparison of FT-IR spectra to show the effect of H2O on the formation of methoxy over

Py-HMOR at 473 K (a) and 543 K (b). The spectra were recorded after DME adsorption (in the presence

or absence of H2O) followed by N2 purge for 30 min.

S28
Figure S21. DME carbonylation over Py-HMOR at 543 K. Reaction conditions: T = 543 K, P = 2.0 MPa,

F = 35 mL min-1, weight of Py-HMOR: 0.20 g, feed gas: 22.7% CO, 60.1% H2, 6.3% Ar, 5.7% DME,

5.2% CO2. The gas composition was the same as the effluent compositions from CuZnAlOx/γ-Al2O3 of

the tandem system in Figure 3e except the absence of H2O and CH3OH.

S29
Figure S22. Stability comparison of DME carbonylation on Py-HMOR under H2 and N2 atmospheres.

Reaction conditions: T = 543 K, P = 2.0 MPa, F = 42 mL min-1, weight of Py-HMOR: 0.10 g. Feed gas

for H2 atmosphere: 22.7% CO, 6.3% Ar, 5.7% DME, 5.2% CO2, H2 as balance gas. Feed gas for N2

atmosphere: 22.7% CO, 6.3% Ar, 5.7% DME, 5.2% CO2, N2 as balance gas.

S30
Table S1. Summary results for ethanol production from syngas on single catalyst.

GHSV CO Conv. SEtOHa YEtOHb

Catalyst T (K) P(MPa) H2/CO Ref.
(mL gcat-1 h-1) (%) (C-mol%) (mmol g-1 h-1)
RhMn@S-1 593 3.0 2.0 3600 42.4 25.6 5.8 1

2%Rh-1%Fe/TiO2 543 2.0 1.0 8000 4.45 39.0 1.5 2

K-MoS2/MMO 583 10.3 1.0 4600 3.3 36.3d 0.6 3
Ni1Mo1K0.05–11%CNTs 558 5.0 1.0 5000 23.1 24.3 3.1 4

CoMo|CuZnAlZr 503 6.0 2.0 2000 17.8 5.1d 0.27 5

ZnCrAlOx|KNiMoS-MMO-5 623 5.0 1.0 3000 10.0 21.7 0.73 6

CoFe-350 533 3.0 2.0 10800 24.0 11 2.1 7
Cu1Co2La 523 3.0 2.0 36000 0.86 10.8 0.23 8
CS/Cu/ZnO/Al2O3 563 5.4 2.0 1875 41.6 5.0 0.29 9
K-LaCo0.7Cu0.3O3−δ 548 6.9 2.0 5000c 20.0 16.2 1.19 10

a: Ethanol selectivity in all products.

b: Ethanol space time yield, calculated from data in the literatures.

c: mL mLcat-1 h-1.

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d: CO2-free selectivity.

S32
Table S2. Summary results for ethanol production from syngas by tandem catalysis.

CO CO2
GHSV SEtOHa YEtOHb
Catalyst T (K) P(MPa) H2/CO Conv. Sel. Ref.
(mL gcat-1 h-1) (C-mol%) (mmol g-1 h-1)
(%) (%)

CuZnAlOx/γ-Al2O3+Py-
543 2.0 2.0 4000 52 27 62 6.5 This work
HMOR+Cu1Zn2AlOx

H-MOR+Cu/ZnO 493 1.5 ≈ 1.0c 2400 2.3 5.1 41 0.8 11

CuZnOX+Cu-MOR+
473 4.6 1.0 895 7.7 3.5 15.6 0.24 12
CuZnOX
503 5 1.0 758 0.7 3 90 0.10 13
K+-ZnO-ZrO2+
H-MOR+Pt/Sn-SiC
543 5 1.0 758 4.0 7 80 0.51 13

ZnAlOX+H-MOR+
643 3 1.0 1500 11 - 52 1.54d 14
ZnAlOX
Cu/ZnAlMgO+HMOR+
483 2.5 4.0 3260 0.4 28 53 0.04 d 15
Cu/ZnAlMgO

CuZnAl-HZSM-5 + Zn-
493 2.0 2.0 2000 7.3 - 69.3 0.59 d 16
HMOR+ CuZnAl

a: Ethanol selectivity in organic products (without CO2).

b: Ethanol space-time yield, calculated from data in the literature.

S33
c: H2/CO/DME= 47.4:50:1

d: The data were estimated from the literatures.

S34
Table S3. Catalytic performance of CuZnAlOx and the powder mixture of CuZnAlOx and γ-Al2O3a

Mass ratio of CO CO2 Selectivityb

CuZnAlOx /𝛄- conv. sel. (C mole%, excluding CO2)
Catalyst
Al2O3 (%) (%) CH3OH DME HC

CuZnAlOx 1/0 9 0 96.1 0 3.3

S1-1 1/1 41 30 5.2 94 0.7

S1-2
2/1 56 31 5.6 94 0.4
(named CuZnAlOx/𝛄-Al2O3)
S1-3 5/1 51 28 8 91 1.0
S1-4 10/1 43 26 13 85 1.8
S1-5c
2/1 12 0 9.8 84.1 5.6
(CuZnAlOx│γ-Al2O3)
S1-6d
10/1 62 30 4 95 0.9
(CuZnAlOx/H-ZSM-5)

a: Reaction conditions: T = 543 K, P = 2.0 MPa, H2/CO = 2, GHSV = 10000 mL g-1 h-1. The total weight

of the catalysts is 0.20 g.

b: HC: hydrocarbons.

c: CuZnAlOx and γ-Al2O3 were separated by quartz wool.

d: Powder mixture of CuZnAlOx and H-ZSM-5.

S35
Table S4. Texture information, chemical compositions and acid properties of zeolite samples

Total acid
Si/Al Surface
Channel Channel size Pore volumec sitesd
Catalyst mole areab
dimension (ring size) (cm3/g) (mmol/g)
ratioa (m2/g)

[001] 3.8*3.8
SAPO-34 3D 0.14 488.3 0.25 0.84
(8MR)
[111] 7.4*7.4
USY 3D 19.7 682.8 0.47 0.36
(12MR)
[001] 4.0*5.5
(10MR)
MCM-22 2D 10.7 488.4 0.48 0.97
[001] 4.1*5.1
(10MR)
[100] 5.1*5.5
(10MR)
ZSM-5(A) 3D 47 336.9 0.23 0.25
[010] 5.3*5.6
(10MR)
[001] 4.2*5.4
(10MR)
ZSM-35 2D 11.5 309.9 0.17 0.82
[010] 3.5*4.8
(8MR)
[001]6.5*7.0
(12MR)
MOR 1D 15.8 434.6 0.24 0.80
[001] 2.6*5.7
(8MR)

a: Si/Al mole ratio was measured by XRF.

b: BET surface area.

c: Pore volume at P/P0 = 0.975.

d: Based on the results of NH3-TPD profiles of H-form samples.

S36
Table S5. Catalytic performance of CuZnAlOx/γ-Al2O3│Py-HMOR│Cu1Zn2AlOx with different catalyst

mass ratios.a

CO CO2 Selectivityb (C mole%, excluding CO2)

Mass ratio
conv. sel.
(g/g/g)
(%) (%) HC CH3OH DME MA AA AC EtOH EA

0.05:0.10:0.35 27 24 2.7 42 1.2 7.5 2.3 0 42 2.1

0.05:0.25:0.20 29 25 5.3 21 0 5.9 2.0 32 25 8.9

0.10:0.10:0.30 47 27 2.1 27 42 1.2 0.2 0 28 2.2

0.10:0.20:0.20 52 28 2.9 21 3 5.5 0 0 62 3.9

0.10:0.30:0.10 53 27 4.2 14 0 26 4.3 11 34 5.7

0.15:0.15:0.20 60 29 1.5 17 35 6.1 0.3 0 36 4.2

0.20:0.20:0.10 67 30 2.0 11 48 9.1 0.7 0 25 4.1

0.20:0.10:0.20 65 30 2.1 10 73 1.2 0.1 0 12 1.5

0.30:0.10:0.10 71 31 1.5 2.4 90 0.2 0 0 5.4 0.5

a: Reaction conditions: T= 543 K, P =2.0 MPa, H2/CO = 2, F = 35 mL min−1.

b: HC: hydrocarbons; MA: methyl acetate; AA: acetic acid; AC: acetone; EA: ethyl acetate.

S37
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