Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis

doi:10.1016/S1872-2067(22)64107-X

Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (8): 2045-2056.DOI: 10.1016/S1872-2067(22)64107-X

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Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis

Zixuan Zhou^a^,^b, Peng Gao^a^,^b^,^*()

^aCAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
^bUniversity of the Chinese Academy of Sciences, Beijing 100049, China

Received:2022-03-07 Accepted:2022-04-07 Online:2022-08-18 Published:2022-06-20
Contact: Peng Gao
About author:Prof. Peng Gao (Chinese Academy of Sciences Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute (SARI), Chinese Academy of Sciences (CAS)) received Ph.D. degree in chemical engineering and Technology from University of Chinese Academy of Sciences and Institute of Coal Chemistry, CAS in 2014. Since at the end of 2013, he has been working in SARI, CAS. He was honored with the Catalysis Rising Star Award from the Catalysis Society of China in 2021, Top Young Talents in Shanghai and Shanghai Rising-Star Award in 2019, and best reviewer award 2021 of Journal of Energy Chemistry. His research interests mainly focus on the conversion of carbon one molecular (CO₂, CO and CH₃OH, etc.) into chemicals and fuels via heterogeneous catalysis. He has published more than 60 peer-reviewed papers, which have been cited more than 3000 times (H index = 30), and was awarded as one of the top 1% of highly cited authors in Royal Society of Chemistry journals, 2019. More than 10 Chinese patents have been authorized respect to his work.
Supported by:
National Natural Science Foundation of China(21773286);National Natural Science Foundation of China(U1832162);National Natural Science Foundation of China(22172189);“Frontier Science” Program of Shell Global Solutions International B.V.(CW373032);Youth Innovation Promotion Association CAS(2018330);“Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21090204);Shanghai Rising-Star Program, China(19QA1409900);Gaolu Air Products and Chemicals (Shanghai) Energy Technology Co., Ltd

Abstract

Abstract:

The hydrogenation of carbon dioxide (CO₂) to produce chemicals and transportation liquid fuels in huge demand via heterogeneous thermochemical catalysis achieved using renewable energy has received increasing attention, and substantial advances have been made in this research field in recent years. In this study, we summarize our progress in the rational design and construction of highly efficient catalysts for CO₂ hydrogenation to methanol, lower olefins, aromatics, and gasoline- and jet fuel-range hydrocarbons. The structure-performance relationship, nature of the active sites, and mechanism of the reactions occurring over these catalysts are explored by combining computational and experimental evidence. The results of this study will promote further fundamental studies and industrial applications of heterogeneous catalysts for CO₂ hydrogenation to produce bulk chemicals and liquid fuels.

Key words: Carbon dioxide hydrogenation, Heterogeneous catalysis, Coupling reaction, Rational design, Reaction mechanism

Zixuan Zhou, Peng Gao. Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis[J]. Chinese Journal of Catalysis, 2022, 43(8): 2045-2056.

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Figures/Tables 6

Fig. 1. (a) Morphologies of the Cu-Zn-Al-Zr-LDH precursor, calcined CuO-ZnO-Al2O3-ZrO2 composite oxide, and reduced Cu-ZnO-Al2O3-ZrO2 catalyst. Reproduced with permission from Ref. [22]. Copyright 2017, Elsevier. (b) Comparison of the CH3OH selectivity obtained by the unmodified and fluorine-modified Cu-ZnO-Al2O3-ZrO2 catalysts for CO2 hydrogenation. Inset: formation of fluorinated Cu-Zn-Al-Zr LDH achieved via the introduction of (AlF6)3- ions into layers. (c) Results of the stability test conducted on the Cu-ZnO-Al2O3-ZrO2 catalyst for CO2 hydrogenation to methanol derived from the phase-pure LDH precursor under the following reaction conditions: 250 °C, 5 MPa, 4000 h-1, and H2/CO2 = 3. Reproduced with permission from Refs. [21] and [28]. Copyright 2015 and 2016, Elsevier.

Fig. 2. (a) Schematic illustration of the most favorable CO2 hydrogenation pathways predicted to occur on the surface of cubic In2O3(110) [c-In2O3(110)], c-In2O3(111), hexagonal In2O3(012) [h-In2O3(012)], and h-In2O3(014). Effects of reaction temperature on the extent of CO2 conversion and CH3OH product selectivity (b) and on the CH3OH yield (c) in the reaction occurring over spherical c-In2O3 (c-In2O3-S) and h-In2O3 nanorod (h-In2O3-R) samples under the following reaction conditions: 300 °C, 5 MPa, 9000 mL gcat-1 h-1, and H2/CO2 = 3. (d) In situ diffuse reflectance infrared Fourier-transform spectroscopy data recorded for surface species formed from CO2 hydrogenation reaction occurring over h-In2O3-R. Reproduced with permission from Ref. [32]. Copyright 2020, Science.

Fig. 3. (a) Effect of the particle size of spent In2O3 (after reaction for 24 h) on the space-time yield of lower olefins from the CO2 hydrogenation reaction under the following reaction conditions: 350 °C, 3 MPa, 9000 mL gcat-1 h-1, and H2/CO2 = 3. Reproduced with permission from Ref. [40]. Copyright 2021 Elsevier. (b) High-resolution transmission electron microscopy images of In2O3 and In1-xZrxOy solid solution oxides. (c) CO2-TPD spectra for the reduced In2O3, ZrO2, and In1-xZrxOy oxides. (d) Energy profiles of the CO2 hydrogenation reaction to CH3OH conducted over the surfaces of In2O3 and In1-xZrxOy, reported in black and red, respectively. Reproduced with permission from Ref. [39]. Copyright 2018, American Chemical Society. (e) Effects of the crystal size and pore structure of the SAPO-34 zeolite on the C2=-C4= product selectivity and olefin/paraffin molecular ratio caused by the CO2 hydrogenation reaction conducted over bifunctional catalysts under the following reaction conditions of 380 °C, 3 MPa, 9000 mL gcat-1 h-1, and H2/CO2 = 3. Reproduced with permission from Ref. [42]. Copyright 2019, John Wiley and Sons.

Fig. 4. (a) Mechanism of the reaction of CO2 hydrogenation to produce aromatic compounds and isoparaffins occurring over the Na-Fe3O4/zeolite composite catalyst. Reproduced with permission from Ref. [67]. Copyright 2019, Royal Society of Chemistry. (b) Morphologies of hierarchical nanocrystalline HZSM-5 aggregates. Reproduced with permission from Ref. [34]. Copyright 2019, American Chemical Society. Transmission electron microscopy images of the short b-axis (c) and chain-like (d) nanocrystalline HZSM-5. (e) Proposed mechanism of the reaction of CO2 hydrogenation to produce aromatic compounds occurring over ZnZrOx/HZMS-5, and the effect of the acidic properties and pore structure of HZSM-5 on the distribution of the produced aromatic compounds. Reproduced with permission from Ref. [60]. Copyright 2021, Elsevier. (f) Catalytic performance of bifunctional catalysts and the sole In2O3 for the reaction of CO2 hydrogenation under the reaction conditions of 340 °C, 3 MPa, 9000 mL gcat-1 h-1, and H2/CO2 = 3, as well as CH3OH conversion over HZSM-5. Reproduced with permission from Ref. [38]. Copyright 2017, Springer Nature.

Fig. 5. (a) Effect of the proximity between the ZnZrOx and HZMS-5 components of the catalyst on system’s catalytic performance under the following reaction conditions: 315 °C, 3 MPa, 1020 mL gcat-1 h-1, and H2/CO2 = 3. (b) Product distribution without CO, CO2 conversion, and CO selectivity over ZnZrOx/HZMS-5 prepared by mixing ZnZrOx and HZSM-5 power by using an agate mortar with different reaction temperatures. Reproduced with permission from Ref. [60]. Copyright 2021, Elsevier. (c) Effect of the proximity between the In2O3 and HZMS-5 components of the catalyst on system’s catalytic performance under the reaction conditions detailed in Fig. 4(f). (d) Detail hydrocarbon distribution over In2O3/HZSM-5 prepared by mixing of granules (500-800 μm) of two components. Reproduced with permission from Ref. [38]. Copyright 2017, Springer Nature.

Fig. 6. Different catalyst systems reported in the literature for CO2-based Fischer-Tropsch synthesis and their main hydrocarbon products and typical selectivity values.

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Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis

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