Highly dispersed Cd cluster supported on TiO2 as an efficient catalyst for CO2 hydrogenation to methanol

doi:10.1016/S1872-2067(21)63907-4

Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (3): 761-770.DOI: 10.1016/S1872-2067(21)63907-4

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Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol

Jijie Wang^a^,^†, Jittima Meeprasert^b^,^†, Zhe Han^a^,^c^,^†, Huan Wang^a, Zhendong Feng^a^,^d, Chizhou Tang^a^,^d, Feng Sha^a^,^c, Shan Tang^a^,^d, Guanna Li^e^,^f, Evgeny A. Pidko^b^,^#(), Can Li^a^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bInorganic Systems Engineering, Department of Chemical Engineering, Delft University of Technology, Van der Maasweg, the Netherlands
^cSchool of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin 300350, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China
^eBiobased Chemistry and Technology, Wageningen University & Research, the Netherlands
^fLaboratory of Organic Chemistry, Wageningen University & Research, the Netherlands

Received:2021-05-27 Revised:2021-05-27 Online:2022-03-18 Published:2022-02-18
Contact: Evgeny A. Pidko, Can Li
About author:Jijie Wang (State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences) received his Ph.D degree in 2013 from Xiamen University. From 2013 to 2017, he did postdoctoral research at Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, his Co-supervisor is Professor Can Li. At the beginning of 2018, he joined the DICP, where he is now a professor of DICP. His researches mainly focus on catalytic hydrogenation of carbon dioxide to methanol, low carbon olefin, aromatic hydrocarbon, etc. He has made original achievements in the catalytic hydrogenation of carbon dioxide to methanol with high selectivity and stability, and developed ZnO-ZrO₂ bimetal oxide solid solution catalyst to open up a new way for the hydrogenation of carbon dioxide. As one of the main contributors, he completed the world's first set of "liquid sunshine methanol" industrial pilot and demonstration projects. He has published 20 papers in Science Advances, Joule and other journals, applied for 14 domestic patents, and 2 international PCT patents. He has received Min Enze Energy and Chemical Industry Award-Youth Progress Award, International Catalytic Conference Young Scientist Award. He joined the editorial board of Chin. J. Catal. in 2020.
First author contact:
^† These authors contributed equally.
Supported by:
National Key R&D Program of China(2017YFB0702800);Fundamental Research Center of Artificial Photosynthesis(22088102);National Natural Science Foundation of China(21802139);Youth Innovation Promotion Association CAS(2019183)

Abstract

Abstract:

The conversion of CO₂ to methanol with high activity and high selectivity remains challenging owing to the kinetic and thermodynamic limitations associated with the low chemical reactivity exhibited by CO₂. Herein, we report a novel Cd/TiO₂ catalyst exhibiting a methanol selectivity of 81%, a CO₂ conversion of 15.8%, and a CH₄ selectivity below 0.7%. A combination of experimental and computational studies revealed that the unique electronic properties exhibited by the Cd clusters supported by the TiO₂ matrix were responsible for the high selectivity of CO₂ hydrogenation to methanol via the HCOO* pathway at the interfacial catalytic sites.

Key words: CO₂ hydrogenation, Methanol, Cd/TiO₂ catalyst, Cd cluster, TiO₂

Jijie Wang, Jittima Meeprasert, Zhe Han, Huan Wang, Zhendong Feng, Chizhou Tang, Feng Sha, Shan Tang, Guanna Li, Evgeny A. Pidko, Can Li. Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol[J]. Chinese Journal of Catalysis, 2022, 43(3): 761-770.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63907-4

https://www.cjcatal.com/EN/Y2022/V43/I3/761

Figures/Tables 4

Fig. 1. Catalytic performance. (a) CO2 conversion and methanol selectivity for various catalysts; (b) Catalytic performance as a function of the Cd/(Cd+Ti) molar ratio; (c) Variation in the CO2 conversion and methanol selectivity exhibited by 3.5% Cd/TiO2 under various pressures and temperatures; (d) Methanol yield and specific activity exhibited by the CuZnO, Cd/TiO2, and ZnO-ZrO2 catalysts at various temperatures. The standard reaction conditions were as follows: 2.0 MPa, H2/CO2 = 3/1, 290 °C, GHSV = 24000 mL·gcat-1·h-1.

Fig. 2. Structural characterization. (a) XRD spectra obtained from the fresh Cd/TiO2 catalysts. (b,c) XRD spectra obtained from the used Cd/TiO2 catalysts. Aberration-corrected STEM-HAADF images of the 0.35% Cd/TiO2 (d), 3.5% Cd/TiO2 (e), and 7% Cd/TiO2 (f) catalysts. The isolated Cd sites are circled in yellow, the Cd clusters are circled in red, and the Cd particles are circled in purple. (g) XPS spectra obtained from the Cd/TiO2 catalysts treated using CO2/H2 mixed gas. (h) EXAFS spectra with k3-weighted data obtained from 0.35% Cd/TiO2 and 3.5% Cd/TiO2. (i) Schematic structure illustration of the Cd/TiO2 catalysts.

Fig. 3. Surface reactivity. (a) CO2-TPD of 3.5% Cd/TiO2, TiO2, and Cd; (b) In-situ DRIFT spectra obtained from surface species formed during CO2 adsorption; (c) H2-TPD of 3.5% Cd/TiO2, TiO2, and Cd; (d) In-situ DRIFT spectra obtained from the surface species formed during the reaction for 3.5% Cd/TiO2.

Fig. 4. DFT calculations. Reaction energy profiles corresponding to CO2 hydrogenation to CH3OH in the Cd4/TiO2 and CdTiO3 catalysts via the formate pathway. (unit: eV). In the case of the Cd4/TiO2 catalyst, the species marked with an asterisk (*) and hash sign (#) interact with the TiO2 site and Cd site of the Cd4/TiO2 catalyst, respectively.

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Highly dispersed Cd cluster supported on TiO₂ as an efficient catalyst for CO₂ hydrogenation to methanol

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