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Title: Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation

Abstract

Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO2 hydrogenation is one of the major topics in CO2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO2/Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 gMeOHkgcat-1h-1 at 220°C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat-1h-1). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO2/Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO2 supported over metallic Cu particles. The ZrO2 islands are highly active for the CO2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm-1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO2/Cu configuration, accounting for the excellent methanol formation activity observed.

Authors:
 [1]; ORCiD logo [2];  [3];  [4];  [5];  [6];  [7];  [7];  [1]; ORCiD logo [1];  [8]; ORCiD logo [6];  [1];  [4]; ORCiD logo [3]; ORCiD logo [9]; ORCiD logo [1]
  1. Peking Univ., Beijing (China). Beijing National Lab. for Molecular Sciences
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Zhejiang Univ. of Technology, Hangzhou (China)
  3. Chinese Academy of Sciences (CAS), Taiyuan (China). State Key Lab. of Coal Conversion; Synfuels China Co. Ltd., Beijing (China). National Center for Coal to Liquids
  4. Tsinghua Univ., Beijing (China)
  5. State Univ. of New York (SUNY), Stony Brook, NY (United States)
  6. Tianjin Univ. of Technology, Tianjin (China). Center for Electron Microscopy
  7. Brookhaven National Lab. (BNL), Upton, NY (United States)
  8. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  9. Brookhaven National Lab. (BNL), Upton, NY (United States); State Univ. of New York (SUNY), Stony Brook, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Key R&D Program of China
OSTI Identifier:
1717902
Alternate Identifier(s):
OSTI ID: 1798203
Report Number(s):
BNL-220639-2020-JAAM
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
SC0012704; AC02-06CH11357; 21725301; 91645115; 21821004; 21932002; 21473229; 91545121; 2017YFB0602200
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Zirconium oxide; Copper; Copper oxide; CO2 hydrogenation

Citation Formats

Wu, Congyi, Lin, Lili, Liu, Jinjia, Zhang, Jingpeng, Zhang, Feng, Zhou, Tong, Rui, Ning, Yao, Siyu, Deng, Yuchen, Yang, Feng, Xu, Wenqian, Luo, Jun, Zhao, Yue, Yan, Binhang, Wen, Xiao-Dong, Rodriguez, José A., and Ma, Ding. Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation. United States: N. p., 2020. Web. https://doi.org/10.1038/s41467-020-19634-8.
Wu, Congyi, Lin, Lili, Liu, Jinjia, Zhang, Jingpeng, Zhang, Feng, Zhou, Tong, Rui, Ning, Yao, Siyu, Deng, Yuchen, Yang, Feng, Xu, Wenqian, Luo, Jun, Zhao, Yue, Yan, Binhang, Wen, Xiao-Dong, Rodriguez, José A., & Ma, Ding. Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation. United States. https://doi.org/10.1038/s41467-020-19634-8
Wu, Congyi, Lin, Lili, Liu, Jinjia, Zhang, Jingpeng, Zhang, Feng, Zhou, Tong, Rui, Ning, Yao, Siyu, Deng, Yuchen, Yang, Feng, Xu, Wenqian, Luo, Jun, Zhao, Yue, Yan, Binhang, Wen, Xiao-Dong, Rodriguez, José A., and Ma, Ding. Fri . "Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation". United States. https://doi.org/10.1038/s41467-020-19634-8. https://www.osti.gov/servlets/purl/1717902.
@article{osti_1717902,
title = {Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation},
author = {Wu, Congyi and Lin, Lili and Liu, Jinjia and Zhang, Jingpeng and Zhang, Feng and Zhou, Tong and Rui, Ning and Yao, Siyu and Deng, Yuchen and Yang, Feng and Xu, Wenqian and Luo, Jun and Zhao, Yue and Yan, Binhang and Wen, Xiao-Dong and Rodriguez, José A. and Ma, Ding},
abstractNote = {Enhancing the intrinsic activity and space time yield of Cu based heterogeneous methanol synthesis catalysts through CO2 hydrogenation is one of the major topics in CO2 conversion into value-added liquid fuels and chemicals. Here we report inverse ZrO2/Cu catalysts with a tunable Zr/Cu ratio have been prepared via an oxalate co-precipitation method, showing excellent performance for CO2 hydrogenation to methanol. Under optimal condition, the catalyst composed by 10% of ZrO2 supported over 90% of Cu exhibits the highest mass-specific methanol formation rate of 524 gMeOHkgcat-1h-1 at 220°C, 3.3 times higher than the activity of traditional Cu/ZrO2 catalysts (159 gMeOHkgcat-1h-1). In situ XRD-PDF, XAFS and AP-XPS structural studies reveal that the inverse ZrO2/Cu catalysts are composed of islands of partially reduced 1–2 nm amorphous ZrO2 supported over metallic Cu particles. The ZrO2 islands are highly active for the CO2 activation. Meanwhile, an intermediate of formate adsorbed on the Cu at 1350 cm-1 is discovered by the in situ DRIFTS. This formate intermediate exhibits fast hydrogenation conversion to methoxy. The activation of CO2 and hydrogenation of all the surface oxygenate intermediates are significantly accelerated over the inverse ZrO2/Cu configuration, accounting for the excellent methanol formation activity observed.},
doi = {10.1038/s41467-020-19634-8},
journal = {Nature Communications},
number = 1,
volume = 11,
place = {United States},
year = {2020},
month = {11}
}

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