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:
-
- Peking Univ., Beijing (China). Beijing National Lab. for Molecular Sciences
- Brookhaven National Lab. (BNL), Upton, NY (United States); Zhejiang Univ. of Technology, Hangzhou (China)
- 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
- Tsinghua Univ., Beijing (China)
- State Univ. of New York (SUNY), Stony Brook, NY (United States)
- Tianjin Univ. of Technology, Tianjin (China). Center for Electron Microscopy
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- 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 Research and Development 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. doi: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 = {Fri Nov 13 00:00:00 EST 2020},
month = {Fri Nov 13 00:00:00 EST 2020}
}
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Unique Properties of Ceria Nanoparticles Supported on Metals: Novel Inverse Ceria/Copper Catalysts for CO Oxidation and the Water-Gas Shift Reaction
journal, January 2013
- Senanayake, Sanjaya D.; Stacchiola, Dario; Rodriguez, Jose A.
- Accounts of Chemical Research, Vol. 46, Issue 8
Integrative CO 2 Capture and Hydrogenation to Methanol with Reusable Catalyst and Amine: Toward a Carbon Neutral Methanol Economy
journal, January 2018
- Kar, Sayan; Sen, Raktim; Goeppert, Alain
- Journal of the American Chemical Society, Vol. 140, Issue 5
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO 2 Hydrogenation Processes
journal, May 2017
- Álvarez, Andrea; Bansode, Atul; Urakawa, Atsushi
- Chemical Reviews, Vol. 117, Issue 14
Intermediate species on zirconia supported methanol aerogel catalysts V. Adsorption of methanol
journal, March 1995
- Bianchi, D.; Chafik, T.; Khalfallah, M.
- Applied Catalysis A: General, Vol. 123, Issue 1
Water-Gas Shift Reaction on a Highly Active Inverse CeO x /Cu(111) Catalyst: Unique Role of Ceria Nanoparticles
journal, October 2009
- Rodriguez, José A.; Graciani, Jesús; Evans, Jaime
- Angewandte Chemie International Edition, Vol. 48, Issue 43
When Density Functional Approximations Meet Iron Oxides
journal, September 2016
- Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang
- Journal of Chemical Theory and Computation, Vol. 12, Issue 10
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts
journal, March 2015
- Studt, Felix; Behrens, Malte; Kunkes, Edward L.
- ChemCatChem, Vol. 7, Issue 7
Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol
journal, March 2019
- Wang, Yuhao; Kattel, Shyam; Gao, Wengui
- Nature Communications, Vol. 10, Issue 1
Reducibility of ZrO 2 /Pt 3 Zr and ZrO 2 /Pt 2D films compared to bulk zirconia: a DFT+U study of oxygen removal and H 2 adsorption
journal, January 2017
- Ruiz Puigdollers, Antonio; Pacchioni, Gianfranco
- Nanoscale, Vol. 9, Issue 20
Intermediate species on zirconia supported methanol aerogel catalysts
journal, November 1993
- Bianchi, Daniel; Chafik, Tarik; Khalfallah, Mohamed
- Applied Catalysis A: General, Vol. 105, Issue 2
Optimizing Binding Energies of Key Intermediates for CO 2 Hydrogenation to Methanol over Oxide-Supported Copper
journal, September 2016
- Kattel, Shyam; Yan, Binhang; Yang, Yixiong
- Journal of the American Chemical Society, Vol. 138, Issue 38
Role of Hydrogen Spillover in Methanol Synthesis over Cu/ZrO2
journal, July 2000
- Jung, Kwang-Deog; Bell, Alexis T.
- Journal of Catalysis, Vol. 193, Issue 2
In-SituInfrared Study of Methanol Synthesis from H2/CO2over Cu/SiO2and Cu/ZrO2/SiO2
journal, November 1997
- Fisher, Ian A.; Bell, Alexis T.
- Journal of Catalysis, Vol. 172, Issue 1
Atomic Resolution Imaging of a Carbon Nanotube from Diffraction Intensities
journal, May 2003
- Zuo, J. M.
- Science, Vol. 300, Issue 5624
Hydrogenation of CO 2 to Methanol: Importance of Metal–Oxide and Metal–Carbide Interfaces in the Activation of CO 2
journal, October 2015
- Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.
- ACS Catalysis, Vol. 5, Issue 11
Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO 2 Hydrogenation to Methanol
journal, November 2016
- Rungtaweevoranit, Bunyarat; Baek, Jayeon; Araujo, Joyce R.
- Nano Letters, Vol. 16, Issue 12
Indium Oxide as a Superior Catalyst for Methanol Synthesis by CO 2 Hydrogenation
journal, March 2016
- Martin, Oliver; Martín, Antonio J.; Mondelli, Cecilia
- Angewandte Chemie International Edition, Vol. 55, Issue 21
Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species
journal, July 2007
- Bjorgen, M.; Svelle, S.; Joensen, F.
- Journal of Catalysis, Vol. 249, Issue 2
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Atomic-scale engineering of indium oxide promotion by palladium for methanol production via CO2 hydrogenation
journal, July 2019
- Frei, Matthias S.; Mondelli, Cecilia; García-Muelas, Rodrigo
- Nature Communications, Vol. 10, Issue 1
Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts
journal, March 2017
- Lin, Lili; Zhou, Wu; Gao, Rui
- Nature, Vol. 544, Issue 7648
Effect of the damping function in dispersion corrected density functional theory
journal, March 2011
- Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
- Journal of Computational Chemistry, Vol. 32, Issue 7
Model estimates of CO2 emissions from soil in response to global warming
journal, May 1991
- Jenkinson, D. S.; Adams, D. E.; Wild, A.
- Nature, Vol. 351, Issue 6324
Beyond Oil and Gas: The Methanol Economy
journal, April 2005
- Olah, George A.
- Angewandte Chemie International Edition, Vol. 44, Issue 18
Rationally Designing Bifunctional Catalysts as an Efficient Strategy To Boost CO 2 Hydrogenation Producing Value-Added Aromatics
journal, December 2018
- Wang, Yang; Tan, Li; Tan, Minghui
- ACS Catalysis, Vol. 9, Issue 2
Formation of a ZnO Overlayer in Industrial Cu/ZnO/Al 2 O 3 Catalysts Induced by Strong Metal-Support Interactions
journal, February 2015
- Lunkenbein, Thomas; Schumann, Julia; Behrens, Malte
- Angewandte Chemie International Edition, Vol. 54, Issue 15
An XPS study of the interaction of oxygen with zirconium
journal, August 1989
- Morant, C.; Sanz, J. M.; Galán, L.
- Surface Science, Vol. 218, Issue 2-3
Global temperature change
journal, September 2006
- Hansen, J.; Sato, M.; Ruedy, R.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 39
CO 2 Activation on Ni/γ–Al 2 O 3 Catalysts by First-Principles Calculations: From Ideal Surfaces to Supported Nanoparticles
journal, June 2016
- Silaghi, Marius-Christian; Comas-Vives, Aleix; Copéret, Christophe
- ACS Catalysis, Vol. 6, Issue 7
Structural analysis of Y3+-doped Mg–Cd ferrites prepared by oxalate co-precipitation method
journal, April 2009
- Gadkari, A. B.; Shinde, T. J.; Vasambekar, P. N.
- Materials Chemistry and Physics, Vol. 114, Issue 2-3
Cu Species Incorporated into Amorphous ZrO 2 with High Activity and Selectivity in CO 2 -to-Methanol Hydrogenation
journal, February 2018
- Tada, Shohei; Katagiri, Ayaka; Kiyota, Keiko
- The Journal of Physical Chemistry C, Vol. 122, Issue 10
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Non-syngas direct steam reforming of methanol to hydrogen and carbon dioxide at low temperature
journal, January 2012
- Yu, Kai Man Kerry; Tong, Weiyi; West, Adam
- Nature Communications, Vol. 3, Issue 1
Promoting Strong Metal Support Interaction: Doping ZnO for Enhanced Activity of Cu/ZnO:M (M = Al, Ga, Mg) Catalysts
journal, April 2015
- Schumann, Julia; Eichelbaum, Maik; Lunkenbein, Thomas
- ACS Catalysis, Vol. 5, Issue 6
In Situ Characterization of Cu/CeO 2 Nanocatalysts for CO 2 Hydrogenation: Morphological Effects of Nanostructured Ceria on the Catalytic Activity
journal, May 2018
- Lin, Lili; Yao, Siyu; Liu, Zongyuan
- The Journal of Physical Chemistry C, Vol. 122, Issue 24
Intermediate species on zirconia supported methanol aerogel catalysts
journal, May 1994
- Bianchi, Daniel; Chafik, T.; Khalfallah, Mohamed
- Applied Catalysis A: General, Vol. 112, Issue 2
Design of Interfacial Sites between Cu and Amorphous ZrO 2 Dedicated to CO 2 -to-Methanol Hydrogenation
journal, July 2018
- Tada, Shohei; Kayamori, Shingo; Honma, Tetsuo
- ACS Catalysis, Vol. 8, Issue 9
Structure and Properties of Zirconia Nanoparticles from Density Functional Theory Calculations
journal, February 2016
- Puigdollers, Antonio Ruiz; Illas, Francesc; Pacchioni, Gianfranco
- The Journal of Physical Chemistry C, Vol. 120, Issue 8
Methanol to Olefins (MTO): From Fundamentals to Commercialization
journal, February 2015
- Tian, Peng; Wei, Yingxu; Ye, Mao
- ACS Catalysis, Vol. 5, Issue 3
Intermediate species on zirconia supported methanol aerogel catalysts
journal, August 1993
- Bianchi, Daniel; Gass, Jean-Louis; Khalfallah, Mohamed
- Applied Catalysis A: General, Vol. 101, Issue 2
Impact of CO 2 -Induced Warming on Simulated Hurricane Intensity and Precipitation: Sensitivity to the Choice of Climate Model and Convective Parameterization
journal, September 2004
- Knutson, Thomas R.; Tuleya, Robert E.
- Journal of Climate, Vol. 17, Issue 18
Isolated Zr Surface Sites on Silica Promote Hydrogenation of CO 2 to CH 3 OH in Supported Cu Catalysts
journal, July 2018
- Lam, Erwin; Larmier, Kim; Wolf, Patrick
- Journal of the American Chemical Society, Vol. 140, Issue 33
Understanding of Enhanced Oxygen Storage Capacity in Ce 0.5 Zr 0.5 O 2 : The Presence of an Anharmonic Pair Distribution Function in the Zr−O 2 Subshell as Analyzed by XAFS Spectroscopy
journal, May 2001
- Lemaux, S.; Bensaddik, A.; van der Eerden, A. M. J.
- The Journal of Physical Chemistry B, Vol. 105, Issue 21
CO 2 -to-Methanol Hydrogenation on Zirconia-Supported Copper Nanoparticles: Reaction Intermediates and the Role of the Metal-Support Interface
journal, January 2017
- Larmier, Kim; Liao, Wei-Chih; Tada, Shohei
- Angewandte Chemie International Edition, Vol. 56, Issue 9
A highly selective and stable ZnO-ZrO 2 solid solution catalyst for CO 2 hydrogenation to methanol
journal, October 2017
- Wang, Jijie; Li, Guanna; Li, Zelong
- Science Advances, Vol. 3, Issue 10
CO 2 hydrogenation to methanol over Cu/ZrO 2 catalysts: Effects of zirconia phases
journal, June 2016
- Witoon, Thongthai; Chalorngtham, Jiraporn; Dumrongbunditkul, Porntipar
- Chemical Engineering Journal, Vol. 293