Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure
Abstract
Cu-ZnO-Al2O3 is the most widely applied catalyst for CO2 hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al2O3 catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al2O3 nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h–1 kg–1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurementsmore »
- Authors:
-
- Univ. of Connecticut, Storrs, CT (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Advanced Manufacturing LLC, East Hartford, CT (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1969362
- Alternate Identifier(s):
- OSTI ID: 1923134
- Report Number(s):
- BNL-224214-2023-JAAM
Journal ID: ISSN 1385-8947
- Grant/Contract Number:
- SC0012704; EE0008423
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Engineering Journal
- Additional Journal Information:
- Journal Volume: 455; Journal ID: ISSN 1385-8947
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; CO2 hydrogenation; Methanol production; ZnO nanorod arrays; Catalyst-support interaction; Cu-ZnO-Al2O3 catalysts
Citation Formats
Sun, Jiyu, Liu, Fangyuan, Salahuddin, Usman, Wu, Mudi, Zhu, Chunxiang, Lu, Xingxu, Zhang, Bo, Zhao, Binchao, Xie, Zhiqiang, Ding, Yunjiang, Li, Dongsheng, Nam, Chang-Yong, Zhang, Feng-Yuan, and Gao, Pu-Xian. Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure. United States: N. p., 2023.
Web. doi:10.1016/j.cej.2022.140559.
Sun, Jiyu, Liu, Fangyuan, Salahuddin, Usman, Wu, Mudi, Zhu, Chunxiang, Lu, Xingxu, Zhang, Bo, Zhao, Binchao, Xie, Zhiqiang, Ding, Yunjiang, Li, Dongsheng, Nam, Chang-Yong, Zhang, Feng-Yuan, & Gao, Pu-Xian. Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure. United States. https://doi.org/10.1016/j.cej.2022.140559
Sun, Jiyu, Liu, Fangyuan, Salahuddin, Usman, Wu, Mudi, Zhu, Chunxiang, Lu, Xingxu, Zhang, Bo, Zhao, Binchao, Xie, Zhiqiang, Ding, Yunjiang, Li, Dongsheng, Nam, Chang-Yong, Zhang, Feng-Yuan, and Gao, Pu-Xian. Thu .
"Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure". United States. https://doi.org/10.1016/j.cej.2022.140559. https://www.osti.gov/servlets/purl/1969362.
@article{osti_1969362,
title = {Optimization and understanding of ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst for enhanced CO2 -methanol conversion at low temperature and pressure},
author = {Sun, Jiyu and Liu, Fangyuan and Salahuddin, Usman and Wu, Mudi and Zhu, Chunxiang and Lu, Xingxu and Zhang, Bo and Zhao, Binchao and Xie, Zhiqiang and Ding, Yunjiang and Li, Dongsheng and Nam, Chang-Yong and Zhang, Feng-Yuan and Gao, Pu-Xian},
abstractNote = {Cu-ZnO-Al2O3 is the most widely applied catalyst for CO2 hydrogenation to methanol. However, it is still a challenge to produce methanol using this catalyst under low-temperature (<250 °C) and low-pressure (<10 bar) conditions with desirable yield and selectivity. In this work, by tuning the experimental processing parameters such as solvent, loading amount, and annealing temperature, highly improved ZnO nanoarray supported Cu-ZnO-Al2O3 catalysts have been successfully demonstrated. Here, by using organic solvent (N,N-dimethylformamide (DMF), acetone, or isopropanol) for dip-coating loading process instead of deionized (DI) water, Cu-ZnO-Al2O3 nanocatalysts was comparatively better dispersed on the nanorod array support with populated and abundant active sites, thus enhancing the methanol yield. With the control of the loading amount and annealing temperature, finely distributed Cu nanoparticles were obtained on the ZnO nanorod surfaces to enhance the interactions between Cu and ZnO nanorod surfaces. Further improvement of the catalyst performance is demonstrated by tuning the reaction space velocity. At 200 °C and 10 bar conditions, the optimized catalyst achieved a methanol yield of 6.46 mol h–1 kg–1 with 100 % selectivity. The good stability after prolonged testing of the catalysts demonstrates the potential practical implementation. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements under the 1 bar reveal that the CO2 hydrogenation to methanol on the ZnO nanoarray supported Cu-ZnO-Al2O3 catalyst follows the CO reaction pathway, due to the surface oxygen vacancies on ZnO nanorods which facilitate CO2 dissociation.},
doi = {10.1016/j.cej.2022.140559},
journal = {Chemical Engineering Journal},
number = ,
volume = 455,
place = {United States},
year = {Thu Feb 02 00:00:00 EST 2023},
month = {Thu Feb 02 00:00:00 EST 2023}
}
Works referenced in this record:
Methanol synthesis from CO2 hydrogenation over Cu based catalyst supported on zirconia modified γ-Al2O3
journal, November 2006
- Zhang, Yiping; Fei, Jinhua; Yu, Yingmin
- Energy Conversion and Management, Vol. 47, Issue 18-19
Effect of Mg and Mn oxide additions on structural and adsorptive properties of Cu/ZnO/ZrO2 catalysts for the methanol synthesis from CO2
journal, August 2003
- Słoczyński, J.; Grabowski, R.; Kozłowska, A.
- Applied Catalysis A: General, Vol. 249, Issue 1
Study of CO2 Hydrogenation to Methanol over Cu-V/γ-Al2O3 Catalyst
journal, March 2007
- Zhang, Yiping; Fei, Jinhua; Yu, Yingmin
- Journal of Natural Gas Chemistry, Vol. 16, Issue 1
CO 2 Hydrogenation to Methanol over Catalysts Derived from Single Cationic Layer CuZnGa LDH Precursors
journal, April 2018
- Li, Molly M. -J.; Chen, Chunping; Ayvalı, Tuğçe
- ACS Catalysis, Vol. 8, Issue 5
Monolithic Ni5Ga3/SiO2/Al2O3/Al-fiber catalyst for CO2 hydrogenation to methanol at ambient pressure
journal, July 2018
- Chen, Pengjing; Zhao, Guofeng; Liu, Ye
- Applied Catalysis A: General, Vol. 562
Single Solid Precursor-Derived Three-Dimensional Nanowire Networks of CuZn-Silicate for CO2 Hydrogenation to Methanol
journal, April 2022
- Shao, Yu; Kosari, Mohammadreza; Xi, Shibo
- ACS Catalysis
Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011
- Wang, Wei; Wang, Shengping; Ma, Xinbin
- Chemical Society Reviews, Vol. 40, Issue 7
E.s.r. investigation of the thermal decomposition of zinc nitrate hexahydrate
journal, January 1977
- Campbell, I. D.
- Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0
Promoting CO2 hydrogenation to methanol by incorporating adsorbents into catalysts: Effects of hydrotalcite
journal, December 2019
- Fang, Xin; Men, Yuhan; Wu, Fan
- Chemical Engineering Journal, Vol. 378
The influence of La doping on the catalytic behavior of Cu/ZrO2 for methanol synthesis from CO2 hydrogenation
journal, July 2011
- Guo, Xiaoming; Mao, Dongsen; Lu, Guanzhong
- Journal of Molecular Catalysis A: Chemical, Vol. 345, Issue 1-2
Mass transport in nanoarray monolithic catalysts: An experimental-theory study
journal, February 2021
- Lu, Xingxu; Tang, Wenxiang; Li, Meilin
- Chemical Engineering Journal, Vol. 405
Catalytic reduction of CO 2 by H 2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities
journal, January 2016
- Porosoff, Marc D.; Yan, Binhang; Chen, Jingguang G.
- Energy & Environmental Science, Vol. 9, Issue 1
Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014
- Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank
- Nature Chemistry, Vol. 6, Issue 4
CO2 hydrogenation to methanol over Cu catalysts supported on La-modified SBA-15: The crucial role of Cu–LaOx interfaces
journal, August 2019
- Chen, Kun; Fang, Huihuang; Wu, Simson
- Applied Catalysis B: Environmental, Vol. 251
Cu-Decorated ZnO Nanorod Array Integrated Structured Catalysts for Low-Pressure CO 2 Hydrogenation to Methanol
journal, December 2017
- Du, Shoucheng; Tang, Wenxiang; Lu, Xingxu
- Advanced Materials Interfaces, Vol. 5, Issue 3
Thermal decomposition of Cu(NO3)2·3H2O at reduced pressures
journal, July 2003
- Morozov, I. V.; Znamenkov, K. O.; Korenev, Yu. M.
- Thermochimica Acta, Vol. 403, Issue 2
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
Ion-Exchange Loading Promoted Stability of Platinum Catalysts Supported on Layered Protonated Titanate-Derived Titania Nanoarrays
journal, May 2019
- Lu, Xingxu; Tang, Wenxiang; Du, Shoucheng
- ACS Applied Materials & Interfaces, Vol. 11, Issue 24
Optimum Cu nanoparticle catalysts for CO2 hydrogenation towards methanol
journal, January 2018
- Zhang, Xue; Liu, Jin-Xun; Zijlstra, Bart
- Nano Energy, Vol. 43
High-Performance and Long-Lived Cu/SiO 2 Nanocatalyst for CO 2 Hydrogenation
journal, June 2015
- Wang, Zhi-Qiao; Xu, Zhong-Ning; Peng, Si-Yan
- ACS Catalysis, Vol. 5, Issue 7
Monitoring the Reaction Mechanism in Model Biogas Reforming by In Situ Transient and Steady-State DRIFTS Measurements
journal, February 2017
- Bobadilla, Luis F.; Garcilaso, Victoria; Centeno, Miguel A.
- ChemSusChem, Vol. 10, Issue 6
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
Activating low-temperature diesel oxidation by single-atom Pt on TiO2 nanowire array
journal, February 2020
- Hoang, Son; Guo, Yanbing; Binder, Andrew J.
- Nature Communications, Vol. 11, Issue 1
State of the art and perspectives in heterogeneous catalysis of CO 2 hydrogenation to methanol
journal, January 2020
- Zhong, Jiawei; Yang, Xiaofeng; Wu, Zhilian
- Chemical Society Reviews, Vol. 49, Issue 5
The role of hydrogen in methanol synthesis over copper catalysts
journal, January 1990
- Burch, R.; Golunski, S. E.; Spencer, M. S.
- Catalysis Letters, Vol. 5, Issue 1
Carbon dioxide hydrogenation over supported Au nanoparticles: Effect of the support
journal, May 2017
- Vourros, A.; Garagounis, I.; Kyriakou, V.
- Journal of CO2 Utilization, Vol. 19
The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts
journal, April 2012
- Behrens, M.; Studt, F.; Kasatkin, I.
- Science, Vol. 336, Issue 6083, p. 893-897
Highly Selective CO 2 Conversion to Methanol in a Bifunctional Zeolite Catalytic Membrane Reactor
journal, July 2021
- Yue, Wenzhe; Li, Yanhong; Wei, Wan
- Angewandte Chemie International Edition, Vol. 60, Issue 33
CO2 activation on Cu-based Zr-decorated nanoparticles
journal, January 2017
- Austin, Natalie; Ye, Jingyun; Mpourmpakis, Giannis
- Catalysis Science & Technology, Vol. 7, Issue 11
Recycling of carbon dioxide to methanol and derived products – closing the loop
journal, January 2014
- Goeppert, Alain; Czaun, Miklos; Jones, John-Paul
- Chem. Soc. Rev., Vol. 43, Issue 23
Theoretical Study of Selective Hydrogenation of CO2 to Methanol over Pt4/In2O3 Model Catalyst
journal, May 2021
- Sun, Kaihang; Rui, Ning; Shen, Chenyang
- The Journal of Physical Chemistry C, Vol. 125, Issue 20
Enhanced activity, selectivity and stability of a CuO-ZnO-ZrO2 catalyst by adding graphene oxide for CO2 hydrogenation to methanol
journal, February 2018
- Witoon, Thongthai; Numpilai, Thanapa; Phongamwong, Thanaree
- Chemical Engineering Journal, Vol. 334
Insights into the Influence of CeO 2 Crystal Facet on CO 2 Hydrogenation to Methanol over Pd/CeO 2 Catalysts
journal, September 2020
- Jiang, Feng; Wang, Shanshan; Liu, Bing
- ACS Catalysis, Vol. 10, Issue 19
Impact of K and Ba promoters on CO 2 hydrogenation over Cu/Al 2 O 3 catalysts at high pressure
journal, January 2013
- Bansode, Atul; Tidona, Bruno; von Rohr, Philipp Rudolf
- Catal. Sci. Technol., Vol. 3, Issue 3
Experimental and theoretical studies of CO2 hydrogenation to methanol on Ru/In2O3
journal, November 2021
- Wu, Qinglei; Shen, Chenyang; Rui, Ning
- Journal of CO2 Utilization, Vol. 53
CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared by precipitation-reduction method
journal, August 2016
- Dong, Xiaosu; Li, Feng; Zhao, Ning
- Applied Catalysis B: Environmental, Vol. 191
Stabilizing Cu + in Cu/SiO 2 Catalysts with a Shattuckite-Like Structure Boosts CO 2 Hydrogenation into Methanol
journal, November 2020
- Yu, Jiafeng; Yang, Meng; Zhang, Jixin
- ACS Catalysis, Vol. 10, Issue 24
Structure–activity relationships of Cu–ZrO 2 catalysts for CO 2 hydrogenation to methanol: interaction effects and reaction mechanism
journal, January 2017
- Wang, Yu Hao; Gao, Wen Gui; Wang, Hua
- RSC Advances, Vol. 7, Issue 14
Flame Synthesis of Cu/ZnO–CeO 2 Catalysts: Synergistic Metal–Support Interactions Promote CH 3 OH Selectivity in CO 2 Hydrogenation
journal, April 2021
- Zhu, Jiadong; Ciolca, Diana; Liu, Liang
- ACS Catalysis, Vol. 11, Issue 8
Synthesis, characterization and activity pattern of carbon nanofibers based copper/zirconia catalysts for carbon dioxide hydrogenation to methanol: Influence of calcination temperature
journal, January 2015
- Ud Din, Israf; Shaharun, Maizatul S.; Subbarao, Duvvuri
- Journal of Power Sources, Vol. 274
Methanol synthesis from CO2 hydrogenation over Cu/γ-Al2O3 catalysts modified by ZnO, ZrO2 and MgO
journal, August 2015
- Ren, Hong; Xu, Cheng-Hua; Zhao, Hao-Yang
- Journal of Industrial and Engineering Chemistry, Vol. 28
ZnO/perovskite core–shell nanorod array based monolithic catalysts with enhanced propane oxidation and material utilization efficiency at low temperature
journal, December 2015
- Wang, Sibo; Ren, Zheng; Song, Wenqiao
- Catalysis Today, Vol. 258
Low-pressure methanol synthesis from CO2 over metal-promoted Ni-Ga intermetallic catalysts
journal, July 2020
- Duyar, Melis S.; Gallo, Alessandro; Snider, Jonathan L.
- Journal of CO2 Utilization, Vol. 39
Green Carbon Science: Scientific Basis for Integrating Carbon Resource Processing, Utilization, and Recycling
journal, July 2013
- He, Mingyuan; Sun, Yuhan; Han, Buxing
- Angewandte Chemie International Edition, Vol. 52, Issue 37
NiO nanosheet array integrated monoliths for low temperature catalytic propane oxidation: A study on the promotion effect of Ce doping
journal, January 2021
- Tang, Wenxiang; Lu, Xingxu; Weng, Junfei
- Catalysis Today, Vol. 360
Morphology-Dependent Interactions of ZnO with Cu Nanoparticles at the Materials’ Interface in Selective Hydrogenation of CO2 to CH3OH
journal, January 2011
- Liao, Fenglin; Huang, Yaqun; Ge, Junwei
- Angewandte Chemie, Vol. 123, Issue 9