Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio
Abstract
In this study, we evaluated aspects of the CO2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu2+, Zr3+, and Zr4+ mixture and two kinds of Zn2+ species. After the H2 reduction process, only Cu2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.
- Authors:
-
[2];
- Univ. of Sao Paulo (Brazil)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Federal Univ. of Sao Carlos (Brazil)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1637476
- Report Number(s):
- BNL-216106-2020-JAAM
Journal ID: ISSN 2212-9820
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of CO2 Utilization
- Additional Journal Information:
- Journal Volume: 41; Journal Issue: C; Journal ID: ISSN 2212-9820
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Cu-ZnO-ZrO2; Surfactant-assisted co-precipitation; Reaction mechanism; Methanol; CO2 hydrogenation
Citation Formats
Marcos, Francielle C. F., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, Jose A., Assaf, José M., Giudici, Reinaldo, and Assaf, Elisabete M. Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio. United States: N. p., 2020.
Web. doi:10.1016/j.jcou.2020.101215.
Marcos, Francielle C. F., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, Jose A., Assaf, José M., Giudici, Reinaldo, & Assaf, Elisabete M. Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio. United States. https://doi.org/10.1016/j.jcou.2020.101215
Marcos, Francielle C. F., Lin, Lili, Betancourt, Luis E., Senanayake, Sanjaya D., Rodriguez, Jose A., Assaf, José M., Giudici, Reinaldo, and Assaf, Elisabete M. Fri .
"Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio". United States. https://doi.org/10.1016/j.jcou.2020.101215. https://www.osti.gov/servlets/purl/1637476.
@article{osti_1637476,
title = {Insights into the methanol synthesis mechanism via CO2 hydrogenation over Cu-ZnO-ZrO2 catalysts: Effects of surfactant/Cu-Zn-Zr molar ratio},
author = {Marcos, Francielle C. F. and Lin, Lili and Betancourt, Luis E. and Senanayake, Sanjaya D. and Rodriguez, Jose A. and Assaf, José M. and Giudici, Reinaldo and Assaf, Elisabete M.},
abstractNote = {In this study, we evaluated aspects of the CO2 hydrogenation mechanism, correlating structure-activity relationships of Cu-ZnO-ZrO2 catalysts prepared by one-pot surfactant-assisted co-precipitation with different surfactant ratios. Identifying the CO2 hydrogenation pathway intermediates is key to controlling the reaction selectivity. Experimental evidence shows that the CO2 is dissociating into CO* and O* onto the surface of the Cu-ZnO-ZrO2 catalyst. The adsorption and dissociation of CO2 were evidenced by a combination of in situ ambient-pressure X-ray Photoelectron Spectroscopy (AP-XPS) and Fourier Transform Infrared Spectroscopy (FTIR) with a transmission cell. AP-XPS showed that the catalysts are composed of a Cu2+, Zr3+, and Zr4+ mixture and two kinds of Zn2+ species. After the H2 reduction process, only Cu2+ was reduced to Cu0. The Zn and Zr species were oxidized by the dissociated O* species. In situ transmission FTIR showed that CO was adsorbed onto the Cu+/0 sites. The catalyst with the higher surfactant molar ratio exhibited the highest CO2 conversion close to the equilibrium conversion, as well as a good methanol formation rate.},
doi = {10.1016/j.jcou.2020.101215},
journal = {Journal of CO2 Utilization},
number = C,
volume = 41,
place = {United States},
year = {Fri Jun 26 00:00:00 EDT 2020},
month = {Fri Jun 26 00:00:00 EDT 2020}
}
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Works referenced in this record:
Hydrogenation of CO2 to methanol and CO on Cu/ZnO/Al2O3: Is there a common intermediate or not?
journal, August 2015
- Kunkes, Edward L.; Studt, Felix; Abild-Pedersen, Frank
- Journal of Catalysis, Vol. 328
Enhanced activity of CuFe/SiO2 catalyst for CO hydrogenation to higher alcohols by pretreating the support with ammonia
journal, May 2015
- Lu, Ruili; Mao, Dongsen; Yu, Jun
- Journal of Industrial and Engineering Chemistry, Vol. 25
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
Novel efficient process for methanol synthesis by CO 2 hydrogenation
journal, January 2016
- Kiss, Anton A.; Pragt, J. J.; Vos, H. J.
- Chemical Engineering Journal, Vol. 284
A Brief Review of Carbon Dioxide Hydrogenation to Methanol Over Copper and Iron Based Catalysts
journal, September 2017
- Tursunov, Obid; Kustov, Leonid; Kustov, Aleksandr
- Oil & Gas Sciences and Technology – Revue d’IFP Energies nouvelles, Vol. 72, Issue 5
Analysis of CO2 utilization for methanol synthesis integrated with enhanced gas recovery
journal, January 2016
- Luu, Minh Tri; Milani, Dia; Abbas, Ali
- Journal of Cleaner Production, Vol. 112
Conversion of CO 2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst
journal, January 2016
- Kothandaraman, Jotheeswari; Goeppert, Alain; Czaun, Miklos
- Journal of the American Chemical Society, Vol. 138, Issue 3
Homogeneous hydrogenation of carbon dioxide to methanol
journal, January 2014
- Li, Yu-Nong; Ma, Ran; He, Liang-Nian
- Catal. Sci. Technol., Vol. 4, Issue 6
Formation of hydrocarbons via CO2 hydrogenation – A thermodynamic study
journal, June 2014
- Torrente-Murciano, L.; Mattia, D.; Jones, M. D.
- Journal of CO2 Utilization, Vol. 6
Carbon capture, storage and utilisation technologies: A critical analysis and comparison of their life cycle environmental impacts
journal, March 2015
- Cuéllar-Franca, Rosa M.; Azapagic, Adisa
- Journal of CO2 Utilization, Vol. 9
Catalytic activation of CO2: Use of secondary CO2 for the production of synthesis gas and for methanol synthesis over copper-based zirconia-containing catalysts
journal, June 2009
- Raudaskoski, R.; Turpeinen, E.; Lenkkeri, R.
- Catalysis Today, Vol. 144, Issue 3-4
Tuning of catalytic CO2 hydrogenation by changing composition of CuO–ZnO–ZrO2 catalysts
journal, June 2016
- Witoon, Thongthai; Kachaban, Nantana; Donphai, Waleeporn
- Energy Conversion and Management, Vol. 118
Direct synthesis of dimethyl ether from CO 2 hydrogenation over Cu–ZnO–ZrO 2 /SO 4 2− –ZrO 2 hybrid catalysts: effects of sulfur-to-zirconia ratios
journal, January 2015
- Witoon, Thongthai; Permsirivanich, Tinnavat; Kanjanasoontorn, Nawapon
- Catalysis Science & Technology, Vol. 5, Issue 4
CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane
journal, November 2013
- Rodriguez, José A.; Evans, Jaime; Feria, Leticia
- Journal of Catalysis, Vol. 307
CO2 hydrogenation to methanol over CuZnGa catalysts prepared using microwave-assisted methods
journal, March 2015
- Cai, Weijie; de la Piscina, Pilar Ramirez; Toyir, Jamil
- Catalysis Today, Vol. 242
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
CO 2 hydrogenation to methanol over CuO–ZnO–ZrO 2 –SiO 2 catalysts: Effects of SiO 2 contents
journal, May 2017
- Phongamwong, Thanaree; Chantaprasertporn, Usanee; Witoon, Thongthai
- Chemical Engineering Journal, Vol. 316
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
Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO2 catalysts in the CO2 hydrogenation to CH3OH
journal, November 2008
- Arena, Francesco; Italiano, Giuseppe; Barbera, Katia
- Applied Catalysis A: General, Vol. 350, Issue 1
Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2
journal, December 2000
- Suh, Young-Woong; Moon, Seung-Hyun; Rhee, Hyun-Ku
- Catalysis Today, Vol. 63, Issue 2-4
CO2 hydrogenation to methanol over CuO-ZnO-ZrO2 catalyst prepared by polymeric precursor method
journal, January 2019
- Chen, Dawei; Mao, Dongsen; Wang, Guo
- Journal of Sol-Gel Science and Technology, Vol. 89, Issue 3
Combustion synthesis of CuO–ZnO–ZrO2 catalysts for the hydrogenation of carbon dioxide to methanol
journal, July 2009
- Guo, Xiaoming; Mao, Dongsen; Wang, Song
- Catalysis Communications, Vol. 10, Issue 13
Recent development in catalytic technologies for methanol synthesis from renewable sources: A critical review
journal, April 2015
- Ali, Khozema Ahmed; Abdullah, Ahmad Zuhairi; Mohamed, Abdul Rahman
- Renewable and Sustainable Energy Reviews, Vol. 44
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
Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry
journal, November 2017
- Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 221
Synergy between active sites of Cu-In-Zr-O catalyst in CO2 hydrogenation to methanol
journal, April 2019
- Yao, Libo; Shen, Xiaochen; Pan, Yanbo
- Journal of Catalysis, Vol. 372
Surfactant-assisted preparation of Cu/ZnO/Al2O3 catalyst for methanol synthesis from syngas
journal, January 2013
- Chu, Zheng; Chen, Haibo; Yu, Yang
- Journal of Molecular Catalysis A: Chemical, Vol. 366
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)
journal, October 2015
- Thommes, Matthias; Kaneko, Katsumi; Neimark, Alexander V.
- Pure and Applied Chemistry, Vol. 87, Issue 9-10
Effect of process parameters on the synthesis of mesoporous nanocrystalline zirconia with triblock copolymer as template
journal, June 2007
- Rezaei, M.; Alavi, S. M.; Sahebdelfar, S.
- Journal of Porous Materials, Vol. 15, Issue 2
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
Cu,Zn-based catalysts for methanol synthesis: On the effect of calcination conditions and the part of residual carbonates
journal, April 2016
- Schumann, Julia; Tarasov, Andrey; Thomas, Nygil
- Applied Catalysis A: General, Vol. 516
How to Prepare a Good Cu/ZnO Catalyst or the Role of Solid State Chemistry for the Synthesis of Nanostructured Catalysts: How to Prepare a Good Cu/ZnO Catalyst
journal, October 2013
- Behrens, Malte; Schlögl, Robert
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 15
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
High performance of Cu/CeO2-Nb2O5 catalysts for preferential CO oxidation and total combustion of toluene
journal, August 2015
- Jardim, Erika de Oliveira; Rico-Francés, Soledad; Abdelouahab-Reddam, Zinab
- Applied Catalysis A: General, Vol. 502
Effect of synthesis parameters on catalytic properties of CuO-CeO2
journal, September 2006
- Avgouropoulos, George; Ioannides, Theophilos
- Applied Catalysis B: Environmental, Vol. 67, Issue 1-2
Highly selective hydrogenation of CO2 to methanol over CuO–ZnO–ZrO2 catalysts prepared by a surfactant-assisted co-precipitation method
journal, April 2015
- Li, Li; Mao, Dongsen; Yu, Jun
- Journal of Power Sources, Vol. 279
Effect of magnetic field on CO2 conversion over Cu-ZnO/ZrO2 catalyst in hydrogenation reaction
journal, December 2016
- Donphai, Waleeporn; Piriyawate, Nuttanun; Witoon, Thongthai
- Journal of CO2 Utilization, Vol. 16
Structure and performance of Cu/ZrO2 catalyst For the synthesis of methanol from CO2 hydrogenation
journal, August 2010
- Zhuang, Hui-dong; Bai, Shao-fen; Liu, Xin-mei
- Journal of Fuel Chemistry and Technology, Vol. 38, Issue 4
XPS, XANES and EXAFS investigations of CuO/ZnO/Al2O3/ZrO2 mixed oxide catalysts
journal, April 2002
- Velu, S.; Suzuki, K.; Gopinath, Chinnakonda S.
- Physical Chemistry Chemical Physics, Vol. 4, Issue 10
Effect of metal oxide additives on the activity and stability of Cu/ZnO/ZrO2 catalysts in the synthesis of methanol from CO2 and H2
journal, August 2006
- Sloczynski, J.; Grabowski, R.; Olszewski, P.
- Applied Catalysis A: General, Vol. 310
Ni/SBA-15 catalysts for CO methanation: effects of V, Ce, and Zr promoters
journal, January 2015
- Li, Haidong; Ren, Jun; Qin, Xiang
- RSC Advances, Vol. 5, Issue 117
Non-equilibrium oxidation states of zirconium during early stages of metal oxidation
journal, March 2015
- Ma, Wen; Herbert, F. William; Senanayake, Sanjaya D.
- Applied Physics Letters, Vol. 106, Issue 10
Ultraviolet-Light-Assisted Formation of ZnO Nanowires in Ambient Air: Comparison of Photoresponsive and Photocatalytic Activities in Zinc Hydroxide
journal, December 2010
- Wu, Jyh Ming; Chen, Yi-Ru
- The Journal of Physical Chemistry C, Vol. 115, Issue 5
Electronic structure and optical properties of Zn(OH) 2 : LDA+U calculations and intense yellow luminescence
journal, January 2015
- Wang, Mingsong; Jiang, Lingxia; Kim, Eui Jung
- RSC Advances, Vol. 5, Issue 106
IR-Spectroscopic Study on the Interface of Cu-Based Methanol Synthesis Catalysts: Evidence for the Formation of a ZnO Overlayer
journal, August 2017
- Schumann, Julia; Kröhnert, Jutta; Frei, Elias
- Topics in Catalysis, Vol. 60, Issue 19-20
A DRIFTS study of CO adsorption and hydrogenation on Cu-based core–shell nanoparticles
journal, January 2012
- Subramanian, Nachal D.; Kumar, Challa S. S. R.; Watanabe, Kazuo
- Catalysis Science & Technology, Vol. 2, Issue 3
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
Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011
- Wang, Wei; Wang, Shengping; Ma, Xinbin
- Chemical Society Reviews, Vol. 40, Issue 7
Study of iron-promoted Cu/SiO2 catalyst on high temperature reverse water gas shift reaction
journal, January 2004
- Chen, C.
- Applied Catalysis A: General, Vol. 257, Issue 1
Methanol Synthesis from Industrial CO2 Sources: A Contribution to Chemical Energy Conversion
journal, January 2017
- Bukhtiyarova, Marina; Lunkenbein, Thomas; Kähler, Kevin
- Catalysis Letters, Vol. 147, Issue 2
Opportunities and prospects in the chemical recycling of carbon dioxide to fuels
journal, November 2009
- Centi, Gabriele; Perathoner, Siglinda
- Catalysis Today, Vol. 148, Issue 3-4
Fundamental studies of methanol synthesis from CO2 hydrogenation on Cu(111), Cu clusters, and Cu/ZnO(0001̄)
journal, January 2010
- Yang, Yixiong; Evans, Jaime; Rodriguez, Jose A.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 33