Screening of Cu-Based Catalysts for Selective Methane to Methanol Conversion

Huang, Erwei; Liu, Ping

doi:10.1021/acs.jpcc.4c01179

Screening of Cu-Based Catalysts for Selective Methane to Methanol Conversion

Journal Article · Fri May 03 00:00:00 EDT 2024 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.4c01179· OSTI ID:2382640

^[1]; ^[2]

Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

Developing selective catalysts for methane conversion to added value chemicals has been considered as a promising approach for efficient utilization of abundant natural gas resources. Here, we present a descriptor-based screening for high methane conversion and methanol selectivity at the interfaces between metal oxide clusters and Cu₂O/Cu(111) support (MO_x/Cu₂O/Cu(111), M = Mg, Fe, Co, Ni, Cu, Zn, Ti, Zr, Sn, Ce) on exposure to the mixture of CH₄/O₂/H₂O. Wherein, the activation energy of direct methane to methanol conversion, *OH + *CH₄ → *CH₃OH + *H, and the ratio for adsorption energy of oxygen and water, E_ads(O₂)/E_ads(H₂O), are identified as the effective descriptor for methane conversion and methanol selectivity, respectively. Finally, by providing an exceptional oxygen and hydroxyl sites with high-lying O 2p states, the MgO/Cu₂O/Cu(111) catalyst is found to be the most promising system among the systems studied, being able to provide the highest methane conversion with high methanol selectivity.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 2382640

Report Number(s):: BNL--225761-2024-JAAM

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 19 Vol. 128; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5 Hammond, Ceri; Forde, Michael M.; Ab Rahim, Mohd Hasbi Angewandte Chemie International Edition, Vol. 51, Issue 21 https://doi.org/10.1002/anie.201108706	journal	April 2012
Stabilization of Catalytically Active Cu ⁺ Surface Sites on Titanium-Copper Mixed-Oxide Films Baber, Ashleigh E.; Yang, Xiaofang; Kim, Hyun You Angewandte Chemie International Edition, Vol. 53, Issue 21 https://doi.org/10.1002/anie.201402435	journal	April 2014
Future Directions and Industrial Perspectives Micro- and macro-kinetics: Their relationship in heterogeneous catalysis Campbell, Charles T. Topics in Catalysis, Vol. 1, Issue 3-4 https://doi.org/10.1007/BF01492288	journal	September 1994
On the usefulness of Campbell's concept of the rate-determining step Baranski, A. Solid State Ionics, Vol. 117, Issue 1-2 https://doi.org/10.1016/S0167-2738(98)00255-0	journal	February 1999
Synergetic C–H bond activation and C–O formation on CuOx facilities facile conversion of methane to methanol Liu, Huixian; Li, Liwen; Qin, Yuyao Applied Surface Science, Vol. 627 https://doi.org/10.1016/j.apsusc.2023.157283	journal	August 2023
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S. Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.033	journal	August 2015
Degree of rate control approach to computational catalyst screening Wolcott, Christopher A.; Medford, Andrew J.; Studt, Felix Journal of Catalysis, Vol. 330 https://doi.org/10.1016/j.jcat.2015.07.015	journal	October 2015
CH3 radical-mediated direct methane to methanol conversion over CuO supported on rutile oxides Liu, Huixian; Qin, Yuyao; Li, Liwen Journal of Catalysis, Vol. 431 https://doi.org/10.1016/j.jcat.2024.115388	journal	March 2024
Natural gas from shale formation – The evolution, evidences and challenges of shale gas revolution in United States Wang, Qiang; Chen, Xi; Jha, Awadhesh N. Renewable and Sustainable Energy Reviews, Vol. 30 https://doi.org/10.1016/j.rser.2013.08.065	journal	February 2014
Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond Tomkins, Patrick; Ranocchiari, Marco; van Bokhoven, Jeroen A. Accounts of Chemical Research, Vol. 50, Issue 2 https://doi.org/10.1021/acs.accounts.6b00534	journal	January 2017
Enzymatic Oxidation of Methane Sirajuddin, Sarah; Rosenzweig, Amy C. Biochemistry, Vol. 54, Issue 14 https://doi.org/10.1021/acs.biochem.5b00198	journal	March 2015
Alkane Oxidation: Methane Monooxygenases, Related Enzymes, and Their Biomimetics Wang, Vincent C. -C.; Maji, Suman; Chen, Peter P. -Y. Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00624	journal	February 2017
Iron and Copper Active Sites in Zeolites and Their Correlation to Metalloenzymes Snyder, Benjamin E. R.; Bols, Max L.; Schoonheydt, Robert A. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00344	journal	December 2017
Understanding Methanol Synthesis on Inverse ZnO/CuO _x /Cu Catalysts: Stability of CH ₃ O Species and Dynamic Nature of the Surface Orozco, Ivan; Huang, Erwei; Mahapatra, Mausumi The Journal of Physical Chemistry C, Vol. 125, Issue 12 https://doi.org/10.1021/acs.jpcc.1c00392	journal	March 2021
Theoretical Insights into Methane C–H Bond Activation on Alkaline Metal Oxides Aljama, Hassan; Nørskov, Jens K.; Abild-Pedersen, Frank The Journal of Physical Chemistry C, Vol. 121, Issue 30 https://doi.org/10.1021/acs.jpcc.7b05838	journal	July 2017
Theoretical Perspective of Promoting Direct Methane-to-Methanol Conversion at Complex Metal Oxide–Metal Interfaces Huang, Erwei; Liu, Ping The Journal of Physical Chemistry Letters, Vol. 14, Issue 29 https://doi.org/10.1021/acs.jpclett.3c01525	journal	July 2023
Highly Selective Methane to Methanol Conversion on Inverse SnO₂/Cu₂O/Cu(111) Catalysts: Unique Properties of SnO₂ Nanostructures and the Inhibition of the Direct Oxidative Combustion of Methane Huang, Erwei; Rui, Ning; Rosales, Rina ACS Catalysis, Vol. 12, Issue 18 https://doi.org/10.1021/acscatal.2c03060	journal	September 2022
Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, Cu) Mahyuddin, M. Haris; Staykov, Aleksandar; Shiota, Yoshihito ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b01721	journal	November 2016
Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites Göltl, Florian; Michel, Carine; Andrikopoulos, Prokopis C. ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b02640	journal	November 2016
The Degree of Rate Control: A Powerful Tool for Catalysis Research Campbell, Charles T. ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00115	journal	March 2017
Understanding and Breaking Scaling Relations in Single-Site Catalysis: Methane to Methanol Conversion by Fe ^IV ═O Gani, Terry Z. H.; Kulik, Heather J. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03597	journal	January 2018
Direct Methane to Methanol: The Selectivity–Conversion Limit and Design Strategies Latimer, Allegra A.; Kakekhani, Arvin; Kulkarni, Ambarish R. ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b00220	journal	June 2018
Dry Reforming of Methane on Single-Site Ni/MgO Catalysts: Importance of Site Confinement Zuo, Zhijun; Liu, Shizhong; Wang, Zichun ACS Catalysis, Vol. 8, Issue 10 https://doi.org/10.1021/acscatal.8b02277	journal	September 2018
Methane-to-Methanol: Activity Descriptors in Copper-Exchanged Zeolites for the Rational Design of Materials Sushkevich, Vitaly L.; van Bokhoven, Jeroen A. ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b01534	journal	May 2019
The Key Role of Support Surface Hydrogenation in the CH ₄ to CH ₃ OH Selective Oxidation by a ZrO ₂ -Supported Single-Atom Catalyst Harrath, Karim; Yu, Xiaohu; Xiao, Hai ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02093	journal	August 2019
Descriptor Design in the Computational Screening of Ni-Based Catalysts with Balanced Activity and Stability for Dry Reforming of Methane Reaction Chen, Shuyue; Zaffran, Jeremie; Yang, Bo ACS Catalysis, Vol. 10, Issue 5 https://doi.org/10.1021/acscatal.9b04429	journal	February 2020
Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature Narsimhan, Karthik; Iyoki, Kenta; Dinh, Kimberly ACS Central Science, Vol. 2, Issue 6 https://doi.org/10.1021/acscentsci.6b00139	journal	April 2016
DFT Virtual Screening Identifies Rhodium–Amidinate Complexes As Potential Homogeneous Catalysts for Methane-to-Methanol Oxidation Fu, Ross; Nielsen, Robert J.; Goddard, William A. ACS Catalysis, Vol. 4, Issue 12 https://doi.org/10.1021/cs5005322	journal	November 2014
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T. Journal of the American Chemical Society, Vol. 131, Issue 23 https://doi.org/10.1021/ja9000097	journal	June 2009
Selective Methane Oxidation to Methanol on ZnO/Cu₂O/Cu(111) Catalysts: Multiple Site-Dependent Behaviors Huang, Erwei; Orozco, Ivan; Ramírez, Pedro J. Journal of the American Chemical Society, Vol. 143, Issue 45 https://doi.org/10.1021/jacs.1c08063	journal	November 2021
Activation and Conversion of Methane to Syngas over ZrO₂/Cu(111) Catalysts near Room Temperature Huang, Erwei; Rui, Ning; Rosales, Rina Journal of the American Chemical Society https://doi.org/10.1021/jacs.3c01980	journal	April 2023
Low-Temperature Conversion of Methane to Methanol on CeO _x /Cu ₂ O Catalysts: Water Controlled Activation of the C–H Bond Zuo, Zhijun; Ramírez, Pedro J.; Senanayake, Sanjaya D. Journal of the American Chemical Society, Vol. 138, Issue 42 https://doi.org/10.1021/jacs.6b08668	journal	October 2016
Methane to Methanol: Structure–Activity Relationships for Cu-CHA Pappas, Dimitrios K.; Borfecchia, Elisa; Dyballa, Michael Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b06472	journal	October 2017
Selective Activation of Methane on Single-Atom Catalyst of Rhodium Dispersed on Zirconia for Direct Conversion Kwon, Yongwoo; Kim, Tae Yong; Kwon, Gihun Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b11010	journal	November 2017
Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal–Support Interactions and Water-Enabled Catalytic Conversion by Site Blocking Lustemberg, Pablo G.; Palomino, Robert M.; Gutiérrez, Ramón A. Journal of the American Chemical Society, Vol. 140, Issue 24 https://doi.org/10.1021/jacs.8b03809	journal	May 2018
New Strategies for Direct Methane-to-Methanol Conversion from Active Learning Exploration of 16 Million Catalysts Nandy, Aditya; Duan, Chenru; Goffinet, Conrad JACS Au, Vol. 2, Issue 5 https://doi.org/10.1021/jacsau.2c00176	journal	April 2022
Activity Descriptors for CO ₂ Electroreduction to Methane on Transition-Metal Catalysts Peterson, Andrew A.; Nørskov, Jens K. The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201461p	journal	January 2012
Crystal structure of a bacterial non-haem iron hydroxylase that catalyses the biological oxidation of methane Rosenzweig, Amy C.; Frederick, Christin A.; Lippard, Stephen J. Nature, Vol. 366, Issue 6455 https://doi.org/10.1038/366537a0	journal	December 1993
Oxidation of methane by a biological dicopper centre Balasubramanian, Ramakrishnan; Smith, Stephen M.; Rawat, Swati Nature, Vol. 465, Issue 7294 https://doi.org/10.1038/nature08992	journal	April 2010
The active site of low-temperature methane hydroxylation in iron-containing zeolites Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L. Nature, Vol. 536, Issue 7616 https://doi.org/10.1038/nature19059	journal	August 2016
Towards the computational design of solid catalysts Nørskov, J.; Bligaard, T.; Rossmeisl, J. Nature Chemistry, Vol. 1, Issue 1, p. 37-46 https://doi.org/10.1038/nchem.121	journal	April 2009
Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8546	journal	June 2015
Understanding trends in C–H bond activation in heterogeneous catalysis Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan Nature Materials, Vol. 16, Issue 2 https://doi.org/10.1038/nmat4760	journal	October 2016
Catalyst design via descriptors Zhao, Zhi-Jian; Gong, Jinlong Nature Nanotechnology, Vol. 17, Issue 6 https://doi.org/10.1038/s41565-022-01120-5	journal	May 2022
Accelerated discovery of CO2 electrocatalysts using active machine learning Zhong, Miao; Tran, Kevin; Min, Yimeng Nature, Vol. 581, Issue 7807 https://doi.org/10.1038/s41586-020-2242-8	journal	May 2020
Active learning across intermetallics to guide discovery of electrocatalysts for CO2 reduction and H2 evolution Tran, Kevin; Ulissi, Zachary W. Nature Catalysis, Vol. 1, Issue 9 https://doi.org/10.1038/s41929-018-0142-1	journal	September 2018
Highly selective oxidation of methane to methanol at ambient conditions by titanium dioxide-supported iron species Xie, Jijia; Jin, Renxi; Li, Ang Nature Catalysis, Vol. 1, Issue 11 https://doi.org/10.1038/s41929-018-0170-x	journal	November 2018
Mechanistic insights into heterogeneous methane activation Latimer, Allegra A.; Aljama, Hassan; Kakekhani, Arvin Physical Chemistry Chemical Physics, Vol. 19, Issue 5 https://doi.org/10.1039/C6CP08003K	journal	January 2017
Metal dimer sites in ZSM-5 zeolite for methane-to-methanol conversion from first-principles kinetic modelling: is the [Cu–O–Cu] ²⁺ motif relevant for Ni, Co, Fe, Ag, and Au? Arvidsson, Adam A.; Zhdanov, Vladimir P.; Carlsson, Per-Anders Catalysis Science & Technology, Vol. 7, Issue 7 https://doi.org/10.1039/C6CY02521H	journal	January 2017
Active sites and mechanisms in the direct conversion of methane to methanol using Cu in zeolitic hosts: a critical examination Newton, Mark A.; Knorpp, Amy J.; Sushkevich, Vitaly L. Chemical Society Reviews, Vol. 49, Issue 5 https://doi.org/10.1039/C7CS00709D	journal	January 2020
Surface characterization and methane activation on SnO _x /Cu ₂ O/Cu(111) inverse oxide/metal catalysts Kang, Jindong; Rui, Ning; Huang, Erwei Physical Chemistry Chemical Physics, Vol. 23, Issue 32 https://doi.org/10.1039/D1CP02829D	journal	January 2021
Enhanced descriptor identification and mechanism understanding for catalytic activity using a data-driven framework: revealing the importance of interactions between elementary steps Liao, Wenjie; Liu, Ping Catalysis Science & Technology, Vol. 12, Issue 12 https://doi.org/10.1039/D2CY00284A	journal	January 2022
Prediction of solid oxide fuel cell cathode activity with first-principles descriptors Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan Energy & Environmental Science, Vol. 4, Issue 10 https://doi.org/10.1039/c1ee02032c	journal	January 2011
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Density functional theory in surface chemistry and catalysis Norskov, J. K.; Abild-Pedersen, F.; Studt, F. Proceedings of the National Academy of Sciences, Vol. 108, Issue 3 https://doi.org/10.1073/pnas.1006652108	journal	January 2011
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Selective anaerobic oxidation of methane enables direct synthesis of methanol Sushkevich, Vitaly L.; Palagin, Dennis; Ranocchiari, Marco Science, Vol. 356, Issue 6337 https://doi.org/10.1126/science.aam9035	journal	May 2017
Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO Song, Youngdong; Ozdemir, Ercan; Ramesh, Sreerangappa Science, Vol. 367, Issue 6479 https://doi.org/10.1126/science.aav2412	journal	February 2020
Particulate methane monooxygenase contains only mononuclear copper centers Ross, Matthew O.; MacMillan, Fraser; Wang, Jingzhou Science, Vol. 364, Issue 6440 https://doi.org/10.1126/science.aav2572	journal	May 2019
Water-promoted interfacial pathways in methane oxidation to methanol on a CeO ₂ -Cu ₂ O catalyst Liu, Zongyuan; Huang, Erwei; Orozco, Ivan Science, Vol. 368, Issue 6490 https://doi.org/10.1126/science.aba5005	journal	April 2020
Bioinspired methane oxidation in a zeolite Scott, Susannah L. Science, Vol. 373, Issue 6552 https://doi.org/10.1126/science.abj4734	journal	July 2021