Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen

Ashwell, Adam P.; Lin, Wei; Hofman, Michelle S.; Yang, Yuxin; Ratner, Mark A.; Koel, Bruce E.; Schatz, George C.

doi:10.1021/jacs.7b09914

Title: Hydrogenation of CO to Methanol on Ni(110) through Subsurface Hydrogen

Journal Article · Thu Nov 09 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b09914· OSTI ID:1413067

Ashwell, Adam P. ^[1];

^[1]; Hofman, Michelle S.; Yang, Yuxin; Ratner, Mark A. ^[1];

;

^[1]

Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States

We present a combined theoretical and experimental study of CO hydrogenation on a Ni(110) surface, including studies of the role of gas-phase atomic hydrogen, surface hydrogen, and subsurface hydrogen reacting with adsorbed CO. Reaction mechanisms leading both to methane and methanol are considered. In the reaction involving surface or subsurface hydrogen, we investigate four possible pathways, using density functional theory to characterize the relative energetics of each intermediate, including the importance of further hydrogenation versus C-O bond breaking, where the latter may lead to methane production. The most energetically favorable outcome is the production of methanol along a pathway involving the sequential hydrogenation of CO to a H₃CO* intermediate, followed by a final hydrogenation to give methanol. In addition, we find that subsurface hydrogen noticeably alters reaction barriers, both passively and through the energy released by diffusion to the surface. Indeed, the effective reaction barriers are even lower than for CO methanolation on Cu(211) and Cu(111) than for Ni(110). In studies of gas-phase H atoms impinging on a CO-adsorbed Ni(110) surface, Born-Oppenheimer molecular dynamics simulations show that direct impact of H is unlikely to result in hydrogenation of CO. This means that Eley-Rideal or hot-atom mechanisms are not important; thus, thermal reactions involving subsurface hydrogen are the primary reaction mechanisms leading to methanol. Finally, we demonstrate experimentally for the first time the production of methanol and formaldehyde from CO hydrogenation on Ni(110) and confirm the role of subsurface hydrogen in the mechanism of this reaction.

View Journal Article

Cite

Export

Save

Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457

OSTI ID:: 1413067

Alternate ID(s):: OSTI ID: 1529566

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 139 Journal Issue: 48; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (44)

The Chemistry of Bulk Hydrogen: Reaction of Hydrogen Embedded in Nickel with Adsorbed CH3 Johnson, A. D.; Daley, S. P.; Utz, A. L. Science, Vol. 257, Issue 5067 https://doi.org/10.1126/science.257.5067.223	journal	July 1992
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
High quality diesel via the Fischer-Tropsch process - a review Dry, Mark E. Journal of Chemical Technology & Biotechnology, Vol. 77, Issue 1 https://doi.org/10.1002/jctb.527	journal	January 2001
Vibrational and electronic properties of monolayer and multilayer fullerene C60 films on rhodium (111) Sellidj, Abdelkrim; Koel, Bruce E. The Journal of Physical Chemistry, Vol. 97, Issue 39 https://doi.org/10.1021/j100141a030	journal	September 1993
Practical and theoretical aspects of the catalytic Fischer-Tropsch process Dry, Mark E. Applied Catalysis A: General, Vol. 138, Issue 2 https://doi.org/10.1016/0926-860X(95)00306-1	journal	May 1996
Mechanistic Study of Carbon Monoxide Methanation over Pure and Rhodium- or Ruthenium-Doped Nickel Catalysts Fajín, José L. C.; Gomes, José R. B.; D. S. Cordeiro, M. Natália The Journal of Physical Chemistry C, Vol. 119, Issue 29 https://doi.org/10.1021/acs.jpcc.5b01837	journal	July 2015
CO hydrogenation to methanol on Cu–Ni catalysts: Theory and experiment Studt, Felix; Abild-Pedersen, Frank; Wu, Qiongxiao Journal of Catalysis, Vol. 293 https://doi.org/10.1016/j.jcat.2012.06.004	journal	September 2012
Reverse Water–Gas Shift or Sabatier Methanation on Ni(110)? Stable Surface Species at Near-Ambient Pressure Roiaz, Matteo; Monachino, Enrico; Dri, Carlo Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.5b13366	journal	March 2016
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
CO2 hydrogenation to formic acid on Ni(110) Peng, Guowen; Sibener, S. J.; Schatz, George C. Surface Science, Vol. 606, Issue 13-14 https://doi.org/10.1016/j.susc.2012.02.027	journal	July 2012
Recent advances in catalytic hydrogenation of carbon dioxide Wang, Wei; Wang, Shengping; Ma, Xinbin Chemical Society Reviews, Vol. 40, Issue 7 https://doi.org/10.1039/c1cs15008a	journal	January 2011
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Structure sensitivity of the methanation reaction: H2-induced CO dissociation on nickel surfaces Andersson, M. P.; Abild-Pedersen, F.; Remediakis, I. N. Journal of Catalysis, Vol. 255, Issue 1 https://doi.org/10.1016/j.jcat.2007.12.016	journal	April 2008
Surface phases of Ni(110) induced by adsorption of deuterium Jackman, T. E.; Griffiths, K.; Unertl, W. N. Surface Science, Vol. 179, Issue 2-3 https://doi.org/10.1016/0039-6028(87)90060-4	journal	January 1987
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
Surface reconstruction and surface explosion phenomena in the nickel (110)/hydrogen system Christmann, K.; Chehab, F.; Penka, V. Surface Science, Vol. 152-153 https://doi.org/10.1016/0039-6028(85)90165-7	journal	April 1985
CO ₂ Hydrogenation to Formic Acid on Ni(111) Peng, Guowen; Sibener, S. J.; Schatz, George C. The Journal of Physical Chemistry C, Vol. 116, Issue 4 https://doi.org/10.1021/jp210408x	journal	January 2012
Tuning Selectivity of CO ₂ Hydrogenation Reactions at the Metal/Oxide Interface Kattel, Shyam; Liu, Ping; Chen, Jingguang G. Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b05362	journal	July 2017
Homogeneous syngas conversion West, Nathan M.; Miller, Alexander J. M.; Labinger, Jay A. Coordination Chemistry Reviews, Vol. 255, Issue 7-8 https://doi.org/10.1016/j.ccr.2010.08.019	journal	April 2011
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
Theoretical Studies on the CO2 Reduction to CH3OH on Cu(211) Liu, Shan Ping; Zhao, Ming; Gao, Wang Electrocatalysis, Vol. 8, Issue 6 https://doi.org/10.1007/s12678-017-0403-9	journal	August 2017
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
The co-adsorption of H2 and CO on Ni(110) Canning, N. D. S.; Chesters, M. A. Surface Science Letters, Vol. 175, Issue 3 https://doi.org/10.1016/0167-2584(86)90334-8	journal	October 1986
Catalytic Carbon Dioxide Reforming of Methane to Synthesis Gas over Activated Carbon Catalyst Song, Qilei; Xiao, Rui; Li, Yanbing Industrial & Engineering Chemistry Research, Vol. 47, Issue 13 https://doi.org/10.1021/ie800117a	journal	July 2008
Hydrogen embedded in Ni: Production by incident atomic hydrogen and detection by high-resolution electron energy loss Johnson, A. D.; Maynard, K. J.; Daley, S. P. Physical Review Letters, Vol. 67, Issue 7 https://doi.org/10.1103/PhysRevLett.67.927	journal	August 1991
Optimizing Binding Energies of Key Intermediates for CO ₂ Hydrogenation to Methanol over Oxide-Supported Copper Kattel, Shyam; Yan, Binhang; Yang, Yixiong Journal of the American Chemical Society, Vol. 138, Issue 38 https://doi.org/10.1021/jacs.6b05791	journal	September 2016
Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis Kuld, S.; Thorhauge, M.; Falsig, H. Science, Vol. 352, Issue 6288 https://doi.org/10.1126/science.aaf0718	journal	May 2016
DFT Study of Formaldehyde and Methanol Synthesis from CO and H ₂ on Ni(111) ^† Remediakis, Ioannis N.; Abild-Pedersen, Frank; Nørskov, Jens K. The Journal of Physical Chemistry B, Vol. 108, Issue 38 https://doi.org/10.1021/jp0493374	journal	September 2004
Hydrogen-Assisted Transformation of CO ₂ on Nickel: The Role of Formate and Carbon Monoxide Vesselli, Erik; Rizzi, Michele; De Rogatis, Loredana The Journal of Physical Chemistry Letters, Vol. 1, Issue 1 https://doi.org/10.1021/jz900221c	journal	November 2009
The Active Site of Methanol Synthesis over Cu/ZnO/Al₂O₃ Industrial Catalysts Behrens, M.; Studt, F.; Kasatkin, I. Science, Vol. 336, Issue 6083, p. 893-897 https://doi.org/10.1126/science.1219831	journal	April 2012
Active sites for CO ₂ hydrogenation to methanol on Cu/ZnO catalysts Kattel, Shyam; Ramírez, Pedro J.; Chen, Jingguang G. Science, Vol. 355, Issue 6331 https://doi.org/10.1126/science.aal3573	journal	March 2017
The selectivity and activity of catalyst for CO hydrogenation to methanol and hydrocarbon: A comparative study on Cu, Co and Ni surfaces Wang, Jingbo; Kawazoe, Yoshiyuki; Sun, Qiang Surface Science, Vol. 645 https://doi.org/10.1016/j.susc.2015.10.035	journal	March 2016
Mechanisms of Hydrogen-Assisted CO ₂ Reduction on Nickel Lin, Wei; Stocker, Kelsey M.; Schatz, George C. Journal of the American Chemical Society, Vol. 139, Issue 13 https://doi.org/10.1021/jacs.7b01538	journal	March 2017
The Unique Chemistry of Hydrogen beneath the Surface: Catalytic Hydrogenation of Hydrocarbons Ceyer, S. T. Accounts of Chemical Research, Vol. 34, Issue 9 https://doi.org/10.1021/ar970030f	journal	September 2001
Role of Strain and Ligand Effects in the Modification of the Electronic and Chemical Properties of Bimetallic Surfaces Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A. Physical Review Letters, Vol. 93, Issue 15 https://doi.org/10.1103/PhysRevLett.93.156801	journal	October 2004
Control and Impact of the Nanoscale Distribution of Supported Cobalt Particles Used in Fischer–Tropsch Catalysis Munnik, Peter; de Jongh, Petra E.; de Jong, Krijn P. Journal of the American Chemical Society, Vol. 136, Issue 20 https://doi.org/10.1021/ja500436y	journal	May 2014
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Consequences of Surface Oxophilicity of Ni, Ni-Co, and Co Clusters on Methane Activation Tu, Weifeng; Ghoussoub, Mireille; Singh, Chandra Veer Journal of the American Chemical Society, Vol. 139, Issue 20 https://doi.org/10.1021/jacs.7b01632	journal	May 2017
Recycling of CO ₂ : Probing the Chemical State of the Ni(111) Surface during the Methanation Reaction with Ambient-Pressure X-Ray Photoelectron Spectroscopy Heine, Christian; Lechner, Barbara A. J.; Bluhm, Hendrik Journal of the American Chemical Society, Vol. 138, Issue 40 https://doi.org/10.1021/jacs.6b06939	journal	September 2016
Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni() Bürgi, T.; Trautman, T. R.; Gostein, M. Surface Science, Vol. 501, Issue 1-2 https://doi.org/10.1016/S0039-6028(01)01755-1	journal	March 2002
Reducing CO ₂ to CO and H ₂ O on Ni(110): The Influence of Subsurface Hydrogen Lin, Wei; Stocker, Kelsey M.; Schatz, George C. The Journal of Physical Chemistry C, Vol. 120, Issue 40 https://doi.org/10.1021/acs.jpcc.6b07849	journal	September 2016
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
A new mechanism for absorption: collision-induced absorption Maynard, Kevin J.; Johnson, Andrew D.; Daley, Sean P. Faraday Discussions of the Chemical Society, Vol. 91 https://doi.org/10.1039/dc9919100437	journal	January 1991
Reaction of CO, CH ₂ O, CH ₃ OH on Zn-Modified Pt(111) Surfaces Martono, Eddie; Vohs, John M. The Journal of Physical Chemistry C, Vol. 117, Issue 13 https://doi.org/10.1021/jp400798q	journal	March 2013