HCOOH decomposition on Pt(111): A DFT study

Scaranto, Jessica; Mavrikakis, Manos

doi:10.1016/j.susc.2015.09.023

HCOOH decomposition on Pt(111): A DFT study

Journal Article · Tue Oct 13 00:00:00 EDT 2015 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2015.09.023· OSTI ID:1406904

Scaranto, Jessica ^[1]; Mavrikakis, Manos ^[2]

Univ. of Wisconsin-Madison, Madison, WI (United States); Department of Chemical and Biological Engineering, University of Wisconsin–Madison
Univ. of Wisconsin-Madison, Madison, WI (United States)

Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO₂ and H₂ or dehydration leading to CO and H₂O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We also considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO₂ is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT); Univ. of Wisconsin-Madison, Madison, WI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Contributing Organization:: EMSL, a national scientific user facility at Pacific Northwest National Laboratory (PNNL); and the National Energy Research Scientific Computing Center (NERSC); the Center for Nanoscale Materials at Argonne National Laboratory (ANL)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; FG02-05ER15731

OSTI ID:: 1406904

Alternate ID(s):: OSTI ID: 1251783

Journal Information:: Surface Science, Journal Name: Surface Science Journal Issue: C Vol. 648; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Kinetics and Mechanism of the Electrooxidation of Formic Acid—Spectroelectrochemical Studies in a Flow Cell Chen, Yan Xia; Heinen, Martin; Jusys, Zenonas Angewandte Chemie International Edition, Vol. 45, Issue 6 https://doi.org/10.1002/anie.200502172	journal	January 2006
The Role of Bridge-Bonded Adsorbed Formate in the Electrocatalytic Oxidation of Formic Acid on Platinum Osawa, Masatoshi; Komatsu, Kei-ichi; Samjeské, Gabor Angewandte Chemie International Edition, Vol. 50, Issue 5 https://doi.org/10.1002/anie.201004782	journal	December 2010
Linear free energy relationships for C1-oxygenate decomposition on transition metal surfaces Barteau, Mark A. Catalysis Letters, Vol. 8, Issue 2-4 https://doi.org/10.1007/BF00764114	journal	January 1991
Erratum to: Sustainable energy: a review of formic acid electrochemical fuel cells Rees, Neil V.; Compton, Richard G. Journal of Solid State Electrochemistry, Vol. 16, Issue 1 https://doi.org/10.1007/s10008-011-1614-2	journal	December 2011
Screening of PdM and PtM catalysts in a multi-anode direct formic acid fuel cell Yu, Xingwen; Pickup, Peter G. Journal of Applied Electrochemistry, Vol. 41, Issue 5 https://doi.org/10.1007/s10800-011-0267-2	journal	March 2011
Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials Loges, Björn; Boddien, Albert; Gärtner, Felix Topics in Catalysis, Vol. 53, Issue 13-14 https://doi.org/10.1007/s11244-010-9522-8	journal	May 2010
Infrared spectroscopic study of methanol and formic acid absorbates on a platinum electrode: Part II. Role of the linear CO(a) derived from methanol and formic acid in the electrocatalytic oxidation of CH₃OH and HCOOH Kunimatsu, K.; Kita, H. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 218, Issue 1-2, p. 155-172 https://doi.org/10.1016/0022-0728(87)87013-4	journal	February 1987
Mechanisms of formic acid, methanol, and carbon monoxide electrooxidation at platinum as examined by single potential alteration infrared spectroscopy Corrigan, Dennis S.; Weaver, Michael J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 241, Issue 1-2 https://doi.org/10.1016/0022-0728(88)85123-4	journal	February 1988
The interaction of formic acid with transition metal surfaces, studied in ultrahigh vacuum Columbia, M. R.; Thiel, P. A. Journal of Electroanalytical Chemistry, Vol. 369, Issue 1-2 https://doi.org/10.1016/0022-0728(94)87077-2	journal	May 1994
Local and collective structure of formate on Pt(111) Jensen, M. B.; Myler, U.; Thiel, P. A. Surface Science, Vol. 290, Issue 1-2 https://doi.org/10.1016/0039-6028(93)90575-5	journal	June 1993
Reversible work transition state theory: application to dissociative adsorption of hydrogen Mills, Gregory; Jónsson, Hannes; Schenter, Gregory K. Surface Science, Vol. 324, Issue 2-3 https://doi.org/10.1016/0039-6028(94)00731-4	journal	February 1995
Adsorption of formic acid on clean and oxygen covered Pt(111) Avery, Neil R. Applications of Surface Science, Vol. 11-12 https://doi.org/10.1016/0378-5963(82)90120-9	journal	July 1982
A first-principles study of surface and subsurface H on and in Ni(111): diffusional properties and coverage-dependent behavior Greeley, Jeff; Mavrikakis, Manos Surface Science, Vol. 540, Issue 2-3 https://doi.org/10.1016/S0039-6028(03)00790-8	journal	August 2003
Reaction channels for the catalytic oxidation of CO on Pt(111) Eichler, A.; Hafner, J. Surface Science, Vol. 433-435 https://doi.org/10.1016/S0039-6028(99)00061-8	journal	August 1999
Surface science studies of model fuel cell electrocatalysts Markovic, N. Surface Science Reports, Vol. 45, Issue 4-6 https://doi.org/10.1016/S0167-5729(01)00022-X	journal	April 2002
RuSn bimetallic catalysts for selective hydrogenation of levulinic acid to γ-valerolactone Wettstein, Stephanie G.; Bond, Jesse Q.; Alonso, David Martin Applied Catalysis B: Environmental, Vol. 117-118, p. 321-329 https://doi.org/10.1016/j.apcatb.2012.01.033	journal	May 2012
New insight into the CO formation mechanism during formic acid oxidation on Pt(111) Zhong, Wenhui; Zhang, Dongju Catalysis Communications, Vol. 29 https://doi.org/10.1016/j.catcom.2012.09.002	journal	December 2012
High power density direct formic acid fuel cells Zhu, Yimin; Ha, Su Y.; Masel, Richard I. Journal of Power Sources, Vol. 130, Issue 1-2 https://doi.org/10.1016/j.jpowsour.2003.11.051	journal	May 2004
Fuel crossover in direct formic acid fuel cells Jeong, Kyoung-Jin; Miesse, Craig M.; Choi, Jong-Ho Journal of Power Sources, Vol. 168, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.02.062	journal	May 2007
Recent advances in direct formic acid fuel cells (DFAFC) Yu, Xingwen; Pickup, Peter G. Journal of Power Sources, Vol. 182, Issue 1, p. 124-132 https://doi.org/10.1016/j.jpowsour.2008.03.075	journal	July 2008
Partial and complete reduction of O2 by hydrogen on transition metal surfaces Ford, Denise C.; Nilekar, Anand Udaykumar; Xu, Ye Surface Science, Vol. 604, Issue 19-20 https://doi.org/10.1016/j.susc.2010.05.026	journal	September 2010
Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compounds Johnstone, Robert A. W.; Wilby, Anna H.; Entwistle, Ian D. Chemical Reviews, Vol. 85, Issue 2 https://doi.org/10.1021/cr00066a003	journal	April 1985
Platinum-Based Nanostructured Materials: Synthesis, Properties, and Applications Chen, Aicheng; Holt-Hindle, Peter Chemical Reviews, Vol. 110, Issue 6 https://doi.org/10.1021/cr9003902	journal	June 2010
Mechanism of the Electrocatalytic Oxidation of Formic Acid on Metals Cuesta, Angel; Cabello, Gema; Osawa, Masatoshi ACS Catalysis, Vol. 2, Issue 5 https://doi.org/10.1021/cs200661z	journal	March 2012
Ni–Fe–S Cubanes in CO ₂ Reduction Electrocatalysis: A DFT Study Varley, J. B.; Hansen, H. A.; Ammitzbøll, N. L. ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs4005419	journal	October 2013
Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition Yoo, Jong Suk; Abild-Pedersen, Frank; Nørskov, Jens K. ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs400664z	journal	March 2014
Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter ACS Catalysis, Vol. 4, Issue 12 https://doi.org/10.1021/cs500737p	journal	November 2014
The temperature and coverage dependences of adsorbed formic acid and its conversion to formate on platinum(111) Columbia, M. R.; Crabtree, A. M.; Thiel, P. A. Journal of the American Chemical Society, Vol. 114, Issue 4 https://doi.org/10.1021/ja00030a017	journal	February 1992
Catalytic Water Formation on Platinum: A First-Principles Study Michaelides, A.; Hu, P. Journal of the American Chemical Society, Vol. 123, Issue 18 https://doi.org/10.1021/ja003576x	journal	May 2001
Theoretical Elucidation of the Competitive Electro-oxidation Mechanisms of Formic Acid on Pt(111) Gao, Wang; Keith, John A.; Anton, Josef Journal of the American Chemical Society, Vol. 132, Issue 51 https://doi.org/10.1021/ja1083317	journal	December 2010
Structure Sensitivity of Methanol Electrooxidation on Transition Metals Ferrin, Peter; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 131, Issue 40 https://doi.org/10.1021/ja904010u	journal	October 2009
Application of In-situ Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy for the Understanding of Complex Reaction Mechanism and Kinetics: Formic Acid Oxidation on a Pt Film Electrode at Elevated Temperatures Chen, Yan Xia; Ye, Shen; Heinen, Martin The Journal of Physical Chemistry B, Vol. 110, Issue 19 https://doi.org/10.1021/jp057463h	journal	May 2006
Mechanistic Studies of Water–Gas-Shift Reaction on Transition Metals Lin, Chia-Hao; Chen, Chung-Liang; Wang, Jeng-Han The Journal of Physical Chemistry C, Vol. 115, Issue 38 https://doi.org/10.1021/jp2034467	journal	September 2011
Energetics of Oxygen Adatoms, Hydroxyl Species and Water Dissociation on Pt(111) Karp, Eric M.; Campbell, Charles T.; Studt, Felix The Journal of Physical Chemistry C, Vol. 116, Issue 49 https://doi.org/10.1021/jp3066794	journal	November 2012
Mechanism of the Water Gas Shift Reaction on Pt: First Principles, Experiments, and Microkinetic Modeling Grabow, Lars C.; Gokhale, Amit A.; Evans, Steven T. The Journal of Physical Chemistry C, Vol. 112, Issue 12 https://doi.org/10.1021/jp7099702	journal	March 2008
Density Functional Theory Comparison of Water Dissociation Steps on Cu, Au, Ni, Pd, and Pt Phatak, Abhijit A.; Delgass, W. Nicholas; Ribeiro, Fabio H. The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp810216b	journal	April 2009
Formic Acid Oxidation at Pt/H ₂ O Interface from Periodic DFT Calculations Integrated with a Continuum Solvation Model Wang, Hui-Fang; Liu, Zhi-Pan The Journal of Physical Chemistry C, Vol. 113, Issue 40 https://doi.org/10.1021/jp9059888	journal	September 2009
Bridge-Bonded Formate: Active Intermediate or Spectator Species in Formic Acid Oxidation on a Pt Film Electrode? ^† Chen, Y. -X.; Heinen, M.; Jusys, Z. Langmuir, Vol. 22, Issue 25 https://doi.org/10.1021/la060928q	journal	December 2006
A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt Neurock, Matthew; Janik, Michael; Wieckowski, Andrzej Faraday Discuss., Vol. 140 https://doi.org/10.1039/B804591G	journal	January 2009
Electrocatalysis of formic acid on palladium and platinum surfaces: from fundamental mechanisms to fuel cell applications Jiang, Kun; Zhang, Han-Xuan; Zou, Shouzhong Phys. Chem. Chem. Phys., Vol. 16, Issue 38 https://doi.org/10.1039/C4CP03151B	journal	January 2014
Reexamination of formic acid decomposition on the Pt(111) surface both in the absence and in the presence of water, from periodic DFT calculations Qi, Yuanyuan; Li, Jingjing; Zhang, Dongju Catalysis Science & Technology, Vol. 5, Issue 6 https://doi.org/10.1039/C5CY00159E	journal	January 2015
Comparative theoretical study of formic acid decomposition on PtAg(111) and Pt(111) surfaces Qi, Yuanyuan; Gao, Jun; Zhang, Dongju RSC Advances, Vol. 5, Issue 27 https://doi.org/10.1039/C5RA01925G	journal	January 2015
Carbon dioxide and formic acid—the couple for environmental-friendly hydrogen storage? Enthaler, Stephan; von Langermann, Jan; Schmidt, Thomas Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/b907569k	journal	January 2010
Oxidation of formic acid on the Pt(111) surface in the gas phase Gao, Wang; Keith, John A.; Anton, Josef Dalton Transactions, Vol. 39, Issue 36 https://doi.org/10.1039/c0dt00404a	journal	January 2010
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
A new technique to calculate steepest descent paths in flexible polyatomic systems Ulitsky, Alexander; Elber, Ron The Journal of Chemical Physics, Vol. 92, Issue 2 https://doi.org/10.1063/1.458112	journal	January 1990
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism Vanderbilt, David Physical Review B, Vol. 41, Issue 11, p. 7892-7895 https://doi.org/10.1103/PhysRevB.41.7892	journal	April 1990
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation Perdew, John P.; Chevary, J. A.; Vosko, S. H. Physical Review B, Vol. 46, Issue 11 https://doi.org/10.1103/PhysRevB.46.6671	journal	September 1992
Implementation of gradient-corrected exchange-correlation potentials in Car-Parrinello total-energy calculations White, J. A.; Bird, D. M. Physical Review B, Vol. 50, Issue 7 https://doi.org/10.1103/PhysRevB.50.4954	journal	August 1994
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Special Points in the Brillouin Zone Chadi, D. J.; Cohen, Marvin L. Physical Review B, Vol. 8, Issue 12 https://doi.org/10.1103/PhysRevB.8.5747	journal	December 1973
Connecting Biomass and Petroleum Processing with a Chemical Bridge Bozell, Joseph J. Science, Vol. 329, Issue 5991, p. 522-523 https://doi.org/10.1126/science.1191662	journal	July 2010
E LECTRONIC S TRUCTURE AND C ATALYSIS ON M ETAL S URFACES Greeley, Jeff; Nørskov, Jens K.; Mavrikakis, Manos Annual Review of Physical Chemistry, Vol. 53, Issue 1 https://doi.org/10.1146/annurev.physchem.53.100301.131630	journal	October 2002

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Carboxyl
Decomposition
Density functional theory
Formate
Formic acid
Pt(111)

HCOOH decomposition on Pt(111): A DFT study

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