Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

Bhandari, Saurabh; Rangarajan, Srinivas; Maravelias, Christos T.; Dumesic, James A.; Mavrikakis, Manos

doi:10.1021/acscatal.9b05424

Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

Journal Article · Wed Mar 04 00:00:00 EST 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b05424· OSTI ID:1764508

Bhandari, Saurabh ^[1]; ^[2]; ^[2]; ^[2]; ^[2]

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

A combination of periodic density functional theory (DFT, PW91-GGA) calculations, reaction kinetics experiments, and mean-field microkinetic modeling is used to derive insights on the reaction mechanism and determine the nature of the active site under reaction conditions for the vapor-phase decomposition of formic acid (FA, HCOOH) over Pt/C catalysts. Microkinetic models formulated using DFT energetics derived on the clean Pt(100) and Pt(111) required large parameter adjustments to reproduce the experimentally measured apparent activation energies and reaction orders. Further, these models predicted high surface coverage of adsorbed carbon monoxide (CO*), inconsistent with the environment of the active site in the DFT calculations on the clean surfaces. Consequently, we reperformed DFT calculations for the entire reaction network on partially CO*-covered (4/9 monolayer, ML) Pt(111) and Pt(100). The resultant microkinetic models, with thermochemistry and kinetics explicitly dependent on CO* coverage, were able to reproduce the experimentally determined activation energies and reaction orders, in addition to being self-consistent in CO* coverage. Our results suggest that Pt(100) is likely poisoned by CO* under typical reaction conditions and does not contribute significantly to the experimentally observed reactivity. Instead, we find that Pt(111) better represents the active site for FA decomposition reaction on Pt/C catalysts. The optimized model on 4/9 ML CO*-covered Pt(111) suggests that the reaction occurs via the carboxyl (COOH*) intermediate and that the spectator CO*-assisted pathways play a significant role under reaction conditions. Lastly, this study underscores the importance of spectator species on the energetics and the mechanism of a catalytic reaction and their key role in developing a model that better addresses the nature of the active site under realistic catalytic reaction conditions.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

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

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

OSTI ID:: 1764508

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (105)

Formic acid decomposition on Au catalysts: DFT, microkinetic modeling, and reaction kinetics experiments Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald AIChE Journal, Vol. 60, Issue 4 https://doi.org/10.1002/aic.14401	journal	February 2014
Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H ₂ /O ₂ Fuel Cells Loges, BjÃ¶rn; Boddien, Albert; Junge, Henrik Angewandte Chemie International Edition, Vol. 47, Issue 21 https://doi.org/10.1002/anie.200705972	journal	May 2008
Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures Ojeda, Manuel; Iglesia, Enrique Angewandte Chemie International Edition, Vol. 48, Issue 26 https://doi.org/10.1002/anie.200805723	journal	June 2009
DFT-Based Coverage-Dependent Model of Pt-Catalyzed NO Oxidation Getman, Rachel B.; Schneider, William F. ChemCatChem, Vol. 2, Issue 11 https://doi.org/10.1002/cctc.201000146	journal	August 2010
A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects Choi, Sang-Il; Herron, Jeffrey A.; Scaranto, Jessica ChemCatChem, Vol. 7, Issue 14 https://doi.org/10.1002/cctc.201500094	journal	April 2015
The Mechanism of CO and CO ₂ Hydrogenation to Methanol over Cu-Based Catalysts Studt, Felix; Behrens, Malte; Kunkes, Edward L. ChemCatChem, Vol. 7, Issue 7 https://doi.org/10.1002/cctc.201500123	journal	March 2015
Hydrogen Generation from Formic Acid Decomposition by Ruthenium Carbonyl Complexes. Tetraruthenium Dodecacarbonyl Tetrahydride as an Active Intermediate Czaun, Miklos; Goeppert, Alain; May, Robert ChemSusChem, Vol. 4, Issue 9 https://doi.org/10.1002/cssc.201000446	journal	March 2011
Biomass Sucrose‐Derived Cobalt@Nitrogen‐Doped Carbon for Catalytic Transfer Hydrogenation of Nitroarenes with Formic Acid Yuan, Man; Long, Yu; Yang, Jin ChemSusChem, Vol. 11, Issue 23 https://doi.org/10.1002/cssc.201802163	journal	October 2018
Cobalt Entrapped in N,S-Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid Guo, Haotian; Gao, Ruixiao; Sun, Mingming ChemSusChem, Vol. 12, Issue 2 https://doi.org/10.1002/cssc.201802392	journal	January 2019
General concepts, assumptions, drawbacks, and misuses in kinetic Monte Carlo and microkinetic modeling simulations applied to computational heterogeneous catalysis Prats, Hèctor; Illas, Francesc; Sayós, Ramón International Journal of Quantum Chemistry, Vol. 118, Issue 9 https://doi.org/10.1002/qua.25518	journal	October 2017
Finding the Rate-Determining Step in a Mechanism Campbell, Charles T. Journal of Catalysis, Vol. 204, Issue 2 https://doi.org/10.1006/jcat.2001.3396	journal	December 2001
Dehydration of carboxylic acids on the MgO(100) surface Peng, X. D.; Barteau, M. A. Catalysis Letters, Vol. 7, Issue 5-6 https://doi.org/10.1007/bf00764930	journal	January 1991
CO and CO2 Hydrogenation to Methanol Calculated Using the BEEF-vdW Functional Studt, Felix; Abild-Pedersen, Frank; Varley, Joel B. Catalysis Letters, Vol. 143, Issue 1 https://doi.org/10.1007/s10562-012-0947-5	journal	December 2012
An overview of spatial microscopic and accelerated kinetic Monte Carlo methods Chatterjee, Abhijit; Vlachos, Dionisios G. Journal of Computer-Aided Materials Design, Vol. 14, Issue 2 https://doi.org/10.1007/s10820-006-9042-9	journal	February 2007
Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals Grabow, Lars C.; Hvolbæk, Britt; Nørskov, Jens K. Topics in Catalysis, Vol. 53, Issue 5-6 https://doi.org/10.1007/s11244-010-9455-2	journal	February 2010
On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts Li, Sha; Scaranto, Jessica; Mavrikakis, Manos Topics in Catalysis, Vol. 59, Issue 17-18 https://doi.org/10.1007/s11244-016-0672-1	journal	August 2016
Catalytic decomposition of carbon-based liquid-phase chemical hydrogen storage materials for hydrogen generation under mild conditions Sánchez, Felipe; Motta, Davide; Dimitratos, Nikolaos Applied Petrochemical Research, Vol. 6, Issue 3 https://doi.org/10.1007/s13203-016-0159-9	journal	June 2016
Activities for the decomposition of formic acid and the acid-base properties of metal oxide catalysts Ai, M. Journal of Catalysis, Vol. 50, Issue 2 https://doi.org/10.1016/0021-9517(77)90038-0	journal	November 1977
The adsorption of formic acid on Y zeolites: A multiple-pulse nuclear magnetic resonance study Duncan, T. Journal of Catalysis, Vol. 67, Issue 1 https://doi.org/10.1016/0021-9517(81)90260-8	journal	January 1981
Effect of CO on Pt-catalyzed decomposition of formic acid in ultrahigh vacuum Columbia, M. R.; Crabtree, A. M.; Thiel, P. A. Journal of Electroanalytical Chemistry, Vol. 345, Issue 1-2 https://doi.org/10.1016/0022-0728(93)80471-S	journal	February 1993
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
Adsorption studies of oxygen and carbon monoxide on a Pt (100) surface Kneringer, G.; Netzer, F. P. Surface Science, Vol. 49, Issue 1 https://doi.org/10.1016/0039-6028(75)90332-5	journal	April 1975
Chemisorption of CO on the Pt(111) surface Ertl, G.; Neumann, M.; Streit, K. M. Surface Science, Vol. 64, Issue 2 https://doi.org/10.1016/0039-6028(77)90052-8	journal	May 1977
Binding states of CO on single crystal planes of Pt McCabe, R. W.; Schmidt, L. D. Surface Science, Vol. 66, Issue 1 https://doi.org/10.1016/0039-6028(77)90402-2	journal	August 1977
Adsorbate island dimensions and interaction energies from vibrational spectra: Co on Pt {001} and Pt {111} Crossley, Alison; A. King, David Surface Science, Vol. 95, Issue 1 https://doi.org/10.1016/0039-6028(80)90132-6	journal	May 1980
A molecular beam investigation of the interactions of CO with a Pt(111) surface Campbell, C. T.; Ertl, G.; Kuipers, H. Surface Science, Vol. 107, Issue 1 https://doi.org/10.1016/0039-6028(81)90621-X	journal	May 1981
Absolute coverages of CO and O on Pt(111); Comparison of saturation CO coverages on Pt(100), (110) and (111) surfaces Norton, P. R.; Davies, J. A.; Jackman, T. E. Surface Science, Vol. 122, Issue 1 https://doi.org/10.1016/0039-6028(82)90054-1	journal	October 1982
Reaction of HCOOH with a Pt(111)-O surface; identification of adsorbed monodentate formate Avery, Neil R. Applications of Surface Science, Vol. 14, Issue 2 https://doi.org/10.1016/0378-5963(83)90093-4	journal	January 1983
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
Formic acid oxidation on single crystal platinum electrodes. Comparison with polycrystalline platinum Clavilier, J.; Parsons, R.; Durand, R. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 124, Issue 1-2 https://doi.org/10.1016/S0022-0728(81)80311-7	journal	July 1981
A study by electrochemically modulated infrared reflectance spectroscopy of the electrosorption of formic acid at a platinum electrode Beden, B.; Bewick, A.; Lamy, C. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 148, Issue 1, p. 147-160 https://doi.org/10.1016/S0022-0728(83)80137-5	journal	June 1983
Reaction intermediate species during the steam reforming of methanol over metal modified molybdenum carbide catalysts Cao, Ji; Ma, Yufei; Guan, Guoqing Applied Catalysis B: Environmental, Vol. 189 https://doi.org/10.1016/j.apcatb.2016.02.021	journal	July 2016
Intrinsic activity of interfacial sites for Pt-Fe and Pt-Mo catalysts in the hydrogenation of carbonyl groups Ro, Insoo; Aragao, Isaias B.; Brentzel, Zachary J. Applied Catalysis B: Environmental, Vol. 231 https://doi.org/10.1016/j.apcatb.2018.02.058	journal	September 2018
Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields Zhang, Jizhe; Sun, Miao; Liu, Xin Catalysis Today, Vol. 233 https://doi.org/10.1016/j.cattod.2013.12.010	journal	September 2014
A review of multiscale modeling of metal-catalyzed reactions: Mechanism development for complexity and emergent behavior Salciccioli, M.; Stamatakis, M.; Caratzoulas, S. Chemical Engineering Science, Vol. 66, Issue 19 https://doi.org/10.1016/j.ces.2011.05.050	journal	October 2011
Fundamental principles of laboratory fixed bed reactor design Hickman, Daniel A.; Degenstein, John C.; Ribeiro, Fabio H. Current Opinion in Chemical Engineering, Vol. 13 https://doi.org/10.1016/j.coche.2016.07.002	journal	August 2016
Decomposition of formic acid for hydrogen production over metal doped nanosheet-like MoC 1−x catalysts Wang, Junli; Cao, Ji; Ma, Yufei Energy Conversion and Management, Vol. 147 https://doi.org/10.1016/j.enconman.2017.05.054	journal	September 2017
Fuelling the hydrogen economy: Scale-up of an integrated formic acid-to-power system van Putten, Robbert; Wissink, Tim; Swinkels, Tijn International Journal of Hydrogen Energy, Vol. 44, Issue 53 https://doi.org/10.1016/j.ijhydene.2019.01.153	journal	November 2019
Selective decomposition of formic acid on molybdenum carbide: A new reaction pathway Flaherty, David W.; Berglund, Sean P.; Mullins, C. Buddie Journal of Catalysis, Vol. 269, Issue 1 https://doi.org/10.1016/j.jcat.2009.10.012	journal	January 2010
Production of CO-free H2 from formic acid. A comparative study of the catalytic behavior of Pt metals on a carbon support Solymosi, F.; Koós, Á.; Liliom, N. Journal of Catalysis, Vol. 279, Issue 1 https://doi.org/10.1016/j.jcat.2011.01.023	journal	April 2011
Pt nanoclusters stabilized by N-doped carbon nanofibers for hydrogen production from formic acid Jia, Lijun; Bulushev, Dmitri A.; Podyacheva, Olga Yu. Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.07.008	journal	November 2013
On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces Lausche, Adam C.; Medford, Andrew J.; Khan, Tuhin Suvra Journal of Catalysis, Vol. 307 https://doi.org/10.1016/j.jcat.2013.08.002	journal	November 2013
Measurement of intrinsic catalytic activity of Pt monometallic and Pt-MoOx interfacial sites over visible light enhanced PtMoOx/SiO2 catalyst in reverse water gas shift reaction Ro, Insoo; Sener, Canan; Stadelman, Thomas M. Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.08.011	journal	December 2016
Review and evaluation of hydrogen production options for better environment Acar, Canan; Dincer, Ibrahim Journal of Cleaner Production, Vol. 218 https://doi.org/10.1016/j.jclepro.2019.02.046	journal	May 2019
Molybdenum carbide catalysed hydrogen production from formic acid – A density functional theory study Luo, Qiquan; Wang, Tao; Walther, Guido Journal of Power Sources, Vol. 246 https://doi.org/10.1016/j.jpowsour.2013.07.102	journal	January 2014
A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals Wellendorff, Jess; Silbaugh, Trent L.; Garcia-Pintos, Delfina Surface Science, Vol. 640 https://doi.org/10.1016/j.susc.2015.03.023	journal	October 2015
HCOOH decomposition on Pt(111): A DFT study Scaranto, Jessica; Mavrikakis, Manos Surface Science, Vol. 648 https://doi.org/10.1016/j.susc.2015.09.023	journal	June 2016
Density functional theory studies of HCOOH decomposition on Pd(111) Scaranto, Jessica; Mavrikakis, Manos Surface Science, Vol. 650 https://doi.org/10.1016/j.susc.2015.11.020	journal	August 2016
Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T. Surface Science, Vol. 650 https://doi.org/10.1016/j.susc.2015.12.008	journal	August 2016
Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T. Surface Science, Vol. 650 https://doi.org/10.1016/j.susc.2015.12.032	journal	August 2016
SBH10: A Benchmark Database of Barrier Heights on Transition Metal Surfaces Mallikarjun Sharada, Shaama; Bligaard, Thomas; Luntz, Alan C. The Journal of Physical Chemistry C, Vol. 121, Issue 36 https://doi.org/10.1021/acs.jpcc.7b05677	journal	September 2017
Sequential-Optimization-Based Framework for Robust Modeling and Design of Heterogeneous Catalytic Systems Rangarajan, Srinivas; Maravelias, Christos T.; Mavrikakis, Manos The Journal of Physical Chemistry C, Vol. 121, Issue 46 https://doi.org/10.1021/acs.jpcc.7b08089	journal	November 2017
Comparison of Coverage-Dependent Binding Energy Models for Mean-Field Microkinetic Rate Predictions Bajpai, Anshumaan; Frey, Kurt; Schneider, William F. Langmuir, Vol. 36, Issue 1 https://doi.org/10.1021/acs.langmuir.9b03563	journal	December 2019
Investigation of Hydrogenation of Formic Acid to Methanol using H ₂ or Formic Acid as a Hydrogen Source Tsurusaki, Akihiro; Murata, Kazuhisa; Onishi, Naoya ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b03194	journal	January 2017
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
Electrons to Reactors Multiscale Modeling: Catalytic CO Oxidation over RuO ₂ Sutton, Jonathan E.; Lorenzi, Juan M.; Krogel, Jaron T. ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.8b00713	journal	April 2018
Progress in Accurate Chemical Kinetic Modeling, Simulations, and Parameter Estimation for Heterogeneous Catalysis Matera, Sebastian; Schneider, William F.; Heyden, Andreas ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01234	journal	June 2019
Apparent Activation Energies in Complex Reaction Mechanisms: A Simple Relationship via Degrees of Rate Control Mao, Zhongtian; Campbell, Charles T. ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02761	journal	August 2019
Kinetic Monte Carlo Simulations Unveil Synergic Effects at Work on Bifunctional Catalysts Prats, Hèctor; Posada-Pérez, Sergio; Rodriguez, José A. ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02813	journal	August 2019
Chlorine Influence on Palladium Doped Nickel Catalysts in Levulinic Acid Hydrogenation with Formic Acid as Hydrogen Source Soszka, Emilia; Reijneveld, Hanna M.; Jędrzejczyk, Marcin ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 11 https://doi.org/10.1021/acssuschemeng.8b03211	journal	September 2018
Theoretical Study of van der Waals Complexes at Surface Sites in Comparison with the Experiment Sauer, J.; Ugliengo, P.; Garrone, E. Chemical Reviews, Vol. 94, Issue 7 https://doi.org/10.1021/cr00031a014	journal	November 1994
Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation Grabow, L. C.; Mavrikakis, M. ACS Catalysis, Vol. 1, Issue 4 https://doi.org/10.1021/cs200055d	journal	February 2011
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
Catalytic reactions on a metal oxide single crystal: switchover of the reaction paths in formic acid decomposition on titanium dioxide TiO2(110) Onishi, Hiroshi; Aruga, Tetsuya; Iwasawa, Yasuhiro Journal of the American Chemical Society, Vol. 115, Issue 22 https://doi.org/10.1021/ja00075a112	journal	November 1993
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
Energetics of Formic Acid Conversion to Adsorbed Formates on Pt(111) by Transient Calorimetry Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T. Journal of the American Chemical Society, Vol. 136, Issue 10 https://doi.org/10.1021/ja412878u	journal	February 2014
Selective Hydrogen Production from Formic Acid Decomposition on Pd–Au Bimetallic Surfaces Yu, Wen-Yueh; Mullen, Gregory M.; Flaherty, David W. Journal of the American Chemical Society, Vol. 136, Issue 31 https://doi.org/10.1021/ja505192v	journal	July 2014
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
Redox Pathways for HCOOH Decomposition over CeO ₂ Surfaces Senanayake, Sanjaya D.; Mullins, David R. The Journal of Physical Chemistry C, Vol. 112, Issue 26 https://doi.org/10.1021/jp8016425	journal	June 2008
Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A. Nature Chemistry, Vol. 8, Issue 4 https://doi.org/10.1038/nchem.2454	journal	February 2016
Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst Tedsree, Karaked; Li, Tong; Jones, Simon Nature Nanotechnology, Vol. 6, Issue 5 https://doi.org/10.1038/nnano.2011.42	journal	April 2011
Hydrogen generation from formic acid and alcohols using homogeneous catalysts Johnson, Tarn C.; Morris, David J.; Wills, Martin Chem. Soc. Rev., Vol. 39, Issue 1 https://doi.org/10.1039/B904495G	journal	January 2010
Kinetic Monte Carlo simulations of heterogeneously catalyzed oxidation reactions Hess, Franziska; Over, Herbert Catal. Sci. Technol., Vol. 4, Issue 3 https://doi.org/10.1039/C3CY00833A	journal	January 2014
Investigation of Pd nanoparticles supported on zeolites for hydrogen production from formic acid dehydrogenation Navlani-García, M.; Martis, M.; Lozano-Castelló, D. Catalysis Science & Technology, Vol. 5, Issue 1 https://doi.org/10.1039/C4CY00667D	journal	January 2015
Implications of coverage-dependent O adsorption for catalytic NO oxidation on the late transition metals Frey, Kurt; Schmidt, David J.; Wolverton, C. Catal. Sci. Technol., Vol. 4, Issue 12 https://doi.org/10.1039/C4CY00763H	journal	January 2014
Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system Singh, Ashish Kumar; Singh, Suryabhan; Kumar, Abhinav Catalysis Science & Technology, Vol. 6, Issue 1 https://doi.org/10.1039/C5CY01276G	journal	January 2016
Identifying systematic DFT errors in catalytic reactions Christensen, Rune; Hansen, Heine A.; Vegge, Tejs Catalysis Science & Technology, Vol. 5, Issue 11 https://doi.org/10.1039/C5CY01332A	journal	January 2015
Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction Reichert, Jenny; Brunner, Birgit; Jess, Andreas Energy & Environmental Science, Vol. 8, Issue 10 https://doi.org/10.1039/C5EE01706H	journal	January 2015
Support effect for nanosized Au catalysts in hydrogen production from formic acid decomposition Zacharska, Monika; Chuvilin, Andrey L.; Kriventsov, Vladimir V. Catalysis Science & Technology, Vol. 6, Issue 18 https://doi.org/10.1039/C6CY00552G	journal	January 2016
Sequential hydrogen production system from formic acid and H ₂ /CO ₂ separation under high-pressure conditions Iguchi, Masayuki; Chatterjee, Maya; Onishi, Naoya Sustainable Energy & Fuels, Vol. 2, Issue 8 https://doi.org/10.1039/C8SE00087E	journal	January 2018
Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited Bozell, Joseph J.; Petersen, Gene R. Green Chemistry, Vol. 12, Issue 4, p. 539-554 https://doi.org/10.1039/b922014c	journal	January 2010
Catalytic conversion of biomass to biofuels Alonso, David Martin; Bond, Jesse Q.; Dumesic, James A. Green Chemistry, Vol. 12, Issue 9, p. 1493-1513 https://doi.org/10.1039/c004654j	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
Improved hydrogen production from formic acid on a Pd/C catalyst doped by potassium Bulushev, Dmitri A.; Jia, Lijun; Beloshapkin, Sergey Chemical Communications, Vol. 48, Issue 35 https://doi.org/10.1039/c2cc31027a	journal	January 2012
Formic acid as a hydrogen source – recent developments and future trends Grasemann, Martin; Laurenczy, Gábor Energy & Environmental Science, Vol. 5, Issue 8 https://doi.org/10.1039/c2ee21928j	journal	January 2012
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
Absolute CO coverage: Direct comparison between the (111) and (110) faces of Ni, Pd, and Pt at 300 K Erley, W.; Wagner, H. The Journal of Chemical Physics, Vol. 72, Issue 3 https://doi.org/10.1063/1.439324	journal	February 1980
Beyond mean-field approximations for accurate and computationally efficient models of on-lattice chemical kinetics Pineda, M.; Stamatakis, M. The Journal of Chemical Physics, Vol. 147, Issue 2 https://doi.org/10.1063/1.4991690	journal	July 2017
Active sites and mechanisms for H ₂ O ₂ decomposition over Pd catalysts Plauck, Anthony; Stangland, Eric E.; Dumesic, James A. Proceedings of the National Academy of Sciences, Vol. 113, Issue 14 https://doi.org/10.1073/pnas.1602172113	journal	March 2016
A self-adjusting platinum surface for acetone hydrogenation Demir, Benginur; Kropp, Thomas; Rivera-Dones, Keishla R. Proceedings of the National Academy of Sciences, Vol. 117, Issue 7 https://doi.org/10.1073/pnas.1917110117	journal	January 2020
Large Sample Properties of Simulations Using Latin Hypercube Sampling Stein, Michael Technometrics, Vol. 29, Issue 2 https://doi.org/10.1080/00401706.1987.10488205	journal	May 1987
Catalytic Decomposition of Formic Acid on Metal Oxides Trillo, J. M.; Munuera, G.; Criado, J. M. Catalysis Reviews, Vol. 7, Issue 1 https://doi.org/10.1080/01614947208064710	journal	January 1972
Kinetic modelling of heterogeneous catalytic systems Stamatakis, Michail Journal of Physics: Condensed Matter, Vol. 27, Issue 1 https://doi.org/10.1088/0953-8984/27/1/013001	journal	November 2014
Formic acid production from carbohydrates biomass by hydrothermal reaction Yun, J.; Jin, F.; Kishita, A. Journal of Physics: Conference Series, Vol. 215 https://doi.org/10.1088/1742-6596/215/1/012126	journal	March 2010
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
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111) Neugebauer, Jörg; Scheffler, Matthias Physical Review B, Vol. 46, Issue 24 https://doi.org/10.1103/PhysRevB.46.16067	journal	December 1992
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
Dipole correction for surface supercell calculations Bengtsson, Lennart Physical Review B, Vol. 59, Issue 19 https://doi.org/10.1103/PhysRevB.59.12301	journal	May 1999
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
Structure Sensitivity of Formic Acid Electrooxidation on Transition Metal Surfaces: A First-Principles Study Elnabawy, Ahmed O.; Herron, Jeffrey A.; Scaranto, Jessica Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0161815jes	journal	January 2018
A Comparison of Three Methods for Selecting Values of Input Variables in the Analysis of Output from a Computer Code McKay, M. D.; Beckman, R. J.; Conover, W. J. Technometrics, Vol. 21, Issue 2 https://doi.org/10.2307/1268522	journal	May 1979
Homogeneous Catalytic Dehydrogenation of Formic Acid: Progress Towards a Hydrogen-Based Economy Laurenczy, Gábor; Dyson, Paul J. Journal of the Brazilian Chemical Society https://doi.org/10.5935/0103-5053.20140235	journal	January 2014

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Formic acid
activation energy
catalystsl chemical reactions
coverage effects
coverage self-consistency
dehydration
density functional theory
microkinetic modeling
organic reactions
platinum catalyst
reaction kinetics experiments
renewable hydrogen production

Reaction Mechanism of Vapor-Phase Formic Acid Decomposition over Platinum Catalysts: DFT, Reaction Kinetics Experiments, and Microkinetic Modeling

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