Abstract
The O–H/C–H scission of methanol on Pt clusters is a crucial step in direct methanol fuel cells applications. The first dehydrogenation process of methanol on Ptnq clusters (n = 5, 13, 19; q = 0, +1, −1) in various charge states is studied. Our findings indicate that methanol adsorbs more easily on cationic Ptn+ than on neutral Ptn or anionic Ptn−. However, the adsorption capacity of methanol on Ptnq gradually decreases with increasing cluster size, especially for CH3OH on Ptn+, which decreases significantly (from −57.61 kcal/mol to −16.41 kcal/mol). Compared with Ptn and Ptn+, the energy barrier of O–H/C–H bond cleavage is significantly reduced by injecting an electron into Ptn to form Ptn−, and the activity of the catalyst is improved. However, the energy barrier of O–H/C–H cleavage increases gradually with cluster size, leading to a decrease in catalytic activity. The effect of charge weakens as cluster size increases, and small clusters with injected electrons exhibit better catalytic activity.
Graphical Abstract Figure
References
1.
Wu
, A. H.
, Hao
, Z.
, He
, G. G.
, and Cai
, D. H.
, 2023
, “Optimization of Hydrogen Ejector Structure in Proton Exchange Membrane Fuel Cell System Under Wide Operating Conditions
,” Energy Sources, Part A
, 46
(1
), pp. 522
–542
. 2.
Kutagulla
, S.
, Le
, N. H.
, Caldino Bohn
, I. T.
, Stacy
, B. J.
, Favela
, C. S.
, Slack
, J. J.
, Baker
, A. M.
, et al, 2023
, “Comparative Studies of Atomically Thin Proton Conductive Films to Reduce Crossover in Hydrogen Fuel Cells
,” ACS Appl. Mater. Interfaces
, 15
(51
), pp. 59358
–59369
. 3.
Alias
, M. S.
, Kamarudin
, S. K.
, Zainoodin
, A. M.
, and Masdar
, M. S.
, 2020
, “Active Direct Methanol Fuel Cell: An Overview
,” Int. J. Hydrogen Energy
, 45
(38
), pp. 19620
–19641
. 4.
Chen
, F.
, Sun
, Y. X.
, Li
, H. Y.
, and Li
, C. J.
, 2022
, “Review and Development of Anode Electrocatalyst Carriers for Direct Methanol Fuel Cell,” Energy Technol.
, 10
(6
), p. 2101086
. 5.
Niu
, C. Y.
, Jiao
, J.
, Xing
, B.
, Wang
, G. C.
, and Bu
, X. H.
, 2010
, “Reaction Mechanism of Methanol Decomposition on Pt-Based Model Catalysts: A Theoretical Study
,” J. Comput. Chem.
, 31
(10
), pp. 2023
–2037
. 6.
Zaragoza
, I. P.
, Salcedo
, R.
, and Vergara
, J.
, 2009
, “DFT: A Dynamic Study of the Interaction of Ethanol and Methanol With Platinum
,” J. Mol. Model.
, 15
(5
), pp. 447
–451
. 7.
Zhong
, W. H.
, Liu
, Y. X.
, and Zhang
, D. J.
, 2012
, “A Comparative Theoretical Study for the Methanol Dehydrogenation to CO Over Pt3 and PtAu2 Clusters
,” J. Mol. Model
, 18
(7
), pp. 3051
–3060
. 8.
Lin
, L.
, Zhu
, Q.
, and Xu
, A. W.
, 2015
, “Anode Catalysts and Cathode Catalysts of Direct Methanol Fuel Cells,” Prog. Chem.
, 27
(9
), pp. 1147
–1157
. 9.
Choi
, J. G.
, Ham
, K.
, Bong
, S.
, and Lee
, J.
, 2022
, “Phosphate-Decorated Pt Nanoparticles as Methanol-Tolerant Oxygen Reduction Electrocatalyst for Direct Methanol Fuel Cells
,” J. Electrochem. Sci. Technol.
, 13
(3
), pp. 354
–361
. 10.
Vu
, T. H. T.
, Nguyen
, T. T.
, Nguyen
, T. H.
, Nguyen
, M. D.
, and Nguyen
, Q. M.
, 2022
, “A New Method for Synthesizing High Performance Few-Layer Graphene Supported Pt Electrocatalysts in Methanol and Ethanol Oxidation
,” Electrochim. Acta
, 380
, p. 138258
. 11.
Giordano
, E.
, Berretti
, E.
, Capozzoli
, L.
, Lavacchi
, A.
, Muhyuddin
, M.
, Santoro
, C.
, Gatto
, I.
, Zaffora
, A.
, and Santamaria
, M.
, 2023
, “Boosting DMFC Power Output by Adding Sulfuric Acid asa Supporting Electrolyte: Effect on Cell Performance Equipped with Platinum and Platinum Group Metal-Free Cathodes
,” J. Power Sources
, 563
, p. 232806
. 12.
Xu
, G. D.
, Ye
, Z. H.
, Zou
, K. Q.
, Li
, C. F.
, Zhou
, D. J.
, Lv
, R. G.
, Huang
, B.
, Li
, J.
, and Cai
, W. W.
, 2023
, “Defect Configuration of Ceria for Pt Anchoring Toward Efficient Methanol Oxidation
,” Int. J. Hydrogen Energy
, 48
(25
), pp. 9344
–9352
. 14.
Karp
, E. M. T.
, Silbaugh
, L.
, Crowe
, M. C.
, and Campbell
, C. T.
, 2012
, “Energetics of Adsorbed Methanol and Methoxy on Pt(111) by Microcalorimetry
,” J. Am. Chem. Soc.
, 134
(50
), pp. 20388
–20395
. 15.
Greeley
, J.
, and Mavrikakis
, M.
, 2002
, “A First-Principles Study of Methanol Decomposition on Pt(111)
,” J. Am. Chem. Soc.
, 124
(24
), pp. 7193
–7201
. 16.
Greeley
, J.
, and Mavrikakis
, M.
, 2004
, “Competitive Paths for Methanol Decomposition on Pt(111)
,” J. Am. Chem. Soc.
, 126
(12
), pp. 3910
–3919
. 17.
Ou
, L.
, 2022
, “Theoretical Insights Into Effect of Surface Composition of Pt-Ru Bimetallic Catalysts on CH3OH Oxidation: Mechanistic Considerations
,” J. Mol. Model
, 13
(6
), p. 149
. 18.
Chen
, Y. W.
, and Ho
, J. J.
, 2009
, “Dehydrogenation of Ethanol on a 2Ru/ZrO2(111) Surface: Density Functional Computations
,” J. Phys. Chem. C
, 113
(15
), pp. 6132
–6139
. 19.
Lin
, Y. C.
, Chou
, H. L.
, Tsai
, M. C.
, Hwang
, B. J.
, Sarma
, L. S.
, Lee
, Y. C.
, Chen
, C. I.
, 2009
, “Combined Experimental and Theoretical Investigation of Nanosized Effects of Pt Catalyst on Their Underlying Methanol Electro-Oxidation Activity
,” J. Phys. Chem. C
, 1133
(21
), pp. 9197
–9205
. 20.
Ferrin
, P.
, and Mavrikakis
, M.
, 2009
, “Structure Sensitivity of Methanol Electrooxidation on Transition Metals
,” J. Am. Chem. Soc.
, 131
(40
), pp. 14381
–14389
. 21.
Xie
, T.
, Hare
, B. J.
, Meza-Morales
, P. J.
, Sievers
, C.
, and Getman
, R. B.
, 2020
, “Identification of the Active Sites in the Dehydrogenation of Methanol on Pt/Al2O3Catalysts
,” J. Phys. Chem. C
, 124
(35
), pp. 19015
–19023
. 22.
Ou
, L.
, 2018
, “Theoretical Insights Into the Effect of Solvation and Sublayer Ru on Pt-Catalytic CH3OH Oxidation Mechanisms in the Aqueous Phase
,” J. Phys. Chem. C
, 122
(26
), pp. 14554
–14565
. 23.
Ou
, L.
, 2018
, “New Insights Into the Pt-Catalyzed CH3OH Oxidation Mechanism: First-Principle Considerations on Thermodynamics, Kinetics, and Reversible Potentials
,” ACS Omega
, 3
(1
), pp. 886
–897
. 24.
Hartnig
, C.
, and Spohr
, E.
, 2005
, “The Role of Water in the Initial Steps of Methanol Oxidation on Pt(111)
,” Chem. Phys.
, 319
(1–3
), pp. 185
–191
. 25.
Pang
, S. K.
, 2015
, “Why Palladium Cathodes Can Bear Resistance to Methanol But Not Platinum Cathodes,” Electrochim. Acta
, 161
, pp. 420
–426
. 26.
Davis
, J. L.
, and Barteau
, M. A.
, 1987
, “Decarbonylation and Decomposition Pathways of Alcohol's on Pd(111)
,” Surf. Sci.
, 187
(2–3
), pp. 387
–406
. 27.
Watanabe
, T.
, Ehara
, M.
, Kuramoto
, K.
, and Nakatsuji
, H.
, 2009
, “Possible Reaction Pathway in Methanol Dehydrogenation on Pt and Ag Surfaces/Clusters Starting From O–H Scission: Dipped Adcluster Model Study
,” Surf. Sci.
, 603
(4
), pp. 641
–646
. 28.
Yuan
, J.
, Wang
, Z.
, Zhang
, Y.
, Shen
, Y. F.
, Han
, D.
, Zhang
, Q.
, Xu
, X.
, and Niu
, L.
, 2008
, “Electrostatic Layer-by-Layer a of Platinum-Loaded Multiwall Carbon Nanotube Multilayer: A Tunable Catalyst Film for Anodic Methanol Oxidation
,” Thin Solid Films
, 516
(18
), pp. 6531
–6535
. 29.
Wang
, J.
, Xi
, J.
, Bai
, Y.
, Shen
, Y.
, Sun
, J.
, Chen
, L.
, Zhu
, W.
, and Qiu
, X.
, 2007
, “Structural Designing of Pt-CeO2/CNTs for Methanol Electro-Oxidation
,” J. Power Sources
, 164
(2
), pp. 555
–560
. 30.
Cui
, G.
, Shen
, P. K.
, Meng
, H.
, Zhao
, J.
, and Wu
, G.
, 2011
, “Tungsten Carbide as Supports for Pt Electrocatalysts With Improved CO Tolerance in Methanol Oxidation
,” J. Power Sources
, 196
(15
), pp. 6125
–6130
. 31.
Zainoodin
, A. M.
, Kamarudin
, S. K.
, and Daud
, W. R. W.
, 2010
, “Electrode in Direct Methanol Fuel Cells
,” Int. J. Hydrogen Energy
, 35
(10
), pp. 4606
–4621
. 32.
Wang
, Q.
, and Ding
, Y.
, 2017
, “Charge Influence on the First Dehydrogenation of Methanol by Ptn q (n = 1–3, q = 0, +1, −1): A Computational Study
,” J. Mol. Model.
, 23
(2
), p. 61
. 33.
Wang
, Q.
, and Ding
, Y.
, 2017
, “Methanol Oxidation on Platinum Catalyst: Why Does the Negatively Charged Surface Perform Better Than the Neutral One?
,” ChemistrySelect
, 2
(1
), pp. 469
–473
. 34.
Frisch
, M. J.
, Trucks
, G. W.
, Schlegel
, H. B.
, Scuseria
, G. E.
, Robb
, M. A.
, Cheeseman
, J. R.
, Montgomery
, J. A.
, et al, 2009
, Gaussian 09, Revision D. 01
, Gaussian, Inc.
, Wallingford, UK
.35.
Dunning
, T. H.
, Jr., and Hay
, P. J.
, 1977
, “Gaussian Basis Sets for Molecular Calculations,” Methods of Electronic Structure Theory: Vol. 3 (Modern Theoretical Chemistry
), H. F.
Schaefer
, ed., pp. 1
–27
.36.
Andrae
, D.
, Haeussermann
, U.
, Dolg
, M.
, Stoll
, H.
, and Preuss
, H.
, 1990
, “Energy-Adjusted Ab Initio Pseudopotentials for the Second and Third row Transition Elements
,” Theor. Chim. Acta
, 77
(2
), pp. 123
–141
. 37.
Hohenberg
, P.
, and Kohn
, W.
, 1964
, “Inhomogeneous Electron Gas
,” Phys. Rev.
, 136
(3B
), pp. B864
–B871
. 38.
Kohn
, W.
, and Sham
, L. J.
, 1965
, “Self-Consistent Equations Including Exchange and Correlation Effects
,” Phys. Rev.
, 140
(4A
), pp. A1133
–A1138
. 
