{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:36:01Z","timestamp":1760146561818,"version":"build-2065373602"},"reference-count":54,"publisher":"MDPI AG","issue":"22","license":[{"start":{"date-parts":[[2024,11,15]],"date-time":"2024-11-15T00:00:00Z","timestamp":1731628800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Ministry of Science, Technological Development and Innovation of the Republic of Serbia","award":["451-03-66\/2024-03\/200026","7739802"],"award-info":[{"award-number":["451-03-66\/2024-03\/200026","7739802"]}]},{"name":"Science Fund of the Republic of Serbia","award":["451-03-66\/2024-03\/200026","7739802"],"award-info":[{"award-number":["451-03-66\/2024-03\/200026","7739802"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Surface morphology is one of the critical factors affecting the performance of electrocatalysts. Thus, with careful manipulation of the surface structures at the atomic level, the effectiveness of the catalyst can be significantly improved. Heat treatment is an effective method for inducing surface atom rearrangement, hence modifying the catalyst\u2019s characteristics. This study investigated the substrate\u2019s influence and the effect of thermal annealing on the morphology and surface reconstruction of platinum (Pt) thin-film catalysts. Our findings indicate that heat treatment in a reductive atmosphere (95% Ar + 5% H2) at 300 \u00b0C can significantly impact the degree of rearrangement of surface atoms. This process induces long-range ordering, resulting in domains with a high proportion of (111) and (100) sites without an epitaxial template. Considering that the reactivity of low-index platinum single crystals for the methanol oxidation reaction follows the following sequence Pt(111) &lt; Pt(110) &lt; Pt(100), increasing the proportion of (100) planes leads to a notable enhancement (up to three times) in performance, compared to untreated catalysts. Furthermore, considering the amount of precious metal consumed, a mass-specific current density obtained on annealed Pt@Ni is larger by one order of magnitude and ~2 times that obtained on Pt@Cr and Pt@GCox catalysts, respectively. Our results demonstrate that an easy-to-implement way of controlling atomic orientations improves catalyst performance. With this contribution, we propose a method for designing improved electrocatalysts, as catalytic reactions occur only at the surface.<\/jats:p>","DOI":"10.3390\/ma17225575","type":"journal-article","created":{"date-parts":[[2024,11,15]],"date-time":"2024-11-15T05:33:04Z","timestamp":1731648784000},"page":"5575","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Enhanced Platinum-Based Thin-Film Catalysts for Electro-Oxidation of Methanol"],"prefix":"10.3390","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0009-0008-9490-2473","authenticated-orcid":false,"given":"Du\u0161an V.","family":"Tripkovi\u0107","sequence":"first","affiliation":[{"name":"Department of Electrochemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njego\u0161eva 12, 11000 Belgrade, Serbia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3548-6832","authenticated-orcid":false,"given":"Dragana L.","family":"Milo\u0161evi\u0107","sequence":"additional","affiliation":[{"name":"Department of Ecology and TechnoEconomics, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njego\u0161eva 12, 11000 Belgrade, Serbia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2157-5754","authenticated-orcid":false,"given":"Sanja I.","family":"Stevanovi\u0107","sequence":"additional","affiliation":[{"name":"Department of Electrochemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njego\u0161eva 12, 11000 Belgrade, Serbia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ksenija Dj.","family":"Popovi\u0107","sequence":"additional","affiliation":[{"name":"Department of Electrochemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njego\u0161eva 12, 11000 Belgrade, Serbia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Vladislava M.","family":"Jovanovi\u0107","sequence":"additional","affiliation":[{"name":"Department of Electrochemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njego\u0161eva 12, 11000 Belgrade, Serbia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,11,15]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1002\/1615-6854(200105)1:1<5::AID-FUCE5>3.0.CO;2-G","article-title":"Fuel Cells-Fundamentals and Applications","volume":"1","author":"Carrette","year":"2001","journal-title":"Fuel Cells"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1016\/0022-0728(94)03648-M","article-title":"Particle Size Effect of Carbon-Supported Platinum Catalysts for the Electrooxidation of Methanol","volume":"382","author":"Frelink","year":"1995","journal-title":"J. Electroanal. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/0022-0728(88)87028-1","article-title":"The Oxidation of Small Organic Molecules. A Survey of Recent Fuel Cell Related Research","volume":"257","author":"Parsons","year":"1988","journal-title":"J. Electroanal. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1795","DOI":"10.1149\/1.2055007","article-title":"Temperature-Dependent Methanol Electro-Oxidation on Well-Characterized Pt-Ru Alloys","volume":"141","author":"Gasteiger","year":"1994","journal-title":"J. Electrochem. Soc."},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Bockris, J.O., Conway, B.E., and White, R.E. (1992). Modern Aspects of Electrochemistry, Springer. [1st ed.].","DOI":"10.1007\/978-1-4615-2876-0"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"267","DOI":"10.1016\/S0022-0728(75)80261-0","article-title":"Electrocatalysis by Ad-Atoms: Part II. Enhancement of the Oxidation of Methanol on Platinum by Ruthenium Ad-Atoms","volume":"60","author":"Watanabe","year":"1975","journal-title":"J. Electroanal. Chem. Interfacial Electrochem."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"de S\u00e1, M.H., Moreira, C.S., Pinto, A.M.F.R., and Oliveira, V.B. (2022). Recent Advances in the Development of Nanocatalysts for Direct Methanol Fuel Cells. Energies, 15.","DOI":"10.3390\/en15176335"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"31202","DOI":"10.1016\/j.ijhydene.2021.07.006","article-title":"Recent Advances in Two-Dimensional Pt Based Electrocatalysts for Methanol Oxidation Reaction","volume":"46","author":"Tian","year":"2021","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3663","DOI":"10.1016\/S0013-4686(02)00336-5","article-title":"Electrocatalysis of Methanol Oxidation","volume":"47","author":"Iwasita","year":"2002","journal-title":"Electrochim. Acta"},{"key":"ref_10","unstructured":"Wieckowski, A. (1999). Andrew Hamnett Mechanism of Methanol Electro-Oxidation. Interfacial Electrochemistry Theory: Experiment, and Applications, CRC Press Taylor &. Francis Group."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/S0167-5729(01)00022-X","article-title":"Surface Science Studies of Model Fuel Cell Electrocatalysts","volume":"45","author":"Ross","year":"2002","journal-title":"Surf. Sci. Rep."},{"key":"ref_12","unstructured":"Vielstich, W., Lamm, A., and Hubert, A. (2003). Gasteiger. Handbook of Fuel Cells: Fundamentals, Technology, Applications, Wiley."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"15332","DOI":"10.1021\/ja8032185","article-title":"Unique Activity of Platinum Adislands in the CO Electrooxidation Reaction","volume":"130","author":"Strmcnik","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"8568","DOI":"10.1021\/jp991826u","article-title":"Effect of Temperature on Surface Processes at the Pt(111)\u2014Liquid Interface: Hydrogen Adsorption, Oxide Formation, and CO Oxidation","volume":"103","author":"Schmidt","year":"1999","journal-title":"J. Phys. Chem. B"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1965","DOI":"10.1021\/acscatal.1c05122","article-title":"Why Methanol Electro-Oxidation on Platinum in Water Takes Place Only in the Presence of Adsorbed OH","volume":"12","author":"Mekazni","year":"2022","journal-title":"ACS Catal."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"5074","DOI":"10.1021\/j100070a022","article-title":"Electrochemistry of Methanol at Low Index Crystal Planes of Platinum. An Integrated Voltammetric and Chronoamperometric Study","volume":"98","author":"Herrero","year":"1994","journal-title":"J. Phys. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1333","DOI":"10.2298\/JSC0612333T","article-title":"Methanol Oxidation at Platinum Electrodes in Acid Solution: Comparison between Model and Real Catalysts","volume":"71","year":"2006","journal-title":"J. Serbian Chem. Soc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"711","DOI":"10.1016\/0013-4686(95)00360-6","article-title":"Structural Effects and Reactivity in Methanol Oxidation on Polycrystalline and Single Crystal Platinum","volume":"41","author":"Xia","year":"1996","journal-title":"Electrochim. Acta"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"184","DOI":"10.1016\/j.jelechem.2005.10.006","article-title":"Potential Dependence of the Saturation CO Coverage of Pt Electrodes: The Origin of the Pre-Peak in CO-Stripping Voltammograms. Part 3: Pt(Poly)","volume":"586","author":"Cuesta","year":"2006","journal-title":"J. Electroanal. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"10021","DOI":"10.1021\/jp055949s","article-title":"Structure Sensitivity of Methanol Electrooxidation Pathways on Platinum: An on-Line Electrochemical Mass Spectrometry Study","volume":"110","author":"Housmans","year":"2006","journal-title":"J. Phys. Chem. B"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.jpowsour.2012.02.011","article-title":"Support Materials for PEMFC and DMFC Electrocatalysts\u2014A Review","volume":"208","author":"Sharma","year":"2012","journal-title":"J. Power Sources"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1016\/j.jpowsour.2006.04.058","article-title":"Key Challenges and Recent Progress in Batteries, Fuel Cells, and Hydrogen Storage for Clean Energy Systems","volume":"159","author":"Chalk","year":"2006","journal-title":"J. Power Sources"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1109","DOI":"10.1016\/j.elecom.2011.07.011","article-title":"An EC-FTIR Study on the Catalytic Role of Pt in Carbon Corrosion","volume":"13","author":"Maillard","year":"2011","journal-title":"Electrochem. Commun."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"421","DOI":"10.1016\/j.apcatb.2016.11.053","article-title":"Design of Active Pt on TiO2 Based Nanofibrous Cathode for Superior PEMFC Performance and Durability at High Temperature","volume":"204","author":"Ji","year":"2017","journal-title":"Appl. Catal. B Environ."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"B906","DOI":"10.1149\/1.3391737","article-title":"Transmission Electron Microscopy Observation of Corrosion Behaviors of Platinized Carbon Blacks under Thermal and Electrochemical Conditions","volume":"157","author":"Liu","year":"2010","journal-title":"J. Electrochem. Soc."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"640","DOI":"10.1016\/j.ijhydene.2012.06.089","article-title":"Innovative Catalyst Supports to Address Fuel Cell Stack Durability","volume":"38","author":"Cerri","year":"2013","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"15820","DOI":"10.1016\/j.ijhydene.2021.02.037","article-title":"Supported Bimetallic Nanoparticles as Anode Catalysts for Direct Methanol Fuel Cells: A Review","volume":"46","author":"Kaur","year":"2021","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2473","DOI":"10.1021\/acscatal.3c03883","article-title":"Metal-Support Interaction between Titanium Oxynitride and Pt Nanoparticles Enables Efficient Low-Pt-Loaded High-Performance Electrodes at Relevant Oxygen Reduction Reaction Current Densities","volume":"14","author":"Logar","year":"2024","journal-title":"ACS Catal."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"17167","DOI":"10.1021\/jacs.0c08139","article-title":"Reaction-Induced Strong Metal-Support Interactions between Metals and Inert Boron Nitride Nanosheets","volume":"142","author":"Fu","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"101250","DOI":"10.1016\/j.mtphys.2023.101250","article-title":"Nanoengineering of Metal-Based Electrocatalysts for Carbon Dioxide (CO2) Reduction: A Critical Review","volume":"38","author":"Pourebrahimi","year":"2023","journal-title":"Mater. Today Phys."},{"key":"ref_31","first-page":"501","article-title":"Phase Transformations and Surface Characterization of the Platinumchromium Coated System","volume":"112","author":"Hanief","year":"2012","journal-title":"J. S. Afr. Inst. Min. Metall."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"16536","DOI":"10.1021\/jacs.7b06846","article-title":"Tuning the Electrocatalytic Oxygen Reduction Reaction Activity and Stability of Shape-Controlled Pt-Ni Nanoparticles by Thermal Annealing -Elucidating the Surface Atomic Structural and Compositional Changes","volume":"139","author":"Beermann","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"15095","DOI":"10.1016\/j.ijhydene.2018.06.062","article-title":"Designing of Some Platinum or Palladium-Based Nanoalloys as Effective Electrocatalysts for Methanol Oxidation Reaction","volume":"43","author":"Hoseini","year":"2018","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"4308","DOI":"10.1016\/j.electacta.2005.02.087","article-title":"Specific Surface Reactions for Identification of Platinum Surface Domains: Surface Characterization and Electrocatalytic Tests","volume":"50","author":"Herrero","year":"2005","journal-title":"Electrochim. Acta"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"6559","DOI":"10.1016\/j.electacta.2008.04.015","article-title":"Preparation and Characterisation of Platinum- And Gold-Coated Copper, Iron, Cobalt and Nickel Deposits on Glassy Carbon Substrates","volume":"53","author":"Papadimitriou","year":"2008","journal-title":"Electrochim. Acta"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1011","DOI":"10.1134\/S1023193510090077","article-title":"Composition, Surface Segregation, and Electrochemical Properties of Binary PtM\/C (M = Co, Ni, Cr) Catalysts","volume":"46","author":"Bogdanovskaya","year":"2010","journal-title":"Russ. J. Electrochem."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"3658","DOI":"10.1021\/la202913b","article-title":"Electro-Oxidation of CO Chem on Pt Nanosurfaces: Solution of the Peak Multiplicity Puzzle","volume":"28","author":"Urchaga","year":"2012","journal-title":"Langmuir"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/j.elecom.2005.11.008","article-title":"CO Monolayer Oxidation on Semi-Spherical and Preferentially Oriented (100) and (111) Platinum Nanoparticles","volume":"8","author":"Herrero","year":"2006","journal-title":"Electrochem. Commun."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"3405","DOI":"10.1007\/s10008-016-3319-z","article-title":"Pt\/C Nanocatalysts for Methanol Electrooxidation Prepared by Water-in-Oil Microemulsion Method","volume":"20","author":"Rogan","year":"2016","journal-title":"J. Solid State Electrochem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2054","DOI":"10.1039\/c0nr00857e","article-title":"Structure Sensitivity and Nanoscale Effects in Electrocatalysis","volume":"3","author":"Koper","year":"2011","journal-title":"Nanoscale"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"2380","DOI":"10.1021\/acscatal.3c05520","article-title":"Design of Advanced Thin-Film Catalysts for Electrooxidation of Formic Acid","volume":"14","author":"Lopes","year":"2024","journal-title":"ACS Catal."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.jcat.2019.01.038","article-title":"Tuning of Catalytic Properties for Electrooxidation of Small Organic Molecules on Pt-Based Thin Films via Controlled Thermal Treatment","volume":"371","author":"Nogueira","year":"2019","journal-title":"J. Catal."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"5144","DOI":"10.1016\/j.electacta.2005.02.070","article-title":"CO Surface Electrochemistry on Pt-Nanoparticles: A Selective Review","volume":"50","author":"Mayrhofer","year":"2005","journal-title":"Electrochim. Acta"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"375","DOI":"10.1039\/B411377B","article-title":"Influence of Particle Agglomeration on the Catalytic Activity of Carbon-Supported Pt Nanoparticles in CO Monolayer Oxidation","volume":"7","author":"Maillard","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"7138","DOI":"10.1021\/jp512283c","article-title":"Small Molecule (CO, H2) Electro Oxidation as an Electrochemical Tool for Characterization of Ni@Pt\/C with Different Pt Coverages","volume":"119","author":"Chen","year":"2015","journal-title":"J. Phys. Chem. C"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"355","DOI":"10.1007\/s10800-005-9072-0","article-title":"Carbon Supported Pt-Cr Alloys as Oxygen-Reduction Catalysts for Direct Methanol Fuel Cells","volume":"36","author":"Antolini","year":"2006","journal-title":"J. Appl. Electrochem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/j.jelechem.2004.06.007","article-title":"Methanol Oxidation at Platinum Electrodes in Alkaline Solution: Comparison between Supported Catalysts and Model Systems","volume":"572","author":"Kowal","year":"2004","journal-title":"J. Electroanal. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"275","DOI":"10.1016\/j.jelechem.2005.03.037","article-title":"Nickel-Underpotential Deposition on Pt(1 1 0) in Sulphate-Containing Media","volume":"580","author":"Chatenet","year":"2005","journal-title":"J. Electroanal. Chem."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"47","DOI":"10.1038\/s44160-023-00387-3","article-title":"Low-Temperature Non-Equilibrium Synthesis of Anisotropic Multimetallic Nanosurface Alloys for Electrochemical CO2 Reduction","volume":"3","author":"Koolen","year":"2024","journal-title":"Nat. Synth."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/S0167-5729(96)00011-8","article-title":"Ultrathin Metal Films and Particles on Oxide Surfaces: Structural, Electronic and Chemisorptive Properties","volume":"27","author":"Campbell","year":"1997","journal-title":"Surf. Sci. Rep."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"9863","DOI":"10.1021\/jp0203806","article-title":"Role of Crystalline Defects in Electrocatalysis: CO Adsorption and Oxidation on Stepped Platinum Electrodes as Studied by in Situ Infrared Spectroscopy","volume":"106","author":"Lebedeva","year":"2002","journal-title":"J. Phys. Chem. B"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"9028","DOI":"10.1021\/acs.jpcc.5b12303","article-title":"Methanol Electro-Oxidation on the Pt Surface: Revisiting the Cyclic Voltammetry Interpretation","volume":"120","author":"Chung","year":"2016","journal-title":"J. Phys. Chem. C"},{"key":"ref_53","doi-asserted-by":"crossref","unstructured":"Yu, R., Zhang, Y., Deng, S., Zhu, R., Zhang, S., Zhang, J., Zhao, Y., and Xia, Z. (2024). Platinum Alloys for Methanol Oxidation Electrocatalysis: Reaction Mechanism and Rational Design of Catalysts with Exceptional Activity and Stability. Catalysts, 14.","DOI":"10.3390\/catal14010060"},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"1049","DOI":"10.1007\/s10008-011-1485-6","article-title":"Carbon-Supported Platinum-Decorated Nickel Nanoparticles for Enhanced Methanol Oxidation in Acid Media","volume":"16","author":"Wang","year":"2012","journal-title":"J. Solid State Electrochem."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/17\/22\/5575\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T16:32:40Z","timestamp":1760113960000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/17\/22\/5575"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,11,15]]},"references-count":54,"journal-issue":{"issue":"22","published-online":{"date-parts":[[2024,11]]}},"alternative-id":["ma17225575"],"URL":"https:\/\/doi.org\/10.3390\/ma17225575","relation":{},"ISSN":["1996-1944"],"issn-type":[{"type":"electronic","value":"1996-1944"}],"subject":[],"published":{"date-parts":[[2024,11,15]]}}}