Abstract
Monodispersed Pt nanoparticles supported on a TiO2 and nitrogen-doped carbon composite (TiO2/NDC) were successfully synthesized via an efficient in situ self-assembly strategy and microwave-assisted polyol process. The Pt/TiO2/NDC catalyst exhibited superior electrocatalytic activity toward the methanol oxidation reaction (MOR). The electrochemically active surface area of the Pt/TiO2/NDC catalyst was twofold higher than that of the Pt/C/NDC catalyst. In addition, the Pt/TiO2/NDC catalyst revealed a better electrocatalytic activity and CO-tolerance as well as a stability toward the MOR. The combined characterization from Fourier transform infrared spectrum, Brunauer-Emmett-Teller surface area, scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometer, thermogravimetric analysis, inductively coupled plasma atomic emissions spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy analyses demonstrated that the superior catalytic performance and stability of the Pt/TiO2/NDC catalysts likely arose from the synergistic effect of their unique morphology and composition as well as the electronic effect between the TiO2/NDC and Pt. This electrocatalyst holds great promise for application in direct methanol fuel cells.
Issue Section:
Research Papers
References
1.
Li
, Y.
, Liang
, L.
, Liu
, C.
, Li
, Y.
, Xing
, W.
, and Sun
, J.
, 2018
, “Self-Healing Proton-Exchange Membranes Composed of Nafion–Poly(Vinyl Alcohol) Complexes for Durable Direct Methanol Fuel Cells
,” Adv. Mater.
, 30
(25
), p. 1707146
. 10.1002/adma.2017071462.
Yang
, Z.
, Li
, M.
, Cui
, P.
, Zhang
, G.
, Jiang
, X.
, and Wang
, Y.
, 2018
, “Designed Formation of Hollow Pt Nanocrystals Supported on MoOx-Modified Carbon for High-Performance Methanol Electro-Oxidation
,” ACS Sustainable Chem. Eng.
, 6
(11
), pp. 14026
–14032
. 10.1021/acssuschemeng.8b025673.
Antolini
, E.
, 2018
, “Photo-Assisted Methanol Oxidation on Pt-TiO2 Catalysts for Direct Methanol Fuel Cells: A Short Review
,” Appl. Catal., B
, 237
, pp. 491
–503
. 10.1016/j.apcatb.2018.06.0294.
Lei
, H.
, Li
, X.
, Sun
, C.
, Zeng
, J.
, Siwal
, S. S.
, and Zhang
, Q.
, “Galvanic Replacement–Mediated Synthesis of Ni-Supported Pd Nanoparticles With Strong Metal–Support Interaction for Methanol Electro-Oxidation
,” Small
, p. 1804722
. 10.1002/smll.2018047225.
Kakade
, B. A.
, Tamaki
, T.
, Ohashi
, H.
, and Yamaguchi
, T.
, 2012
, “Highly Active Bimetallic PdPt and CoPt Nanocrystals for Methanol Electro-Oxidation
,” J. Phys. Chem. C
, 116
(13
), pp. 7464
–7470
. 10.1021/jp300140s6.
Huang
, L.
, Wang
, Z.
, Gong
, W.
, and Shen
, P. K.
, 2018
, “Atomic Platinum Skin Under Synergy of Cobalt for Enhanced Methanol Oxidation Electrocatalysis
,” ACS Appl. Mater. Interfaces
, 10
(50
), pp. 43716
–43722
. 10.1021/acsami.8b170707.
Narayanamoorthy
, B.
, Datta
, K. K. R.
, Eswaramoorthy
, M.
, and Balaji
, S.
, 2014
, “Highly Active and Stable Pt3Rh Nanoclusters as Supportless Electrocatalyst for Methanol Oxidation in Direct Methanol Fuel Cells
,” ACS Catal.
, 4
(10
), pp. 3621
–3629
. 10.1021/cs500628m8.
Kwon
, S.
, Ham
, D. J.
, Kim
, T.
, Kwon
, Y.
, Lee
, S. G.
, and Cho
, M.
, 2018
, “Active Methanol Oxidation Reaction by Enhanced CO Tolerance on Bimetallic Pt/Ir Electrocatalysts Using Electronic and Bifunctional Effects
,” ACS Appl. Mater. Interfaces
, 10
(46
), pp. 39581
–39589
. 10.1021/acsami.8b090539.
Luo
, F.
, Zhang
, Q.
, Qu
, K.
, Guo
, L.
, Hu
, H.
, Yang
, Z.
, Cai
, W.
, and Cheng
, H.
, 2019
, “Decorated PtRu Electrocatalyst for Concentrated Direct Methanol Fuel Cells
,” ChemCatChem
, 11
(4
), pp. 1238
–1243
. 10.1002/cctc.20180180110.
Wang
, K.
, Sriphathoorat
, R.
, Luo
, S.
, Tang
, M.
, Du
, H.
, and Shen
, P. K.
, 2016
, “Ultrathin PtCu Hexapod Nanocrystals With Enhanced Catalytic Performance for Electro-Oxidation Reactions
,” J. Mater. Chem. A.
, 4
(35
), pp. 13425
–13430
. 10.1039/C6TA05230D11.
Liu
, J.
, Xu
, G.
, Liu
, B.
, and Zhang
, J.
, 2017
, “A Dendritic Core-Shell Cu@PtCu Alloy Electrocatalyst Resulting in an Enhanced Electron Transfer Ability and Boosted Surface Active Sites for an Improved Methanol Oxidation Reaction
,” Chem. Commun.
, 53
(54
), pp. 7457
–7460
. 10.1039/C7CC01559C12.
Li
, X.
, Zhou
, Y.
, Du
, Y.
, Xu
, J.
, Wang
, W.
, Chen
, Z.
, and Cao
, J.
, 2019
, “PtCu Nanoframes as Ultra-High Performance Electrocatalysts for Methanol Oxidation
,” Int. J. Hydrogen Energy.
, 44
(33
), pp. 18050
–18057
. 10.1016/j.ijhydene.2019.05.07213.
Kwon
, T.
, Jun
, M.
, Kim
, H. Y.
, Oh
, A.
, Park
, J.
, Baik
, H.
, Joo
, S. H.
, and Lee
, K.
, 2018
, “Vertex-Reinforced PtCuCo Ternary Nanoframes as Efficient and Stable Electrocatalysts for the Oxygen Reduction Reaction and the Methanol Oxidation Reaction
,” Adv. Funct. Mater.
, 28
(13
), p. 1706440
. 10.1002/adfm.20170644014.
Han
, S.-H.
, Liu
, H.-M.
, Chen
, P.
, Jiang
, J.-X.
, and Chen
, Y.
, 2018
, “Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation
,” Adv. Energy Mater.
, 8
(24
), p. 1801326
. 10.1002/aenm.20180132615.
Gan
, L.
, Cui
, C.
, Heggen
, M.
, Dionigi
, F.
, Rudi
, S.
, and Strasser
, P.
, 2014
, “Element-specific Anisotropic Growth of Shaped Platinum Alloy Nanocrystals
,” Science
, 346
(6216
), pp. 1502
–1506
. 10.1126/science.126121216.
Sanetuntikul
, J.
, Ketpang
, K.
, and Shanmugam
, S.
, 2015
, “Hierarchical Nanostructured Pt8Ti-TiO2/C as an Efficient and Durable Anode Catalyst for Direct Methanol Fuel Cells
,” ACS Catal.
, 5
(12
), pp. 7321
–7327
. 10.1021/acscatal.5b0139017.
Xu
, H.
, Wang
, A.-L.
, Tong
, Y.-X.
, and Li
, G.-R.
, 2016
, “Enhanced Catalytic Activity and Stability of Pt/CeO2/PANI Hybrid Hollow Nanorod Arrays for Methanol Electro-Oxidation
,” ACS Catal.
, 6
(8
), pp. 5198
–5206
. 10.1021/acscatal.6b0101018.
Zhou
, Y.
, Hu
, X.-C.
, Liu
, X.-H.
, and Wen
, H.-R.
, 2015
, “Core–Shell Hierarchical WO2/WO3 Microspheres as an Electrocatalyst Support for Methanol Electrooxidation
,” Chem. Commun.
, 51
(83
), pp. 15297
–15299
. 10.1039/C5CC06603D19.
Zhou
, Q.
, Pan
, Z.
, Wu
, D.
, Hu
, G.
, Wu
, S.
, Chen
, C.
, Lin
, L.
, and Lin
, Y.
, 2019
, “Pt-CeO2/TiN NTs Derived From Metal Organic Frameworks as High-Performance Electrocatalyst for Methanol Electrooxidation
,” Int. J. Hydrogen Energy
, 44
(21
), pp. 10646
–10652
. 10.1016/j.ijhydene.2019.01.23120.
Han
, J.
, Yang
, L.
, Yang
, L.
, Jiang
, W.
, Luo
, X.
, and Luo
, S.
, 2018
, “PtRu Nanoalloys Loaded on Graphene and TiO2 Nanotubes co-Modified Ti Wire as an Active and Stable Methanol Oxidation Electrocatalyst
,” Int. J. Hydrogen Energy
, 43
(15
), pp. 7338
–7346
. 10.1016/j.ijhydene.2018.02.17621.
Wang
, Y.
, Wang
, J.
, Han
, G.
, Du
, C.
, Sun
, Y.
, Du
, L.
, An
, M.
, Yin
, G.
, Gao
, Y.
, and Song
, Y.
, 2019
, “Superior Catalytic Performance and CO Tolerance of Ru@Pt/C-TiO2 Electrocatalyst Toward Methanol Oxidation Reaction
,” Appl. Surf. Sci.
, 473
, pp. 943
–950
. 10.1016/j.apsusc.2018.12.21122.
Yoon
, S.
, Oh
, K.
, Liu
, F.
, Seo
, J. H.
, Somorjai
, G. A.
, Lee
, J. H.
, and An
, K.
, 2018
, “Specific Metal–Support Interactions Between Nanoparticle Layers for Catalysts With Enhanced Methanol Oxidation Activity
,” ACS Catal.
, 8
(6
), pp. 5391
–5398
. 10.1021/acscatal.8b0027623.
Sui
, X.-L.
, Wang
, Z.-B.
, Yang
, M.
, Huo
, L.
, Gu
, D.-M.
, and Yin
, G.-P.
, 2014
, “Investigation on C–TiO2 Nanotubes Composite as Pt Catalyst Support for Methanol Electrooxidation
,” J. Power Sources
, 255
, pp. 43
–51
. 10.1016/j.jpowsour.2014.01.00124.
Zhu
, J.
, Zhao
, X.
, Xiao
, M.
, Liang
, L.
, Liu
, C.
, Liao
, J.
, and Xing
, W.
, 2014
, “The Construction of Nitrogen-Doped Graphitized Carbon–TiO2 Composite to Improve the Electrocatalyst for Methanol Oxidation
,” Carbon
, 72
, pp. 114
–124
. 10.1016/j.carbon.2014.01.06225.
Chu
, Y. Y.
, Cao
, J.
, Dai
, Z.
, and Tan
, X. Y.
, 2014
, “A Novel Pt/CeO2 Catalyst Coated with Nitrogen-Doped Carbon With Excellent Performance for DMFCs
,” J. Mater. Chem. A
, 2
(11
), p. 4038
. 10.1039/c3ta14418f26.
Zhang
, J.
, Liu
, X.
, Xing
, A.
, and Liu
, J.
, 2018
, “Template-Oriented Synthesis of Nitrogen-Enriched Porous Carbon Nanowhisker by Hollow TiO2 Spheres Nanothorns for Methanol Electrooxidation
,” ACS Appl. Energy Mater.
, 1
(6
), pp. 2758
–2768
. 10.1021/acsaem.8b0042027.
Zhu
, J.
, Xiao
, M.
, Zhao
, X.
, Liu
, C.
, and Xing
, W.
, 2015
, “Titanium Dioxide Encapsulated in Nitrogen-Doped Carbon Enhances the Activity and Durability of Platinum Catalyst for Methanol Electro-Oxidation Reaction
,” J. Power Sources
, 292
, pp. 78
–86
. 10.1016/j.jpowsour.2015.05.04128.
Ting
, C.-C.
, Liu
, C.-H.
, Tai
, C.-Y.
, Hsu
, S.-C.
, Chao
, C.-S.
, and Pan
, F.-M.
, 2015
, “The Size Effect of Titania-Supported Pt Nanoparticles on the Electrocatalytic Activity Towards Methanol Oxidation Reaction Primarily via the Bifunctional Mechanism
,” J. Power Sources
, 280
, pp. 166
–172
. 10.1016/j.jpowsour.2015.01.08129.
Yang
, F.
, Ma
, L.
, Gan
, M.
, Zhang
, J.
, Yan
, J.
, Huang
, H.
, Yu
, L.
, Li
, Y.
, Ge
, C.
, and Hu
, H.
, 2015
, “Polyaniline-Functionalized TiO2–C Supported Pt Catalyst for Methanol Electro-Oxidation
,” Synth. Met.
, 205
, pp. 23
–31
. 10.1016/j.synthmet.2015.03.01730.
Mentus
, S.
, Ciric-Marjanovic
, G.
, Trchova
, M.
, and Stejskal
, J.
, 2009
, “Conducting Carbonized Polyaniline Nanotubes
,” Nanotechnology
, 20
(24
), p. 245601
. 10.1088/0957-4484/20/24/24560131.
Zhang
, J.
, Zhang
, X.
, Zhou
, Y.
, Guo
, S.
, Wang
, K.
, Liang
, Z.
, and Xu
, Q.
, 2014
, “Nitrogen-Doped Hierarchical Porous Carbon Nanowhisker Ensembles on Carbon Nanofiber for High-Performance Supercapacitors
,” ACS Sustainable Chem. Eng.
, 2
(6
), pp. 1525
–1533
. 10.1021/sc500221s32.
Aijaz
, A.
, Masa
, J.
, Rosler
, C.
, Xia
, W.
, Weide
, P.
, Botz
, A. J.
, Fischer
, R. A.
, Schuhmann
, W.
, and Muhler
, M.
, 2016
, “Co@Co3O4 Encapsulated in Carbon Nanotube-Grafted Nitrogen-Doped Carbon Polyhedra as an Advanced Bifunctional Oxygen Electrode
,” Angew. Chem. Int. Ed. Engl.
, 55
(12
), pp. 4087
–4091
. 10.1002/anie.20150938233.
Daşdelen
, Z.
, Yıldız
, Y.
, Eriş
, S.
, and Şen
, F.
, 2017
, “Enhanced Electrocatalytic Activity and Durability of Pt Nanoparticles Decorated on GO-PVP Hybride Material for Methanol Oxidation Reaction
,” Appl. Catal., B
, 219
, pp. 511
–516
. 10.1016/j.apcatb.2017.08.01434.
Liu
, C.-S.
, Liu
, X.-C.
, Wang
, G.-C.
, Liang
, R.-P.
, and Qiu
, J.-D.
, 2014
, “Preparation of Nitrogen-Doped Graphene Supporting Pt Nanoparticles as a Catalyst for Oxygen Reduction and Methanol Oxidation
,” J. Electroanal. Chem.
, 728
, pp. 41
–50
. 10.1016/j.jelechem.2014.06.02435.
Huang
, H.
, Ye
, G.
, Yang
, S.
, Fei
, H.
, Tiwary
, C. S.
, Gong
, Y.
, Vajtai
, R.
, Tour
, J. M.
, Wang
, X.
, and Ajayan
, P. M.
, 2015
, “Nanosized Pt Anchored onto 3D Nitrogen-Doped Graphene Nanoribbons Towards Efficient Methanol Electrooxidation
,” J. Mater. Chem. A
, 3
(39
), pp. 19696
–19701
. 10.1039/C5TA05372B36.
Zhang
, J.
, Ma
, L.
, Gan
, M.
, Fu
, S.
, and Zhao
, Y.
, 2016
, “TiN@Nitrogen-Doped Carbon Supported Pt Nanoparticles as High-Performance Anode Catalyst for Methanol Electrooxidation
,” J. Power Sources
, 324
, pp. 199
–207
. 10.1016/j.jpowsour.2016.05.08337.
Zhang
, L.
, Gao
, A.
, Liu
, Y.
, Wang
, Y.
, and Ma
, J.
, 2014
, “PtRu Nanoparticles Dispersed on Nitrogen-Doped Carbon Nanohorns as an Efficient Electrocatalyst for Methanol Oxidation Reaction
,” Electrochim. Acta
, 132
, pp. 416
–422
. 10.1016/j.electacta.2014.03.18038.
Silva
, R.
, Voiry
, D.
, Chhowalla
, M.
, and Asefa
, T.
, 2013
, “Efficient Metal-Free Electrocatalysts for Oxygen Reduction: Polyaniline-Derived N- and O-Doped Mesoporous Carbons
,” J. Am. Chem. Soc.
, 135
(21
), pp. 7823
–7826
. 10.1021/ja402450a39.
Jiang
, Z.-Z.
, Wang
, Z.-B.
, Chu
, Y.-Y.
, Gu
, D.-M.
, and Yin
, G.-P.
, 2011
, “Carbon Riveted Microcapsule Pt/MWCNTs-TiO2 Catalyst Prepared by In Situ Carbonized Glucose With Ultrahigh Stability for Proton Exchange Membrane Fuel Cell
,” Energy Environ. Sci.
, 4
(7
), p. 2558
. 10.1039/c1ee01091c40.
Zhu
, T.
, Zhou
, J.
, Li
, Z.
, Li
, S.
, Si
, W.
, and Zhuo
, S.
, 2014
, “Hierarchical Porous and N-Doped Carbon Nanotubes Derived From Polyaniline for Electrode Materials in Supercapacitors
,” J. Mater. Chem. A
, 2
(31
), p. 12545
. 10.1039/C4TA01465K41.
Peng
, X.
, Chen
, D.
, Yang
, X.
, Wang
, D.
, Li
, M.
, Tseng
, C. C.
, Panneerselvam
, R.
, Wang
, X.
, Hu
, W.
, Tian
, J.
, and Zhao
, Y.
, 2016
, “Microwave-Assisted Synthesis of Highly Dispersed PtCu Nanoparticles on Three-Dimensional Nitrogen-Doped Graphene Networks With Remarkably Enhanced Methanol Electrooxidation
,” ACS Appl. Mater. Interfaces
, 8
(49
), pp. 33673
–33680
. 10.1021/acsami.6b1180042.
Bhuvanendran
, N.
, Ravichandran
, S.
, Zhang
, W.
, Ma
, Q.
, Xu
, Q.
, Khotseng
, L.
, and Su
, H.
, 2020
, “Highly Efficient Methanol Oxidation on Durable PtxIr/MWCNT Catalysts for Direct Methanol Fuel Cell Applications
,” Int. J. Hydrogen Energy
.10.1016/j.ijhydene.2019.12.17643.
Jin
, M.
, Lu
, S.-Y.
, Zhong
, X.
, Liu
, H.
, Liu
, H.
, Gan
, M.
, and Ma
, L.
, 2020
, “Spindle-Like MOF Derived TiO2@NC–NCNTs Composite With Modulating Defect Site and Graphitization Nanoconfined Pt NPs as Superior Bifunctional Fuel Cell Electrocatalysts
,” ACS Sustainable Chem. Eng
. 10.1021/acssuschemeng.9b0632944.
Bai
, G.
, Liu
, C.
, Gao
, Z.
, Lu
, B.
, Tong
, X.
, Guo
, X.
, and Yang
, N.
, 2019
, “Atomic Carbon Layers Supported Pt Nanoparticles for Minimized CO Poisoning and Maximized Methanol Oxidation
,” Small
, 15
(38
), p. e1902951
. 10.1002/smll.20190295145.
Long
, G.-f.
, Li
, X.-h.
, Wan
, K.
, Liang
, Z.-x.
, Piao
, J.-h.
, and Tsiakaras
, P.
, 2017
, “Pt/CN-Doped Electrocatalysts: Superior Electrocatalytic Activity for Methanol Oxidation Reaction and Mechanistic Insight into Interfacial Enhancement
,” Appl. Catal., B
, 203
, pp. 541
–548
. 10.1016/j.apcatb.2016.10.05546.
Sui
, X.-L.
, Wang
, Z.-B.
, Xia
, Y.-F.
, Yang
, M.
, Zhao
, L.
, and Gu
, D.-M.
, 2015
, “A Rapid Synthesis of TiO2 Nanotubes in an Ethylene Glycol System by Anodization as a Pt-Based Catalyst Support for Methanol Electrooxidation
,” RSC Adv.
, 5
(45
), pp. 35518
–35523
. 10.1039/C5RA04112K47.
Sui
, X.-L.
, Wang
, Z.-B.
, Li
, C.-Z.
, Zhang
, J.-J.
, Zhao
, L.
, Gu
, D.-M.
, and Gu
, S.
, 2015
, “Multiphase Sodium Titanate/Titania Composite Nanostructures as Pt-Based Catalyst Supports for Methanol Oxidation
,” J. Mater. Chem. A
, 3
(2
), pp. 840
–846
. 10.1039/C4TA05150E48.
Zhao
, L.
, Wang
, Z.-B.
, Li
, J.-L.
, Zhang
, J.-J.
, Sui
, X.-L.
, and Zhang
, L.-M.
, 2015
, “A Newly-Designed Sandwich-Structured Graphene-Pt-Graphene Catalyst With Improved Electrocatalytic Performance for Fuel Cells
,” J. Mater. Chem. A
, 3
(10
), pp. 5313
–5320
. 10.1039/C4TA06172A49.
Chen
, J.
, Li
, S.
, Du
, J.
, Liu
, J.
, Yu
, M.
, Meng
, S.
, and Wang
, B.
, 2015
, “Superior Methanol Electrooxidation Activity and CO Tolerance of Mesoporous Helical Nanospindle-Like CeO2 Modified Pt/C
,” RSC Adv.
, 5
(79
), pp. 64261
–64267
. 10.1039/C5RA09047D50.
Zhou
, Y.
, Hu
, X.-C.
, Fan
, Q.
, and Wen
, H.-R.
, 2016
, “Three-dimensional Crumpled Graphene as an Electro-Catalyst Support for Formic Acid Electro-Oxidation
,” J. Mater. Chem. A
, 4
(12
), pp. 4587
–4591
. 10.1039/C5TA09956K51.
Jiang
, Z.-Z.
, Wang
, Z.-B.
, Chu
, Y.-Y.
, Gu
, D.-M.
, and Yin
, G.-P.
, 2011
, “Ultrahigh Stable Carbon Riveted Pt/TiO2–C Catalyst Prepared by In Situ Carbonized Glucose for Proton Exchange Membrane Fuel Cell
,” Energy Environ. Sci.
, 4
(3
), pp. 728
–735
. 10.1039/C0EE00475H52.
Sheng
, J.
, Kang
, J.
, Ye
, H.
, Xie
, J.
, Zhao
, B.
, Fu
, X.-Z.
, Yu
, Y.
, Sun
, R.
, and Wong
, C.-P.
, 2018
, “Porous Octahedral PdCu Nanocages as Highly Efficient Electrocatalysts for the Methanol Oxidation Reaction
,” J. Mater. Chem. A
, 6
(9
), pp. 3906
–3912
. 10.1039/C7TA07879JCopyright © 2020 by ASME
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