PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO2 Shells for Methanol Oxidation

Sekar, Archana; Metzger, Nathaniel; Rajendran, Sabari; Elangovan, Ayyappan; Cao, Yonghai; Peng, Feng; Li, Xianglin; Li, Jun

doi:10.1021/acsanm.1c03742

PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO₂ Shells for Methanol Oxidation

Journal Article · Wed Jan 05 23:00:00 EST 2022 · ACS Applied Nano Materials

DOI:https://doi.org/10.1021/acsanm.1c03742· OSTI ID:1865176

^[1]; Metzger, Nathaniel ^[2]; Rajendran, Sabari ^[3]; ^[3]; ^[4]; ^[5]; ^[2]; ^[3]

Kansas State Univ., Manhattan, KS (United States); Kansas State University
Univ. of Kansas School of Engineering, Lawrence, KS (United States)
Kansas State Univ., Manhattan, KS (United States)
South China Univ. of Technology, Guangzhou (China)
Guangzhou Univ. (China)

The methanol oxidation reaction (MOR) is the limiting factor in direct methanol fuel cells (DMFC). There is an urgent need to improve the catalytic activity and stability of MOR catalysts. This study reports a highly active PtRu catalyst for MOR based on a hybrid multifunctional catalyst support consisting of a conformal amorphous hydrogenated TiO₂ shell wrapped around the oxygenated N-doped carbon nanotube core, denoted as PtRu/TiO₂/ ONCNT-400. Both the TiO₂ shell and the subsequent PtRu nanoparticles are deposited by a rapid microwave-assisted synthesis processes. The hydrogenated TiO₂ shell is found to exhibit a strong interaction with the deposited PtRu catalyst nanoparticles and effectively prevent them from agglomeration during the postdeposition thermal annealing to form more active crystalline PtRu alloy catalysts. In addition, the defective hydrogenated TiO₂ shell enhances the PtRu catalyst activity by the synergistic effects of partial charge transfer from TiO₂ to PtRu and high oxophilicity, which improves the kinetics of oxidation of poisonous CO intermediate to CO₂. The mass activity for MOR and long-cycling stability of the PtRu/TiO₂/ONCNT-400 catalyst surpass the two benchmark commercial PtRu/C catalysts from Johnson Matthey (JM) and Tanaka KiKinzoku (TKK), respectively. Furthermore, the results demonstrate that PtRu/TiO₂/ONCNT-400 can serve as an efficient catalyst for MOR in DMFC.

View Accepted Manuscript (DOE)

Research Organization:: Kansas State Univ., Manhattan, KS (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008440

OSTI ID:: 1865176

Alternate ID(s):: OSTI ID: 2568159

Journal Information:: ACS Applied Nano Materials, Journal Name: ACS Applied Nano Materials Journal Issue: 3 Vol. 5; ISSN 2574-0970

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (67)

Irrelevance of Carbon Monoxide Poisoning in the Methanol Oxidation Reaction on a PtRu Electrocatalyst Chen, De-Jun; Tong, YuYe J. Angewandte Chemie International Edition, Vol. 54, Issue 32 https://doi.org/10.1002/anie.201503917	journal	July 2015
Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts Garg, Aaron; Milina, Maria; Ball, Madelyn Angewandte Chemie International Edition, Vol. 56, Issue 30 https://doi.org/10.1002/anie.201704632	journal	June 2017
Enhancing Methanol Oxidation Reaction with Platinum‐based Catalysts using a N‐Doped Three‐dimensional Graphitic Carbon Support Elangovan, Ayyappan; Xu, Jiayi; Sekar, Archana ChemCatChem, Vol. 12, Issue 23 https://doi.org/10.1002/cctc.202001162	journal	September 2020
Highly Enhanced Methanol Electrooxidation on Pt/N−CNT‐Decorated FeP** Liu, Dongqin; Yang, Guangxing; Zhang, Qiao ChemElectroChem, Vol. 8, Issue 13 https://doi.org/10.1002/celc.202100314	journal	May 2021
Supported Noble Metals on Hydrogen-Treated TiO ₂ Nanotube Arrays as Highly Ordered Electrodes for Fuel Cells Zhang, Changkun; Yu, Hongmei; Li, Yongkun ChemSusChem, Vol. 6, Issue 4 https://doi.org/10.1002/cssc.201200828	journal	February 2013
Intrinsic Effect of Carbon Supports on the Activity and Stability of Precious Metal Based Catalysts for Electrocatalytic Alcohol Oxidation in Fuel Cells: A Review Zhang, Jin; Lu, Shanfu; Xiang, Yan ChemSusChem, Vol. 13, Issue 10 https://doi.org/10.1002/cssc.202000048	journal	April 2020
Microwave-Assisted Synthesis of Metallic Nanomaterials in Liquid Phase Tsuji, Masaharu ChemistrySelect, Vol. 2, Issue 2 https://doi.org/10.1002/slct.201700011	journal	January 2017
Carbon-Coated Anatase TiO2 Nanocomposite as a High-Performance Electrocatalyst Support Shanmugam, Sangaraju; Gedanken, Aharon Small, Vol. 3, Issue 7 https://doi.org/10.1002/smll.200600636	journal	July 2007
Structure and Chemical Composition of a Supported Pt-Ru Electrocatalyst for Methanol Oxidation Radmilovic, V.; Gasteiger, H. A.; Ross, P. N. Journal of Catalysis, Vol. 154, Issue 1 https://doi.org/10.1006/jcat.1995.1151	journal	June 1995
Investigation of Pt–Ru nanoparticle catalysts for low temperature methanol electro-oxidation Garcia, G.; Baglio, V.; Stassi, A. Journal of Solid State Electrochemistry, Vol. 11, Issue 9 https://doi.org/10.1007/s10008-007-0274-8	journal	February 2007
Synthesis of Nanowire TiO2 Thin Films by Hydrothermal Treatment and their Photoelectrochemical Properties Kitano, Masaaki; Mitsui, Ryo; Eddy, Diana Rakhmawaty Catalysis Letters, Vol. 119, Issue 3-4 https://doi.org/10.1007/s10562-007-9243-1	journal	September 2007
Nanoparticulate TiO2-promoted PtRu/C catalyst for methanol oxidation: TiO2 nanoparticles promoted PtRu/C catalyst for MOR Wang, Wei; Wang, Hui; Key, Julian Ionics, Vol. 19, Issue 3 https://doi.org/10.1007/s11581-012-0773-1	journal	August 2012
TiO2 thin film deposition from solution using microwave heating Vigil, Elena; Saadoun, Lahcen; Ayllón, José A. Thin Solid Films, Vol. 365, Issue 1 https://doi.org/10.1016/S0040-6090(99)00946-3	journal	April 2000
Formation of carbon supported PtRu alloys: an XRD analysis Antolini, E.; Cardellini, F. Journal of Alloys and Compounds, Vol. 315, Issue 1-2 https://doi.org/10.1016/S0925-8388(00)01260-3	journal	February 2001
Synthesis of TiO2 photocatalyst thin film by solvothermal method with a small amount of water and its photocatalytic performance Lee, Sang-Hyeun; Kang, Misook; Cho, Sung M. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 146, Issue 1-2 https://doi.org/10.1016/S1010-6030(01)00553-6	journal	December 2001
Electrocatalytic activity and stability of niobium-doped titanium oxide supported platinum catalyst for polymer electrolyte membrane fuel cells Huang, Sheng-Yang; Ganesan, Prabhu; Popov, Branko N. Applied Catalysis B: Environmental, Vol. 96, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.02.025	journal	April 2010
Surface Ru enriched structurally ordered intermetallic PtFe@PtRuFe core-shell nanostructure boosts methanol oxidation reaction catalysis Wang, Qingmei; Chen, Siguo; Li, Pan Applied Catalysis B: Environmental, Vol. 252 https://doi.org/10.1016/j.apcatb.2019.04.023	journal	September 2019
Tuning Pt-skinned PtAg nanotubes in nanoscales to efficiently modify electronic structure for boosting performance of methanol electrooxidation Ouyang, Yirui; Cao, Haijie; Wu, Huijie Applied Catalysis B: Environmental, Vol. 265 https://doi.org/10.1016/j.apcatb.2020.118606	journal	May 2020
Engineering three-dimensional nitrogen-doped carbon black embedding nitrogen-doped graphene anchoring ultrafine surface-clean Pd nanoparticles as efficient ethanol oxidation electrocatalyst Li, Shuwen; Shu, Junhao; Ma, Sizhuo Applied Catalysis B: Environmental, Vol. 280 https://doi.org/10.1016/j.apcatb.2020.119464	journal	January 2021
Sub-stoichiometric titanium oxide-supported platinum electrocatalyst for polymer electrolyte fuel cells Ioroi, Tsutomu; Siroma, Zyun; Fujiwara, Naoko Electrochemistry Communications, Vol. 7, Issue 2 https://doi.org/10.1016/j.elecom.2004.12.007	journal	February 2005
3-D composite electrodes for high performance PEM fuel cells composed of Pt supported on nitrogen-doped carbon nanotubes grown on carbon paper Saha, Madhu Sudan; Li, Ruying; Sun, Xueliang Electrochemistry Communications, Vol. 11, Issue 2 https://doi.org/10.1016/j.elecom.2008.12.013	journal	February 2009
Preparation and characterization of a PtRu/C nanocatalyst for direct methanol fuel cells Guo, J. W.; Zhao, T. S.; Prabhuram, J. Electrochimica Acta, Vol. 51, Issue 4 https://doi.org/10.1016/j.electacta.2005.05.056	journal	November 2005
PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation Chetty, Raghuram; Kundu, Shankhamala; Xia, Wei Electrochimica Acta, Vol. 54, Issue 17 https://doi.org/10.1016/j.electacta.2009.02.073	journal	July 2009
Supported bimetallic nanoparticles as anode catalysts for direct methanol fuel cells: A review Kaur, Akaljot; Kaur, Gagandeep; Singh, Prit Pal International Journal of Hydrogen Energy, Vol. 46, Issue 29 https://doi.org/10.1016/j.ijhydene.2021.02.037	journal	April 2021
Studies on the electrocatalytic properties of PtRu/C-TiO2 toward the oxidation of methanol Wang, Zhenyao; Chen, Ge; Xia, Dingguo Journal of Alloys and Compounds, Vol. 450, Issue 1-2 https://doi.org/10.1016/j.jallcom.2006.10.158	journal	February 2008
Electron transfer dependent catalysis of Pt on N-doped carbon nanotubes: Effects of synthesis method on metal-support interaction Ning, Xiaomei; Li, Yuhang; Dong, Baoqiang Journal of Catalysis, Vol. 348 https://doi.org/10.1016/j.jcat.2017.02.011	journal	April 2017
Enhanced methanol oxidation activity and stability of Pt particles anchored on carbon-doped TiO2 nanocoating support Qin, Yuan-Hang; Li, Yunfeng; Lv, Ren-Liang Journal of Power Sources, Vol. 278 https://doi.org/10.1016/j.jpowsour.2014.12.096	journal	March 2015
Essential analysis of cyclic voltammetry of methanol electrooxidation using the differential electrochemical mass spectrometry Lai, Lihua; Yang, Guangxing; Zhang, Qiao Journal of Power Sources, Vol. 509 https://doi.org/10.1016/j.jpowsour.2021.230397	journal	October 2021
Effect of oxygen based functional groups on the nucleation of TiO2 by atomic layer deposition: A theoretical and experimental study Borbón-Nuñez, H. A.; Muñiz, J.; El Hachimi, A. G. Materials Chemistry and Physics, Vol. 267 https://doi.org/10.1016/j.matchemphys.2021.124588	journal	July 2021
Structural Evolution from Metal–Organic Framework to Hybrids of Nitrogen-Doped Porous Carbon and Carbon Nanotubes for Enhanced Oxygen Reduction Activity Zhang, Linjie; Wang, Xiuyun; Wang, Ruihu Chemistry of Materials, Vol. 27, Issue 22 https://doi.org/10.1021/acs.chemmater.5b02708	journal	November 2015
Methanol Electro-Oxidation on the Pt Surface: Revisiting the Cyclic Voltammetry Interpretation Chung, Dong Young; Lee, Kyung-Jae; Sung, Yung-Eun The Journal of Physical Chemistry C, Vol. 120, Issue 17 https://doi.org/10.1021/acs.jpcc.5b12303	journal	April 2016
Characterization of Electronic Transport through Amorphous TiO ₂ Produced by Atomic Layer Deposition Nunez, Paul; Richter, Matthias H.; Piercy, Brandon D. The Journal of Physical Chemistry C, Vol. 123, Issue 33 https://doi.org/10.1021/acs.jpcc.9b04434	journal	June 2019
Enhanced Performance of Oxygen-Functionalized Multiwalled Carbon Nanotubes as Support for Pt and Pt–Ru Bimetallic Catalysts for Methanol Electrooxidation Xiong, Wen; Mehrabadi, Bahareh A. T.; Karakolos, Stavros G. ACS Applied Energy Materials, Vol. 3, Issue 6 https://doi.org/10.1021/acsaem.0c00477	journal	May 2020
Self-Doping Surface Oxygen Vacancy-Induced Lattice Strains for Enhancing Visible Light-Driven Photocatalytic H ₂ Evolution over Black TiO ₂ Gao, Jiaqi; Xue, Jinbo; Jia, Shufang ACS Applied Materials & Interfaces, Vol. 13, Issue 16 https://doi.org/10.1021/acsami.1c01101	journal	April 2021
In Situ Tuning of Defects and Phase Transition in Titanium Dioxide by Lithiothermic Reduction Wang, Chao; Yang, Jingjing; Li, Taozhu ACS Applied Materials & Interfaces, Vol. 12, Issue 5 https://doi.org/10.1021/acsami.9b18359	journal	January 2020
Palladium Nanoparticles Anchored on Three-Dimensional Nitrogen-Doped Carbon Nanotubes as a Robust Electrocatalyst for Ethanol Oxidation Yang, Honglei; Zhang, Xueyao; Zou, Hai ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 6 https://doi.org/10.1021/acssuschemeng.8b01157	journal	May 2018
Development of a Titanium Dioxide-Supported Platinum Catalyst with Ultrahigh Stability for Polymer Electrolyte Membrane Fuel Cell Applications Huang, Sheng-Yang; Ganesan, Prabhu; Park, Sehkyu Journal of the American Chemical Society, Vol. 131, Issue 39 https://doi.org/10.1021/ja904810h	journal	October 2009
Nitrogen Doping Effects on Carbon Nanotubes and the Origin of the Enhanced Electrocatalytic Activity of Supported Pt for Proton-Exchange Membrane Fuel Cells Chen, Yougui; Wang, Jiajun; Liu, Hao The Journal of Physical Chemistry C, Vol. 115, Issue 9 https://doi.org/10.1021/jp108864y	journal	February 2011
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
The Scherrer equation versus the 'Debye-Scherrer equation' Holzwarth, Uwe; Gibson, Neil Nature Nanotechnology, Vol. 6, Issue 9 https://doi.org/10.1038/nnano.2011.145	journal	August 2011
Microwave-assisted Low-temperature Growth of Thin Films in Solution Reeja-Jayan, B.; Harrison, Katharine L.; Yang, K. Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep01003	journal	December 2012
Ultrahigh stable carbon riveted Pt/TiO ₂ –C catalyst prepared by in situ carbonized glucose for proton exchange membrane fuel cell Jiang, Zheng-Zhi; Wang, Zhen-Bo; Chu, Yuan-Yuan Energy Environ. Sci., Vol. 4, Issue 3 https://doi.org/10.1039/C0EE00475H	journal	January 2011
An overview of metal oxide materials as electrocatalysts and supports for polymer electrolyte fuel cells Zhang, Zhonghua; Liu, Jie; Gu, Junjie Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C3EE43886D	journal	January 2014
Oxygen vacancy and hole conduction in amorphous TiO ₂ Pham, Hieu H.; Wang, Lin-Wang Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP04209C	journal	January 2015
Synthesis and characterization of mixed phase anatase TiO ₂ and sodium-doped TiO ₂ (B) thin films by low pressure chemical vapour deposition (LPCVD) Chimupala, Yothin; Hyett, Geoffrey; Simpson, Robert RSC Adv., Vol. 4, Issue 89 https://doi.org/10.1039/C4RA07570F	journal	January 2014
Very low amount of TiO ₂ on N-doped carbon nanotubes significantly improves oxygen reduction activity and stability of supported Pt nanoparticles Zhao, Anqi; Masa, Justus; Xia, Wei Physical Chemistry Chemical Physics, Vol. 17, Issue 16 https://doi.org/10.1039/C5CP00369E	journal	January 2015
SnO ₂ nanocrystal-decorated mesoporous ZSM-5 as a precious metal-free electrode catalyst for methanol oxidation Cui, Xiangzhi; Zhu, Yan; Hua, Zile Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C5EE00240K	journal	January 2015
Rational syntheses of core–shell Fe@(PtRu) nanoparticle electrocatalysts for the methanol oxidation reaction with complete suppression of CO-poisoning and highly enhanced activity Matin, Md. Abdul; Lee, Eunjik; Kim, Hyunchul Journal of Materials Chemistry A, Vol. 3, Issue 33 https://doi.org/10.1039/C5TA03809J	journal	January 2015
Surface stoichiometry of ‘titanium suboxide’ Part IVolumetric and FTIR study Haerudin, Hery; Bertel, Stephan; Kramer, Reinhard Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 10 https://doi.org/10.1039/a707714i	journal	January 1998
Stoichiometry of “titanium suboxide” Eder, Dominik; Kramer, Reinhard Physical Chemistry Chemical Physics, Vol. 5, Issue 6 https://doi.org/10.1039/b210004e	journal	February 2003
The formation of nitrogen-containing functional groups on carbon nanotube surfaces: a quantitative XPS and TPD study Kundu, Shankhamala; Xia, Wei; Busser, Wilma Physical Chemistry Chemical Physics, Vol. 12, Issue 17 https://doi.org/10.1039/b923651a	journal	January 2010
Hydrogenated titania: synergy of surface modification and morphology improvement for enhanced photocatalytic activity Zheng, Zhaoke; Huang, Baibiao; Lu, Jibao Chemical Communications, Vol. 48, Issue 46 https://doi.org/10.1039/c2cc32220j	journal	January 2012
Origin of the current peak of negative scan in the cyclic voltammetry of methanol electro-oxidation on Pt-based electrocatalysts: a revisit to the current ratio criterion Hofstead-Duffy, Augusta M.; Chen, De-Jun; Sun, Shi-Gang Journal of Materials Chemistry, Vol. 22, Issue 11 https://doi.org/10.1039/c2jm15426a	journal	January 2012
Increasing Pt oxygen reduction reaction activity and durability with a carbon-doped TiO2 nanocoating catalyst support Huang, Kan; Sasaki, Kotaro; Adzic, Radoslav R. Journal of Materials Chemistry, Vol. 22, Issue 33 https://doi.org/10.1039/c2jm32234j	journal	January 2012
Revealing the enhanced catalytic activity of nitrogen-doped carbon nanotubes for oxidative dehydrogenation of propane Chen, Chunlin; Zhang, Jian; Zhang, Bingsen Chemical Communications, Vol. 49, Issue 74 https://doi.org/10.1039/c3cc41500g	journal	January 2013
Black anatase titania enabling ultra high cycling rates for rechargeable lithium batteries Myung, Seung-Taek; Kikuchi, Masaru; Yoon, Chong Seung Energy & Environmental Science, Vol. 6, Issue 9 https://doi.org/10.1039/c3ee41960f	journal	January 2013
Methanol oxidation in acid on ordered NiTi Mancharan, Ramasamy; Goodenough, John B. Journal of Materials Chemistry, Vol. 2, Issue 8 https://doi.org/10.1039/jm9920200875	journal	January 1992
Hydrogenation and hydrogen diffusion at the anatase TiO ₂ (101) surface Nagatsuka, Naoki; Wilde, Markus; Fukutani, Katsuyuki The Journal of Chemical Physics, Vol. 152, Issue 7 https://doi.org/10.1063/1.5142776	journal	February 2020
Homogenous decoration of Pt and PtSn alloy nanoparticles onto multi-walled carbon nanotubes Zhu, Hongliang; Chen, Jing; Li, Xue Materials Research Express, Vol. 6, Issue 11 https://doi.org/10.1088/2053-1591/ab44e4	journal	September 2019
Electrical Properties of Some Titanium Oxides Bartholomew, Robert F.; Frankl, D. R. Physical Review, Vol. 187, Issue 3 https://doi.org/10.1103/PhysRev.187.828	journal	November 1969
A selective electrocatalyst–based direct methanol fuel cell operated at high concentrations of methanol Feng, Yan; Liu, Hui; Yang, Jun Science Advances, Vol. 3, Issue 6 https://doi.org/10.1126/sciadv.1700580	journal	June 2017
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals Chen, X.; Liu, L.; Yu, P. Y. Science, Vol. 331, Issue 6018 https://doi.org/10.1126/science.1200448	journal	January 2011
Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation Hu, S.; Shaner, M. R.; Beardslee, J. A. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1251428	journal	May 2014
The Impact of Carbon Stability on PEM Fuel Cell Startup and Shutdown Voltage Degradation Yu, Paul T.; Gu, Wenbin; Makharia, Rohit 210th ECS Meeting, ECS Transactions https://doi.org/10.1149/1.2356199	conference	January 2006
Stability of Corrosion-Resistant Magnéli-Phase Ti[sub 4]O[sub 7]-Supported PEMFC Catalysts at High Potentials Ioroi, Tsutomu; Senoh, Hiroshi; Yamazaki, Shin-ichi Journal of The Electrochemical Society, Vol. 155, Issue 4 https://doi.org/10.1149/1.2833310	journal	January 2008
Effects of Cathode Inlet Relative Humidity on PEMFC Durability during Startup–Shutdown Cycling Kim, Jae Hong; Cho, Eun Ae; Jang, Jong Hyun Journal of The Electrochemical Society, Vol. 157, Issue 1 https://doi.org/10.1149/1.3254170	journal	January 2010
Effect of nitrogen atomic percentage on N+-bombarded MWCNTs in cytocompatibility and hemocompatibility Zhao, Mengli; Cao, Ye; Liu, Xiaoqi Nanoscale Research Letters, Vol. 9, Issue 1 https://doi.org/10.1186/1556-276X-9-142	journal	March 2014

Similar Records

Related Subjects

36 MATERIALS SCIENCE
CO oxidation
PtRu nanoparticles
catalysts
deposition
hydrogenated TiO2
methanol oxidation reaction (MOR)
microwave synthesis
oxidation
oxides
platinum
strong metal−support interaction (SMSI)
ultrathin shell

PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO2 Shells for Methanol Oxidation

Citation Formats

References (67)

Similar Records

Related Subjects

PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO₂ Shells for Methanol Oxidation