Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Wei, Kecheng; Lin, Honghong; Zhao, Xueru; Zhao, Zhonglong; Marinkovic, Nebojsa; Morales, Michael; Huang, Zhennan; Perlmutter, Laura; Guan, Huanqin; Harris, Cooro; Chi, Miaofang; Lu, Gang; Sasaki, Kotaro; Sun, Shouheng

doi:10.1021/jacs.3c07027

Title: Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Journal Article · 22 August 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c07027 · OSTI ID:2005159

Wei, Kecheng ^[1];

^[1]; Zhao, Xueru ^[2];

^[3];

^[4]; Morales, Michael ^[1]; Huang, Zhennan ^[5]; Perlmutter, Laura ^[1];

^[1]; Harris, Cooro ^[1];

^[5];

^[6];

^[2];

^[1]

Brown Univ., Providence, RI (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Inner Mongolia Univ., Hohhot (China)
Columbia Univ., New York, NY (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
California State University, Northridge (CSUN), CA (United States)

Efficient C–C bond cleavage and oxidation of alcohols to CO₂ is the key to developing highly efficient alcohol fuel cells for renewable energy applications. In this work, we report the synthesis of core/shell Au/Pt nanowires (NWs) with stepped Pt clusters deposited along the ultrathin (2.3 nm) stepped Au NWs as an active catalyst to effectively oxidize alcohols to CO₂. The catalytic oxidation reaction is dependent on the Au/Pt ratios, and the Au_1.0/Pt_0.2 NWs have the largest percentage (~75%) of stepped Au/Pt sites and show the highest activity for ethanol electro-oxidation, reaching an unprecedented 196.9 A/mg_Pt (32.5 A/mg_Pt+Au). This NW catalyst is also active in catalyzing the oxidation of other primary alcohols, such as methanol, n-propanol, and ethylene glycol. In situ X-ray absorption spectroscopy and infrared spectroscopy are used to characterize the catalyst structure and to identify key reaction intermediates, providing concrete evidence that the synergy between the low-coordinated Pt sites and the stepped Au NWs is essential to catalyze the alcohol oxidation reaction, which is further supported by DFT calculations that the C–C bond cleavage is indeed enhanced on the undercoordinated Pt–Au surface. Here, our study provides important evidence that a core/shell structure with stepped core/shell sites is essential to enhance electrochemical oxidation of alcohols and will also be central to understanding electro-oxidation reactions and to the future development of highly efficient direct alcohol fuel cells for renewable energy applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2005159

Report Number(s):: BNL--224823-2023-JAAM; GRP-COSC--4

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 34 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (45)

Promoting Effect of Ni(OH) ₂ on Palladium Nanocrystals Leads to Greatly Improved Operation Durability for Electrocatalytic Ethanol Oxidation in Alkaline Solution Huang, Wenjing; Ma, Xian-Yin; Wang, Han Advanced Materials, Vol. 29, Issue 37 https://doi.org/10.1002/adma.201703057	journal	August 2017
Porous Trimetallic PtRhCu Cubic Nanoboxes for Ethanol Electrooxidation Han, Shu-He; Liu, Hui-Min; Chen, Pei Advanced Energy Materials, Vol. 8, Issue 24 https://doi.org/10.1002/aenm.201801326	journal	June 2018
Origin of Low CO2 Selectivity on Platinum in the Direct Ethanol Fuel Cell Kavanagh, Richard; Cao, Xiao-Ming; Lin, Wen-Feng Angewandte Chemie International Edition, Vol. 51, Issue 7 https://doi.org/10.1002/anie.201104990	journal	January 2012
Pt3Ag alloy wavy nanowires as highly effective electrocatalysts for ethanol oxidation reaction Fu, Xiaoyang; Wan, Chengzhang; Zhang, Aixin Nano Research, Vol. 13, Issue 5 https://doi.org/10.1007/s12274-020-2754-4	journal	April 2020
On the mechanism of ethanol electro-oxidation on Pt and PtSn catalysts: electrochemical and in situ IR reflectance spectroscopy studies Vigier, F.; Coutanceau, C.; Hahn, F. Journal of Electroanalytical Chemistry, Vol. 563, Issue 1 https://doi.org/10.1016/J.JELECHEM.2003.08.019	journal	February 2004
Theoretical surface science and catalysis—calculations and concepts Hammer, B.; Nørskov, J. K. Impact of Surface Science on Catalysis, p. 71-129 https://doi.org/10.1016/S0360-0564(02)45013-4	book	January 2000
Effects of electrolyte pH and composition on the ethanol electro-oxidation reaction Lai, Stanley C. S.; Kleijn, Steven E. F.; Öztürk, Fatma T. Z. Catalysis Today, Vol. 154, Issue 1-2 https://doi.org/10.1016/j.cattod.2010.01.060	journal	September 2010
Electrooxidation of ethanol on a Pt electrode in acid solutions: in situ ATR-SEIRAS study Shao, M. H.; Adzic, R. R. Electrochimica Acta, Vol. 50, Issue 12 https://doi.org/10.1016/j.electacta.2004.10.063	journal	April 2005
In situ FTIR spectroscopic studies of electrooxidation of ethanol on Pd electrode in alkaline media Zhou, Zhi-You; Wang, Qiang; Lin, Jian-Long Electrochimica Acta, Vol. 55, Issue 27 https://doi.org/10.1016/j.electacta.2010.02.071	journal	November 2010
Supported PtAu catalysts with different nano-structures for ethanol electrooxidation Zhou, Weijiang; Li, Miao; Zhang, Lan Electrochimica Acta, Vol. 123 https://doi.org/10.1016/j.electacta.2013.12.153	journal	March 2014
Catalysts in direct ethanol fuel cell (DEFC): An overview Akhairi, M. A. F.; Kamarudin, S. K. International Journal of Hydrogen Energy, Vol. 41, Issue 7 https://doi.org/10.1016/j.ijhydene.2015.12.145	journal	February 2016
An in-situ electrochemical IR investigation of solution CO electro-oxidation on a polycrystalline Au surface in an alkaline electrolyte: Identification of active reaction intermediates Chen, De-Jun; Tong, YuYe J. Journal of Electroanalytical Chemistry, Vol. 800 https://doi.org/10.1016/j.jelechem.2017.04.045	journal	September 2017
Formic acid oxidation on Pt–Au nanoparticles: Relation between the catalyst activity and the poisoning rate Obradović, M. D.; Rogan, J. R.; Babić, B. M. Journal of Power Sources, Vol. 197 https://doi.org/10.1016/j.jpowsour.2011.09.043	journal	January 2012
Sensitivity and Reproducibility in Infrared Spectroscopic Measurements at Single-Crystal Electrode Surfaces Faguy, Peter W.; Marinkovic, Nebojsa S. Analytical Chemistry, Vol. 67, Issue 17 https://doi.org/10.1021/ac00113a012	journal	September 1995
PdAu Alloy Nanoparticles for Ethanol Oxidation in Alkaline Conditions: Enhanced Activity and C1 Pathway Selectivity Lin, Honghong; Muzzio, Michelle; Wei, Kecheng ACS Applied Energy Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsaem.9b01674	journal	October 2019
Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S. ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01862	journal	December 2015
Selective Surface Engineering of Heterogeneous Nanostructures: In Situ Unraveling of the Catalytic Mechanism on Pt–Au Catalyst Kong, Fanpeng; Du, Chunyu; Ye, Jinyu ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b01901	journal	October 2017
Electro-Oxidation of Ethanol Using Pt ₃ Sn Alloy Nanoparticles Liu, Yifan; Wei, Miaojin; Raciti, David ACS Catalysis, Vol. 8, Issue 11 https://doi.org/10.1021/acscatal.8b03763	journal	September 2018
Subnanometer PtRh Nanowire with Alleviated Poisoning Effect and Enhanced C–C Bond Cleavage for Ethanol Oxidation Electrocatalysis Zhu, Yiming; Bu, Lingzheng; Shao, Qi ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01375	journal	June 2019
Composition-Graded Cu–Pd Nanospheres with Ir-Doped Surfaces on N-Doped Porous Graphene for Highly Efficient Ethanol Electro-Oxidation in Alkaline Media Luo, Liuxuan; Fu, Cehuang; Yang, Fan ACS Catalysis, Vol. 10, Issue 2 https://doi.org/10.1021/acscatal.9b05292	journal	December 2019
Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C–C Bond Li, Meng; Cullen, David A.; Sasaki, Kotaro Journal of the American Chemical Society, Vol. 135, Issue 1 https://doi.org/10.1021/ja306384x	journal	December 2012
Active and Selective Conversion of CO ₂ to CO on Ultrathin Au Nanowires Zhu, Wenlei; Zhang, Yin-Jia; Zhang, Hongyi Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja5095099	journal	November 2014
Comprehensive Mechanism and Structure-Sensitivity of Ethanol Oxidation on Platinum: New Transition-State Searching Method for Resolving the Complex Reaction Network Wang, Hui-Fang; Liu, Zhi-Pan Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja801648h	journal	August 2008
Direct 12-Electron Oxidation of Ethanol on a Ternary Au(core)-PtIr(Shell) Electrocatalyst Liang, Zhixiu; Song, Liang; Deng, Shiqing Journal of the American Chemical Society, Vol. 141, Issue 24 https://doi.org/10.1021/jacs.9b03474	journal	April 2019
Determination of O and OH Adsorption Sites and Coverage in Situ on Pt Electrodes from Pt L ₂₃ X-ray Absorption Spectroscopy Teliska, M.; O'Grady, W. E.; Ramaker, D. E. The Journal of Physical Chemistry B, Vol. 109, Issue 16 https://doi.org/10.1021/jp0502003	journal	April 2005
Investigation into the Competitive and Site-Specific Nature of Anion Adsorption on Pt Using In Situ X-ray Absorption Spectroscopy Arruda, Thomas M.; Shyam, Badri; Ziegelbauer, Joseph M. The Journal of Physical Chemistry C, Vol. 112, Issue 46 https://doi.org/10.1021/jp8067359	journal	October 2008
Ethanol Oxidation on Carbon-Supported Pt, PtRu, and PtSn Catalysts Studied by Operando X-ray Absorption Spectroscopy Melke, Julia; Schoekel, Alexander; Dixon, Ditty The Journal of Physical Chemistry C, Vol. 114, Issue 13 https://doi.org/10.1021/jp909342w	journal	March 2010
Electrochemical Reactivity of Ethanol on Porous Pt and PtRu: Oxidation/Reduction Reactions in 1 M HClO ₄ Schmidt, Volkmar M.; Ianniello, Remo; Pastor, Elena The Journal of Physical Chemistry, Vol. 100, Issue 45 https://doi.org/10.1021/jp9617027	journal	January 1996
Effects of Surface Step Density on the Electrochemical Oxidation of Ethanol to Acetic Acid Tarnowski, David J.; Korzeniewski, Carol The Journal of Physical Chemistry B, Vol. 101, Issue 2 https://doi.org/10.1021/jp962450c	journal	January 1997
Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols Li, Meng; Liu, Ping; Adzic, Radoslav R. The Journal of Physical Chemistry Letters, Vol. 3, Issue 23 https://doi.org/10.1021/jz3016155	journal	November 2012
Ternary Pt/Rh/SnO₂ electrocatalysts for oxidizing ethanol to CO₂ Kowal, A.; Li, M.; Shao, M. Nature Materials, Vol. 8, Issue 4, p. 325-330 https://doi.org/10.1038/NMAT2359	journal	January 2009
Ethanol electrooxidation onto stepped surfaces modified by Ru deposition: electrochemical and spectroscopic studies Del Colle, V.; Berná, A.; Tremiliosi-Filho, G. Physical Chemistry Chemical Physics, Vol. 10, Issue 25 https://doi.org/10.1039/B802683A	journal	January 2008
The atomic AXAFS and Δμ XANES techniques as applied to heterogeneous catalysis and electrocatalysis Ramaker, D. E.; Koningsberger, D. C. Physical Chemistry Chemical Physics, Vol. 12, Issue 21 https://doi.org/10.1039/B927120C	journal	January 2010
Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media Spendelow, Jacob S.; Wieckowski, Andrzej Physical Chemistry Chemical Physics, Vol. 9, Issue 21 https://doi.org/10.1039/b703315j	journal	January 2007
The role of the steps in the cleavage of the C–C bond during ethanol oxidation on platinum electrodes Colmati, Flavio; Tremiliosi-Filho, Germano; Gonzalez, Ernesto R. Physical Chemistry Chemical Physics, Vol. 11, Issue 40 https://doi.org/10.1039/b907250k	journal	January 2009
A straightforward implementation of in situ solution electrochemical ¹³ C NMR spectroscopy for studying reactions on commercial electrocatalysts: ethanol oxidation Huang, L.; Sorte, E. G.; Sun, S. -G. Chemical Communications, Vol. 51, Issue 38 https://doi.org/10.1039/c5cc00862j	journal	January 2015
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
Decomposition pathways of methanol on the PtAu(111) bimetallic surface: A first-principles study Yuan, Dingwang; Gong, Xingao; Wu, Ruqian The Journal of Chemical Physics, Vol. 128, Issue 6 https://doi.org/10.1063/1.2835545	journal	February 2008
Well-to-wheels energy use and greenhouse gas emissions of ethanol from corn, sugarcane and cellulosic biomass for US use Wang, Michael; Han, Jeongwoo; Dunn, Jennifer B. Environmental Research Letters, Vol. 7, Issue 4 https://doi.org/10.1088/1748-9326/7/4/045905	journal	December 2012
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
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
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Effect of Strain on the Reactivity of Metal Surfaces Mavrikakis, M.; Hammer, B.; Nørskov, J. K. Physical Review Letters, Vol. 81, Issue 13 https://doi.org/10.1103/PhysRevLett.81.2819	journal	September 1998
Recent Advances on Electro-Oxidation of Ethanol on Pt- and Pd-Based Catalysts: From Reaction Mechanisms to Catalytic Materials Wang, Ye; Zou, Shouzhong; Cai, Wen-Bin Catalysts, Vol. 5, Issue 3 https://doi.org/10.3390/catal5031507	journal	September 2015

Similar Records

Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

Journal Article · 2016 · Journal of the American Chemical Society · OSTI ID:1329805

Hu, J.; Wu, L.; Kuttiyiel, K.; +7 more

Ternary CoPtAu Nanoparticles as a General Catalyst for Highly Efficient Electro‐oxidation of Liquid Fuels

Journal Article · 2019 · Angewandte Chemie (International Edition) · OSTI ID:1547604

Li, Junrui; Jilani, Safia Z.; Lin, Honghong; +8 more

Ternary CoPtAu Nanoparticles as a General Catalyst for Highly Efficient Electro‐oxidation of Liquid Fuels

Journal Article · 2019 · Angewandte Chemie · OSTI ID:1546814

Li, Junrui; Jilani, Safia Z.; Lin, Honghong; +8 more

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
DFT calculations
alcohol oxidation reaction
bimetallic nanowires
carbon-carbon bond cleavage
catalysts
electro-oxidation
ethanol
gold
in situ spectroscopy
low-coordination surface
oxidation
platinum

Title: Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C–C Cleavage in C2+ Alcohol Electro-oxidation Reactions

Citation Formats

References (45)

Similar Records

Related Subjects