Phosphorous incorporation in Pd2Sn alloys for electrocatalytic ethanol oxidation

Yu，Xiaoting1,2; Liu，Junfeng3; Li，Junshan4; Luo，Zhishan5,6; Zuo，Yong1,2; Xing，Congcong1,7; Llorca，Jordi7; Nasiou，Déspina8; Arbiol，Jordi8,9; Pan，Kai10; Kleinhanns，Tobias11; Xie，Ying10; Cabot，Andreu1,9

2020-11-01

10.1016/j.nanoen.2020.105116

Nano Energy   影响因子和分区

2211-2855

2211-3282

Direct ethanol fuel cells (DEFCs) show a huge potential to power future electric vehicles and portable electronics, but their deployment is currently limited by the unavailability of proper electrocatalysis for the ethanol oxidation reaction (EOR). In this work, we engineer a new electrocatalyst by incorporating phosphorous into a palladium-tin alloy and demonstrate a significant performance improvement toward EOR. We first detail a synthetic method to produce PdSn:P nanocrystals that incorporate 35% of phosphorus. These nanoparticles are supported on carbon black and tested for EOR. PdSn:P/C catalysts exhibit mass current densities up to 5.03 A mg, well above those of PdSn/C, PdP/C and Pd/C reference catalysts. Furthermore, a twofold lower Tafel slope and a much longer durability are revealed for the PdSn:P/C catalyst compared with Pd/C. The performance improvement is rationalized with the aid of density functional theory (DFT) calculations considering different phosphorous chemical environments. Depending on its oxidation state, surface phosphorus introduces sites with low energy OH adsorption and/or strongly influences the electronic structure of palladium and tin to facilitate the oxidation of the acetyl to acetic acid, which is considered the EOR rate limiting step. DFT calculations also points out that the durability improvement of PdSn:P/C catalyst is associated to the promotion of OH adsorption that accelerates the oxidation of intermediate poisoning CO, reactivating the catalyst surface.

Electrocatalysis Ethanol oxidation reaction Nanoparticle Palladium Phosphide

SCI ; EI

英语

其他

Spanish Ministerio de Economia y Competitividad through the project SEHTOP[ENE2016-77798 -C4 -3-R][ENE201785087-C3] ; Jiangsu University Foundation[4111510011] ; China Postdoctoral Science Foundation[2019M663468] ; Generalitat de Catalunya[2017 SGR 327][2017 SGR 1246] ; Severo Ochoa Programme (MINECO)[SEV-2017-0706] ; MICINN/FEDER[RTI2018-093996-B-C31] ; GC[2017 SGR 128]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied

WOS:000581738300030

ELSEVIER

20203008975964

Electrocatalysts ; Palladium compounds ; Catalyst poisoning ; Oxidation ; Tin alloys ; Direct ethanol fuel cells (DEFC) ; Electronic structure ; Palladium ; Palladium alloys ; Carbon black ; Electrocatalysis ; Ethanol ; Ethanol fuels ; Reaction intermediates ; Density functional theory

Liquid Fuels:523 ; Tin and Alloys:546.2 ; Precious Metals:547.1 ; Fuel Cells:702.2 ; Nanotechnology:761 ; Electrochemistry:801.4.1 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Solid State Physics:933

2-s2.0-85088386479

Scopus

1.Catalonia Institute for Energy Research - IREC,Barcelona,Sant Adrià de Besòs,08930,Spain
2.Department of Electronic and Biomedical Engineering,Universitat de Barcelona,Barcelona,08028,Spain
3.Institute for Energy Research,School of Chemistry and Chemical Engineering,Jiangsu University,Zhenjiang,212013,China
4.Institute of Fundamental and Frontier Sciences,University of Electronic Science and Technology of China,Chengdu,610054,China
5.Department of Chemistry,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
6.SUSTech Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
7.Institute of Energy Technologies,Department of Chemical Engineering and Barcelona Research Center in Multiscale Science and Engineering,Universitat Politècnica de Catalunya,EEBE,Barcelona,08019,Spain
8.Catalan Institute of Nanoscience and Nanotechnology (ICN2),CSIC and BIST,Campus UAB,Barcelona,Bellaterra,08193,Spain
9.ICREA,Barcelona,Pg. Lluís Companys 23,08010,Spain
10.Key Laboratory of Functional Inorganic Material Chemistry,Ministry of Education,Heilongjiang University,Harbin,150080,China
11.IST Austria,Klosterneuburg,Am Campus 1,3400,Austria

Yu，Xiaoting,Liu，Junfeng,Li，Junshan,et al. Phosphorous incorporation in Pd2Sn alloys for electrocatalytic ethanol oxidation[J]. Nano Energy,2020,77.

Yu，Xiaoting.,Liu，Junfeng.,Li，Junshan.,Luo，Zhishan.,Zuo，Yong.,...&Cabot，Andreu.(2020).Phosphorous incorporation in Pd2Sn alloys for electrocatalytic ethanol oxidation.Nano Energy,77.

Yu，Xiaoting,et al."Phosphorous incorporation in Pd2Sn alloys for electrocatalytic ethanol oxidation".Nano Energy 77(2020).