Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation

Li, Shenzhou1; Wang, Gang2,3; Lv, Houfu4,5; Lin, Zijie1; Liang, Jiashun1; Liu, Xuan1; Wang, Yang-Gang2,3; Huang, Yunhui1; Wang, Guoxiong4; Li, Qing1

2024-06-21

10.1021/jacs.4c00618

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Reactive metal-support interaction (RMSI) is an emerging way to regulate the catalytic performance for supported metal catalysts. However, the induction of RMSI by the thermal reduction is often accompanied by the encapsulation effect on metals, which limits the mechanism research and applications of RMSI. In this work, a gradient orbital coupling construction strategy was successfully developed to induce RMSI in Pt-carbide system without a reductant, leading to the formation of L1(2)-PtxM-MCy (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W) intermetallic electrocatalysts. Density functional theory (DFT) calculations suggest that the gradient coupling of the d(M)-2p(C)-5d(Pt) orbital would induce the electron transfer from M to C covalent bonds to Pt NPs, which facilitates the formation of C vacancy (C-v) and the subsequent M migration (occurrence of RMSI). Moreover, the good correlation between the formation energy of C-v and the onset temperature of RMSI in Pt-MCx systems proves the key role of nonmetallic atomic vacancy formation for inducing RMSI. The developed L1(2)-Pt3Ti-TiC catalyst exhibits excellent acidic methanol oxidation reaction activity, with mass activity of 2.36 A mg(Pt)(-1) in half-cell and a peak power density of 187.9 mW mg(Pt)(-1) in a direct methanol fuel cell, which is one of the best catalysts ever reported. DFT calculations reveal that L1(2)-Pt3Ti-TiC favorably weakens *CO absorption compared to Pt-TiC due to the change of the absorption site from Pt to Ti, which accounts for the enhanced MOR performance.

SCI ; EI

英语

通讯

Guangdong Provincial Pearl River Talents Program["22122202","22125205"] ; National Nature Science Foundation of China[22022504] ; NSFC[2019QN01L353] ; Guangdong "Pearl River" Talent Plan[JCYJ20210324103608023] ; Shenzhen Science and Technology Program[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:001252894500001

AMER CHEMICAL SOC

20242616508066

Catalyst supports ; Density functional theory ; Direct methanol fuel cells (DMFC) ; Electrocatalysts ; Methanol ; Methanol fuels ; Platinum compounds

Liquid Fuels:523 ; Fuel Cells:702.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Huazhong Univ Sci & Technol, Sch Mat Sci & Engn, State Key Lab Mat Proc & Die & Mould Technol, Wuhan 430074, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis Chem, Shenzhen 518055, Peoples R China
4.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian Natl Lab Clean Energy, Dalian 116000, Peoples R China
5.Suzhou Lab, Suzhou 215000, Peoples R China

Li, Shenzhou,Wang, Gang,Lv, Houfu,et al. Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(26):17659-17668.

Li, Shenzhou.,Wang, Gang.,Lv, Houfu.,Lin, Zijie.,Liang, Jiashun.,...&Li, Qing.(2024).Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(26),17659-17668.

Li, Shenzhou,et al."Constructing Gradient Orbital Coupling to Induce Reactive Metal-Support Interaction in Pt-Carbide Electrocatalysts for Efficient Methanol Oxidation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.26(2024):17659-17668.