title: Interfacial electronic effects control the reaction selectivity of platinum catalysts.
abstract: Tuning the electronic structure of heterogeneous metal catalysts has emerged as an effective strategy to optimize their catalytic activities. By preparing ethylenediamine-coated ultrathin platinum nanowires as a model catalyst, here we demonstrate an interfacial electronic effect induced by simple organic modifications to control the selectivity of metal nanocatalysts during catalytic hydrogenation. This we apply to produce thermodynamically unfavourable but industrially important compounds, with ultrathin platinum nanowires exhibiting an unexpectedly high selectivity for the production of N-hydroxylanilines, through the partial hydrogenation of nitroaromatics. Mechanistic studies reveal that the electron donation from ethylenediamine makes the surface of platinum nanowires highly electron rich. During catalysis, such an interfacial electronic effect makes the catalytic surface favour the adsorption of electron-deficient reactants over electron-rich substrates (that is, N-hydroxylanilines), thus preventing full hydrogenation. More importantly, this interfacial electronic effect, achieved through simple organic modifications, may now be used for the optimization of commercial platinum catalysts.
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Guangxu
authors.initials: G
authors.lastname: Chen
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Chaofa
authors.initials: C
authors.lastname: Xu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Xiaoqing
authors.initials: X
authors.lastname: Huang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.
authors.forename: Jinyu
authors.initials: J
authors.lastname: Ye
authors.affiliation: Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Lin
authors.initials: L
authors.lastname: Gu
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
authors.forename: Gang
authors.initials: G
authors.lastname: Li
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
authors.forename: Zichao
authors.initials: Z
authors.lastname: Tang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Binghui
authors.initials: B
authors.lastname: Wu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Huayan
authors.initials: H
authors.lastname: Yang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Zipeng
authors.identifier: 0000-0003-1135-6742
authors.initials: Z
authors.lastname: Zhao
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.
authors.forename: Zhiyou
authors.initials: Z
authors.lastname: Zhou
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Gang
authors.initials: G
authors.lastname: Fu
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, Xiamen 361005, China.|National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
authors.forename: Nanfeng
authors.initials: N
authors.lastname: Zheng