Interfacial electronic effects control the reaction selectivity of platinum catalysts

Nature Materials
Guangxu ChenNanfeng Zheng

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.

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Citations

Jun 21, 2016·Journal of the American Chemical Society·Zhi CaoChristopher J Chang
Jan 14, 2017·Journal of the American Chemical Society·Pengxin LiuNanfeng Zheng
Apr 12, 2017·Chemistry : a European Journal·Sanjeevi JayakumarQihua Yang
Mar 10, 2017·Science Advances·Kezhu JiangXiaoqing Huang
Jun 22, 2017·Journal of the American Chemical Society·Johannes B ErnstFrank Glorius
Jul 29, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Weiyue ZhaoXun Wang
Mar 7, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Liane M RossiCamila P Ferraz
Jun 23, 2018·Small·Lie WuXue-Feng Yu
Jun 5, 2018·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Yang YangDaojian Cheng
Jul 25, 2018·Advanced Materials·Bing NiXun Wang
May 24, 2019·Chemistry : a European Journal·Lili ZhangHaihui Wang
Oct 2, 2019·Chemical Society Reviews·Huilong FeiXiangfeng Duan
Apr 29, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Yunhee ChoHyoyoung Lee
Apr 23, 2017·Scientific Reports·S E StancaH-G Meyer
Apr 11, 2018·Nature Communications·Liang WangFeng-Shou Xiao
Dec 17, 2016·Angewandte Chemie·Giacomo M LariJavier Pérez-Ramírez

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