王海，现为浙江大学化学工程与生物工程学院副研究员，长期开展高效加氢金属催化剂的设计与制备工作，以期解决加氢过程中金属催化剂普遍面临的失活及选择性差等问题，取得了系列研究成果。目前已发表论文30余篇，以第一/共一/共同通讯作者身份在Nature Catalysis、J. Am. Chem. Soc、Adv. Funct. Mater.、ACS Catalysis（3篇）等期刊发表论文20篇，授权专利9项。曾获“博新计划”，2023年“中国催化新秀奖”，2023年中国化工学会“基础研究成果奖”一等奖等。

Abstract:

Supported metal catalysts, which usually comprise metal NPs supported on the surface of solid carriers, have been extensively used in the fine chemical synthesis, such as the heterogeneous catalytic hydrogenations. However, for molecules with strong and preferential chemisorption on metal surface, the metal sites can be blocked and cause an activity loss of up to two to three orders of magnitude. For example, during the hydrogenation of N-heterocyclic compounds (e.g., pyridines, quinolines, and amino-containing molecules), the nitrogen moiety of substrates or products can strongly coordinate to the metal sites and form a densely packed molecular layer, thus reducing the accessible metal sites for hydrogenation. To alleviate this problem, high temperature (>200 °C) and ultra-high pressure of hydrogen (15~30 MPa) are usually used in industry to increase the degree of H2 coverage on metal surface to boost the hydrogenation. Furthermore, the strongly-coordinated molecules can break the metal-metal (M-M) bonds, leading to the metal leaching. It is therefore highly desirable for rational design and synthesis of supported metal catalyst to boost the hydrogenation of strongly-coordinated molecules with both high activity and good stability.

We overcome such an inherent limitation of metal catalyst by two strategies, including the modulation of the steric adsorption of molecules on metal NPs surface for activity enhancement and modulation of the electronic structure of the metal NPs for stability improvement. Specifically, the steric adsorption of molecules on metal NPs surface was achieved by the modification of metal NPs surface with porous silica layers, which enables the unique sterically guided molecular adsorption on metal surface, avoiding the formation of densely packed molecular layer and providing free metal sites for H2 adsorption, showing good conversion and product selectivity[1,2]. The modulation of the electronic structure of the metal NPs was achieved through the construction of strong metal-support interactions[3-5], where the electron transfer from support to metal surface significantly inhibit the molecules bond to metal surface via π orbitals of the molecule’s ring or the nitrogen’s lone pair of electrons, resulting in good stability[6]. Overall, these strategies reported here may open up possibilities for the development of highly active and stable metal catalysts in the future.