Subnanometric bimetallic Pt-Pd clusters in zeolites for efficient hydrogen production and selective tandem hydrogenation of nitroarenes  

作　　者：Jiafu Li Tao Cai Yanran Feng Xia Liu Ning Wang Qiming Sun 

机构地区：[1]Institute of Sustainable Energy and Resources,College of Chemistry and Chemical Engineering,Key Laboratory of Shandong Provincial Universities for Functional Molecules and Materials,Qingdao University,Qingdao 266071,China [2]Innovation Center for Chemical Sciences,College of Chemistry,Chemical Engineering and Materials Science,Jiangsu Key Laboratory of Advanced Negative Carbon Technologies,Soochow University,Suzhou 215123,China

出　　处：《Science China Chemistry》2024年第9期2911-2917,共7页中国科学（化学英文版）

基　　金：supported by the National Key R&D Program of China(2022YFA1506000);the National Natural Science Foundation of China(22105110,22109110,22206094);the Natural Science Foundation of Shandong Province(ZR2021QB162,ZR2023YQ014);the Youth Innovation Team Project of Shandong Provincial Education Department(022KJ143);the Taishan Scholar Youth Expert Program in Shandong Province(tsqn202211122);the Gusu Innovation and Entrepreneurship Leading Talents Program(ZXL2022497);the Jiangsu Distinguished Professor Program;the Natural Science Foundation of Jiangsu Province(BK20210698)。

摘　　要：The solvolysis of ammonia borane(AB)and the hydrogenation of nitroarenes represent significant reactions for hydrogen generation and value-added chemical synthesis.The strategic engineering of the catalysts is imperative for surmounting obstacles associated with their stability and catalytic efficiency.In this work,subnanometric bimetallic Pt–Pd clusters were encapsulated within silicalite-1(S-1)zeolites through a ligand-protected in-situ hydrothermal synthesis method.The synergetic effect of bimetallic composition and zeolite confinement markedly enhances the catalytic performance of representative Pt_(0.5)Pd_(0.5)@S-1-H catalyst,affording exceptional turnover frequency(TOF)values of 1,043 and 573 mol_(H_(2))mol_(metal)^(-1)min^(-1)for AB hydrolysis and methanolysis at ambient conditions,respectively,surpassing most of the state-of-the-art Pt-based catalysts.Kinetic and isotopic experiments reveal that the bimetallic catalytic system remarkably boosts the O-H cleavage of water,thereby facilitating the H_(2) production from AB hydrolysis.Remarkably,a conspicuous synergistic effect is demonstrated in the shape-selective tandem hydrogenation of nitroarenes,with the bimetallic catalyst facilitating both AB hydrolysis and nitroarene hydrogenation,giving a high TOF value of 1,260 h^(-1)under atmospheric pressure.This study not only demonstrates the effectiveness of bimetallic nanocatalysts encapsulated in zeolites for hydrogen production from chemical hydrogen storage materials,but also paves the way for the design of catalysts with multifunctional active sites capable of synergistically promoting tandem catalytic processes.

关 键 词：subnanometer bimetallic cluster zeolite synergistic effect ammonia borane solvolysis selective tandem hydrogenation 

分 类 号：O643.36[理学—物理化学] TQ116.2[理学—化学]