Soluble porous organic cages as homogenizers and electron-acceptors for homogenization of heterogeneous alloy nanoparticle catalysts with enhanced catalytic activity  

可溶性多孔有机笼作为均质剂与电子受体:实现多相合金纳米颗粒催化剂的均质化和高性能化

作　　者：Hele Guo Yali Liu Hongliang Dong Wei Zong Kaibin Chu Weiwei Li Zhongli Fan Guanjie He Yue-E Miao Ivan P.Parkin Feili Lai Tianxi Liu 郭和乐;刘雅丽;董洪亮;宗伟;楚凯斌;李威威;范中丽;何冠杰;缪月娥;Ivan P.Parkin;赖飞立;刘天西(Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,International Joint Research Laboratory for Nano Energy Composites,Jiangnan University,Wuxi 214122,China;State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,College of Materials Science and Engineering,Donghua University,Shanghai 201620,China;Department of Chemistry,KU Leuven,Leuven 3001,Belgium;Center for High Pressure Science and Technology Advanced Research,Shanghai 201203,China;Christopher Ingold Laboratory,Department of Chemistry,University College London,London WCiH OAJ,UK;Department of Chemical Engineering,University College London,London WCiE 7JE,UK;Department of Molecular Spectroscopy,Max Planck Institute for Polymer Research,Mainz 55128,Germany)

机构地区：[1]Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,International Joint Research Laboratory for Nano Energy Composites,Jiangnan University,Wuxi 214122,China [2]State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,College of Materials Science and Engineering,Donghua University,Shanghai 201620,China [3]Department of Chemistry,KU Leuven,Leuven 3001,Belgium [4]Center for High Pressure Science and Technology Advanced Research,Shanghai 201203,China [5]Christopher Ingold Laboratory,Department of Chemistry,University College London,London WCiH OAJ,UK [6]Department of Chemical Engineering,University College London,London WCiE 7JE,UK [7]Department of Molecular Spectroscopy,Max Planck Institute for Polymer Research,Mainz 55128,Germany

出　　处：《Science Bulletin》2022年第23期2428-2437,M0004,共11页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China (52161135302 and 21674019);the Research Foundation of Flanders (FWO Grant No. 1298323N);the Natural Science Foundation of Shanghai (20ZR1401400);the Shanghai Scientific and Technological Innovation Project (18JC1410600);the Program of Shanghai Academic Research Leader (17XD1400100);the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program (LZB2021002)。

摘　　要：The creation of ultrafine alloy nanoparticles(<5 nm) that can maintain surface activity and avoid aggregation for heterogeneous catalysis has received much attention and is extremely challenging.Here,ultrafine PtRh alloy nanoparticles imprisoned by the cavities of reduced chiral covalent imine cage(PtRh@RCC3) are prepared successfully by an organic molecular cage(OMC) confinement strategy,while the soluble RCC3 can act as a homogenizer to homogenize the heterogeneous PtRh alloy in solution.Moreover,the X-ray absorption near-edge structure(XANES) results show that the RCC3 can act as an electron-acceptor to withdraw electrons from Pt,leading to the formation of higher valence Pt atoms,which is beneficial to improving the catalytic activity for the reduction of 4-nitrophenol.Attributed to the synergistic effect of Pt/Rh atoms and the unique function of the RCC3,the reaction rate constants of Pt_(1)Rh_(16)@RCC3 are 49.6,8.2,and 5.5 times than those of the Pt_(1)Rh_(16)bulk,Pt@RCC3 and Rh@RCC3,respectively.This work provides a feasible strategy to homogenize heterogeneous alloy nanoparticle catalysts in solution,showing huge potential for advanced catalytic application.开发能够保持表面活性并稳定分散的超细合金纳米颗粒(<5 nm)用于多相催化已受到广泛关注,并具有极大的挑战性.本文提出有机分子笼限域策略,并成功制备了手性共价亚胺笼空腔“禁锢”超细铂铑合金纳米颗粒(PtRh@RCC3)的纳米复合材料.其中,可溶性RCC3可以作为均质剂,使溶液中的多相铂铑合金均质化.此外,X射线吸收近边结构结果表明:RCC3还可以作为电子受体从铂原子中提取电子,从而形成更高价的铂原子,这有利于提高4-硝基苯酚还原的催化活性,由于铂、铑原子的协同作用和RCC3的独特功能,Pt_(1)Rh_(16)@RCC3对4-硝基苯酚的催化还原反应速率常数分别是Pt_(1)Rh_(16)块体、Pt@RCC3和Rh@RCC3的49.6、8.2和5.5倍.该工作为溶液中均质化合金纳米颗粒多相催化剂提供了一种可行的策略,在先进的催化应用领域表现出巨大的潜力.

关 键 词：Soluble organic cage Heterogeneous catalysts Ultrafine alloy nanoparticle 4-Nitrophenol reduction reaction 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O643.36[理学—物理化学]