文献类型：期刊文献

中文题名：Rapid synthesis of Pd single‐atom/cluster as highly active catalysts for Suzuki coupling reactions

英文题名：Pd单原子/团簇高效催化铃木偶联反应

作者：Hehe Wei[1,4];Xiaoyang Li[2];Bohan Deng[1];Jialiang Lang[1];Ya Huang[1];Xingyu Hua[2];Yida Qiao[2];Binghui Ge[3];Jun Ge[2];Hui Wu[1]

机构：[1]State Key Laboratory of New Ceramics and Fine Processing,School of Materials Science and Engineering,Tsinghua University,Beijing 100084,China;[2]Key Lab for Industrial Biocatalysis,Ministry of Education,Department of Chemical Engineering,Tsinghua University,Beijing 100084,China;[3]Institutes of Physical Science and Information Technology,Anhui University,Hefei 230601,Anhui,China;[4]Key Laboratory for Advanced Materials,Center for Computational Chemistry and Research Institute of Industrial Catalysis,East China University of Science and Technology,Shanghai 200237,China

年份：2022

卷号：43

期号：4

起止页码：1058

中文期刊名：Chinese Journal of Catalysis

外文期刊名：催化学报（英文）

收录：CSTPCD;;Scopus;CSCD:【CSCD2021_2022】；

基金：This work was supported by the National Natural Science Foundation of China (51788104, 51661135025, 21878174), the National Key Research and Development Plan of China (2016YFA0204300), Beijing Natural Science Foundation (JQ19005) and Shanghai Sailing Program (21YF1409400).

语种：英文

中文关键词：Pd single‐atom/cluster catalyst;Suzuki coupling reactions;Solution rapid annealing;Energy barrier;High yield

外文关键词：钯单原子/团簇催化剂;铃木偶联反应;溶液快速退火;能垒;高产率

摘要：Palladium(Pd)‐based catalysts are essential to drive high‐performance Suzuki coupling reactions,which are powerful tools for the synthesis of functional organic compounds.Herein,we developed a solution‐rapid‐annealing process to stabilize nitrogen‐mesoporous carbon supported Pd single‐atom/cluster(Pd/NMC)material,which provided a catalyst with superior performance for Suzuki coupling reactions.In comparison with commercial palladium/carbon(Pd/C)catalysts,the Pd/NMC catalyst exhibited significantly boosted activity(100%selectivity and 95%yield)and excellent stability(almost no decay in activity after 10 reuse cycles)for the Suzuki coupling reactions of chlorobenzenes,together with superior yield and excellent selectivity in the fields of the board scope of the reactants.Moreover,our newly developed rapid annealing process of precursor solutions is applied as a generalized method to stabilize metal clusters(e.g.Pd,Pt,Ru),opening new possibilities in the construction of efficient highly dispersed metal atom and sub‐nanometer cluster catalysts with high performance.
铃木偶联反应是合成聚烯烃、苯乙烯和联苯衍生物等功能性有机化合物的有力工具,广泛应用于精细化工、制药和生化工业领域.钯(Pd)基催化剂是目前性能最好的铃木偶联反应催化剂,但钯的低丰度和高成本限制了其大规模应用.因此,提高Pd原子的利用效率,降低Pd用量至关重要.减小金属纳米粒子的尺寸,使其成为小团簇甚至孤立的金属原子是实现金属原子高利用率的有效方法之一.此外,与纳米晶体相比,高度分散的Pd原子和具有低配位和不饱和构型的亚纳米团簇可能会导致催化活性位点数量增加,进而提升Pd基催化剂的性能.然而,高表面自由能使得合成高度分散的Pd单原子和亚纳米团簇变得困难,因此,如何制备具有优异铃木偶联反应催化性能的Pd单原子/团簇催化剂是一个极具挑战性的课题.本文开发了一种溶液快速退火(SRA)工艺来稳定氮掺杂介孔碳负载的Pd单原子/团簇(Pd/NMC),制得的催化剂表现出较好的催化铃木偶联反应性能.透射电子显微镜结果表明,所制Pd/NMC催化剂中Pd以单原子和小金属团簇(粒径为0.3-1.1 nm)的形式高度分散在氮掺杂介孔碳载体的表面;X射线衍射结果表明,该催化剂没有与Pd相关的衍射峰,进一步证明了Pd以单原子和小金属团簇,而非纳米晶的形式存在.这得益于SRA工艺创造的不平衡热条件,抑制了Pd原子的团聚,提高了Pd原子在载体表面的分散性.与商业Pd/C催化剂相比,Pd/NMC催化剂对氯苯的铃木偶联反应表现出更好的催化性能(100%的选择性和95%的产率)和稳定性(循环使用10次后活性几乎没有衰减),此外对其他衍生物底物同样表现出较好的催化性能.第一性原理计算表明,在Pd(111)上联苯解吸的吉布斯自由能为3.24 eV,显著高于Pd_(1)/NMC(0.72 eV)和Pd_(13)/NMC(1.31 eV),在理论上同样证明了与Pd纳米颗粒相比,Pd单原子/团簇催化剂更有利于反应物的转化.此外,本文新开发的前驱体SRA工艺可被用作稳定金属团簇(例如Pd、Pt、Ru)的通用方法,为构建高效、高度分散的金属原子和亚纳米团簇催化剂提供了新的可能性.