催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1058-1065.DOI: 10.1016/S1872-2067(21)63968-2

• 论文 • 上一篇    下一篇

Pd单原子/团簇高效催化铃木偶联反应

魏呵呵a,d,, 黎晓阳b,, 邓铂瀚a,, 郎嘉良a, 黄雅a, 华星宇b, 乔奕达b, 葛炳辉c,$(), 戈钧b,#(), 伍晖a,*()   

  1. a清华大学材料科学与工程学院, 新型陶瓷与精细加工国家重点实验室, 北京100084
    b清华大学化工系, 工业生物催化教育部重点实验室, 北京100084
    c安徽大学物质科学与信息技术研究院, 安徽合肥230601
    d华东理工大学计算化学中心, 工业催化研究所, 上海200237
  • 收稿日期:2021-08-23 接受日期:2021-08-23 出版日期:2022-03-05 发布日期:2022-03-01
  • 通讯作者: 葛炳辉,戈钧,伍晖
  • 作者简介:第一联系人:

    共同第一作者

  • 基金资助:
    国家自然科学基金(51788104);国家自然科学基金(51661135025);国家自然科学基金(21878174);国家重点研发计划(2016YFA0204300);北京市自然科学基金(JQ19005);上海市扬帆计划(21YF1409400)

Rapid synthesis of Pd single-atom/cluster as highly active catalysts for Suzuki coupling reactions

Hehe Weia,d,, Xiaoyang Lib,, Bohan Denga,, Jialiang Langa, Ya Huanga, Xingyu Huab, Yida Qiaob, Binghui Gec,$(), Jun Geb,#(), Hui Wua,*()   

  1. aState Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
    bKey Lab for Industrial Biocatalysis, Ministry of Education, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
    cInstitutes of Physical Science and Information Technology, Anhui University, Hefei 230601, Anhui, China
    dKey Laboratory for Advanced Materials, Center for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China
  • Received:2021-08-23 Accepted:2021-08-23 Online:2022-03-05 Published:2022-03-01
  • Contact: Binghui Ge, Jun Ge, Hui Wu
  • About author:First author contact:

    Contributed equally to this work.

  • Supported by:
    National Natural Science Foundation of China(51788104);National Natural Science Foundation of China(51661135025);National Natural Science Foundation of China(21878174);National Key Research and Development Plan of China(2016YFA0204300);Beijing Natural Science Foundation(JQ19005);Shanghai Sailing Program(21YF1409400)

摘要:

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Pd1/NMC (0.72 eV)和Pd13/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.

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

Abstract:

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.

Key words: Pd single-atom/cluster catalyst, Suzuki coupling reactions, Solution rapid annealing, Energy barrier, High yield