Ionic-liquid-assisted synthesis of metal single-atom catalysts for benzene oxidation to phenol  

离子液体辅助合成金属单原子催化剂用于苯氧化制苯酚

作　　者：Qikai Shen Peipei Li Weiming Chen Hongqiang Jin Jia Yu Lei Zhu Zhucheng Yang Runqing Zhao Lirong Zheng Weiguo Song Changyan Cao 沈齐凯;李佩佩;陈伟明;晋红强;于珈;朱磊;杨翥成;赵润卿;郑黎荣;宋卫国;曹昌燕(Beijing National Laboratory for Molecular Sciences,Laboratory of Molecular Nanostructures and Nanotechnology,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China;University of Chinese Academy of Sciences,Beijing 100049,China;Beijing Synchrotron Radiation Facility(BSRF),Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]Beijing National Laboratory for Molecular Sciences,Laboratory of Molecular Nanostructures and Nanotechnology,CAS Research/Education Center for Excellence in Molecular Sciences,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190,China [2]University of Chinese Academy of Sciences,Beijing 100049,China [3]Beijing Synchrotron Radiation Facility(BSRF),Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Science China Materials》2022年第1期163-169,共7页中国科学（材料科学（英文版）

基　　金：the financial support from the National Key R&D Program of China(2018YFA0208504 and 2018YFA0703503);the National Natural Science Foundation of China(21932006);the Youth Innovation Promotion Association of CAS(2017049).

摘　　要：Ionic liquids(ILs)have the advantages of low cost,eco-friendliness,abundant heteroatoms,excellent solubility,and coordinated ability with metal ions.These features make ILs a suitable precursor for fabricating metal singleatom catalysts(SACs).Herein,we prepared various metal single atoms anchored on ultrathin N-doped nanosheets(denoted as Cu_(1)/NC,Fe_(1)/NC,Co_(1)/NC,Ni_(1)/NC,and Pd_(1)/NC)by direct pyrolysis using ILs and g-C_(3)N_(4)nanosheets as templates.Taking benzene oxidation to phenol with H_(2)O_(2)as a model reaction to evaluate their catalytic performance and potential applications,Cu_(1)/NC calcined at 1000℃(denoted as Cu1/NC-1000)exhibits the highest activity with a turnover frequency of about 200 h^(-1)in the first 1 h at 60℃,which is better than that of most metal SACs reported in the literature.High benzene conversion of 82% with high phenol selectivity of 96% and excellent recyclability were achieved using the Cu_(1)/NC-1000 catalyst.This study provides an efficient general strategy for fabricating SACs using ILs for catalytic applications.离子液体具有成本低、环境友好、杂原子丰富、溶解性好、与金属离子良好的配位能力等优点,是一种理想的用于制备金属单原子催化剂的前驱体材料.在本文中,我们利用离子液体与金属的强配位能力,以g-C_(3)N_(4)纳米片为结构模板,合成了多种锚定在氮掺杂超薄碳纳米片上的金属单原子催化剂(分别简写为Cu_(1)/NC、Fe_(1)/NC、Co_(1)/NC、Ni_(1)/NC和Pd_(1)/NC).将上述金属单原子催化剂用于双氧水氧化苯制苯酚反应中,1000℃煅烧得到的铜单原子催化剂(Cu_(1)/NC-1000)表现出最高的活性,60℃时反应1 h的转换频率(TOF)约为200 h^(-1),优于文献报道的大多数金属单原子催化剂.随着反应时间延长,最终苯的转化率可达82%,苯酚的选择性维持在96%.此外,Cu_(1)/NC-1000催化剂具有良好的循环稳定性.本研究为制备单原子催化剂提供了一种新的有效的普适性策略.

关 键 词：single-atom catalysis copper benzene oxidation ionic liquids 

分 类 号：TQ243.12[化学工程—有机化工] TQ426