首页|(Catecholate)CuⅠ2-Displayed Porous Organic Polymers as Efficient Heterogeneous Catalysts for the Mild and Selective Aerobic Oxidation of Alcohols

(Catecholate)CuⅠ2-Displayed Porous Organic Polymers as Efficient Heterogeneous Catalysts for the Mild and Selective Aerobic Oxidation of Alcohols

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Porous organic polymers(POPs)containing catalyti-cally active sites are of paramount importance for heterogeneous catalysis.However,the catalytically active sites of reported POPs are mostly limited to mononuclear metal species.Herein,we report the reaction between catechol-containing POPs(Cat-POPs)and[CuⅠMes]n to afford the corresponding CuⅠ2-CatPOPs with a putative vicinal binuclear(cate-cholate)CuⅠ2 moiety.The resulting CuⅠ2-CatPOPs ex-hibit high Brunauer-Emmett-Teller surface areas,good stability,and excellent catalytic activity toward the aerobic oxidation of a broad range of primary and secondary alcohols under mild conditions,with either 2,2,6,6-tetramethylpiperidinyl-N-oxyl or 9-azabicyclo[3.3.0]nonane-N-oxyl as the cocatalyst.As green aer-obic oxidation catalysts,the CuⅠ2-CatPOPs are much more active than the corresponding mononuclear CuⅡ-CatPOPs,where each catecholate moiety only sup-ports one CuⅡ center;CuⅠ-ConPOPs,where the binding sites for CuⅠ is a nonvicinal 1,4-dihydroxybenzene moi-ety;and the homogeneous analogue(3,6-di-tert-butyl catecholate)CuⅠ2.These results are consistent with a proposed vicinal binuclear CuⅠ2 structure that can efficiently activate molecular oxygen for the aerobic oxidation of alcohols,mechanistically similar to that observed in dicopper-containing oxygenases.Our results demonstrate the facile preparation of POPs with binuclear catalytically active sites that function as green heterogeneous catalysts for efficient oxida-tion of alcohols.

porous organic polymersbinuclear copper(Ⅰ)heterogeneous catalysisaerobic oxidationgreen chemistry

Youlong Zhu、Debabrata Mukherjee、Theodore R.Helgert、SonBinh T.Nguyen

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Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education,School of Chemistry,Sun Yat-sen University,Guangzhou 510006

Chemical Sciences and Engineering Division,Argonne National Laboratory,Argonne,IL 60439

Department of Chemical Sciences,Indian Institute of Science Education and Research Kolkata,West Bengal 741246

Optima Chemical Group,LLC,Douglas,GA 31535

Department of Chemistry,International Institute for Nanotechnology,Northwestern University,Evanston,IL 60208

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国家自然科学基金Guangdong Basic and Applied Basic Research Foundation广州市科技计划Sun Yatsen University Startup FundingDTRAU.S.Department of Energy(DOE) to the Institute of Catalysis for Energy Processes(ICEP)at Northwestern University美国能源部项目Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,BiosciencesNSF-NSECNSF-MRSECKeck Foundationstate of IllinoisNorthwestern University

521033282020A1515110575202102020422HDTRA1-14-1-0014DE FG02-03-ER154757DEAC02-06CH11357

2023

10.31635/ccschem.022.202101765

中国化学会会刊(英文)

中国化学会会刊(英文)

CSCD
ISSN：
年,卷(期)：2023.5(2)
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