Synthesis of Cu Single Atoms Supported on Mesoporous Graphitic Carbon Nitride and Their Application in Liquid-Phase Aerobic Oxidation of Cyclohexene

被引:86
作者
Bueker, Julia [1 ]
Huang, Xiubing [1 ,4 ]
Bitzer, Johannes [1 ,2 ]
Kleist, Wolfgang [2 ]
Muhler, Martin [1 ,3 ]
Peng, Baoxiang [1 ,3 ]
机构
[1] Ruhr Univ Bochum, Lab Ind Chem, D-44780 Bochum, Germany
[2] TU Kaiserslautern, Dept Chem, D-67663 Kaiserslautern, Germany
[3] Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany
[4] Univ Sci & Technol Beijing, Sch Mat Sci & Engn, Beijing 100083, Peoples R China
关键词
cyclohexene oxidation; 2-cyclohexene-1-hydroperoxide; ATR-IR; copper single atoms; EXAFS; ADIPIC ACID; SELECTIVE OXIDATION; HYDROGEN-PEROXIDE; G-C3N4; NANOSHEETS; ALLYLIC OXIDATION; OXYGEN REDUCTION; H-2; EVOLUTION; COPPER; ABSORPTION; CATALYSTS;
D O I
10.1021/acscatal.1c01468
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Different loadings of Cu single atoms were anchored on a graphitic carbon nitride (g-C3N4) matrix using a two-step thermal synthesis method and applied in liquid-phase cyclohexene oxidation under mild conditions using molecular O-2 as the oxidizing agent. The oxidation state of Cu was determined to be Cu+, which is in linear coordination with two neighboring nitrogen atoms at a distance of 1.9 angstrom. The catalyst with 0.9 wt % Cu pyrolyzed at 380 degrees C was found to exhibit the best catalytic performance with the highest conversion up to 82% with an allylic selectivity of 55%. It also showed high reusability over four catalytic runs without any detectable Cu leaching. Cyclohexene oxidation followed first-order kinetics with an apparent activation energy of 66.2 kJ mol(-1). The addition of hydroquinone as a radical scavenger confirmed that cyclohexene oxidation proceeds via a radical mechanism. Time-resolved in situ attenuated total reflection infrared (ATR-IR) spectroscopy was carried out to qualitatively monitor the cyclohexene oxidation pathways. The comparison with the homogeneous analogue Cu(I) iodide indirectly verified the linearly N-coordinated single Cu(I) species to be the active sites for cyclohexene oxidation.
引用
收藏
页码:7863 / 7875
页数:13
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