Yuan Min1, Xiao Zhou2,3, Jie-Jie Chen4, Wenxing Chen5, Fangyao Zhou6, Zhiyuan Wang6, Jia Yang6, Can Xiong6, Ying Wang7, Fengting Li7, Han-Qing Yu1, Yuen Wu8. 1. CAS Key Laboratory of Urban Pollutant Conversion, Department of Environmental Science and Engineering, University of Science and Technology of China, 230026, Hefei, China. 2. Department of Applied Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, 230026, Hefei, China. zhoux08@mail.ustc.edu.cn. 3. College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, 200092, Shanghai, China. zhoux08@mail.ustc.edu.cn. 4. CAS Key Laboratory of Urban Pollutant Conversion, Department of Environmental Science and Engineering, University of Science and Technology of China, 230026, Hefei, China. chenjiej@ustc.edu.cn. 5. Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, 100081, Beijing, China. 6. Department of Applied Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, 230026, Hefei, China. 7. College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, 200092, Shanghai, China. 8. Department of Applied Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, 230026, Hefei, China. yuenwu@ustc.edu.cn.
Abstract
The construction of enzyme-inspired artificial catalysts with enzyme-like active sites and microenvironment remains a great challenge. Herein, we report a single-atomic-site Co catalyst supported by carbon doped boron nitride (BCN) with locally polarized B-N bonds (Co SAs/BCN) to simulate the reductive dehalogenases. Density functional theory analysis suggests that the BCN supports, featured with ionic characteristics, provide additional electric field effect compared with graphitic carbon or N-doped carbon (CN), which could facilitate the adsorption of polarized organochlorides. Consistent with the theoretical results, the Co SAs/BCN catalyst delivers a high activity with nearly complete dechlorination (~98%) at a potential of -0.9 V versus Ag/AgCl for chloramphenicol (CAP), showing that the rate constant (k) contributed by unit mass of metal (k/ratio) is 4 and 19 times more active than those of the Co SAs/CN and state-of-the-art Pd/C catalyst, respectively. We show that Co single atoms coupled with BCN host exhibit high stability and selectivity in CAP dechlorination and suppress the competing hydrogen evolution reaction, endowing the Co SAs/BCN as a candidate for sustainable conversion of organic chloride.
The construction of enzyme-inspired artificial catalysts with enzyme-like active n class="Chemical">sites and microenvironment remains a great challenge. Herein, we report a single-atomic-site Co catalyst supported by carbon dopedboron nitride (BCN) with locally polarized B-Nbonds (Co SAs/BCN) to simulate the reductive dehalogenases. Density functional theory analysis suggests that the BCN supports, featured with ionic characteristics, provide additional electric field effect compared with graphitic carbon or N-dopedcarbon (CN), which could facilitate the adsorption of polarized organochlorides. Consistent with the theoretical results, the Co SAs/BCN catalyst delivers a high activity with nearly complete dechlorination (~98%) at a potential of -0.9 V versus Ag/AgCl for chloramphenicol (CAP), showing that the rate constant (k) contributed by unit mass of metal (k/ratio) is 4 and 19 times more active than those of the Co SAs/CN and state-of-the-art Pd/C catalyst, respectively. We show that Co single atoms coupled with BCN host exhibit high stability and selectivity in CAP dechlorination and suppress the competing hydrogen evolution reaction, endowing the Co SAs/BCN as a candidate for sustainable conversion of organic chloride.
Authors: Dmitry V Shtansky; Andrei T Matveev; Elizaveta S Permyakova; Denis V Leybo; Anton S Konopatsky; Pavel B Sorokin Journal: Nanomaterials (Basel) Date: 2022-08-16 Impact factor: 5.719