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Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions |
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| Authors: | Tianqi Liu Ge Li Dr. Nannan Shen Dr. Linqin Wang Dr. Brian J. J. Timmer Dr. Alexander Kravchenko Dr. Shengyang Zhou Ying Gao Yi Yang Hao Yang Prof. Bo Xu Dr. Biaobiao Zhang Prof. Mårten S. G. Ahlquist Prof. Licheng Sun |
| Affiliation: | 1. Department of Chemistry, School of Engineering Sciences in, Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10044 Stockholm, Sweden These authors contributed equally to this work.;2. Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10691 Stockholm, Sweden These authors contributed equally to this work.;3. State Key Laboratory of Radiation Medicine and Protection, School for Radiological and Interdisciplinary Sciences (RAD−X) and, Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Soochow University, 215123 Suzhou, China;4. Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, 310024 Hangzhou, China;5. Department of Chemistry, School of Engineering Sciences in, Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10044 Stockholm, Sweden;6. Nanotechnology and Functional Materials, Department of Materials Sciences and Engineering, The Ångström Laboratory, Uppsala University, 751 03 Uppsala, Sweden;7. Wallenberg Wood Science Center, Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, Stockholm, 10044 Sweden;8. Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry Biotechnology and Health, KTH Royal Institute of Technology, 10691 Stockholm, Sweden |
| Abstract: | The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man-made molecular catalysts. Herein, four Ru-bda (bda=2,2′-bipyridine-6,6′-dicarboxylate) based molecular water oxidation catalysts with well-defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high-valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6-fold rate increase for water oxidation catalysis has been achieved. |
| Keywords: | hydrophobicity intermediates outer sphere proton transfer third coordination sphere water oxidation |