Jing Yang1, Lei Wang2, Shaoqi Zhan3, Haiyuan Zou1, Hong Chen4, Mårten S G Ahlquist3, Lele Duan5,6, Licheng Sun7,8,9. 1. Department of Chemistry, Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen, 518055, People's Republic of China. 2. Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, 10044, Stockholm, Sweden. 3. Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, 10044, Stockholm, Sweden. 4. School of Environmental Science & Engineering, Southern University of Science and Technology, Shenzhen, 518055, People's Republic of China. 5. Department of Chemistry, Shenzhen Grubbs Institute and Guangdong Provincial Key Laboratory of Energy Materials for Electric Power, Southern University of Science and Technology, Shenzhen, 518055, People's Republic of China. duanll@sustech.edu.cn. 6. State Key Laboratory of Fine Chemicals, DUT - KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian, 116012, People's Republic of China. duanll@sustech.edu.cn. 7. Department of Chemistry, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, 10044, Stockholm, Sweden. lichengs@kth.se. 8. State Key Laboratory of Fine Chemicals, DUT - KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian, 116012, People's Republic of China. lichengs@kth.se. 9. Center of Artificial Photosynthesis for Solar Fuels, School of Science, Westlake University, 310024, Hangzhou, China. lichengs@kth.se.
Abstract
Significant advances during the past decades in the design and studies of Ru complexes with polypyridine ligands have led to the great development of molecular water oxidation catalysts and understanding on the O-O bond formation mechanisms. Here we report a Ru-based molecular water oxidation catalyst [Ru(bds)(pic)2] (Ru-bds; bds2- = 2,2'-bipyridine-6,6'-disulfonate) containing a tetradentate, dianionic sulfonate ligand at the equatorial position and two 4-picoline ligands at the axial positions. This Ru-bds catalyst electrochemically catalyzes water oxidation with turnover frequencies (TOF) of 160 and 12,900 s-1 under acidic and neutral conditions respectively, showing much better performance than the state-of-art Ru-bda catalyst. Density functional theory calculations reveal that (i) under acidic conditions, the high valent Ru intermediate RuV=O featuring the 7-coordination configuration is involved in the O-O bond formation step; (ii) under neutral conditions, the seven-coordinate RuIV=O triggers the O-O bond formation; (iii) in both cases, the I2M (interaction of two M-O units) pathway is dominant over the WNA (water nucleophilic attack) pathway.
Significant advances during the past decades in the design and studies of Ru complexes with n class="Chemical">polypyridine ligands have led to the great development of molecular water oxidation catalysts and understanding on the O-O bond formation mechanisms. Here we report a Ru-based molecular water oxidation catalyst [Ru(bds)(pic)2] (Ru-bds; bds2- = 2,2'-bipyridine-6,6'-disulfonate) containing a tetradentate, dianionic sulfonate ligand at the equatorial position and two 4-picoline ligands at the axial positions. This Ru-bds catalyst electrochemically catalyzes water oxidation with turnover frequencies (TOF) of 160 and 12,900 s-1 under acidic and neutral conditions respectively, showing much better performance than the state-of-art Ru-bda catalyst. Density functional theory calculations reveal that (i) under acidic conditions, the high valent Ru intermediate RuV=O featuring the 7-coordination configuration is involved in the O-O bond formation step; (ii) under neutral conditions, the seven-coordinate RuIV=O triggers the O-O bond formation; (iii) in both cases, the I2M (interaction of two M-O units) pathway is dominant over the WNA (water nucleophilic attack) pathway.
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