Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

Zhuo，Qiming1; Zhan，Shaoqi2; Duan，Lele1,3; Liu，Chang1; Wu，Xiujuan1; Ahlquist，Mårten S.G.2; Li，Fusheng1; Sun，Licheng1,4

2021-03-01

10.1016/S1872-2067(20)63671-3

Chinese Journal of Catalysis   影响因子和分区

1872-2067

1872-2067

A molecular [Ru(bda)]-type (bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand (Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene (3F) or styrene (St) blocking units on the surface of glassy carbon (GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via (1) the radical coupling interaction between the two metallo-oxyl radicals (I2M) in the homo-coupling polymer (poly-1), and (2) the water nucleophilic attack (WNA) pathway in poly-1+P3F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

Dipole moment O–O bond formation Reaction kinetics Second coordination sphere Water oxidation catalyst

SCI ; EI

英语

其他

Fundamental Research Funds for the Central Universities[DUT19LK16] ; Natural Science Foundation of China[21120102036][91233201][21771098] ; National Basic Research Program of China (973 program)[2014CB239402] ; State Key Laboratory of Fine Chemicals[KF1802] ; Swedish Research Council[2017-00935]

Chemistry ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Engineering, Chemical

WOS:000582726000010

SCIENCE PRESS

20203409063393

Oxidation ; Association reactions ; Catalysts ; Electrochemical electrodes ; Polymerization ; Carboxylation ; Chemical bonds ; Coordination reactions ; Free radical reactions ; Kinetics ; Styrene ; Reaction intermediates ; Surface reactions ; Spheres

Fluid Flow, General:631.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Polymerization:815.2 ; Classical Physics; Quantum Theory; Relativity:931

CHEMISTRY

2-s2.0-85089411355

Scopus

1.State Key Laboratory of Fine Chemicals,Institute of Artificial Photosynthesis,DUT-KTH Joint Education and Research Centre on Molecular Devices,Institute for Energy Science and Technology,Dalian University of Technology,Dalian,116024,China
2.Department of Theoretical Chemistry and Biology,School of Engineering Sciences in Chemistry,Biotechnology and Health,KTH Royal Institute of Technology,Stockholm,10691,Sweden
3.Department of Chemistry and Shenzhen Grubbs Institute,Southern University of Science and Technology (SUSTech),Shenzhen,518055,China
4.Department of Chemistry,School of Engineering Sciences in Chemistry,Biotechnology and Health,KTH Royal Institute of Technology,Stockholm,10044,Sweden

Zhuo，Qiming,Zhan，Shaoqi,Duan，Lele,等. Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering[J]. Chinese Journal of Catalysis,2021,42(3):460-469.

Zhuo，Qiming.,Zhan，Shaoqi.,Duan，Lele.,Liu，Chang.,Wu，Xiujuan.,...&Sun，Licheng.(2021).Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering.Chinese Journal of Catalysis,42(3),460-469.

Zhuo，Qiming,et al."Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering".Chinese Journal of Catalysis 42.3(2021):460-469.