Switching O–O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts

Zhang，Biaobiao1; Zhan，Shaoqi2; Liu，Tianqi1; Wang，Linqin1; Ken Inge，A.3; Duan，Lele4; Timmer，Brian J.J.1; Kravchenko，Oleksandr1; Li，Fei5; Ahlquist，Mårten S.G.2; Sun，Licheng1,5

2021-03-01

10.1016/j.jechem.2020.06.036

Journal of Energy Chemistry   影响因子和分区

2095-4956

Understanding the seven coordination and O–O coupling pathway of the distinguished Ru-bda catalysts is essential for the development of next generation efficient water-oxidation catalysts based on earth-abundant metals. This work reports the synthesis, characterization and catalytic properties of a monomeric ruthenium catalyst Ru-bnda (Hbnda = 2,2′-bi(nicotinic acid)-6,6′-dicarboxylic acid) featuring steric hindrance and enhanced hydrophilicity on the backbone. Combining experimental evidence with systematic density functional theory calculations on the Ru-bnda and related catalysts Ru-bda (Hbda = 2,2ʹ-bipyridine-6,6ʹ-dicarboxylic acid), Ru-pda (Hpda = 1,10-phenanthroline-2,9-dicarboxylic acid), and Ru-biqa (Hbiqa = (1,1ʹ-biisoquinoline)-3,3ʹ-dicarboxylic acid), we emphasized that seven coordination clearly determines presence of Ru[dbnd]O with high spin density on the O atom, i.e. oxo with radical properties, which is one of the necessary conditions for reacting through the O–O coupling pathway. However, an additional factor to make the condition sufficient is the favorable intermolecular face-to-face interaction for the generation of the pre-reactive [Ru[dbnd]O···O[dbnd]Ru], which may be significantly influenced by the secondary coordination environments. This work provides a new understanding of the structure–activity relationship of water-oxidation catalysts and their potential to adopt I2M pathway for O–O bond formation.

Oxygen evolution O–O bond formation Ruthenium Water oxidation

SCI ; EI

英语

其他

Swedish Research Council[2017-00935] ; National Natural Science Foundation of China[21120102036] ; National Basic Research Program of China (973 program)[2014CB239402] ; Swedish National Infrastructure for Uppsala Multidisciplinary Center for Advanced Computational Science (UPPMAX)[SNIC2017-1-339]

Chemistry ; Energy & Fuels ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Energy & Fuels ; Engineering, Chemical

WOS:000605246200012

ELSEVIER

20202908952525

Oxygen ; Ruthenium compounds ; Chelation ; Density functional theory ; Ruthenium ; Oxidation ; Chemical bonds ; Coordination reactions

Precious Metals:547.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

2-s2.0-85087937040

Scopus

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

Zhang，Biaobiao,Zhan，Shaoqi,Liu，Tianqi,等. Switching O–O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts[J]. Journal of Energy Chemistry,2021,54:815-821.

Zhang，Biaobiao.,Zhan，Shaoqi.,Liu，Tianqi.,Wang，Linqin.,Ken Inge，A..,...&Sun，Licheng.(2021).Switching O–O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts.Journal of Energy Chemistry,54,815-821.

Zhang，Biaobiao,et al."Switching O–O bond formation mechanism between WNA and I2M pathways by modifying the Ru-bda backbone ligands of water-oxidation catalysts".Journal of Energy Chemistry 54(2021):815-821.