21:I[432972,["/_next/static/chunks/bb923814e1f4d2e9.js","/_next/static/chunks/dd3ee9f5b7716ca6.js","/_next/static/chunks/4204a0ae82542ca8.js","/_next/static/chunks/1270dead247da766.js","/_next/static/chunks/6e1aa89a642f40be.js","/_next/static/chunks/2d7aa753e81324a8.js","/_next/static/chunks/8ffd0b71567920d8.js","/_next/static/chunks/67ea6dfd21f16c5f.js","/_next/static/chunks/24eb4379f68013fd.js","/_next/static/chunks/b8cd775ffdf935bd.js","/_next/static/chunks/983103cd9eb7b428.js","/_next/static/chunks/263f2cdcb9aa2341.js","/_next/static/chunks/294b9525248c8e5f.js"],"default"] 22:T50d,Herein, we report the importance of structure regulation on the O-O bond formation process in binuclear iron catalysts. Three complexes, [Fe₂ (μ-O)(OH₂ )₂ (TPA)₂ ]⁴⁺ (1), [Fe₂ (μ-O)(OH₂ )₂ (6-HPA)]⁴⁺ (2) and [Fe₂ (μ-O)(OH₂ )₂ (BPMAN)]⁴⁺ (3), have been designed as electrocatalysts for water oxidation in 0.1 M NaHCO₃ solution (pH 8.4). We found that 1 and 2 are molecular catalysts and that O-O bond formation proceeds via oxo-oxo coupling rather than by the water nucleophilic attack (WNA) pathway. In contrast, complex 3 displays negligible catalytic activity. DFT calculations suggested that the anti to syn isomerization of the two high-valent Fe=O moieties in these catalysts takes place via the axial rotation of one Fe=O unit around the Fe-O-Fe center. This is followed by the O-O bond formation via an oxo-oxo coupling pathway at the Fe^IV Fe^IV state or via oxo-oxyl coupling pathway at the Fe^IV Fe^V state. Importantly, the rigid BPMAN ligand in complex 3 limits the anti to syn isomerization and axial rotation of the Fe=O moiety, which accounts for the negligible catalytic activity.23:T421,Water splitting is one of the most promising solutions for storing solar energy in a chemical bond. Water oxidation is still the bottleneck step because of its inherent difficulty and the limited understanding of the O-O bond formation mechanism. Molecular catalysts provide a platform for understanding this process in depth and have received wide attention since the first Ru-based catalyst was reported in 1982. Ru^V =O is considered a key intermediate to initiate the O-O bond formation through either a water nucleophilic attack (WNA) pathway or a bimolecular coupling (I2M) pathway. Herein, we report a Ru-based catalyst that displays water oxidation reactivity with Ru^IV =(O) with the help of a redox-active ligand at pH 7.0. The results of electrochemical studies and DFT calculations disclose that ligand oxidation could significantly improve the reactivity of Ru^IV =O toward water oxidation. Under these conditions, sustained water oxidation catalysis occurs at reasonable rates with low overpotential (ca. 183 mV).24:T4a6,We report herein the first nonheme CuFe oxygen reduction catalyst ([Cu^II (bpbp)(μ-OAc)₂ Fe^III ]²⁺ , CuFe-OAc), which serves as a functional model of cytochrome c oxidase and can catalyze oxygen reduction to water with a turnover frequency of 2.4×10³ s^-1 and selectivity of 96.0 % in the presence of Et₃ NH⁺ . This performance significantly outcompetes its homobimetallic analogues (2.7 s^-1 of CuCu-OAc with %H₂ O₂ selectivity of 98.9 %, and inactive of FeFe-OAc) under the same conditions. Structure-activity relationship studies, in combination with density functional theory calculation, show that the CuFe center efficiently mediates O-O bond cleavage via a Cu^II (μ-η¹ : η² -O₂ )Fe^III peroxo intermediate in which the peroxo ligand possesses distinctive coordinating and electronic character. Our work sheds light on the nature of Cu/Fe heterobimetallic cooperation in oxygen reduction catalysis and demonstrates the potential of this synergistic effect

#	Concept	H-Index	Publications	Citations
1	Engineering	3	3	84
2	Chemical Engineering	3	3	84
3	Chemistry	3	3	84
4	Catalysis	3	3	84
5	Electrochemistry	1	1	52

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