The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic...The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.展开更多
Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferr...Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferrocenes[FeCp(η^(5)-P_(2)C_(3)R_(3))](2a-c)in 71-78%yield.The structures of 2a-c were confirmed by NMR,UV-Vis spectroscopy and X-ray structure analysis,and supported by DFT calculations.Electrochemical studies of 2a-c in CH3CN demonstrate a pronounced reversible one-electron oxidation,while in the solid state,all 3,4,5-triaryl-1,2-diphosphaferrocenes show fully reversible oxidation and reduction waves,which indicates the stability of the oxidized form.Regardless of the substituent(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4)),the studied 1,2-diphosphaferrocenes have similar oxidation and reduction potentials.展开更多
文摘The oxygen evolution reaction(OER)is a key process in water splitting for hydrogen production,yet its sluggish kinetics pose significant challenges for catalyst development.In this work,we present the first systematic study on isostructural 2D coordination polymers(CPs)based on 1,10-ferrocenediyl-bis(H-phosphinic)acid,with cobalt,manganese,and cadmium metals as electrocatalysts for OER.These polymers were synthesized via a facile solution reaction,yielding crystalline materials with excellent structural integrity.The electrocatalytic performance of CPs composites,prepared with carbon and phosphonium ionic liquid,was evaluated in 0.1 M KOH using a three-electrode system.Notably,the Co-and Cd-based CPs demonstrated exceptional OER activity,achieving an overpotential as low as 236–255 mV at 10 mA cm^(-2),surpassing those of many previously reported CP-based OER catalysts.Furthermore,these materials exhibited high stability over prolonged electrolysis,maintaining their activity without significant degradation.This work not only introduces a new class of ferrocenyl phosphinatebased CPs as highly active and durable OER catalysts but also provides valuable insights into their structureactivity relationships,paving the way for future advancements in electrocatalysis.
基金funded by the grant of the Russian Science Foundation,grant number 21-73-10204The authors gratefully acknowledge the Assigned Spectral-Analytical Center of FRC Kazan Scientific Center of RAS(NMR,X-ray,electrochemical measurements)and the scholarship program of the German Academic Exchange Service(DAAD,X-ray structure determination of 2b)Y.S.G.is grateful for the support of the Ministry of Science and Higher Education of the Russia Federation.
文摘Aryl-substituted sodium 1,2-diphosphacyclopentadienides Na(P_(2)C_(3)R_(3))(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4))(1a-c)react with[FeCp(η^(6)-C_(6)H_(5)CH_(3))][PF6]to give heteroleptic 3,4,5-triaryl-1,2-diphosphaferrocenes[FeCp(η^(5)-P_(2)C_(3)R_(3))](2a-c)in 71-78%yield.The structures of 2a-c were confirmed by NMR,UV-Vis spectroscopy and X-ray structure analysis,and supported by DFT calculations.Electrochemical studies of 2a-c in CH3CN demonstrate a pronounced reversible one-electron oxidation,while in the solid state,all 3,4,5-triaryl-1,2-diphosphaferrocenes show fully reversible oxidation and reduction waves,which indicates the stability of the oxidized form.Regardless of the substituent(R=Ph,4-Me-C_(6)H_(4),4-Cl-C_(6)H_(4)),the studied 1,2-diphosphaferrocenes have similar oxidation and reduction potentials.
