Water oxidation catalytic ability of polypyridine complex containing a μ-OH, μ-O_2 dicobalt(iii) core

Two polypyridine complexes containingμ‐OH,μ‐O2dicobalt(III)cores,[(TPA)CoIII(μ‐OH)(μ‐O2)CoIII(TPA)](ClO4)3and[(BPMEN)CoIII(μ‐OH)(μ‐O2)CoIII(BPMEN)](ClO4)3(TPA=tris(2‐pyridylmethyl)amine,BPMEN=N,N′‐dimethyl‐N,N′‐bis(pyridin‐2‐ylmethyl)ethane‐1,2‐diamine),have previously been reported as inactive in the light‐driven water oxidation reaction(ACS Catal.,2016,6,5062?5068).Herein,another dicobalt(III)compound,μ‐OH,μ‐O2‐[{(enN4)2Co2}](ClO4)3(enN4=1,6‐bis(2‐pyridyl‐2,5‐diazaocta‐2,6‐diene),with a similar core structure was synthesized,characterized,and applied to the light‐driven water oxidation reaction.Collective experiments showed that the complex itself was also inactive in the light‐driven water oxidation,and that the activity observed originated from Co(II)impurities.This research establishes that complexes possessing aμ‐OH,μ‐O2dicobalt(III)core structure are not appropriate choices for true molecular catalysts ofwater oxidation.

Influences of chemical reactions on polysulfide reduction reaction process on promotor surface in Li-S batteries

Polar promotors have been proven effective in catalyzing the polysulfide(PS)reduction reaction(PSRR)process in lithium-sulfur(Li-S)batteries.However,the promotor surface tends to be poisoned due to the accumulation of insoluble discharging products of lithium disulfide(Li_(2)S_(2))and lithium sulfide(Li_(2)S)during Li-S battery operation.Herein,we investigate the detailed PSRR mechanism on the surface of manganese sulfides(MnS)as a representative promoter by performing in-situ Raman mapping measurements.The catalytic ability of MnS enables thorough electrochemical reduction of PSs to Li_(2)S_(2) and Li_(2)S on the MnS surface.The generated Li_(2)S_(2) and Li_(2)S then adsorb the dissolved PSs via chemical reactions among sulfur species during the subsequent PSRR process.This phenomenon mitigates promotor poisoning and continuously improves the reversible capacity.Consequently,the assembled Li-S cell demonstrates excellent electrochemical performance after introducing a conductive interlayer containing a thin piece of carbon nanotube film and MnS promotors.