Bromine is an irreplaceable reagent for many important applications including necessary additive for flame retardants and rubber treatment.However,the toxicity,causticity,and vaporability of bromine make the safe usag...Bromine is an irreplaceable reagent for many important applications including necessary additive for flame retardants and rubber treatment.However,the toxicity,causticity,and vaporability of bromine make the safe usage and transportation of bromine challenging,which can be alleviated by the bromine prefixation.Herein,vacancy-ordered bromide perovskites such as Cs^(4)Sb_(2)Br_(12)and Cs_(2)PdBr_(6)are selected out for the bromine fixation through density-functional theory calculations and experiments.The redox within the bromide perovskites is designed to provide the driving force for the reversible release and fixation of bromine.Heating and cooling the title bromide perovskites in a necked ampoule make the bromine visible and separable from the solid residue.The composition engineering(i.e.,Cs_(4)Sb_(2)Br_(12)vs Rb_(4)Sb_(2)Br_(12),and Cs_(4)Sb_(2)Br_(12)vs Cs_(2)PdBr_(6))can effectively tune the stability(against water and high temperature)and the bromine storage capacity(from9.30%to 18.76%).In addition,this work can provide a one-step preparation method for the liquid bromine without further purification.展开更多
基金supported by National Natural Science Foundation of China(NSFC)(No.21871048,51802039)NSF of Fujian Province(2019J01266)+3 种基金the State Key Laboratory Program of Structural Chemistry in China(20190014)supported by the Thousand Young Talents Program of Chinathe Startup Fund of HUSTthe Director Fund of Wuhan National Laboratory for Optoelectronics
文摘Bromine is an irreplaceable reagent for many important applications including necessary additive for flame retardants and rubber treatment.However,the toxicity,causticity,and vaporability of bromine make the safe usage and transportation of bromine challenging,which can be alleviated by the bromine prefixation.Herein,vacancy-ordered bromide perovskites such as Cs^(4)Sb_(2)Br_(12)and Cs_(2)PdBr_(6)are selected out for the bromine fixation through density-functional theory calculations and experiments.The redox within the bromide perovskites is designed to provide the driving force for the reversible release and fixation of bromine.Heating and cooling the title bromide perovskites in a necked ampoule make the bromine visible and separable from the solid residue.The composition engineering(i.e.,Cs_(4)Sb_(2)Br_(12)vs Rb_(4)Sb_(2)Br_(12),and Cs_(4)Sb_(2)Br_(12)vs Cs_(2)PdBr_(6))can effectively tune the stability(against water and high temperature)and the bromine storage capacity(from9.30%to 18.76%).In addition,this work can provide a one-step preparation method for the liquid bromine without further purification.