Exploitation of stable proton conducting materials with high stability and excellent conductivity is becom-ing more important but challenging.Herein,two novel porous transition metal-organic frameworks(MOFs),formulate...Exploitation of stable proton conducting materials with high stability and excellent conductivity is becom-ing more important but challenging.Herein,two novel porous transition metal-organic frameworks(MOFs),formulated as[Zn(btzip)(H_(2)O)]·H_(2)O(LCUH-107)and[Ni(btzip)(H_(2)btzip)]·4H_(2)O(LCUH-108),are successfully synthesized.LCUH-107 and LCUH-108 exhibit excellent thermal and chemical stabilities.LCUH-108 has a suitable pore size(8.36Å×5.74Å)to load trifluoroacetic acid(TFA,5.72Å×5.65Å×5.06Å),which is larger than that of LCUH-107(3.50Å×2.04Å).Therefore,TFA molecules can be loaded into the pores of LCUH-108 while they were only loaded onto the surface of LCUH-107.Both TFA/LCUH-107(2.95×10^(-2)S cm^(−1))and TFA@LCUH-108(2.05×10^(-1)S cm^(−1))exhibit excellent proton con-duction at 80℃and 100%relative humidity(RH);in particular,the proton conductivity value of TFA@LCUH-108 can be as high as 10-1 S cm^(−1),which might be due to the fact that TFA molecules can be confined into their suitable pores and finally form strong continuous and stable hydrogen-bonding networks.The TFA molecules loaded into the suitable pores of LCUH-108 play a key role in improving greatly the proton conductivity of LCUH-108,while TFA molecules loaded onto the surface of LCUH-107 can only slightly improve the proton conductivity of LCUH-107,which can be confirmed by various con-trast tests and simulated calculations.This work gives a novel strategy to design efficient artificial crystal-line catalysts for proton conduction.展开更多
基金supported by the National Natural Science Foundation of China(21401095,21801107,22178157)the Natural Science Foundation of Shandong Province(ZR2022MB010,ZR2019MB068,ZR2021QB123)+5 种基金the Project of Shandong Province Higher Educational Science and Technology Program(KJ2018BZC043 and J18KA113)the Liaocheng University Start-up Fund for Doctoral Scientific Research(318050104 and 318052017)the Scientific Research Fund of Liaocheng University(318011913)the Youth Innovation Team of Shandong Colleges and Universities(2019KJC027 and 2020KJC012)the Open Fund of Liaocheng University(2020CESNCTKL02)the Shandong Students Innovation and Entrepreneurship Training Program(319260210).
文摘Exploitation of stable proton conducting materials with high stability and excellent conductivity is becom-ing more important but challenging.Herein,two novel porous transition metal-organic frameworks(MOFs),formulated as[Zn(btzip)(H_(2)O)]·H_(2)O(LCUH-107)and[Ni(btzip)(H_(2)btzip)]·4H_(2)O(LCUH-108),are successfully synthesized.LCUH-107 and LCUH-108 exhibit excellent thermal and chemical stabilities.LCUH-108 has a suitable pore size(8.36Å×5.74Å)to load trifluoroacetic acid(TFA,5.72Å×5.65Å×5.06Å),which is larger than that of LCUH-107(3.50Å×2.04Å).Therefore,TFA molecules can be loaded into the pores of LCUH-108 while they were only loaded onto the surface of LCUH-107.Both TFA/LCUH-107(2.95×10^(-2)S cm^(−1))and TFA@LCUH-108(2.05×10^(-1)S cm^(−1))exhibit excellent proton con-duction at 80℃and 100%relative humidity(RH);in particular,the proton conductivity value of TFA@LCUH-108 can be as high as 10-1 S cm^(−1),which might be due to the fact that TFA molecules can be confined into their suitable pores and finally form strong continuous and stable hydrogen-bonding networks.The TFA molecules loaded into the suitable pores of LCUH-108 play a key role in improving greatly the proton conductivity of LCUH-108,while TFA molecules loaded onto the surface of LCUH-107 can only slightly improve the proton conductivity of LCUH-107,which can be confirmed by various con-trast tests and simulated calculations.This work gives a novel strategy to design efficient artificial crystal-line catalysts for proton conduction.
