The low-efficiency CO_(2) uptake capacity and insufficient photogenerated exciton dissociation of current metal halide perovskite(MHP)nanocrystals with end-capping ligands extremely restrict their application in the f...The low-efficiency CO_(2) uptake capacity and insufficient photogenerated exciton dissociation of current metal halide perovskite(MHP)nanocrystals with end-capping ligands extremely restrict their application in the field of artificial photosynthesis.Herein,we demonstrate that ligand-free CsPbBr_(3) with calliandralike nanostructure(LF-CPB CL)can be synthesized easily through a ligand-free seed-assisted dissolutionrecrystallization growth process,exhibiting significantly enhanced CO_(2) uptake capacity.More specifically,the abundant surface bromine(Br)vacancies in ligand-free MHP materials are demonstrated to be beneficial to photogenerated carrier separation.The electron consumption rate of LF-CPB CL for photocatalytic CO_(2) reduction increases 7 and 20 times over those of traditional ligand-capping CsPbBr_(3)nanocrystal(L-CPB NC)and bulk CsPbBr_(3),respectively.Moreover,the absence of ligand hindrance can facilitate the interfacial electronic coupling between LF-CPB CL and tetra(4-carboxyphenyl)porphyrin iron(Ⅲ)chloride(Fe-TCPP)cocatalyst,bringing forth significantly accelerated interfacial charge separation.The LF-CPB CL/Fe-TCPP exhibits a total electron consumption rate of 145.6μmol g^(-1) h^(-1) for CO_(2)photoreduction coupled with water oxidation which is over 14 times higher than that of L-CPB NC/FeTCPP.展开更多
Excellent optical properties involving strong visible light response and superior carrier transport endow metal halide perovskites(MHP)with a fascinating prospect in the field of photocatalysis.Nevertheless,the poor s...Excellent optical properties involving strong visible light response and superior carrier transport endow metal halide perovskites(MHP)with a fascinating prospect in the field of photocatalysis.Nevertheless,the poor stability of MHP nanocrystals(NCs)in water-contained system,especially without the protection of long alkyl chain ligands,severely restricts their photocatalytic performance.In this context,we report an effortless strategy for the generation of ligand-free MHP NCs based photocatalyst with high water tolerance,by coating PbI_(2)on the surface of ligand-free formamidinium lead bromide(FAPb Br_(3))NCs via the facile procedure of in-situ conversion with the aid of ZnI_(2).Under the protection of PbI_(2)layer,the resultant FAPb Br_(3)/PbI_(2)composite exhibits significantly ameliorated stability in an artificial photosynthesis system with CO_(2)and H_(2)O vapor as feedstocks.Moreover,the formation of compact PbI_(2)layer can accelerate the separation of photogenerated carriers in FAPbBr_(3)NCs,bringing forth a remarkable improvement of CO_(2)photoreduction efficiency with an impressive electron consumption yield of 2053μmol/g in the absence of organic sacrificial agents,which is 7-fold over that of pristine FAPb Br_(3)NCs.展开更多
基金financially supported by the Natural Science Foundation of Tianjin City(17JCJQJC43800)the National Key R&D Program of China(2017YFA0700104)+1 种基金the National Science Foundation of China(21931007,U21A20286)Jiangsu Funding Program for Excellent Postdoctoral Talent and the 111 Project of China(D17003)。
文摘The low-efficiency CO_(2) uptake capacity and insufficient photogenerated exciton dissociation of current metal halide perovskite(MHP)nanocrystals with end-capping ligands extremely restrict their application in the field of artificial photosynthesis.Herein,we demonstrate that ligand-free CsPbBr_(3) with calliandralike nanostructure(LF-CPB CL)can be synthesized easily through a ligand-free seed-assisted dissolutionrecrystallization growth process,exhibiting significantly enhanced CO_(2) uptake capacity.More specifically,the abundant surface bromine(Br)vacancies in ligand-free MHP materials are demonstrated to be beneficial to photogenerated carrier separation.The electron consumption rate of LF-CPB CL for photocatalytic CO_(2) reduction increases 7 and 20 times over those of traditional ligand-capping CsPbBr_(3)nanocrystal(L-CPB NC)and bulk CsPbBr_(3),respectively.Moreover,the absence of ligand hindrance can facilitate the interfacial electronic coupling between LF-CPB CL and tetra(4-carboxyphenyl)porphyrin iron(Ⅲ)chloride(Fe-TCPP)cocatalyst,bringing forth significantly accelerated interfacial charge separation.The LF-CPB CL/Fe-TCPP exhibits a total electron consumption rate of 145.6μmol g^(-1) h^(-1) for CO_(2)photoreduction coupled with water oxidation which is over 14 times higher than that of L-CPB NC/FeTCPP.
基金the Natural Science Foundation of Tianjin City(No.17JCJQJC43800)。
文摘Excellent optical properties involving strong visible light response and superior carrier transport endow metal halide perovskites(MHP)with a fascinating prospect in the field of photocatalysis.Nevertheless,the poor stability of MHP nanocrystals(NCs)in water-contained system,especially without the protection of long alkyl chain ligands,severely restricts their photocatalytic performance.In this context,we report an effortless strategy for the generation of ligand-free MHP NCs based photocatalyst with high water tolerance,by coating PbI_(2)on the surface of ligand-free formamidinium lead bromide(FAPb Br_(3))NCs via the facile procedure of in-situ conversion with the aid of ZnI_(2).Under the protection of PbI_(2)layer,the resultant FAPb Br_(3)/PbI_(2)composite exhibits significantly ameliorated stability in an artificial photosynthesis system with CO_(2)and H_(2)O vapor as feedstocks.Moreover,the formation of compact PbI_(2)layer can accelerate the separation of photogenerated carriers in FAPbBr_(3)NCs,bringing forth a remarkable improvement of CO_(2)photoreduction efficiency with an impressive electron consumption yield of 2053μmol/g in the absence of organic sacrificial agents,which is 7-fold over that of pristine FAPb Br_(3)NCs.
