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Tailoring morphology symmetry of bismuth vanadate photocatalysts for efficient charge separation

Science China Chemistry 2023年第12期66卷 3611-3619页

作者： Yuting Deng Hongpeng Zhou Chenwei Ni Fengke Sun Wenchao Jiang Ruotian Chen Wenming Tian Can Li Rengui Li State Key Laboratory of Catalysis Dalian National Laboratory for Clean EnergyiChEM(Collaborative Innovation Center of Chemistry for Energy Materials)Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of SciencesBeijing 100049China State Key Laboratory of Molecular Reaction Dynamics and the Dynamic Research Center for Energy and Environmental Materials Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China

Although spatial charge separation between different facets of semiconductor crystals has been recognized as a general strategy in photocatalysis, the vital role of crystal morphology symmetry in charge separation properties still remains elusive. Herein,taking monoclinic bismuth vanadate(BiVO_(4)) as a platform, we found distinct charge separation difference via rationally tailoring the morphology symmetry from octahedral to truncated octahedral crystals. For octahedral BiVO_(4), photogenerated electrons and holes can be separated between edges and quasi-equivalent facets. However, as for truncated octahedral crystals,photogenerated electrons tend to transfer to {010} facets while photogenerated holes prefer to accumulate on {120} facets, thus realizing the spatial separation of photogenerated charge between different facets. Morphology tailoring of BiVO_(4) crystals leads to a significantly improved photogenerated charge separation efficiency and photocatalytic water oxidation activity. The built-in electric field for driving the separation of photogenerated electrons and holes is considered to be modulated by tuning the morphology symmetry of BiVO_(4) crystals. This work discloses the significant roles of morphology symmetry in photogenerated charge separation and facilitates the rational design of artificial photocatalysts.

关键词： bismuth vanadate morphology symmetry tailoring photocatalysis spatial charge separation

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Coupling of Cu Catalyst and Phosphonated Ru Complex Light Absorber with TiO2 as Bridge to Achieve Superior Visible Light CO2 Photoreduction

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Transactions of Tianjin University 2020年第6期26卷 470-478页

作者： Rongjie Xu Hua Xu Shangbo Ning Qiqi Zhang Zhongshan Yang Jinhua Ye TJU-NIMS International Collaboration Laboratory School of Materials Science and EngineeringTianjin UniversityTianjin 300072China School of Chemistry and Environmental Engineering Wuhan Institute of TechnologyWuhan 430205China International Center for Materials Nanoarchitectonics(WPI-MANA) National Institute for Materials Science(NIMS)Namiki 1-1Tsukuba-ShiIbaraki 305-0044Japan Graduate School of Chemical Sciences and Engineering Hokkaido UniversitySapporo 060-0814Japan

Visible light photocatalytic CO2 conversion is a promising solution to global warming and energy shortage.Herein,we build a well-designed bridge-like nanostructure,that is,the phosphonated Ru complex(RuP)light absorber–TiO2 bridge–Cu catalyst.In this nanostructure,brookite TiO2 serving as a bridge is spatially connected to the RuP and Cu on each of its sides and could thus physically separate the photoexcited holes and electrons over the RuP and Cu,respectively.Given its eff ective charge separation,this RuP–TiO2–Cu assembly exhibits superior CO2 photoreduction activity relative to RuP–SiO2–Cu under visible light irradiation(λ>420 nm).The catalytic activity is further optimized by adopting brookite TiO2 with various electronic band structures.Results reveal the rapid movement of electrons from the RuP through the conduction band of TiO2 and fi nally to the Cu surface.This property is crucial in CO2 photoreduction activity.

关键词： Visible light photocatalysis CO2 photoreduction spatial charge separation

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