Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has...Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.展开更多
Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinem...Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinement effect,which are distinct from conventional metal nanoparticles(NPs).Nevertheless,metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs,markedly reducing the photosensitization of metal NCs.Herein,maneuvering the generic instability of metal NCs,we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical(PEC)water splitting reaction.For conceptual demonstration,we proposed two quintessential heterostructures,which include TNTAs-Au_(25)heterostructure fabricated by electrostatically depositing glutathione(GSH)-protected Au_(25)(GSH)_(18)NCs on the TiO_(2)nanotube arrays(TNTAs)substrate,and TNTAs-Au heterostructure constructed by triggering self-transformation of Au_(25)(GSH)_(18)NCs to plasmonic Au NPs in TNTAs-Au_(25)via calcination.The results indicate that photoelectrons produced over Au_(25)NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation.This is mainly ascribed to the significantly accelerated carrier transport kinetics,prolonged carrier lifespan,and substantial photosensitization effect of Au_(25)NCs compared with plasmonic Au NPs,resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au_(25)relative to plasmonic TNTAs-Au counterpart under visible light irradiation.Our work would provide important implications for rationally designing atomically precise metal NCsbased photosystems toward solar energy conversion.展开更多
文摘Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalizedπelectrons along the molecular chain framework.Up to date,origin of insulating polymer regulated charge transfer has not yet been uncovered.In this work,we unleash the root origin of charge transport capability of insulating polymer in photocatalysis.We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides(TMCs),which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics,triggering the generation of defect over TMCs for prolonging carrier lifetime,and acting as hole-trapping mediator for retarding charge recombination.These synergistic roles contribute to the charge transfer of insulating polymer.Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.
基金support by the Award Program for Minjiang Scholar Professorshipfinancially supported by the National Natural Science Foundation of China(Nos.21703038,22072025)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR147)。
文摘Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinement effect,which are distinct from conventional metal nanoparticles(NPs).Nevertheless,metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs,markedly reducing the photosensitization of metal NCs.Herein,maneuvering the generic instability of metal NCs,we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical(PEC)water splitting reaction.For conceptual demonstration,we proposed two quintessential heterostructures,which include TNTAs-Au_(25)heterostructure fabricated by electrostatically depositing glutathione(GSH)-protected Au_(25)(GSH)_(18)NCs on the TiO_(2)nanotube arrays(TNTAs)substrate,and TNTAs-Au heterostructure constructed by triggering self-transformation of Au_(25)(GSH)_(18)NCs to plasmonic Au NPs in TNTAs-Au_(25)via calcination.The results indicate that photoelectrons produced over Au_(25)NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation.This is mainly ascribed to the significantly accelerated carrier transport kinetics,prolonged carrier lifespan,and substantial photosensitization effect of Au_(25)NCs compared with plasmonic Au NPs,resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au_(25)relative to plasmonic TNTAs-Au counterpart under visible light irradiation.Our work would provide important implications for rationally designing atomically precise metal NCsbased photosystems toward solar energy conversion.
