Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stac...Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.展开更多
Most biological photoredox reactions occur in sophisticated molecular assemblies consisting of highly organized light-harvesting moieties and catalytic centers.Mimicking these prototypes by creating supramolecular ass...Most biological photoredox reactions occur in sophisticated molecular assemblies consisting of highly organized light-harvesting moieties and catalytic centers.Mimicking these prototypes by creating supramolecular assemblies could be a potentially viable approach toward artificial photosynthesis.Although self-assembled organic materials are known to carry out water splitting reactions,developing self-assembled organic materials for photocatalytic overall water splitting still remains a critical challenge.Herein,we first demonstrate that crystalline organic nanosheets assembled from linear oligo(phenylene butadiynylene)(OPB)are able to catalyze overall water splitting under visible light irradiation.Further investigations reveal that the photocatalytic activity of self-assembled organic structures is closely related to the crystalline structure along with the corresponding electronic structure.Structural disorders in OPB nanosheets and extrinsic factors such as adsorbed water molecules will induce the formation of electron traps which can make the OPB nanosheets thermodynamically unfavorable for photocatalytic overall water splitting.The deactivation mechanism unveiled in this study provides crucial insights into the assembling of artificial organic materials for future solar-to-chemical energy conversion.展开更多
Developing“green”catalytic systems with desirable performance such as good water solubility,recyclability,and switchability is a great challenge.Here,to address this challenge,we extend the concept of polymeric unim...Developing“green”catalytic systems with desirable performance such as good water solubility,recyclability,and switchability is a great challenge.Here,to address this challenge,we extend the concept of polymeric unimolecular micelles(a typical selfassembled structure)to the construction of a stimuli-responsive and recoverable molecular catalyst with single-metal atoms that exhibits switchable photocatalytic activity for water splitting.展开更多
基金supported by the National Natural Science Foundations of China(21965024,22269016,51721002)the Inner Mongolia funding(2020JQ01,21300-5223601)the funding of Inner Mongolia University(10000-21311201/137,213005223601/003,21300-5223707)。
文摘Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.
基金the National Key R&D Program of China(2017YFA0207301,2016YFA0200602,and 2018YFA0208702)the National Natural Science Foundation of China(21875235,21573211,and 21633007)+2 种基金the Anhui Initiative in Quantum Information Technologies(AHY090200)the China Postdoctoral Science Foundation(BX20200317)the Fundamental Research Funds for the Central Universities。
文摘Most biological photoredox reactions occur in sophisticated molecular assemblies consisting of highly organized light-harvesting moieties and catalytic centers.Mimicking these prototypes by creating supramolecular assemblies could be a potentially viable approach toward artificial photosynthesis.Although self-assembled organic materials are known to carry out water splitting reactions,developing self-assembled organic materials for photocatalytic overall water splitting still remains a critical challenge.Herein,we first demonstrate that crystalline organic nanosheets assembled from linear oligo(phenylene butadiynylene)(OPB)are able to catalyze overall water splitting under visible light irradiation.Further investigations reveal that the photocatalytic activity of self-assembled organic structures is closely related to the crystalline structure along with the corresponding electronic structure.Structural disorders in OPB nanosheets and extrinsic factors such as adsorbed water molecules will induce the formation of electron traps which can make the OPB nanosheets thermodynamically unfavorable for photocatalytic overall water splitting.The deactivation mechanism unveiled in this study provides crucial insights into the assembling of artificial organic materials for future solar-to-chemical energy conversion.
基金supported by the National Natural Science Foundation of China(21774076,21890730,21890733,and 51773115)the Program for Basic Research of Shanghai Science and Technology Commission(17JC1403200,19JC1410400,and 19JC1410404)+1 种基金the Program of Shanghai Academic Research Leader(19XD1421700)the Shanghai Eastern Scholar Program.The authors appreciate Shanghai Synchrotron Radiation Facility(SSRF)(Beamline BL14W1 and BL11B)for the synchrotron beam time.
文摘Developing“green”catalytic systems with desirable performance such as good water solubility,recyclability,and switchability is a great challenge.Here,to address this challenge,we extend the concept of polymeric unimolecular micelles(a typical selfassembled structure)to the construction of a stimuli-responsive and recoverable molecular catalyst with single-metal atoms that exhibits switchable photocatalytic activity for water splitting.
