Simultaneously Effi cient Solar Light Harvesting and Charge Transfer of Hollow Octahedral Cu_(2)S/CdS p-n Heterostructures for Remarkable Photocatalytic Hydrogen Generation

Solar-driven water splitting is a promising alternative to industrial hydrogen production.This study reports an elaborate design and synthesis of the integration of cadmium sulfi de(CdS)quantum dots and cuprous sulfi de(Cu_(2)S)nanosheets as three-dimensional(3D)hollow octahedral Cu_(2)S/CdS p-n heterostructured architectures by a versatile template and one-pot sulfi dation strategy.3D hierarchical hollow nanostructures can strengthen multiple refl ections of solar light and provide a large specifi c surface area and abundant reaction sites for photocatalytic water splitting.Owing to the construction of the p-n heterostructure as an ideal catalytic model with highly matched band alignment at Cu_(2)S/CdS interfaces,the emerging internal electric fi eld can facilitate the space separation and transfer of photoexcited charges between CdS and Cu_(2)S and also enhance charge dynamics and prolong charge lifetimes.Notably,the unique hollow Cu_(2)S/CdS architectures deliver a largely enhanced visible-light-driven hydrogen generation rate of 4.76 mmol/(g·h),which is nearly 8.5 and 476 times larger than that of pristine CdS and Cu_(2)S catalysts,respectively.This work not only paves the way for the rational design and fabrication of hollow photocatalysts but also clarifi es the crucial role of unique heterostructure in photocatalysis for solar energy conversion.

Engineering single–atom active sites anchored covalent organic frameworks for efficient metallaphotoredox C-N cross–coupling reactions

Photoredox catalysis has become an indispensable solution for the synthesis of small organic molecules.However,the precise construction of single-atomic active sites not only determines the catalytic performance,but also avails the understanding of structure–activity relationship.Herein,we develop a facile approach to immobilize single-atom Ni sites anchored porous covalent organic framework(COF)by use of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,6-diformylpyridine(Ni SAS/TD-COF).Ni SAS/TDCOF catalyst achieves excellent catalytic performance in visible-light-driven catalytic carbon–nitrogen cross-coupling reaction between aryl bromides and amines under mild conditions.The reaction provides amine products in excellent yields(71%–97%)with a wide range of substrates,including aryl and heteroaryl bromides with electron-deficient,electron-rich and neutral groups.Notably,Ni SAS/TD-COF could be recovered from the reaction mixture,corresponding to the negligible loss of photoredox performance after several cycles.This work provides a promising opportunity upon rational design of single-atomic active sites on COFs and the fundamental insight of photoredox mechanism for sustainable organic transformation.