A highly efficient Z‐scheme photocatalytic system constructed with 1D CdS and 2D CoS2 exhibited high photocatalytic hydrogen‐evolution activity of 5.54 mmol h−1 g−1 with an apparent quantum efficiency of 10.2 % at 420 nm. More importantly, its interfacial charge migration pathway was unraveled: The electrons are efficiently transferred from CdS to CoS2 through a transition atomic layer connected by Co–S5.8 coordination, thus resulting in more photogenerated carriers participating in surface reactions. Furthermore, the charge‐trapping and charge‐transfer processes were investigated by transient absorption spectroscopy, which gave an estimated charge‐separation yield of approximately 91.5 % and a charge‐separated‐state lifetime of approximately (5.2±0.5) ns in CdS/CoS2. This study elucidates the key role of interfacial atomic layers in heterojunctions and will facilitate the development of more efficient Z‐scheme photocatalytic systems.
The activity of heterogeneous photocatalytic H2O2 activation in Fenton‐like processes is closely related to the local electron density of reaction centre atoms. However, the recombination of electron‐hole pairs arising from random charge transfer greatly restricts the oriented electron delivery to active center. Here we show a defect engineered iron single atom photocatalyst (Fe1‐Nv/CN, single Fe atoms dispersed on carbon nitride with abundant nitrogen vacancies) for the activation of H2O2 under visible light irradiation. Based on DFT calculations and transient absorption spectroscopy results, the engineered nitrogen vacancies serve as the electron trap sites, which can directionally drive the electrons to concentrate on Fe atoms. The formation of highly concentrated electrons density at Fe sites significantly improves the H2O2 conversion efficiency. Therefore, the optimized single atom catalyst exhibiting a higher ciprofloxacin degradation activity, which was up to 18 times that of pristine CN.
Asymmetric catalysis is one of the most attractive strategies to obtain important enantiomerically pure chemicals with high quality and production. In addition, thanks to the abundant and sustainable advantages of solar energy, photocatalysis possesses great potential in environmentally benign reactions. Undoubtedly, asymmetric photocatalysis meets the strict demand of modern chemistry: environmentally friendly and energy‐sustainable alternatives. Compared with homogeneous asymmetric photocatalysis, heterogeneous catalysis has features of easy separation, recovery, and reuse merits, thus being cost‐ and time‐effective. Herein, the state‐of‐the‐art progress in asymmetric photocatalysis by heterogeneous nanomaterials is addressed. The discussion comprises two sections based on the type of nanomaterials: typical inorganic semiconductors like TiO2 and quantum dots and emerging porous materials including metal–organic frameworks, porous organic polymers, and organic cages. Finally, the challenges and future developments of heterogeneous asymmetric photocatalysis are proposed.
Single-atom photocatalysts have shown their fascinating strengths in enhancing charge transfer dynamics; however, rationally designing coordination sites by metal doping to stabilize isolated atoms is still challenging. Here, a one-unit-cell ZnIn 2 S 4 (ZIS) nanosheet with abundant Cu dopants serving as the suitable support to achieve a single atom Pt catalyst (Pt 1 /Cu-ZIS) is reported, and hence the metal single atom-metal dopant interaction at an atomic level is disclosed. Experimental results and density functional theory calculations highlight the unique stabilizing effect (Pt-Cu interaction) of single Pt atoms in Cu-doped ZIS, while apparent Pt clusters are observed in pristine ZIS. Specifically, Pt-Cu interaction provides an extra coordination site except three S sites on the surface, which induces a higher diffusion barrier and makes the single atom more stable on the surface. Apart from stabilizing Pt single atoms, Pt-Cu interaction also serves as the efficient channel to transfer electrons from Cu trap states to Pt active sites, thereby enhancing the charge separation and transfer efficiency. Remarkably, the Pt 1 /Cu-ZIS exhibits a superb activity, giving a photocatalytic hydrogen evolution rate of 5.02 mmol g −1 h −1 , nearly 49 times higher than that of pristine ZIS.
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