Recently, Professor Su Yaorong's team from our institute published their latest research findings titled "Achieving Free-Electron Transfer Reversal and dz2-Orbital Occupancy Modulation on Core-shell NiS@Au Cocatalysts for Highly Selective H2O2 Photosynthesis" in the prestigious international academic journal *Angewandte Chemie International Edition*. The School of New Materials and New Energy is the first completing unit and the first corresponding unit. Associate Researcher Zhong Wei and Associate Professor Meng Aiyun are the co-first authors, while Professor Su Yaorong is the first corresponding author. Professors Yu Huigen and Yu Jiaguo from China University of Geosciences (Wuhan) are the co-corresponding authors.

Hydrogen peroxide (H2O2) is a clean fuel that is easy to store and transport, and it is widely used as an environmentally friendly oxidizing agent in industries such as organic synthesis, drinking water treatment, wastewater treatment, and healthcare. However, the traditional anthraquinone method for synthesizing H2O2 has issues with high energy consumption, significant environmental pollution, and complex process flows. In recent years, photocatalytic oxygen reduction to produce H2O2 using semiconductor materials has shown advantages such as mild reaction conditions, simple and controllable operation, and low energy consumption, making it one of the effective alternatives to the anthraquinone method for preparing H2O2. Nevertheless, reported semiconductor photocatalytic materials still suffer from weak adsorption capacity for oxygen molecules and poor selectivity in two-electron oxygen reduction to produce H2O2, leading to low efficiency in photocatalytic H2O2 production.

In response to the aforementioned issues, Professor Su Yaorong's research team adopted a targeted adsorption-in situ photoelectron reduction strategy to synthesize a core-shell type NiS@Au hetero-assisted catalyst on the surface of typical g-C3N4 semiconductor materials. This catalyst achieved efficient and highly selective oxygen reduction for H2O2 production in air, with a H2O2 formation rate as high as 5.3 mmol/h/g. Experimental characterization combined with theoretical calculations demonstrated that the coupling of NiS with Au nanoparticles can induce the reverse transfer of free electrons from the Au shell to the NiS core, reducing the dz2 orbital occupancy state of surface Au atoms. This enhances the adsorption and stabilization of *OOH intermediates, ultimately endowing the NiS@Au hetero-assisted agent with high-selectivity for two-electron oxygen reduction to produce H2O2. Additionally, the core-shell NiS@Au agent can rapidly transfer photogenerated electrons, thereby suppressing the recombination of photogenerated electron-hole pairs. This study established an effective regulatory mechanism linking active site electronic structure, interfacial catalytic reaction kinetics, and photocatalytic H2O2 production efficiency, providing important technical and theoretical support for the controlled preparation of functional nanomaterials and their applications in energy conversion.

Figure 1 Schematic diagram of NiS-induced interface free electron inversion to reduce the dz2 orbital occupancy state of Au atoms to achieve highly selective photocatalytic production of H2O2

This work was supported by the National Natural Science Foundation of China, Guangdong Provincial Basic and Applied Basic Research Foundation, Guangdong Provincial Education Department, Shenzhen Science and Technology Innovation Commission, Shenzhen Key Laboratory of Super Diamond and Functional Crystal Application Technology.

Angewandte Chemie International Edition (German Journal of Applied Chemistry) was founded in 1888. It is the official flagship journal of the German Chemical Society (GDCh). It is one of the most influential journals in the international field of chemistry. The current impact factor is 16.1, and it is a TOP journal in the first zone and Nature Index journal of the Chinese Academy of Sciences.

Original link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202425038