@article{Zhang2026, 
author = {Yihong Zhang and Yilong Yang and Haishan Zhu and Yuen Zheng and Jiaqi Shen and Heju Guo and Longzhou Jin and Dan Liu and Silin Liu and Junshu Wu and Kaidong Xu and Yong Zhao and Songcan Wang and Chunqiang Zhuang},
title = {Engineering molecular-semiconductor interfaces via vacancy-triggered π–d coupling for H2O2 photosynthesis},
year = {2026},
journal = {Nano Research},
keywords = {photocatalytic H2O2 production, oxygen reduction reaction, oxygen vacancies, interfacial π–d coupling, orbital-level interface engineering, organic–inorganic hybrid interface},
url = {https://www.sciopen.com/article/10.26599/NR.2026.94909255},
doi = {10.26599/NR.2026.94909255},
abstract = {Photocatalytic H2O2 production is limited by slow interfacial charge transfer and poorly controlled adsorption of oxygen intermediates, which reduce the selectivity of the two-electron oxygen reduction reaction. We prepared an oxygen-vacancy-rich In-TCPP@W18O49 heterointerface to investigate the role of π–d orbital coupling in oxygen reduction. Experiments and calculations show that oxygen vacancies enhance hybridization between the π states of In-TCPP and the W 5d states of W18O49. This interaction promotes interfacial charge redistribution and modifies the local electronic structure of surface W sites. The resulting electronic changes facilitate interfacial electron transfer and regulate the adsorption energies of *O2 and *OOH intermediates, favoring a selective two-electron pathway for H2O2 formation. The optimized In-TCPP@W18O49 produces H2O2 at 1045 μmol g-1 h-1 in pure water under ambient air, 10.7 times higher than W18O49, with a solar-to-chemical conversion efficiency of 1.66 %. These findings indicate how oxygen-vacancy-enhanced π–d coupling may influence oxygen reduction and provide insights into designing selective solar-driven oxygen reduction photocatalysts.}
}