Abstract
The photocatalytic conversion of CO_2 into hydrocarbons using sustainable solar energy offers a promising strategy to address the global energy crisis and achieve carbon neutrality. However, conventional p-block photocatalysts are often limited by inefficient electron transfer, which restricts the reaction to a two-electron reduction pathway, primarily yielding CO and impeding the formation of high-value hydrocarbons like CH_4. Herein, we construct a novel BiOCl-BiO(HCOO) heterostructure (denoted as BiOCH), which features interfacial chelating interactions between the [Bi2O_2]~(2+) and [HCOO]~- layers within the BiO(HCOO) component, for efficient photocatalytic CO_2 reduction to CH_4. This unique heterostructure broadens the light absorption spectrum and facilitates the separation of photoinduced charges. More importantly, the interfacial Bi-O chelation in BiO(HCOO) modulates the local electronic microenvironment of Bi sites. Mechanistic studies reveal that this modulation enhances the coupling between the C-2p orbital of the*CHO intermediate and the Bi-p orbital, thereby lowering the Gibbs free energy barrier for the critical*CO-to-*CHO step and promoting CH_4 generation. Consequently, the optimized BiOCH catalyst achieves a remarkable CH_4 production rate of 42.95 µmol⋅g~(-1)⋅h~(-1) with a high electron selectivity of 95.38%. This work provides a novel design strategy of organic-inorganic hybrid layered structures for steering photocatalytic CO_2 reduction toward value-added hydrocarbons.
NETL
NSTL
Wiley