Integrating Localized Surface Plasmon Resonance and Electronic Metal–Support Interactions for Facilitating Photothermal Sabatier Reaction

Abstract Plasma‐mediated photothermal catalysis, harnessing the localized surface plasmon resonance (LSPR) effect to improve light utilization and generate hot electrons for chemical reactions, is an intriguing and booming field. However, conventional plasmonic particles composed of noble metals such as Au and Ag often suffer from narrow absorption spectra confined to the visible region, coupled with instability and prohibitively high costs, thereby limiting their practical applicability. To address this obstacle, a noble‐metal‐free dual plasmonic Ni/VN composite is developed using an in situ segregation method, which integrates metal‐semiconductor LSPR to achieve full‐spectrum (200–2500 nm) responsiveness, significantly boosting photothermal conversion efficiency. Meanwhile, the interfacial microenvironment‐induced electronic metal–support interactions strengthen the adsorption and activation capabilities of reactants and intermediates, effectively lowering energy barriers and thus conferring exceptional activity and stability. As a demonstration using the Sabatier reaction, the optimal catalyst demonstrates a remarkable CH ₄ production rate of 89.4 mmol g ⁻¹ h ⁻¹ with a selectivity above 99% under Xenon lamp irradiation without any external heat source, which exceeds the activities of Ni/VN‐w catalyst produced by conventional deposition method and the commercial Ni@Al ₂ O ₃ ‐SiO ₂ catalyst. This work offers valuable insights into the precise design of noble‐metal‐free catalyst and the development of plasmonic photothermal catalysts for reducing carbon footprints.