Synergistic Electron–Photon Effect over Engineered Pt–Cr Clusters Enables Sustainable and Sulfur-Resistant Methane Combustion

Efficient low-temperature catalytic combustion is paramount for CH 4 abatement, yet its practical implementation is severely hampered by a persistent trade-off between high catalytic activity and robust sulfur resistance. Herein, we report a synergistic electron-photon strategy where Cr modification first precisely tunes the electronic structure of a Pt–Ti-based catalyst, creating an optimized catalyst foundation that is then powerfully leveraged by incident photon-assisted catalysis to optimize the reaction path. Specifically, Cr incorporation on Pt 8 Cr 2 /r-TiO 2 engineered highly dispersed Pt–Cr oxide clusters with a unique interfacial synergy. Characterizations and DFT studies confirmed that these clusters feature significantly increased Pt 4+ active sites stabilized by Pt–Cr electron transfer while also weakening the Pt–O bond and inducing abundant surface oxygen vacancies. These foundational electronic modifications by Cr greatly enhanced intrinsic low-temperature activity and, by inducing interfacial electron enrichment, suppressed SO 2 adsorption. Critically, the subsequent injection of photons unlocked an exceptional photothermal synergistic performance. The T 90 for CH 4 combustion decreased by an additional 71.3 °C under the photothermal catalytic strategy. Photoassisted kinetic analysis and in situ DRIFTS revealed that photon irradiation substantially enhanced the chemisorption of CH 4 molecules on the catalyst surface, significantly lowered the apparent activation energy, and altered the reaction pathway. Enhanced charge separation efficiency, facilitated by the engineered cluster-support interface, promoted O 2 activation and established a charge barrier to repel SO 2 species. Thus, through this synergistic interplay of atomic-scale electronic modulation and subsequent photon-driven enhancement, the Pt 8 Cr 2 /r-TiO 2 catalyst exhibited remarkable stability, enabling sustainable low-temperature activity even under 200 ppm of SO 2 . This work provides fundamental insights into designing highly active, antipoisoning and noble-metal-reduced catalysts for challenging combustion reactions, paving new avenues for environmental catalysis technologies.