Synergistic Electron–Photon Effect over Engineered Pt–Cr Clusters Enables Sustainable and Sulfur-Resistant Methane Combustion
Yannan Li, Bin Hu, Kaijie Liu, Songyun Tao, Yaqun He, Xiachuan Li, Zhaoxu Yuan, Yangfei Fang, Xiangguang Yang, Yibo Zhang
Abstract
High Resolution Image Download MS PowerPoint Slide 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.