Interfacial Ru–C Coupling Harnesses Photoexcited Hot Electrons to Sustain Oxygen Cycling in Photothermal Methane Dry Reforming
Abstract
ABSTRACT Methane dry reforming (DRM) remains challenged by the difficulty of simultaneously achieving high activity and long‐term stability under moderate‐temperature operation. Here we report sub‐2 nm Ru clusters anchored on chemically stable multi‐walled carbon nanotubes (Ru/MWCNTs) as a non‐oxide photothermal platform for efficient and durable DRM below 600 °C. Strong Ru–C π–d coupling delocalizes interfacial electrons and stabilizes metallic Ru, enabling broadband generation and interfacial utilization of photoexcited hot electrons under illumination. The resulting interface selectively activates CO 2 to generate highly labile Ru–O* species and sustains a fast, fully reversible Ru 0 /Ru–O cycle without relying on lattice oxygen from an oxygen‐carrier support. Rapid interfacial oxygen turnover promotes an oxygen‐assisted CH 3 O* pathway, delivering a turnover frequency of 25 s −1 . Consequently, Ru/MWCNTs achieves CO and H 2 formation rates of 632 and 526 mol g Ru −1 h −1 , respectively, a light‐to‐fuel efficiency of 25.4%, stable operation for 120 h, and robust activity across a wide CH 4 /CO 2 feed‐ratio window (0.43–2.33). Isothermal monochromatic irradiation together with operando, electronic, and kinetic analyses identify Ru–C interfacial coupling, rather than metallicity alone, as the key origin of the photothermal enhancement.
Article Details
Authors (11)
Kai Kang
Pingfang Zhang
Key Lab for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Feringa Nobel Prize Scientist Joint Research Center State Key Laboratory of Green Chemical Engineering and Industrial Catalysis Institute of Fine Chemicals School of Chemistry and Molecular Engineering Shanghai Engineering Research Center for Multi‐Media Environmental Catalysis and Resource East China University of Science and Technology Shanghai China
Cong Liu
Junxian Qin
Institute for Catalysis, Hokkaido University, N-21, W-10, Sapporo 001-0021, Japan
Ningqiang Zhang
Takashi Toyao
Hokkaido University , , N-21, W-10 , ,
Kenichi Shimizu
Institute For Catalysis Hokkaido University Sapporo Japan
Xiaoming Cao
Zedong Wang
Key Lab for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Feringa Nobel Prize Scientist Joint Research Center State Key Laboratory of Green Chemical Engineering and Industrial Catalysis Institute of Fine Chemicals School of Chemistry and Molecular Engineering Shanghai Engineering Research Center for Multi‐Media Environmental Catalysis and Resource East China University of Science and Technology Shanghai China
Yansong Lu
Lingzhi Wang