Liberating C-H Bond Activation: Achieving 56% Quantum Efficiency in Photocatalytic Cyclohexane Dehydrogenation.

The technology of liquid organic hydrogen carriers presents great promise for large-scale hydrogen storage. Nevertheless, the activation of inert C(sp3)-H bonds in hydrocarbon carriers poses formidable challenges, resulting in a sluggish dehydrogenation process and necessitating high operating temperatures. Here, we break the shackles of C-H bond activation under visible light irradiation by fabricating subnanometer Pt clusters on defective Ce-Zr solid solutions. We achieved an unprecedented hydrogen production rate of 2601 mmol gcat.-1 h-1 (turnover frequency >50,000 molH2 molPt-1 h-1) from cyclohexane, surpassing the most advanced thermo- and photocatalysts. By optimizing the temperature-dominated hydrogen transfer process, achievable by harnessing hitherto wasted infrared light in sunlight, an astonishing 56% apparent quantum efficiency and a 5.2% solar-to-hydrogen efficiency are attained at 353 K. Our research stands as one of the most effective photocatalytic processes to date, holding profound practical significance in the utilization of solar energy and the exploitation of alkanes.

Light-Induced Nonoxidative Coupling of Methane Using Stable Solid Solutions.

Achieving efficient and direct conversion of methane under mild conditions is of great significance for innovations in the chemical industry. However, the efficiency and lifetime of most catalysts remain too far from practical requirements, since it is difficult to break the first C-H bond of methane as well as to suppress the following complete dehydrogenation (or overoxidation) and the resulting carbonaceous deposition (or CO2 ). Here, we report that wurtzite GaN:ZnO solid solutions exhibit unique and unprecedented photocatalytic performances for the nonoxidative coupling of methane at room temperature, exclusively generating ethane with nearly stoichiometric H2 . High conversion rate (>330 µmol g-1 h-1 ), long-term stability (>70 h), and superior coke-resistance were achieved. At 293 K, the methane conversion exceeds 7 %, comparable to the equilibrium conversion of thermal catalysis at 910 K. Mechanistic studies revealed that the N-ZnGa -ON units and the absence of acid sites on the surface played crucial roles in reactivity and coke resistance, respectively.

Photocatalytic non-oxidative conversion of methane.

The direct conversion of methane to hydrogen and high-value hydrocarbons under mild conditions is an ideal, carbon-neutral method for utilizing natural gas resources. Compared with traditional high-temperature thermal catalytic methods, using clean light energy to activate inert C-H bonds in methane can not only significantly reduce the reaction temperature and avoid catalyst deactivation, but also surpass the limitations of thermodynamic equilibrium and provide new reaction pathways. This paper provides a comprehensive review of developments in the field of photocatalytic non-oxidative conversion of methane (PNOCM), while also highlighting our contributions, particularly focusing on catalyst design, product selectivity, and the underlying photophysical and chemical mechanisms. The challenges and potential solutions are also evaluated. The goal of this feature article is to establish a foundational understanding and stimulate further research in this emerging area.