Photothermal carbon dioxide hydrogenation represents a promising route to reduce the emission of greenhouse gas CO₂ and produce value-added chemicals, but the selectivity and stability of photothermal catalysts need to be improved. Herein, we report the rational fabrication of well-defined Ag₂₄Au cluster decorated highly ordered nanorod-like mesoporous Co₃O₄ (Ag₂₄Au/meso-Co₃O₄) for highly efficient and selective CO₂ hydrogenation. The orderly assembled meso-Co₃O₄ nanorods were prepared via a nanocasting method, offering large surface area and abundant active sites for CO₂ adsorption and conversion. Moreover, the catalytic activity and selectivity were further improved by molecule-like Ag₂₄Au cluster decoration and reaction temperature optimization. The Ag₂₄Au/meso-Co₃O₄ composite catalyst exhibited an ultrahigh CH₄ yield rate of 204 mmol·g⁻¹·h⁻¹ and a greatly improved CH₄ selectivity of 82% for CO₂ hydrogenation, significantly higher than those of pristine meso-Co₃O₄ catalyst. The mechanism of the photothermal catalytic performance improvement was verified by CO₂ temperature-programmed desorption and time-resolved transient photoluminescence, revealing that CO₂ molecules underwent a vigorous adsorption and rapid activation process over Ag₂₄Au/meso-Co₃O₄. The hot electrons created by the localized surface plasmon resonance effect of Ag₂₄Au clusters facilitated the charge transfer for subsequent multi-electron CO₂ hydrogeneration processes, resulting in a significant increase in the productivity and selectivity for CO₂-to-CH₄ conversion. This work suggests that the rational coupling of well-defined metal atom clusters and ordered transition metal compound nanostructures could open a new avenue towards photo-induced green chemistry processes for efficient CO₂ recycling and reutilization.

光热二氧化碳加氢是减少温室气体CO ₂排放和生产高附加值化学品的有前景的途径，但光热催化剂的选择性和稳定性有待提高。在此，我们报告了定义明确的Ag ₂₄ Au 簇装饰的高度有序的纳米棒状介孔Co ₃ O ₄ (Ag ₂₄ Au/meso-Co ₃ O ₄ ) 的合理制造，用于高效和选择性的CO ₂加氢。通过纳米浇铸法制备有序组装的介观-Co ₃ O ₄纳米棒，为CO提供了大的表面积和丰富的活性位点₂吸附与转化。此外，通过分子状Ag ₂₄ Au簇修饰和反应温度优化，进一步提高了催化活性和选择性。Ag ₂₄ Au/meso-Co ₃ O ₄复合催化剂具有204 mmol·g ^-1 _· h ^{-1的超高CH} ₄收率和82%的CO 2 加氢选择性_，显着高于这些催化剂。原始内消旋Co ₃ O ₄催化剂。_{CO 2}验证了光热催化性能提高的机理程序升温脱附和时间分辨瞬态光致发光，揭示了CO _{2分子在Ag 24} Au/meso-Co ₃ O ₄上经历了强烈的吸附和快速活化过程。_{Ag 24} Au 簇的局部表面等离子体共振效应产生的热电子促进了后续多电子 CO ₂加氢过程的电荷转移，从而显着提高了 CO ₂生成 CH _{4的产率和选择性}转换。这项工作表明，定义明确的金属原子簇和有序过渡金属化合物纳米结构的合理耦合可以为光致绿色化学过程开辟一条新途径，以实现高效的 CO ₂回收和再利用。