Photothermal catalytic CO₂ reduction is an attractive process to efficiently convert solar energy into chemical energy with mitigation of global carbon emissions, but it remains a great challenge in achieving high conversion efficiency due to the limited sunlight capturing capacity and lack of highly efficient catalysts. Herein, we report a Ga-Cu/CeO₂ catalyst synthesized by direct pyrolysis of the Ga and Cu-containing Ce-metal-organic frameworks for efficient photothermal catalytic CO₂ hydrogenation. Because of the highly dispersed Ga and Cu species in CeO₂, the optimized catalyst 10Cu5Ga/CeO₂ (10 wt% Cu and 5 wt% Ga) achieved a CO production rate of 111.2 mmol g⁻¹ h⁻¹ with nearly 100 % selectivity under full solar spectrum irradiation, which is superior to most reported Cu and other earth-abundant metals-based photothermal catalysts. Mechanism studies demonstrated that the synergy of photothermal heating/conversion and light-promotion contributed to the substantially increased CO production. In situ DRIFTS results revealed that the introduction of Ga enhanced the formation of formate species, the key intermediates in CO₂ hydrogenation, and light irradiation facilitated the decomposition of formate species to carbonyl, thus enhancing CO production. This work provides a potential strategy towards the synthesis of efficient catalysts for photothermal CO₂ reduction.

光热催化CO ₂还原是有效地将太阳能转化为化学能并减少全球碳排放的一个有​​吸引力的过程，但由于阳光捕获能力有限且缺乏高效催化剂，实现高转化效率仍然是一个巨大的挑战。在此，我们报告了一种通过直接热解含 Ga 和 Cu 的 Ce-金属-有机骨架合成的 Ga-Cu/CeO ₂催化剂，用于有效的光热催化 CO ₂加氢。由于在 CeO _{2 中}高度分散的 Ga 和 Cu 物种，优化的催化剂 10Cu5Ga/CeO ₂（10 wt% Cu 和 5 wt% Ga）实现了 111.2 mmol g ^-1 h ^-1的 CO 产率在全太阳光谱照射下具有近 100% 的选择性，优于大多数报道的 Cu 和其他地球丰富的金属基光热催化剂。机理研究表明，光热加热/转换和光促进的协同作用有助于大幅增加 CO 产量。原位 DRIFTS 结果表明，Ga 的引入促进了甲酸盐物质的形成，甲酸盐物质是 CO ₂加氢的关键中间体，光照射促进了甲酸盐物质分解为羰基，从而提高了 CO 的产生。这项工作为合成用于光热 CO ₂还原的高效催化剂提供了一种潜在的策略。