Solar-driven CO₂ hydrogenation to synthesize value-added products with two or more carbons (C₂₊), such as paraffins and olefins, provides an alternative and potential route to solve both issues of energy shortage and environmental pollution. Nevertheless, it remains challenge to develop an efficient catalyst with high selectivity toward C₂₊ production. Herein, a series of NiFe-based catalysts have been successfully fabricated by thermal treatments of NiFe-Prussian blue analogues (NiFe-PBAs) in continuous air and H₂ conditions. Upon H₂ reduction at 250–500 °C, the obtained samples (denoted as NiFe-x) with chemical compositions of oxides, metal/oxide heterostructures and alloys, can be finely tuned. Under UV-Vis light irradiation, the NiFe-x catalysts display distinct CO₂ hydrogenation performance, among which NiFe-300 catalyst affords a state-of-art CO₂ conversion of 34.7 % and C_2–4 selectivity of 33.6 %, respectively. Comprehensive characterizations using X-ray absorption fine structure, Mössbauer spectroscopy and steady-state photoluminescence reveal that the best-performance of NiFe-300 catalyst was composed of NiFe_x alloys and Fe₂O₃ oxides, in which the formed heterostructure can facilitate efficient charge separation and increase the surface charge density, leading to the high selectivity to C_2–4 products. This study demonstrates that the Prussian blue analogues offer a new platform for the development of solar-driven catalysts for the production of value-added hydrocarbons from CO₂ hydrogenation.

太阳能驱动的 CO _{2加氢合成具有两个或多个碳 (C 2+} )的增值产品，如链烷烃和烯烃，为解决能源短缺和环境污染问题提供了一种替代和潜在的途径。_{然而，开发对C 2+}生产具有高选择性的高效催化剂仍然是一个挑战。_{在此，通过在连续空气和 H 2}条件下对 NiFe-普鲁士蓝类似物 (NiFe-PBA) 进行热处理，成功制备了一系列 NiFe 基催化剂。在 H ₂在 250–500 °C 还原，得到的样品（表示为 NiFe-x）具有氧化物、金属/氧化物异质结构和合金的化学成分，可以进行微调。在紫外-可见光照射下，NiFe-x 催化剂表现出独特的 CO ₂加氢性能，其中 NiFe-300 催化剂的 CO ₂转化率分别为 34.7 % 和 C _2-4选择性为 33.6 %。使用 X 射线吸收精细结构、穆斯堡尔光谱和稳态光致发光的综合表征表明，NiFe-300 催化剂的最佳性能是由 NiFe _x合金和 Fe ₂ O _3组成氧化物，其中形成的异质结构可以促进有效的电荷分离并增加表面电荷密度，从而导致对C _2-4产物的高选择性。_{这项研究表明，普鲁士蓝类似物为开发太阳能驱动催化剂提供了一个新平台，用于通过 CO 2}加氢生产增值烃。