Solar photocatalytic CO₂ reduction into valuable fuels shows great potential in solving the environmental and energy crises but remains a challenging goal. Herein, we present a strategy for the synthesis of frame-in-cage dodecahedral hybrids (ZnSe–CdSe@NC FC) composed of ZnSe–CdSe heterojunctions embedded within a nitrogen-doped carbon matrix through the simultaneous selenization and decomposition of a Zn-zeolitic imidazolate framework (ZIF-8) and the subsequent cation-exchange reaction with the assistance of ascorbic acid. The frame-in-cage microstructure of the dodecahedral particles can be obtained at a relatively low ramping rate (2 °C min⁻¹). The conversion from ZnSe@NC FC to ZnSe–CdSe@NC FC and CdSe@NC FC can be realized by extending the cation-exchange reaction time with the assistance of ascorbic acid. In the ZnSe–CdSe@NC FC catalyst, the ZnSe–CdSe heterojunction and the unique frame-in-cage structure could provide effective mass/charge transfer, abundant active sites, and enhanced incident light utilization. Meanwhile, the high light-to-heat conversion ability of nitrogen-doped carbon realizes a photothermal synergistic effect throughout the photocatalytic process. These advantages make the ZnSe–CdSe@NC FC with optimized composition exhibit superior activity and high stability in photo-thermocatalytic CO₂ reduction with a higher CO generation rate of 31.62 μmol h⁻¹ g⁻¹, which is much higher than that under single photocatalysis and thermocatalysis conditions. This work provides a promising strategy to design desired catalysts for photo-thermocatalytic CO₂ reduction.

中文翻译：

---

ZIF 衍生的 ZnSe-CdSe 笼中框架杂化物嵌入 N 掺杂碳基质中，用于将 CO2 高效光热转化为燃料

太阳能光催化 CO ₂还原成有价值的燃料在解决环境和能源危机方面显示出巨大的潜力，但仍然是一个具有挑战性的目标。在此，我们提出了一种通过同时硒化和分解锌沸石来合成由嵌入氮掺杂碳基质中的 ZnSe-CdSe 异质结组成的笼中十二面体杂化物 (ZnSe–CdSe@NC FC) 的策略咪唑酯骨架（ZIF-8）和随后在抗坏血酸的帮助下进行的阳离子交换反应。十二面体颗粒的笼中微结构可以以相对较低的升温速率（2°C min ^-1）。ZnSe@NC FC 向 ZnSe–CdSe@NC FC 和 CdSe@NC FC 的转化可以通过在抗坏血酸的帮助下延长阳离子交换反应时间来实现。在 ZnSe–CdSe@NC FC 催化剂中，ZnSe–CdSe 异质结和独特的笼中框架结构可以提供有效的质量/电荷转移、丰富的活性位点和增强的入射光利用率。同时，氮掺杂碳的高光热转换能力在整个光催化过程中实现了光热协同效应。这些优势使得具有优化组成的 ZnSe-CdSe@NC FC 在光热催化 CO ₂还原中表现出优异的活性和高稳定性，具有更高的 CO 生成率，达到 31.62 μmol h ^-1 g ^-1，远高于单一光催化和热催化条件下的值。这项工作为设计用于光热催化 CO ₂还原的所需催化剂提供了一种有前景的策略。