低浓度二氧化碳(烟气中15%、空气中720 mg/m³级)的高效捕集与电催化转化是实现碳减排与资源化利用的重要技术路径. 然而, 受限于CO₂传质不足、杂质气体引发的竞争反应以及产物分离成本高等因素, 传统电催化体系在低浓度条件下面临显著性能衰减的问题. 金属−有机框架(MOF)材料凭借其可设计的多孔结构、可调控的化学环境以及高度集成化的功能潜力, 为突破上述瓶颈提供了独特的平台. 本文围绕MOF基材料在低浓度CO₂电催化转化中的应用进展, 系统梳理并总结了几类代表性的设计策略: 从单一MOF内部实现CO₂捕集-催化双功能集成, 到MOF基分子筛膜-电解池的器件级耦合, 实现烟气或空气源CO₂的原位富集、纯化与高选择性转化. 相关研究揭示了低浓度CO₂电催化转化从分子尺度活性位点调控, 到反应环境优化, 再到器件级系统集成的递进式创新思路. 最后, 结合当前研究现状, 对该领域在催化机理、耐杂质体系构建等方面面临的挑战与发展机遇进行了展望.

Efficient capture and electrocatalytic conversion of low-concentration carbon dioxide (15% in flue gas and 720 mg/m³ in ambient air) represents a promising pathway toward carbon emission mitigation and value-added chemical production. In principle, directly utilizing dilute CO₂ streams could bypass energy-intensive purification steps and improve the overall process economics. However, electrocatalytic CO₂ reduction (eCO₂RR) under low CO₂ partial pressures is fundamentally limited by sluggish CO₂ mass transfer, severe competition from the hydrogen evolution reaction, and performance deterioration induced by impurities (e.g., O₂, NO_x, and SO₂). Moreover, conventional neutral/alkaline electrolytes suffer from pronounced carbonate formation, leading to substantial carbon losses and low single-pass carbon efficiency. These challenges indicate that simply improving intrinsic catalytic activity is insufficient; instead, new materials and system-level strategies are required to simultaneously enrich CO₂, regulate interfacial microenvironments, and decouple separation from conversion. Metal-organic frameworks (MOF), featuring tailorable pore architectures, designable pore chemistry, and the capability of integrating multiple functions into a single material or device component, provide a unique platform to address the above limitations. This Perspective highlights recent advances in MOF-based materials for eCO₂RR using low-concentration CO₂ feedstocks, with an emphasis on representative design paradigms spanning “molecular-scale synergy - reaction-environment regulation - device-level integration”. First, capture and conversion can be coupled within individual MOFs by embedding CO₂-philic motifs and catalytic centers into the same porous scaffold, enabling preferential CO₂ enrichment, and facilitated transport to active sites under simulated flue gas. Second, reaction-environment engineering, particularly under acidic conditions, offers a viable solution to suppress carbonate formation and enhance carbon utilization; protonation of N-rich frameworks can strengthen CO₂ adsorption/transport while limiting proton accessibility to catalytic sites, leading to high Faradaic efficiency and improved single-pass conversion even with dilute CO₂ inputs. Third, device-level strategies further decouple CO₂ purification from downstream electrolysis by integrating MOF-based molecular sieving mixed-matrix membranes (e.g., MOF/PIM-1 composites) into membrane electrode assemblies, allowing in situ enrichment of flue gas- or air-derived CO₂ and impurity removal prior to catalytic conversion. Collectively, these advances demonstrate how MOFs can enable progressive innovations from materials design to interfacial regulation and electrolyzer integration. Finally, key challenges and opportunities are discussed, including mechanistic understanding under complex impurity mixtures, long-term stability, scalable manufacturing of MOF-based layers and membranes, and compatibility with industrial capture and electrolysis infrastructures.