Metal–organic frameworks (MOFs) with adjustable structures, diverse chemical functionalities, and excellent CO₂ capture ability have shown important potential application in the photocatalytic reduction of CO₂ to valuable fuel to curb the energy crisis. In this work, a series of new isostructural lanthanide-organic frameworks based on hexanuclear {Ln₆O₈} clusters, {(DMA)₂ [Ln₆(μ₃–OH)₈(H₂O)₆(SBTC)₃]}_n (Ln-MOFs, Ln = Eu, Dy, Gd, Tb, Yb; H₄SBTC = 5,5′-(ethene-1,2-diyl) di-isophthalic acid; DMA = dimethylamine cation) were synthesized by the solvothermal method. Ln-MOFs were metal–organic frameworks formed by {Ln₆(μ₃–OH)₈} clusters and poly(carboxylic acid) ligands H₄SBTC, which exhibited excellent photocatalytic properties for the reduction of CO₂ to CO. Among these Ln-MOFs, the production rate of photocatalytic reduction of CO₂ to CO by Eu-MOF was 663.00 μmol·h^–1·g^–1 and the selectivity reached 94.2%, utilizing [Ru(bpy)₃]Cl₂·6H₂O as photosensitizers. Experimental characterizations and density functional theory (DFT) calculations unveiled that the effective charge separation, strong CO₂ binding affinity, weak H₂O adsorption energy, as well as low reaction energy barriers for the *COOH intermediates over Eu-MOF play an important role in possessing superior photoactivity. This study provides insights into the field of Ln-MOF materials for efficient photocatalytic CO₂ reduction and conversion applications.

中文翻译：

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基于 {Ln6O8} 团簇的高稳定性镧系元素有机框架，光催化将 CO2 还原为 CO


具有可调节结构、多种化学官能团和出色的 CO₂ 捕获能力的金属有机框架 （MOFs） 在光催化将 CO₂ 还原为有价值的燃料以遏制能源危机方面显示出重要的潜在应用。在这项工作中，一系列基于六核 {Ln₆O₈} 簇、{（DMA）₂ [Ln₆（μ₃–OH）₈（H₂O）₆（SBTC）₃]}_n （Ln-MOFs， Ln = Eu， Dy， Gd， Tb， Yb;H₄SBTC = 5,5′-（乙烯-1,2-二基）二间苯二甲酸;DMA = 二甲胺阳离子）是通过溶剂热法合成的。Ln-MOF 是由 {Ln₆（μ_3-OH）₈} 簇和聚（羧酸）配体 H₄SBTC 形成的金属有机框架，表现出优异的光催化性能，可将 CO₂ 还原为 CO。在这些 Ln-MOF 中，利用 [Ru（bpy）₃]Cl₂·6H₂O 作为光敏剂，Eu-MOF 光催化还原 CO₂ 制 CO 的速率为 663.00 μmol·h^–1·g^–1，选择性达到 94.2%。实验表征和密度泛函理论 （DFT） 计算揭示了 Eu-MOF 上 *COOH 中间体的有效电荷分离、强 CO₂ 结合亲和力、弱 H₂O 吸附能以及低反应能垒在具有优异的光活性方面发挥着重要作用。本研究为用于高效光催化 CO₂ 还原和转化应用的 Ln-MOF 材料领域提供了见解。