Bimetallic metal-organic framework (MOFs) alloys, in which heterogeneous metal clusters are incorporated into their backbone, are capable of highly selective separations and catalysis. Due to limitations in our fundamental understanding of their alloying, however, established methods result in phase-separated or amorphous two-dimensional (2D) MOFs or lack precise control over alloy ratios. Here, our results demonstrate 2D MOF alloys where metal cation ratios (M¹ and M²) in M¹_xM²_1-xBDC (M¹ or M²= Zn, Cu, Ni, Co, Fe, Mn) can be engineered on demand by controlling the metal salt dissociation constants. Resulting MOF alloys exhibit a highly 2D nature with excellent crystallinity and minute control over metal cation ratios. Our experimental and theoretical results show that their electronic bandgaps and photoexcited carrier lifetimes can be engineered by metal cation alloying. Interestingly, 2D alloyed MOFs enable high-efficiency photo-catalytic water reduction performance in Co/Ni MOF alloys owing to the spatially separated metal clusters in 2D MOF alloys.

中文翻译：

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通过合金化在二维 vdW 金属-有机骨架中进行电子和催化工程

双金属金属有机骨架 (MOF) 合金，其中异质金属簇结合到其主链中，能够进行高度选择性的分离和催化。然而，由于我们对其合金化的基本理解的局限性，已建立的方法导致相分离或非晶二维 (2D) MOF 或缺乏对合金比例的精确控制。在这里，我们的结果证明了 2D MOF 合金，其中金属阳离子比率（M ¹和 M ²）在 M ¹ _x M ² _1-x BDC（M ¹或 M ²= Zn、Cu、Ni、Co、Fe、Mn）可以通过控制金属盐解离常数按需设计。所得的 MOF 合金表现出高度的二维性质，具有出色的结晶度和对金属阳离子比率的细微控制。我们的实验和理论结果表明，它们的电子带隙和光激发载流子寿命可以通过金属阳离子合金化来设计。有趣的是，由于二维 MOF 合金中空间分离的金属簇，二维合金 MOF 使 Co/Ni MOF 合金具有高效的光催化减水性能。