Rational Design of a Low-Cost, High-Performance Metal-Organic Framework for Hydrogen Storage and Carbon Capture.
Rational Design of a Low-Cost, High-Performance Metal-Organic Framework for Hydrogen Storage and Carbon Capture.
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低成本，高性能金属有机框架的合理设计，用于氢气和碳捕获。
DOI：
10.1021/acs.jpcc.6b10363
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发表时间：
2017-01-19
期刊：
影响因子：
--
通讯作者：
Haranczyk M
中科院分区：
文献类型：
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作者：
Witman M;Ling S;Gladysiak A;Stylianou KC;Smit B;Slater B;Haranczyk M
我们提出了MOF-74类似物的硅设计，这里称为M2(dhfua) [M = Mg, Fe, Co, Ni, Zn]，具有比原来的M2（DOBDC）系列更强的小分子吸附性能。由2,3-二羟基富马酸酯（dhfua）构成，这是一种脂肪族配体，比芳香的2,5-二氧化苯-1,4-二羧酸酯（DOBDC）小，M2（dhfua）框架具有更小的通道直径，导致开放金属位点的体积密度更高，并显着提高了体积氢（H2）储存潜力。此外，孔道中两个相邻开放金属位点之间的距离减小导致CO2的结合模式为每两个相邻金属一个分子，结合能量显著增强。通过对guest-framework相互作用的色散校正密度泛函理论（DFT）计算和二元CO2:H2O混合物吸附行为的经典模拟，我们从理论上预测M2（dhfua）系列在吸附湿烟气流时优于M2（DOBDC）系列的碳捕获替代方案。在我们的模拟中，改进的二氧化碳吸收和湿度耐受性可以根据金属选择和吸附温度进行调节，这与显著降低的配体费用相结合，提高了这种材料的二氧化碳捕获和H2储存潜力。通过混合DFT计算验证了Mg2（dhfua）的动力学稳定性和弹性稳定性，证明了其在实验合成中的重要潜力。
We present the in silico design of a MOF-74 analogue, hereon known as M2(DHFUMA) [M = Mg, Fe, Co, Ni, Zn], with enhanced small-molecule adsorption properties over the original M2(DOBDC) series. Constructed from 2,3-dihydroxyfumarate (DHFUMA), an aliphatic ligand which is smaller than the aromatic 2,5-dioxidobenzene-1,4-dicarboxylate (DOBDC), the M2(DHFUMA) framework has a reduced channel diameter, resulting in higher volumetric density of open metal sites and significantly improved volumetric hydrogen (H2) storage potential. Furthermore, the reduced distance between two adjacent open metal sites in the pore channel leads to a CO2 binding mode of one molecule per two adjacent metals with markedly stronger binding energetics. Through dispersion-corrected density functional theory (DFT) calculations of guest–framework interactions and classical simulation of the adsorption behavior of binary CO2:H2O mixtures, we theoretically predict the M2(DHFUMA) series as an improved alternative for carbon capture over the M2(DOBDC) series when adsorbing from wet flue gas streams. The improved CO2 uptake and humidity tolerance in our simulations is tunable based upon metal selection and adsorption temperature which, combined with the significantly reduced ligand expense, elevates this material’s potential for CO2 capture and H2 storage. The dynamical and elastic stabilities of Mg2(DHFUMA) were verified by hybrid DFT calculations, demonstrating its significant potential for experimental synthesis.