A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification.
A single-ligand ultra-microporous MOF for precombustion CO2 capture and hydrogen purification.
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DOI：
10.1126/sciadv.1500421
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发表时间：
2015-12
期刊：
影响因子：
13.6
通讯作者：
Vaidhyanathan R
中科院分区：
文献类型：
--
作者：
Nandi S;De Luna P;Daff TD;Rother J;Liu M;Buchanan W;Hawari AI;Woo TK;Vaidhyanathan R
单一的基于小配体的超微孔MOF显示出高CO2选择性和用于H2纯化的PSA工作能力。由单个小配体构建的金属有机框架（M0 F）通常具有高稳定性，是刚性的，并且具有通常简单且易于规模化的合成。然而，它们通常是超微孔的，并且不具有适于气体分离应用的大表面积。我们报道了一种具有立方骨架的超微孔（3.5和4.8个微孔）Ni-（4-吡啶基羧酸酯）2，其表现出非常高的CO2/H2选择性（在10巴，40°C下，20：80为285，40：60为230）和工作容量（3.95 mmol/g），使其适合于在典型的燃烧前CO2捕获条件（1至10巴的压力摆动）下进行氢气纯化。它表现出容易的CO2吸附-解吸循环，并且具有约3 × 10−9 m2/s的CO2自扩散率，这比沸石13 X高两个数量级，并且与用于该应用的其他最佳性能的MOF相当。模拟揭示了高密度的结合位点，允许有利的CO2-CO2相互作用和大的合作结合能。由小配体产生的超微孔确保了水解、流体静力学稳定性、保质期和对潮湿气流的稳定性。
A single small-ligand–based ultra-microporous MOF showing high CO2 selectivity and PSA working capacity for H2 purification. Metal organic frameworks (MOFs) built from a single small ligand typically have high stability, are rigid, and have syntheses that are often simple and easily scalable. However, they are normally ultra-microporous and do not have large surface areas amenable to gas separation applications. We report an ultra-microporous (3.5 and 4.8 Å pores) Ni-(4-pyridylcarboxylate)2 with a cubic framework that exhibits exceptionally high CO2/H2 selectivities (285 for 20:80 and 230 for 40:60 mixtures at 10 bar, 40°C) and working capacities (3.95 mmol/g), making it suitable for hydrogen purification under typical precombustion CO2 capture conditions (1- to 10-bar pressure swing). It exhibits facile CO2 adsorption-desorption cycling and has CO2 self-diffusivities of ~3 × 10−9 m2/s, which is two orders higher than that of zeolite 13X and comparable to other top-performing MOFs for this application. Simulations reveal a high density of binding sites that allow for favorable CO2-CO2 interactions and large cooperative binding energies. Ultra-micropores generated by a small ligand ensures hydrolytic, hydrostatic stabilities, shelf life, and stability toward humid gas streams.