Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags,ACS Applied Materials & Interfaces

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Tuning Carbon Dioxide Adsorption Affinity of Zinc(II) MOFs by Mixing Bis(pyrazolate) Ligands with N-Containing Tags
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2019-07-05 00:00:00 , DOI: 10.1021/acsami.9b08015
Rebecca Vismara ₁ , Giulia Tuci ₂ , Alessia Tombesi , Konstantin V. Domasevitch ₃ , Corrado Di Nicola , Giuliano Giambastiani _{2,

4,

5} , Michele R. Chierotti ₆ , Simone Bordignon ₆ , Roberto Gobetto ₆ , Claudio Pettinari , Andrea Rossin _{2,

4} , Simona Galli _{1,

4}

Affiliation

The four zinc(II) mixed-ligand metal–organic frameworks (MIXMOFs) Zn(BPZ)_x(BPZNO₂)_1–x, Zn(BPZ)_x(BPZNH₂)_1–x, Zn(BPZNO₂)_x(BPZNH₂)_1–x, and Zn(BPZ)_x(BPZNO₂)_y(BPZNH₂)_1–x−y (H₂BPZ = 4,4′-bipyrazole; H₂BPZNO₂ = 3-nitro-4,4′-bipyrazole; H₂BPZNH₂ = 3-amino-4,4′-bipyrazole) were prepared through solvothermal routes and fully investigated in the solid state. Isoreticular to the end members Zn(BPZ) and Zn(BPZX) (X = NO₂, NH₂), they are the first examples ever reported of (pyr)azolate MIXMOFs. Their crystal structure is characterized by a three-dimensional open framework with one-dimensional square or rhombic channels decorated by the functional groups. Accurate information about ligand stoichiometric ratio was determined (for the first time on MIXMOFs) through integration of selected ligands skeleton resonances from ¹³C cross polarized magic angle spinning solid-state NMR spectra collected on the as-synthesized materials. Like other poly(pyrazolate) MOFs, the four MIXMOFs are thermally stable, with decomposition temperatures between 708 and 726 K. As disclosed by N₂ adsorption at 77 K, they are micro-mesoporous materials with Brunauer–Emmett–Teller specific surface areas in the range 400–600 m²/g. A comparative study (involving also the single-ligand analogues) of CO₂ adsorption capacity, CO₂ isosteric heat of adsorption (Q_st), and CO₂/N₂ selectivity in equimolar mixtures at p = 1 bar and T = 298 K cast light on interesting trends, depending on ligand tag nature or ligand stoichiometric ratio. In particular, the amino-decorated compounds show higher Q_st values and CO₂/N₂ selectivity vs the nitro-functionalized analogues; in addition, tag “dilution” [upon passing from Zn(BPZX) to Zn(BPZ)_x(BPZX)_1–x] increases CO₂ adsorption selectivity over N₂. The simultaneous presence of amino and nitro groups is not beneficial for CO₂ uptake. Among the compounds studied, the best compromise among uptake capacity, Q_st, and CO₂/N₂ selectivity is represented by Zn(BPZ)_x(BPZNH₂)_1–x.

中文翻译：

通过将双（吡唑酸酯）配体与含N的标签混合来调节MOF的二氧化碳吸附亲和力

四个锌（II）混合配体金属-有机骨架（MIXMOFs）Zn（BPZ）_x（BPZNO ₂）_{1- x}，Zn（BPZ）_x（BPZNH ₂）_{1- x}，Zn（BPZNO ₂）_x（BPZNH ₂）_{1- x}和Zn（BPZ）_x（BPZNO ₂）_y（BPZNH ₂）_{1- x - y}（H ₂ BPZ = 4,4'-联吡唑； H ₂ BPZNO ₂ = 3-nitro-4,4 ′-联吡唑; H ₂ BPZNH ₂＝ 3-氨基-4，4′-联吡唑）是通过溶剂热法制备的，并在固态下进行了充分研究。与末端成员Zn（BPZ）和Zn（BPZX）（X = NO ₂，NH ₂）等规，它们是（pyr）偶氮酸酯MIXMOF的第一个实例。它们的晶体结构的特征是三维开放框架，具有由功能基团装饰的一维正方形或菱形通道。测定配体对的化学计量比的准确信息（首次上MIXMOFs）通过从积分所选的配体骨架的共振¹³在合成后的材料上收集的C交叉极化的魔角旋转固态NMR光谱。像其他聚吡咯酸酯MOF一样，这四种MIXMOF都是热稳定的，分解温度在708至726 K之间。正如在77 K的N ₂吸附所揭示的那样，它们是微介孔材料，其Brunauer-Emmett-Teller比表面积为。范围400–600 m ² / g。在p = 1 bar和T等摩尔混合物中，CO ₂吸附能力，CO ₂等量吸附热（Q _st）和CO ₂ / N ₂选择性的比较研究（还涉及单配体类似物）= 298 K将光投向有趣的趋势，具体取决于配体标签的性质或配体化学计量比。尤其是，与硝基官能化的类似物相比，氨基修饰的化合物显示出更高的Q _st值和CO ₂ / N ₂选择性。此外，标记“稀释” [从Zn（BPZX）传递到Zn（BPZ）_x（BPZX）_{1- x时}]提高了对N _2的CO ₂吸附选择性。氨基和硝基的同时存在对吸收CO ₂不利。在研究的化合物中，吸收能力，Q _st和CO ₂ / N ₂之间的最佳折衷选择性用Zn（BPZ）_x（BPZNH ₂）_{1- x表示}。

更新日期：2019-07-05

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