Hygroscopic metal-organic framework MIL-160(Al): In-situ time-dependent ATR-FTIR and gravimetric study of mechanism and kinetics of water vapor sorption.
Hygroscopic metal-organic framework MIL-160(Al): In-situ time-dependent ATR-FTIR and gravimetric study of mechanism and kinetics of water vapor sorption.
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DOI：
10.1016/j.saa.2021.120550
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发表时间：
2022-02-15
期刊：
影响因子：
--
通讯作者：
Samokhvalov A
中科院分区：
文献类型：
--
作者：
Henry B;Samokhvalov A
金属-有机骨架（MOFs）是一种高度多孔的配位聚合物，在分离、环境修复、催化和生物医学等领域有着广泛的应用。虽然许多MOFs在水和水溶液中不稳定，但铝MOFs（Al-MOFs）提供了前所未有的稳定性。首先，我们合成了不寻常的高吸湿性Al-MOF MIL-160（Al），纯化它，并指定FTIR峰的特定基团作为潜在的水结合位点。此外，我们引入了一种新的方法，在现场的时间依赖ATR-FTIR光谱检测MIL-160（铝）的特异性结合位点，并研究了反应的进展。具体来说，我们结合联合收割机在原位的时间依赖ATR-FTIR光谱与使用水作为“光谱探针”，以确定结合位点的MIL-160（铝）和它们的演变过程中的反应。原位时间依赖性ATR-FTIR光谱提供了水与以下基团键合的证据：μ-OH基团、2，5-FDCA 2 −连接体中的羧酸根阴离子COO−、连接体呋喃环中的氧原子以及连接体呋喃环的C-C和C-H键。然后，我们进行的MIL-160（铝）在空气中的吸附水蒸气的机制和动力学研究使用的两个互补的原位时间依赖性的方法相结合：ATR-FTIR光谱和重量分析。水蒸气在MIL-160（Al）上的吸附导致固态吸附复合物，其中每单位MIL-160（Al）具有多达四个水分子。MIL-160（Al）的吸水动力学符合准一级动力学规律，这与原位时变ATR-FTIR揭示的动力学和时间尺度是一致的。ATR-FTIR光谱法和重量法这两种原位时间依赖性方法的结合，形成了一种新的强大的实验方法，可以方便地研究环境和受控环境中各种固-气反应的机理、化学计量和化学动力学。
Metal-organic frameworks (MOFs) are advanced highly porous coordination polymers of high interest to separations, environmental remediation, catalysis, and biomedicine. While many MOFs are unstable in water and aqueous solutions, aluminum MOFs (Al-MOFs) offer an unprecedented stability. First, we synthesize unusual highly hygroscopic Al-MOF MIL-160(Al), purify it and assign FTIR peaks to specific groups as potential water binding sites. Further, we introduce a novel method of in-situ time-dependent ATR-FTIR spectroscopy to detect specific binding sites in MIL-160(Al) and investigate the progress of reaction. Specifically, we combine in-situ time-dependent ATR-FTIR spectroscopy with using water as “spectroscopic probe” to determine binding sites in MIL-160(Al) and their evolution during the reaction. The in-situ time-dependent ATR-FTIR spectra provide evidence of water bonding to: the μ-OH group, the carboxylate anion COO− in 2,5-FDCA2− linker, oxygen atom in the furan ring of the linker, and the C–C and C–H bonds of the furan ring of the linker. Then, we conduct mechanistic and kinetic study of sorption of water vapor on MIL-160(Al) in air using the combination of two complementary in-situ time-dependent methods: the ATR-FTIR spectroscopy and gravimetric analysis. Water vapor sorption on MIL-160(Al) results in the solid-state adsorption complex with up to four water molecules per unit of MIL-160(Al). Chemical kinetics of water sorption on MIL-160(Al) follows a pseudo-first order rate law and it is consistent with dynamics and timescale revealed by in-situ time-dependent ATR-FTIR. The combination of two in-situ time-dependent methods, the ATR-FTIR spectroscopy and gravimetry, forms a new powerful experimental approach to facilely study mechanisms, stoichiometry and chemical kinetics of various solid-gas reactions in the ambient and controlled environments.
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影响因子：
7.2
作者：
Qian, Xukun;Yadian, Boluo;Huang, Yizhong
通讯作者：
Huang, Yizhong
影响因子：
4
作者：
Bismondo, A;Di Bernardo, P;Rao, LF
通讯作者：
Rao, LF
DOI：
10.1021/acs.jced.5b00692
发表时间：
2015-11-01
期刊：
JOURNAL OF CHEMICAL AND ENGINEERING DATA
影响因子：
--
作者：
Li, Chen;Xiong, Zhenhu;Wu, Chunsheng
通讯作者：
Wu, Chunsheng
影响因子：
3.6
作者：
Grinnell, Cole;Samokhvalov, Alexander
通讯作者：
Samokhvalov, Alexander
DOI：
10.3390/nano8110916
发表时间：
2018-11-07
期刊：
Nanomaterials (Basel, Switzerland)
影响因子：
--
作者：
Chedid G;Yassin A
通讯作者：
Yassin A