Sustainable functionalized metal-organic framework NH2-MIL-101(Al) for CO2 separation under cryogenic conditions

Babar, Muhammad; Mubashir, Muhammad; Ahmad, Mahmood; Saqib, Sidra; Ullah, Sami; Bustam, Mohamad Azmi; Show, Pau Loke

doi:10.1016/j.envpol.2021.116924

“…Many researches have tried to improve both the CO 2 adsorption capacity and selectivity of MOFs, for instance, ligand functionalization [38,39], incorporation of open metal sites [29,40,41], construction of specific pores [17], and pre-/postmodification for amine grafting/impregnation [36,[42][43][44][45][46][47][48]. Zhu et al [42] reported that the polyethyleneimine-modified UiO-66-NH 2 (Zr) exhibited a considerable enhancement toward CO 2 /N 2 adsorption selectivity (48 vs. 25) and moderate desorption energy (68 kJ/mol CO 2 ).…”

Section: Introductionmentioning

confidence: 99%

Enhanced CO₂ Adsorption and Selectivity of CO₂/N₂ on Amine@ZIF-8 Materials

Zhang

¹

,

Li

²

,

Zhao

³

et al. 2022

Adsorption Science & Technology

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The ZIF-8 crystals were successfully postsynthetically modified using methylamine (MA), ethylenediamine (ED), and N, N ′ -dimethylethylenediamine (MMEN) to improve their adsorption performance toward CO2. Results showed that, compared with the original ZIF-8, the BET specific surface area of MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 has increased by 118.2%, 92.0%, and 29.8%, respectively. In addition, their total pore volume increased separately by 130.8%, 100%, and 48.7%. The adsorption capacities of CO2 on the amine-modified ZIF-8 samples followed the order MA − ZIF − 8 > MMEN − ZIF − 8 > ED − ZIF − 8 > ZIF − 8 . The CO2 adsorption capacities at 298 K on MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 were increased by 118.2%, 90.2%, and 29.8%, respectively. What is more, the CO2/N2 selectivities calculated using an IAST model of the amine@ZIF-8 samples at 0.01 bar and 298 K were also significantly improved and followed the order MA − ZIF − 8 31.4 > ED − ZIF − 8 25.1 > MMEN − ZIF − 8 14.1 > ZIF − 8 11.5 , which increased by 173.0%, 121.4%, and 22.6%, respectively. The isosteric heat of CO2 adsorption ( Q st ) on the MA-ZIF-8, MMEN-ZIF-8, and ED-ZIF-8 all becomes higher, while Q st of N2 on these samples was slightly lower in comparison with that on the ZIF-8. Furthermore, after six recycle runs of gravimetric CO2 adsorption-desorption on MA-ZIF-8, the adsorption performance of CO2 is still very good, indicating that the MA-ZIF-8 sample has good regeneration performance and can be applied into industrial CO2 adsorption and separation.

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“…In addition, the position of the ─C═C double bond disappeared at 1641 cm −1 of the 1c curve, and the peak that appeared at 1420 cm −1 belonged to the symmetric stretching vibration of -COO − in acrylic acid, which qualitatively proved that PAA was successfully grafted to the MIL-101(Al)-NH 2 -net. [19][20]27]…”

Section: Ftir Resultsmentioning

confidence: 99%

“…[ 19 ] MIL‐101(Al)‐NH 2 , PAA, and MAP morphologies were analyzed using a ULTRA plus field emission scanning electron microscope (SEM, Zeiss, Germany) after coating the samples with gold film. [ 20 ] The morphological analysis of the MIL‐101(Al)‐NH 2, PAA, and MAP were carried out using transmission electron microscopy (TEM, JEM‐2100). The Brunauer‐Emmett‐Teller (BET, (America Micromeritics ASAP 2460) surface area measurements of the PAA, and MAP were performed with N 2 adsorption‐desorption isotherms at 77 K. The stabilities of MIL‐101(Al)‐NH 2 , PAA, and MAP were evaluated by thermogravimetric analysis (TGA) [ 21 ] and derivative thermogravimetry (DTG) under a nitrogen atmosphere from 25 to 800 °C at 10 °C min −1 with Mettler‐Toledo Group in Switzerland.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Properties of MIL‐101(Al)‐NH₂ Polymers Capable of Absorbing Vapor, Liquid Water Simultaneously

Yang,

Zhang,

Xu

et al. 2023

Advanced Sustainable Systems

2

0

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Modified MIL‐101(Al)‐NH2 (MIL‐101(Al)‐NH2‐net) is used as a crosslinking agent and acrylic acid (AA) as a monomer, the MIL‐101(Al)‐NH2‐net grafted polyacrylic acid (MIL‐101(Al)‐NH2‐net‐g‐PAA (MAP)) composite water‐absorbent material is synthesized using the free radical polymerization method to study the application of composite absorbent materials in water collection. The structure and morphology of the composite water‐absorbent material are characterized using Fourier transform infrared spectrometry (FTIR), scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer Emmett Teller (BET), and thermogravimetric analysis (TG), and the contents of ammonium persulfate (APS), MIL‐101(Al)‐NH2‐net, and neutralization degree of AA are optimized. Under optimal conditions, the water absorption ratios of the composite materials in distilled water, tap water, and 0.9% NaCl solution are 744, 169.5, and 85.5 g g−1. In addition, the properties of collecting water vapor are investigated. At 25 °C, 50% Relative Humidity (RH), 70% RH, and 90% RH, the MAP water vapor adsorption capacity is 0.0312, 0.5760, and 1.6856 g g−1, respectively. The water vapor adsorption of MIL‐101(Al)‐NH2 and MIL‐101(Al)‐NH2 self‐polymerization products are 0.025 and 0.1278 g g−1, respectively. The result showed that autopolymerization can improve the water vapor adsorption performance.

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“…This indicates that TGA might overestimate the structural thermal stability of this type of MOFs, as this analysis only reflects the temperature at which the linker combustion occurs. 16,52 Noteworthy, in both cases (as-synthesized and DCM-activated MOF), the color of the powder changed from chocolate to caramel after framework decomposition. The main change on the TGA curve of the DCM-activated MOF compared to the as-synthesized material is reflected by the plateau after solvent removal around 150°C, indicating facilitated solvent removal from this sample and the stability of the sample with emptied pores until 200°C.…”

Section: Thermal Stability and Porositymentioning

confidence: 99%

Synthesis, structure and thermal stability of a mesoporous titanium(III) amine containing MOF with improved hydrogen sorption properties

Steenhaut

¹

,

Lacour

²

,

Barozzino‐Consiglio

³

et al. 2021

Preprint

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The first mesoporous bimetallic TiIII/Al metal-organic framework (MOF) containing amine functionalities on its linkers has been selectively obtained by converting the cheap commercially available (TiCl3)3AlCl3 into Ti3-xAlxCl3(THF)3 and reacting this complex with 2-aminoterephthalic acid in DMF under soft solvothermal conditions. This compound is structurally related to the previously described NH2-MIL-101(M) (M = Cr, Al and Fe) MOFs. Thermal gravimetric analyses and in situ PXRD measurements demonstrated that this highly air-sensitive TiIII-containing MOF is structurally stable up to 200°C. Nuclear magnetic resonance (NMR) spectroscopy, elemental and inductively-coupled plasma (ICP) analyses revealed that NH2-MIL-101(TiIII) contains trinuclear Ti3(μ3-O)Cl(DMF)2(RCOO)6 clusters with strongly bound DMF molecules, and a small amount of aluminum. Sorption experiments reveal a higher affinity of this MOF for hydrogen compared to the previously described monometallic unfunctionalized MIL-101(TiIII) MOF.

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Sustainable functionalized metal-organic framework NH2-MIL-101(Al) for CO2 separation under cryogenic conditions

Cited by 27 publications

References 91 publications

Enhanced CO₂ Adsorption and Selectivity of CO₂/N₂ on Amine@ZIF-8 Materials

Enhanced CO₂ Adsorption and Selectivity of CO₂/N₂ on Amine@ZIF-8 Materials

Synthesis, Properties of MIL‐101(Al)‐NH₂ Polymers Capable of Absorbing Vapor, Liquid Water Simultaneously

Synthesis, structure and thermal stability of a mesoporous titanium(III) amine containing MOF with improved hydrogen sorption properties

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Sustainable functionalized metal-organic framework NH2-MIL-101(Al) for CO2 separation under cryogenic conditions

Cited by 27 publications

References 91 publications

Enhanced CO2 Adsorption and Selectivity of CO2/N2 on Amine@ZIF-8 Materials

Enhanced CO2 Adsorption and Selectivity of CO2/N2 on Amine@ZIF-8 Materials

Synthesis, Properties of MIL‐101(Al)‐NH2 Polymers Capable of Absorbing Vapor, Liquid Water Simultaneously

Synthesis, structure and thermal stability of a mesoporous titanium(III) amine containing MOF with improved hydrogen sorption properties

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Product

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About

Enhanced CO₂ Adsorption and Selectivity of CO₂/N₂ on Amine@ZIF-8 Materials

Enhanced CO₂ Adsorption and Selectivity of CO₂/N₂ on Amine@ZIF-8 Materials

Synthesis, Properties of MIL‐101(Al)‐NH₂ Polymers Capable of Absorbing Vapor, Liquid Water Simultaneously