Regulation of hydrophobicity and water adsorption of MIL-101(Cr) through post-synthetic modification

Li, Yang; Wang, Hao-Tian; Zhao, Yuyun; Lv, Jie; Zhang, Xin; Chen, Qiang; Lǐ, Jiànróng

doi:10.1016/j.inoche.2021.108741

Cited by 22 publications

(11 citation statements)

References 39 publications

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“…[66] On the other hand, HNO 3 -MIL-101(Cr) has reaction mixtures with molar ratios of Cr:H 2 BDC:HNO 3 :H 2 O = 1:1:1:277 [12,69,73,88] or 1:1:1:265. [18,31,72] The reaction conditions for HCl-MIL-101(Cr) and HNO 3 -MIL-101(Cr) bear close semblance to the HF-based syntheses at 200-220 °C for 8, [12,17,18,55,62,70,72,74] 10, [59,65,82] 12, [57,60,64,66,71] or even 15 h. [68,81,86,87] Reports suggest that using HCl instead of HF reduces the MIL-101(Cr) particle sizes (e.g., decreasing from 500-1500 to 200-1200 nm) [17] whereas replacing HF with HNO 3 seems to increase MIL-101(Cr) crystallite sizes (e.g., increasing from 560-1100 to 720-1490 nm). [31,69] Specifically, by lowering the pH of the reaction mixture, HNO 3 reduces the crystal nucleation speeds to form larger crystallites.…”

Section: Mineral Acidsmentioning

confidence: 61%

“…[82] This result indicates that besides collecting water sorption isotherms, water contact angle measurements provide a quick estimate of a sample's hydrophilicity. [82,174] While MIL-101(Cr) and its functionalized counterparts are promising, there remain obstacles to their industrial applications. Figure 12 charts MIL-101(Cr)'s progress toward real-world applications using De Lange et al's framework for developing MOF-based adsorption-driven heat pumps.…”

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 97%

“…Specifically, Li et al introduced n-propyl, n-hexyl and n-dodecyl groups to MIL-101(Cr)'s open Cr 3+ sites to attain increasingly hydrophobic samples from MIL-101(Cr)-pro, -hex to -dod. [82] Not only do the increasing carbon chain lengths result in decreasing water uptake capacity, but the samples' water contact angles also increased from 17.9°, 34.3°, 56.4°to 146.5°. [82] This result indicates that besides collecting water sorption isotherms, water contact angle measurements provide a quick estimate of a sample's hydrophilicity.…”

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 99%

“…Replacing HF with mineral acids that penetrate tissues less readily [16] is an alternative. MIL-101(Cr) syntheses using hydrochloric acid (HCl), [17,55,[57][58][59][60][61][62][63][64][65][66][67] nitric acid (HNO 3 ), [12,18,31,[68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86][87] and even sulfuric acid (H 2 SO 4 ) [12] as mineralizers have been reported. [11] Although HCl is a stronger acid than HNO 3 , H 2 SO 4 , and HF (Table 3), MIL-101(Cr) synthesized using HCl (denoted HCl-MIL-101(Cr)) in molar ratios such as 1 Cr:1 H 2 BDC:1 HCl:266 H 2 O remains highly crystalline.…”

Section: Mineral Acidsmentioning

confidence: 99%

“…[191] Therefore, these working conditions have inspired rationally designed functionalized MIL-101(Cr). [82] Table 4 reflects examples of functionalized MIL-101(Cr) from the articles surveyed in Section 2.…”

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 99%

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Elucidating Improvements to MIL‐101(Cr)’s Porosity and Particle Size Distributions based on Innovations and Fine‐Tuning in Synthesis Procedures

Wee

Chinnappan

Ramakrishna

2023

Adv Materials Inter

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Among the existing metal–organic frameworks (MOFs), MIL‐101(Cr) is renowned for its stability in air and water. As a result, MIL‐101(Cr) has numerous potential applications ranging from adsorptive cooling to catalysis. The industrial‐scale production of MIL‐101(Cr) is necessary before realizing these applications. Yet, there remain two main bottlenecks in preparing MIL‐101(Cr) in bulk: the toxicity of hydrofluoric acid (HF) used in conventional MIL‐101(Cr) synthesis and the challenge of ensuring that the as‐prepared MIL‐101(Cr) is highly porous with specific Brunauer–Emmett–Teller surface area (SBET) above 4000 m2 g−1. On the laboratory scale, MIL‐101(Cr) often presents SBET 2300–3500 m2 g−1. The synthesis and purification procedures often influence the yield, particle size, porosity, and other properties of MIL‐101(Cr). This critical review examines trends in MIL‐101(Cr) preparation procedures and the MOF's resulting properties to elucidate areas for improvement toward its real‐world applications. The purification processes for conventional HF‐based MIL‐101(Cr) whereby porosities vary despite the same synthesis approach are first investigated. Next, the reported additives for substituting HF and their influence on the resulting MIL‐101(Cr)’s porosity and particle size are discussed. The selection of additives may be application‐specific: exemplified in the examination of MIL‐101(Cr)’s preparation, its corresponding water sorption capacity, and desiccant‐related applications.

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Section: Mineral Acidsmentioning

confidence: 61%

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 97%

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 99%

Section: Mineral Acidsmentioning

confidence: 99%

Section: Effects Of Functional Groups On Mil-101(cr)'s Water Uptake C...mentioning

confidence: 99%

See 3 more Smart Citations

Elucidating Improvements to MIL‐101(Cr)’s Porosity and Particle Size Distributions based on Innovations and Fine‐Tuning in Synthesis Procedures

Wee

Chinnappan

Ramakrishna

2023

Adv Materials Inter

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Room Temperature Hydroxyl Group‐Assisted Preparation of Hydrophobicity‐Adjustable Metal‐Organic Framework UiO‐66 Composites: Towards Continuous Oil Collection and Emulsion Separation

Xiang

Liu

Zhu

et al. 2023

Chemistry A European J

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Developing a straightforward and effective hydrophobic modification for metalÀ organic frameworks (MOFs) under mild conditions is meaningful for MOF applications.Here, a post-synthetic modification approach assisted with metal hydroxyl groups at room temperature is reported to induce hydrophobicity in the hydrophilic UiO-66. The bonding between ZrÀ OH in UiO-66 and n-tetradecylphosphonic acid (TDPA) is the vital force for the modifier TDPA. Superhydrophobic and superoleophilic composites were constructed for efficient oil-water separation by coating TDPAmodified UiO-66 (P-UiO-66) on commercial melamine sponges (MS) and filter papers (FP) with water contact angles of 153.2°and 155.6°, respectively. The P-UiO-66/MS composite could quickly and selectively absorb oily liquids up to 43 times its weight from water. The P-UiO-66/MS achieved continuous oil collection with high separation efficiencies (� 99.4 %). In addition, P-UiO-66/FP and P-UiO-66/MS showed high separation efficiencies for water-in-oil emulsions (� 98.5 %) and oil-in-water emulsions, respectively, with high resistance to low/high temperatures and acid/base conditions. The metal hydroxyl group-assisted post-synthetic modification strategy offers a facile and broad way to prepare hydrophobic MOFs for promising applications in environmental fields.

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Bifunctionally Hydrophobic MOF‐Supported Platinum Catalyst for the Removal of Ultralow Concentration Hydrogen Isotope

Heo,

Jang,

Jeong

et al. 2024

Energy & Environ Materials

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Water often presents significant challenges in catalysts by deactivating active sites, poisoning the reaction, and even degrading composite structure. These challenges are amplified when the water participates as a reactant and is fed as a liquid phase, such as trickle bed‐type reactors in a hydrogen‐water isotope exchange (HIE) reaction. The key balance in such multiphase reactions is the precise control of catalyst design to repel bulk liquid water while diffusing water vapor. Herein, a platinum‐incorporated metal‐organic framework (MIL‐101) based bifunctional hydrophobic catalyst functionalized with long alkyl chains (C12, dodecylamine) and further manufactured with poly(vinylidene fluoride), Pt@MIL‐101‐12/PVDF, has been developed which can show dramatically improved catalytic activity under multi‐phase reactions involving hydrogen gas and liquid water. Pt@MIL‐101‐12/PVDF demonstrates enhanced macroscopic water‐blocking properties, with a notable reduction of over 65% in water adsorption capacity and newly introduced liquid water repellency, while exhibiting a negligible increase in mass transfer resistance, i.e., bifunctional hydrophobicity. Excellent catalytic activity, evaluated via HIE reaction, and its durability underscore the impact of bifunctional hydrophobicity. In situ DRIFTS analysis elucidates water adsorption/desorption dynamics within the catalyst composite, highlighting reinforced water diffusion at the microscopic level, affirming the catalyst's bifunctionality in different length scales. With demonstrated radiation resistance, Pt@MIL‐101‐12/PVDF emerges as a promising candidate for isotope exchange reactions.

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Regulation of hydrophobicity and water adsorption of MIL-101(Cr) through post-synthetic modification

Cited by 22 publications

References 39 publications

Elucidating Improvements to MIL‐101(Cr)’s Porosity and Particle Size Distributions based on Innovations and Fine‐Tuning in Synthesis Procedures

Elucidating Improvements to MIL‐101(Cr)’s Porosity and Particle Size Distributions based on Innovations and Fine‐Tuning in Synthesis Procedures

Room Temperature Hydroxyl Group‐Assisted Preparation of Hydrophobicity‐Adjustable Metal‐Organic Framework UiO‐66 Composites: Towards Continuous Oil Collection and Emulsion Separation

Bifunctionally Hydrophobic MOF‐Supported Platinum Catalyst for the Removal of Ultralow Concentration Hydrogen Isotope

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