Extra-framework zirconium clusters in metal organic framework DUT-67 controlled by the choice of the metal precursor

Precisvalle, Nicola; Ho, Phuoc Hoang; Cacciaguerra, Thomas; Deabate, S.; Girard, Luc; Toquer, Guillaume; Nguyen, Khoa D.; Le, Ha V.; Renzo, Francesco Di; Martucci, Annalisa; Trens, Philippe

doi:10.1016/j.micromeso.2021.111293

Cited by 7 publications

(10 citation statements)

References 66 publications

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“…Both MOFs were synthesized based on previous literature. 64 The main preparation process was as follows: 0.138 g of ZrCl 4 or 0.192 g of HfCl 4 (0.6 mmol) was placed into 7.5 mL solvent solution (a mixture of N,Ndimethylformamide (DMF) and 1-methyl-2-pyrrolidinone (NMP) in equal volume) and then mixed with 2.7 mL formic acid (FA) to form solution A. Solution B was prepared by dissolving 0.0663 g 2,5thiophene dicarboxylic acid (H 2 TDC) in 7.5 mL solvent mixture.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Motivated by the above considerations, we prepared two isostructural MOFs, DUT-67(Hf) and DUT-67(Zr) according to the literature. 64 Unexpectedly, the two compounds manifest excellent proton conductivity. Under 100 °C and 98% RH, their best proton conductivities (σ) can reach 2.98 × 10 −3 and 3.86 × 10 −3 S cm −1 , respectively.…”

Section: ■ Introductionmentioning

confidence: 96%

“…Motivated by the above considerations, we prepared two isostructural MOFs, DUT-67(Hf) and DUT-67(Zr) according to the literature . Unexpectedly, the two compounds manifest excellent proton conductivity.…”

Section: Introductionmentioning

confidence: 99%

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Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

et al. 2023

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In the field of sensing, finding high-performance amine molecular sensors has always been a challenging topic. Here, two highly stable 3D MOFs DUT-67(Hf) and DUT-67(Zr) with large specific surface areas and hierarchical pore structures were conveniently synthesized by solvothermal reaction of ZrCl 4 /HfCl 4 with a simple organic ligand, 2,5-thiophene dicarboxylic acid (H 2 TDC) according to literature approach. By analyzing TGA data, it was found that the two MOFs have defects (unsaturated metal sites) that can interact with substrates (H 2 O and volatile amine gas), which is conducive to proton transfer and amine compound identification. Further experiments showed that at 100 °C and 98% relative humidity (RH), the optimized proton conductivities of DUT-67(Zr) and DUT-67(Hf) can reach the high values of 2.98 × 10 −3 and 3.86 × 10 −3 S cm −1 , respectively. Moreover, the room temperature sensing characteristics of MOFs' to amine gases were evaluated at 68, 85 and 98% RHs, respectively. Impressively, the prepared MOFs-based sensors have the desired stability and higher sensitivity to amines. Under 68% RH, the detection limits of DUT-67(Zr) or DUT-67(Hf) for volatile amine gases were 0.5 (methylamine), 0.5 (dimethylamine) and 1 ppm (trimethylamine), and 0.5 (methylamine), 0.5 (dimethylamine) and 0.5 ppm (trimethylamine), respectively. As far as we know, this is the best performance of ammonia room temperature sensors in the past proton-conductive MOF sensors.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 96%

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Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

et al. 2023

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“…MOF-808 and DUT-67 were selected for investigation because of their relatively higher hydrothermal stability and tolerance to aqueous pH variations than other MOFs, warranting potential applications in adsorption and catalysis. ,,, ZrO(NO 3 ) 2 has been used as a metal precursor for synthesizing the said MOFs under solvothermal conditions with good crystallinity. , However, their aqueous medium synthesis using this precursor is not known. In the case of MOF-808, the first attempts using water with low-concentration acetic acid as a modulator under stirring at 368 K failed to form a crystalline product (Figure S1a).…”

Section: Resultsmentioning

confidence: 99%

“…20,24,34,39 ZrO(NO 3 ) 2 has been used as a metal precursor for synthesizing the said MOFs under solvothermal conditions with good crystallinity. 36,40 However, their aqueous medium synthesis using this precursor is not known. In the case of MOF-808, the first attempts using water with low-concentration acetic acid as a modulator under stirring at 368 K failed to form a crystalline product (Figure S1a).…”

Section: Characterizations Of the Synthesized Mofsmentioning

confidence: 99%

Facile Aqueous Medium Synthesis of Highly Stable Zr-MOFs with Promising CO₂/CH₄ Adsorption Selectivity for Natural Gas and Biogas Upgradation

Wamba,

Dalakoti,

Singh

et al. 2023

Ind. Eng. Chem. Res.

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Efficient CO2/CH4 separation is an important topic for the energy sector because of its implication in the economic upgradation of natural gas and biogas. Due to their excellent stability and high porosity, Zr-based MOFs are the best adsorbent candidates for targeted industrial applications through the adsorptive separation route. Herein, we report a scalable process for the synthesis of MOF-808(Zr) and DUT-67(Zr) analogues in aqueous solutions using zirconyl nitrate as a metal precursor and evaluate them as an adsorbent for CO2/CH4 separation. The as-synthesized materials were thoroughly characterized to verify the phase formation of the desired MOFs. They show similar porosity and stability to that obtained from conventional metal sources. Notably, at 298 K, the CO2 sorption analysis of MOF-808@N shows a relatively high uptake of 5.6 mmol/g at 10 bar. The CO2/CH4 selectivity in the same conditions for a 50:50 v/v binary mixture is 9.2, higher than that of well-known reported MOF adsorbents. The excellent separation performance was attributed to the large micropore volume and defect sites in the MOF framework. This study suggests that zirconyl nitrate could be an effective metal salt precursor for synthesizing Zr-MOFs for natural gas and biogas upgrading.

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Capture Fluorocarbon and Chlorofluorocarbon from Air Using DUT‐67 for Safety and Semi‐Quantitative Analysis

Xiong,

Song,

Wang

et al. 2024

Advanced Science

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Fluoro‐ and chlorofluorocabons (FC/CFCs) are important refrigerants, solvents, and fluoropolymers in industry while being toxic and carrying high global warming potential. Detection and reclamation of FC/CFCs based on adsorption technology with highly selective adsorbents is important to labor safety and environmental protection. Herein, the study reports an integrated method to combine capture, separation, enrichment, and analysis of representative FC/CFCs (chlorodifluoromethane(R22) and 1,1,1,2‐tetrafluoroethane (R134a)) by using the highly stable and porous Zr‐MOF, DUT‐67. Gas adsorption and breakthrough experiments demonstrate that DUT‐67 has high R22/R134a uptake (124/116 cm3 g−1) and excellent R22/R134a/CO2 separation performance (IAST selectivities of R22/CO2 and R134a/CO2 ranging from 51.4 to 33.3, and 31.1 to 25.8), even in rather low concentration and humid conditions. A semi‐quantitative analysis protocol is set up to analyze the low concentrations of R22/R134a based on the high selective R22/R134a adsorption ability, fast adsorption kinetics, water‐resistant utility, facile regeneration, and excellent recyclability of DUT‐67. In situ single‐crystal X‐ray diffraction, theoretical calculations, and in situ diffuse reflectance infrared Fourier transform spectra have been employed to understand the adsorption mechanism. This work may provide a potential adsorbent for purge and trap technique under room temperature, thus promoting the application of MOFs for VOCs sampling and quantitative analysis.

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Extra-framework zirconium clusters in metal organic framework DUT-67 controlled by the choice of the metal precursor

Cited by 7 publications

References 66 publications

Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

Facile Aqueous Medium Synthesis of Highly Stable Zr-MOFs with Promising CO₂/CH₄ Adsorption Selectivity for Natural Gas and Biogas Upgradation

Capture Fluorocarbon and Chlorofluorocarbon from Air Using DUT‐67 for Safety and Semi‐Quantitative Analysis

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Extra-framework zirconium clusters in metal organic framework DUT-67 controlled by the choice of the metal precursor

Cited by 7 publications

References 66 publications

Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

Two Dual-Function Zr/Hf-MOFs as High-Performance Proton Conductors and Amines Impedance Sensors

Facile Aqueous Medium Synthesis of Highly Stable Zr-MOFs with Promising CO2/CH4 Adsorption Selectivity for Natural Gas and Biogas Upgradation

Capture Fluorocarbon and Chlorofluorocarbon from Air Using DUT‐67 for Safety and Semi‐Quantitative Analysis

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Product

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Facile Aqueous Medium Synthesis of Highly Stable Zr-MOFs with Promising CO₂/CH₄ Adsorption Selectivity for Natural Gas and Biogas Upgradation