Co/Ni mixed-metal sited MOF-74 material as hydrogen adsorbent

Villajos, José A.; Orcajo, Gisela; Martos, Carmen; Botas, Juan A.; Villacañas, Jesús; Calleja, Guillermo

doi:10.1016/j.ijhydene.2015.01.113

Cited by 86 publications

(63 citation statements)

References 34 publications

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“…This deviation decreased with increasing Ni nominal value. These values are close to those reported by Villajos et al . in isomorphous substitution of Co nodes by Ni in MOF‐74.…”

Section: Resultssupporting

confidence: 91%

“…Modification of MOFs, considering their structures, can be realized using various methods. Changing the connectivity of inorganic segments, substituting structural metal nodes to create mixed‐metal MOFs, , replacement of organic linkers, immobilization of functional sites, e.g. unsaturated open metal sites, amide or hydroxylic sites, and carbonization can be named as modification methods.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture

Abdoli

Razavian

Fatemi

2019

Applied Organom Chemis

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An open metal site framework named UTSA-16 was synthesized and modified as a high-capacity adsorbent for reversible CO 2 capture. Partial substitution of intrinsic Co 2+ sites of UTSA-16 with Ni 2+ centres was realized in the molar composition range 0-75% Ni with the aim of increasing CO 2 uptake. Synthesized bimetallic Nix-UTSA-16 (x = 0, 20, 50, 75) materials were characterized using various techniques to assess the influence of chemical composition on CO 2 binding affinity and any subsequent physical change in morphology, crystal size and porosity on the total uptake. Experimental isotherm adsorption studies showed the following trend for CO 2 adsorption capacity employing the Nix-UTSA-16 series: Ni20-UTSA-16 > UTSA-16 > Ni50-UTSA-16 > Ni75-UTSA-16. According to the dynamic breakthrough CO 2 profiles measured for a mixture of CO 2 and CH 4 (15/85 molar ratio), Ni20-UTSA-16 exhibited 2 times the breakthrough time with 1.5 times the loading capacity at 75 Nml min −1 feed flow rate, compared to the parent UTSA-16. In addition, the Ni20-UTSA-16 bimetallic metal-organic framework exhibited lower isosteric heat of adsorption compared to UTSA-16 (ΔH ave = 28.54 versus 46.85 kJ mol −1 ).As a result, more than 95% of its capacity was restored by applying a partial vacuum for only 1 h at room temperature without involving any other timeand energy-consuming regenerative step.

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“…This deviation decreased with increasing Ni nominal value. These values are close to those reported by Villajos et al . in isomorphous substitution of Co nodes by Ni in MOF‐74.…”

Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture

Abdoli

Razavian

Fatemi

2019

Applied Organom Chemis

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“…The experimental H 2 uptake is 35.8 mg/g in the saturated adsorption state at 77 K. The highest predicted excess H 2 uptakes from the VDW, UFF and Dreiding FFs are 35.72 mg/g, 125.40 mg/g, and 27.19 mg/g, respectively, and the prediction using the VDW FF is in excellent agreement with the experimental value (35.8 mg/g) . Additionally, the VDW FF correctly predicted the adsorption capacity of H 2 in Zn‐MOF‐74, as shown in Figure l . However, the results using UFF and Dreiding do not match the experimental measurement.…”

Section: Resultssupporting

confidence: 66%

“…[13] Additionally, the VDW FF correctly predicted the adsorption capacity of H 2 in Zn-MOF-74, as shown in Figure 5l. [40] However, the results using UFF and Dreiding do not match the experimental measurement. Overall, the VDW FF can well predict the gas adsorption in several representative porous materials.…”

Section: Gas Uptakementioning

confidence: 89%

Accurate van der Waals force field for gas adsorption in porous materials

et al. 2017

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An accurate van der Waals force field (VDW FF) was derived from highly precise quantum mechanical (QM) calculations. Small molecular clusters were used to explore van der Waals interactions between gas molecules and porous materials. The parameters of the accurate van der Waals force field were determined by QM calculations. To validate the force field, the prediction results from the VDW FF were compared with standard FFs, such as UFF, Dreiding, Pcff, and Compass. The results from the VDW FF were in excellent agreement with the experimental measurements. This force field can be applied to the prediction of the gas density (H , CO , C H , CH , N , O ) and adsorption performance inside porous materials, such as covalent organic frameworks (COFs), zeolites and metal organic frameworks (MOFs), consisting of H, B, N, C, O, S, Si, Al, Zn, Mg, Ni, and Co. This work provides a solid basis for studying gas adsorption in porous materials. © 2017 Wiley Periodicals, Inc.

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“…In the past, the mixed‐metal method has been considered in improving CO 2 adsorption selectivity in zeolitic imidazolate frameworks, and enhancing guest (H 2 , CH 4 , and CO 2 ) adsorption capacity using Zn/Co and Co/Ni mixed‐metal in MOF‐74. As MOF‐74 mixing with more than two types of metal ions has been successfully synthesized, it is therefore possible to prepare mmen‐M 2 (dobpdc) with Mg and Zn co‐mixing for tuning the CO 2 capture efficiency.…”

Section: Introductionmentioning

confidence: 99%

Tuning carbon dioxide capture capability with structural and compositional design in mmen‐(Mg,Zn) (dobpdc) metal‐organic framework: density functional theory investigation

2018

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This paper presents a materials design for tuning the CO2‐capture capability of mixed‐metal‐organic framework mmen‐(ZnxMg1‐x)2(dobpdc) using density functional theory. The structural stability of a mixed‐metal structure with respect to its parent single‐metal species was investigated via energy of mixing (ΔEmix). We found that the ΔEmix of all mixed‐metal structures are negative, signifying exothermic mixing. This then indicates that mixed‐metal structures are energetically preferable compared with their non‐interacting single‐metal species. Moreover, the magnitudes of ΔEmix of all mixed‐metal structures are lower than 1 kJ/mol, implying an ‘ideal mixing’. Density‐of‐state analysis also reveals that the electronic structures of both Mg and Zn in mixed‐metal structures are not significantly different from those in parent single‐metal species, suggesting weak chemical interaction between Mg and Zn in mixed‐metal structures. For CO2‐adsorbed mmen‐(ZnxMg1‐x)2(dobpdc), we found that the adsorption energy (Eads) is a linear function of mixing ratio (x), and does not depend on how Mg and Zn atoms are arranged in forming different mixed‐metal structures. This can be described by the weak chemical interaction between Mg and Zn in a mixed‐metal structure. Consequently, Eads can then be predicted conveniently from the mixing ratio, while the adsorption properties of parent single‐metal species can be tuned with the proposed mixed‐metal method. We then expect that the knowledge of materials design using a mixed‐metal approach presented in this work would benefit the community in providing the ability to tune CO2 capture capability efficiently in the materials studied. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Co/Ni mixed-metal sited MOF-74 material as hydrogen adsorbent

Cited by 86 publications

References 34 publications

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture

Accurate van der Waals force field for gas adsorption in porous materials

Tuning carbon dioxide capture capability with structural and compositional design in mmen‐(Mg,Zn) (dobpdc) metal‐organic framework: density functional theory investigation

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Co/Ni mixed-metal sited MOF-74 material as hydrogen adsorbent

Cited by 86 publications

References 34 publications

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO2 capture

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO2 capture

Accurate van der Waals force field for gas adsorption in porous materials

Tuning carbon dioxide capture capability with structural and compositional design in mmen‐(Mg,Zn) (dobpdc) metal‐organic framework: density functional theory investigation

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About

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture

Bimetallic Ni–Co‐based metal–organic framework: An open metal site adsorbent for enhancing CO₂ capture