Impact of dehydration and mechanical amorphization on the magnetic properties of Ni(<scp>ii</scp>)-MOF-74

Muratović, Senada; Karadeniz, Bahar; Stolar, Tomislav; Lukin, Stipe; Halász, Ivan; Herak, Mirta; Mali, Gregor; Krupskaya, Yulia; Kataev, V.; Žilić, Dijana; Užarević, Krunoslav

doi:10.1039/d0tc00844c

Cited by 26 publications

(20 citation statements)

References 75 publications

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“…The recent theoretical study has shown that the linker-metal bonds in MOF-74 materials are dynamic and can brake under certain conditions . Similar observations of the appearance of the uncoordinated carbonyl group were also recently described in the case of mechanochemical amorphization of Ni-MOF-74, where the amorphization led to spin-crossover and significant drop in magnetization . Furthermore, there seems to be a correlation between the mechanochemical amorphization and the introduction of defects as observed by Bennett et al in zirconia-based MOFs …”

Section: Resultssupporting

confidence: 73%

“…Finally, after 90 more minutes of milling, brown-reddish powder which corresponded to c-ZnCu-MOF-74 was formed, washed three times with a small volume of MeOH, and vacuum-dried. In order to amorphize the crystalline bimetallic MOF and prepare a-ZnCu-MOF-74, c-ZnCu-MOF-74 was held under vacuum at 150 °C overnight to remove the guest and coordinated solvent, after which the sample was milled for 90 min (Figure a) …”

Section: Methodsmentioning

confidence: 99%

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Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

Stolar

Prašnikar

Martinez

et al. 2021

ACS Appl. Mater. Interfaces

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111

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Selective catalytic reduction of CO 2 to methanol has tremendous importance in the chemical industry. It mitigates two critical issues in the modern society, the overwhelming climate change and the dependence on fossil fuels. The most used catalysts are currently based on mixed copper and zinc phases, where the high surface of active copper species is a critical factor for the catalyst performance. Motivated by the recent breakthrough in the controllable synthesis of bimetallic MOF-74 materials by ball milling, we targeted to study the potential of ZnCu-MOF-74 for catalytic CO 2 reduction. Here, we tested whether the nanosized channels decorated with readily accessible and homogeneously distributed Zn and Cu metal sites would be advantageous for the catalytic CO 2 reduction. Unlike the inactive monometallic Cu-MOF-74, ZnCu-MOF-74 shows moderate catalytic activity and selectivity for the methanol synthesis. Interestingly, the postsynthetic mechanochemical treatment of desolvated ZnCu-MOF-74 resulted in amorphization and a significant increase in both the activity and selectivity of the catalyst despite the destruction of the well-ordered and porous MOF-74 architecture. The results emphasize the importance of defects for the MOF catalytic activity and the potential of amorphous MOFs to be considered as heterogeneous catalysts. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and 13 C magic angle-spinning nuclear magnetic resonance (MAS NMR) were applied to establish quantitative structure− reactivity relationships. The apparent activation energy of rate reaction kinetics has indicated different pathway mechanisms, primarily through reverse water−gas shift (RWGS). Prolonged time on stream productivity, stability and deactivation were assessed, analysing the robustness or degradation of metal−organic framework nanomaterials. Scalable MOF production processes are making the latter more appealing within emerging industrial decarbonisation, in particular for carbon capture and utilisation (CCU) or hydrogen carrier storage. Acknowledging scale, the costs of fabrication are paramount.

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Section: Resultssupporting

confidence: 73%

Section: Methodsmentioning

confidence: 99%

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

Stolar

Prašnikar

Martinez

et al. 2021

ACS Appl. Mater. Interfaces

Self Cite

111

View full text Add to dashboard Cite

show abstract

“…Metal-organic frameworks (MOFs), assembled from organic ligands and metal ions/clusters [1][2][3], have been attracted researcher's attention over the last few years by virtue of their fascinating architectures and topologies [4] as well as broad potential applications such as gas adsorption/separation [5,6], luminescence [7,8], catalysis [9,10], magnetic [11,12], sensing [13,14], and so on. Many chemists are working hard to explore new strategies in order to synthesize target materials, but it is very challenging to synthesize MOFs owning expected structure and performance [15,16].…”

Section: Introductionmentioning

confidence: 99%

A 2D Porous Pb-MOF Based on 2-Nitroimidazole: CO <sub>2</sub> Adsorption, Electronic Structure and Luminescence

Wang

Song

et al. 2021

SSRN Journal

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A new porous metal-organic framework, [Pb 5 (Ac) 7 (nIm) 3 ] n (1), has been successfully synthesized by employing 2-nitroimidazole ligand and Pb 2+ ion. 1 contains novel the ribbon-shaped Pb-O SBU and reveals a 2D porous framework with a 1D tubular channel. Moreover, 1 shows moderate adsorption uptake towards CO 2 and luminescence properties from intraligand charge transfer. We further con rmed nitro group and metal ion are important adsorption sites by GCMC simulations, and the electronic structures of 1 was investigated.

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“…In contrast, the interchain interaction between the more than 7 Å distant Cu(II) centers, sitting in the neighboring chains, is an order of magnitude weaker. Because of this, various MOF-74(Me) materials were studied as model linear ferro- (Me = Fe, Co, Ni) or antiferro-magnets (Me = Mn, Cu). − …”

Section: Resultsmentioning

confidence: 99%

Hyperfine Coupling Constants in Cu-Based Crystalline Compounds: Solid-State NMR Spectroscopy and First-Principles Calculations with Isolated-Cluster and Extended Periodic-Lattice Models

Mali

Mazaj

2021

J. Phys. Chem. C

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NMR spectroscopy is a powerful tool for structural analysis of solids, especially if it is complemented by computations of NMR observables, such as chemical shifts and quadrupole coupling constants. In paramagnetic solids, chemical shifts can be greatly affected by hyperfine couplings among the unpaired electrons and atomic nuclei. In this study 13 C MAS NMR spectra of three representative crystalline solids (a simple coordination compound of copper and alanine and two complex copper-based metal−organic framework materials) were measured, and the observed paramagnetic shifts were correlated with the hyperfine coupling constants, calculated along two different density functional theory-based approaches. The first approach employed an isolated-cluster model, and the second one used an extended-lattice model and periodic boundary conditions. For both approaches the calculated isotropic hyperfine coupling constants correlated very well with the measured paramagnetic shifts and thus allowed the assignment of the 13 C NMR signals, spread over the region of 1000 ppm. This assignment to individual carbon crystallographic sites was in complete agreement with the experimentally derived assignment.

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Impact of dehydration and mechanical amorphization on the magnetic properties of Ni(ii)-MOF-74

Abstract: While desolvation process does not influence the magnetism of Ni-MOF-74, amorphization causes partial nickel(ii) spin-crossover from S = 1 to S = 0 and the decrease of the bulk magnetization.

Cited by 26 publications

References 75 publications

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

A 2D Porous Pb-MOF Based on 2-Nitroimidazole: CO <sub>2</sub> Adsorption, Electronic Structure and Luminescence

Hyperfine Coupling Constants in Cu-Based Crystalline Compounds: Solid-State NMR Spectroscopy and First-Principles Calculations with Isolated-Cluster and Extended Periodic-Lattice Models

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Impact of dehydration and mechanical amorphization on the magnetic properties of Ni(ii)-MOF-74

Abstract: While desolvation process does not influence the magnetism of Ni-MOF-74, amorphization causes partial nickel(ii) spin-crossover from S = 1 to S = 0 and the decrease of the bulk magnetization.

Cited by 26 publications

References 75 publications

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO2 Reduction Reaction to Methanol

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO2 Reduction Reaction to Methanol

A 2D Porous Pb-MOF Based on 2-Nitroimidazole: CO <sub>2</sub> Adsorption, Electronic Structure and Luminescence

Hyperfine Coupling Constants in Cu-Based Crystalline Compounds: Solid-State NMR Spectroscopy and First-Principles Calculations with Isolated-Cluster and Extended Periodic-Lattice Models

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Product

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Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol

Scalable Mechanochemical Amorphization of Bimetallic Cu−Zn MOF-74 Catalyst for Selective CO₂ Reduction Reaction to Methanol