A 3D stable Mn(II) metal-organic framework based on a flexible tetracarboxylate precursor and its photocatalytic properties

Wang, Jun; Zhou, Dan; Wang, Guang-Li; Lu, Lu; Pan, Ying; Singh, Amita; Kumar, Abhinav

doi:10.1016/j.ica.2019.04.020

Cited by 15 publications

(3 citation statements)

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“…12 Owing to visible light response and excellent redox behavior, these MOF photocatalysts are being explored for CO 2 reduction, solar water splitting, photoreduction, photochemical transformations of small molecules, and photocatalytic degradation of organic pollutants. [13][14][15][16][17][18][19] One of the requirements for an efficient photocatalyst is its long-term photostability. Since the metalligand interactions in MOFs are coordinative, they are subjected to break under UV/visible irradiations.…”

Section: Introductionmentioning

confidence: 99%

Terephthalate and trimesate metal–organic frameworks of Mn, Co, and Ni: exploring photostability by spectroscopy

et al. 2021

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Section: Introductionmentioning

confidence: 99%

Terephthalate and trimesate metal–organic frameworks of Mn, Co, and Ni: exploring photostability by spectroscopy

et al. 2021

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“…The total density of state reveals a significant bandgap of (1 .79 eV), revealing a non-metallic character of this material (see Figure S3). Further, we have analysed the partial density of the state (pdos plot) for hydrogen-bound MOF to gain insight into the bonding [82,83] (Figure 4). The following points emerge from this data (i) for the site I two variations are noted with the peak corresponding to the conduction band of d z 2 orbital moving towards the Fermi level upon H 2 binding, and the corresponding valance band d z 2 orbital getting further stabilised, affirming the bonding picture described earlier also holds valid for the periodic systems (Figure S2).…”

Section: Chemphyschemmentioning

confidence: 99%

A Theoretical Perspective to Decipher the Origin of High Hydrogen Storage Capacity in Mn(II) Metal‐Organic Framework

2022

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Herein, we report a detailed periodic DFT investigation of Mn(II)-based [(Mn 4 Cl) 3 (BTT) 8 ] 3À (BTT 3À = 1,3,5-benzenetristetrazolate) metal-organic framework (MOF) to explore various hydrogen binding pockets, nature of MOF…H 2 interactions, magnetic coupling and, H 2 uptake capacity. Earlier experiments found an uptake capacity of 6.9 wt % of H 2, with the heat of adsorption estimated to be ~10 kJ/mol, which is one among the highest for any MOFs reported. Our calculations unveil different binding sites with computed binding energy varying from À 6 to À 15 kJ/mol. The binding of H 2 at the Mn 2 + site is found to be the strongest (site I), with H 2 found to bind Mn 2 + ion in a η 2 fashion with a distance of 2.27 Å and binding energy of À 15.4 kJ/mol. The bonding analysis performed using NBO and AIM reveal a strong donation of σ (H 2 ) to the d z 2 orbital of the Mn 2 + ion responsible for such large binding energy. The other binding pockets, such as À Cl (site II) and BTT ligands (site III and IV) were found to be weaker, with the binding energy decreasing in the order I > II > III > IV. The average binding energy computed for these four sites put together is 9.6 kJ/mol, which is in excellent agreement with the experimental value of ~10 kJ/mol. We have expanded our calculations to compute binding energy for multiple sites simultaneously, and in this model, the binding energy per site was found to decrease as we increased the number of H 2 molecules suggesting electronic and steric factors controlling the overall uptake capacity. The calculated adsorption isotherm using the GCMC method reproduces the experimental observations. Further, the magnetic coupling computed for the unbound MOF reveals moderate ferromagnetic and strong antiferromagnetic coupling within the tetrameric {Mn 4 } unit leading to a three-up-onedown spin configuration as the ground state. These were then coupled ferromagnetically to other tetrameric units in the MOF network. The magnetic coupling was found to alter only marginally upon gas binding, suggesting that both exchange interaction and the spin-states are unlikely to play a role in the H 2 uptake. This is contrary to the O 2 uptake studied lately, where strong dependence on exchange-coupling/spin state was witnessed, suggesting exchange-coupling/magnetic field dependent binding as a viable route for gas separation.

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“…Such POM/MOF composites have also been applied in photocatalysis dye degradation. [82][83][84][85][86][87][88][89][90][91][92] Besides the advantages in surface area and high catalytic activity, MOFs with suitable organic ligands can absorb visible light and improve the light utilization rate of POM-based photocatalysts.…”

Section: Pom-based Metal-organic Framework (Pomofs)mentioning

confidence: 99%

Application of polyoxometalates in photocatalytic degradation of organic pollutants

et al. 2021

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A 3D stable Mn(II) metal-organic framework based on a flexible tetracarboxylate precursor and its photocatalytic properties

Cited by 15 publications

References 64 publications

Terephthalate and trimesate metal–organic frameworks of Mn, Co, and Ni: exploring photostability by spectroscopy

Terephthalate and trimesate metal–organic frameworks of Mn, Co, and Ni: exploring photostability by spectroscopy

A Theoretical Perspective to Decipher the Origin of High Hydrogen Storage Capacity in Mn(II) Metal‐Organic Framework

Application of polyoxometalates in photocatalytic degradation of organic pollutants

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