Direction of theoretical and experimental investigation into the mechanism of n-HA/Si-PA-SC@Ag as a bio-based heterogeneous catalyst in the reduction reactions

Sisakhti, Zohreh Nouripour; Malmir, Masoumeh; Bisafar, Masoumeh Bagheri; Heravi, Majid Μ.; Hosseinnejad, Tayebeh

doi:10.1038/s41598-022-26200-3

Cited by 7 publications

(4 citation statements)

References 63 publications

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“…Furthermore, the close agreement between the calculated and experimental structural data verifies the reliability of the proposed designed structural model. In our computational design, we have achieved a balance between accuracy and efficiency by considering the findings from our recently published computational investigations. , To elucidate the electronic properties of the essential intramolecular interactions between the reactant and catalysts, we focused on performing a topological analysis of the electron density for our designed GLY-MIL88B and GLY-MIL88B-PMA compounds using the quantum theory of atoms in molecules (QTAIM) method at a higher level of theory . In this respect, the wave functions corresponding to the optimized geometries of GLY-MIL88B and GLY-MIL88B-PMA compounds were calculated at the B3LYP/6-311+G** and TPSSH/6-311+G** levels of theory and then employed as input files for the AIM2000 program package .…”

Section: Resultsmentioning

confidence: 99%

Unraveling High Chemoselectivity in Oxidative Dehydration of Glycerol into Acrylic Acid over a Bifunctional Metal–Organic Framework–Polyoxometalate Composite Catalyst

Koley,

Chandra Shit,

Yoshida

et al. 2024

ACS Catal.

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The selective conversion of glycerol into acrylic acid (AA) using polyoxometalate catalysts poses a challenge due to low conversion and selectivity, as the acrolein intermediate is not effectively stabilized on the catalyst surface. In this study, we introduce a novel approach to develop a bifunctional active catalyst that incorporates dehydration and oxidation active sites while also confining these sites within a porous material to enhance product selectivity. A unique synthetic method was devised to create such a bifunctional catalyst (MIL88B-800PMA) comprising a metal− organic framework (MIL88B) and polyoxometalate (PMA). These catalysts demonstrated 100% conversion with 96.4% selectivity toward AA under mild reaction conditions. The complete encapsulation of PMA can account for the high catalytic activity within the pores of the MOF, facilitating the chemical bond formation and structural modulation between PMA and the MOF, as confirmed by detailed X-ray absorption spectroscopy (XAS) analysis. The presence of oxidative species such as Mo 6+ and Fe 2+ , along with oxygen vacancies, promotes the highest catalytic conversion and selectivity. A comprehensive kinetic study, including in situ ATR-IR analysis, illustrates the formation and stabilization of the specific intermediate acrolein, guiding the selective formation of AA. This finding is corroborated by theoretical quantum chemistry calculations, offering a quantitative understanding of the surface interaction between glycerol and the Brønsted acid sites present on the MIL88B and PMA composite catalysts. Additionally, the activation energy of the synthesized catalysts is evaluated, aiding in the comprehension of the underlying reasons for their high catalytic activity.

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Section: Resultsmentioning

confidence: 99%

Unraveling High Chemoselectivity in Oxidative Dehydration of Glycerol into Acrylic Acid over a Bifunctional Metal–Organic Framework–Polyoxometalate Composite Catalyst

Koley,

Chandra Shit,

Yoshida

et al. 2024

ACS Catal.

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“…We have displayed schematically our designed molecular models in Figure a,b, titled as HMF-Cu-BTC and HMF-Cu-BTC_PMA, considering the previously reported modeling for the Cu-BTC compound in terms of size and structure . As the first step of calculations, we have determined the optimized structure of HMF-Cu-BTC and HMF-Cu-BTC_PMA molecular models at the M06/6-31G* level of theory. , The M06/6-31G* obtained optimized structures, and the corresponding cartesian coordinates of atoms of HMF-Cu-BTC and HMF-Cu-BTC_PMA models are presented in supplementary data (Figure S13 and Table S11, respectively). In the case of Mo atoms, the Jorge-ATZP basis set was employed which has been augmented with diffuse (s and p symmetries) and polarization (p, d, f, and g symmetries) functions .…”

Section: Results and Discussionmentioning

confidence: 99%

“…It is worthwhile to mention that in our computational design, we have considered an appropriate compromise between accuracy and time saving efficiency of computational procedure which were examined in our recently published computational investigations. 53,54 We have verified that all the real frequencies of the normal modes of vibrations are positive to confirm that the stationary points found are indeed minima on the potential energy surface. All DFT computations have been performed applying the GAMESS suite of programs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Elucidation of Active Sites and Mechanistic Pathways of a Heteropolyacid/Cu-Metal–Organic Framework Catalyst for Selective Oxidation of 5-Hydroxymethylfurfural via Ex Situ X-ray Absorption Spectroscopy and In Situ Attenuated Total Reflection-Infrared Studies

et al. 2023

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Chemoselective oxidation of 5-hydroxymethylfurfural (HMF) over nonnoble metals to produce a bioplastic monomer, 2,5-furandicarboxylic acid (FDCA), under alkaline-free conditions is challenging and worthy of investigation. HMF oxidation into FDCA involves the concurrent oxidation of primary alcohol and an aldehyde functional group into carboxylic groups, which therefore demand a bifunctional catalyst containing dual active sites and chemoselective oxidation of HMF. The present work demonstrated the formation of new selective active sites in a composite porous material (Cu-BTC_PMA) that consists of Cu-BTC (metal−organic framework (MOF)) and polyoxometalate (POM). The porous framework provides (Cu-BTC_PMA) the desired chemoselectivity, while a selective Cu metal center in Cu-BTC (MOF) and Cu−O−Mo sites functions as active sites for the concurrent oxidation of HMF into FDCA. This catalyst exhibited a HMF conversion of 89% and an FDCA selectivity of 92.3% under base-free and mild reaction conditions. In detail, X-ray absorption spectroscopy analysis demonstrated the chemical bond tuning, as well as electronic structural modulations of MOF and POM at the molecular level, which directs the formation of new synergistic interfacial active sites and charge transfer states. This phenomenon causes the generation of the unique redox environment of copper and the multiple oxidation states along with the oxygen vacancy in the Cu-BTC_PMA catalyst, which most likely behaves as active sites for base-free oxidation. A kinetics study of this reaction was followed using in situ attenuated total reflection-infrared spectroscopy, demonstrating the stabilization of the specific intermediates that lead to the formation of FDCA. Moreover, we made comparative density functional theory and quantum theory of atoms in molecules investigations on the surface interaction between the reactant (HMF) and two catalyst models of Cu-BTC and Cu-BTC_PMA to interpret quantitatively the higher catalytic activity of the Cu-BTC_PMA catalyst. The kinetics study also evaluates the rate-determining step and activation energy for the multistep oxidation reactions.

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“…However, the development of an efficient catalytic system for the reduction of nitro compounds remains a challenging task. Motivated by the aforementioned considerations and building upon our previous research in the field of heterogeneous catalysts, [68][69][70][71][72][73][74][75][76][77][78] we have proposed a novel approach for the reduction of nitro compounds by introducing a magnetic catalyst based on MOF and CN nanosheets. In this study, Cu-based MOF was selected due to their high catalytic activity, availability, costeffectiveness, and simplicity of synthesis.…”

Section: Introductionmentioning

confidence: 99%

An efficient catalytic reduction of nitroarenes over metal‐organic framework‐derived magnetic graphitic carbon nitride nanosheet

Malmir,

Heravi,

Jahani

2023

Applied Organom Chemis

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Metal–organic frameworks (MOFs) have emerged as highly viable and environmentally friendly alternatives to traditional catalysts within the catalytic family. This project delves into the investigation and subsequent reporting of the remarkable catalytic performance exhibited by magnetic Ox‐CN‐Cu‐MOF in the reduction of nitroarenes. The synthesis of magnetic Ox‐CN‐Cu‐MOF was achieved through a streamlined and intricate process, with its structure meticulously identified via various analytical methods including high‐resolution transmision electron microscopy (HRTEM), X‐ray diffraction (XRD), scanning electron microscopy/energy dispersive X‐ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET), vibrating‐sample magnetometry (VSM) and thermogravimetric (TG) analysis. Of particular significance, the loading of copper (Cu) and its potential leaching were effectively detected through inductively coupled plasma optical emission spectroscopy (ICP‐OES) analysis. The catalytic efficacy of magnetic Ox‐CN‐Cu‐MOF was evaluated during the conversion of nitro compounds o related‐amines utilizing NaBH4 as the reductant. Remarkably, the unique structure and Lewis acidic properties of copper in the metal nodes contributed to the exceptional catalytic behavior exhibited by the magnetic Ox‐CN‐Cu‐MOF catalyst, surpassing that of previously reported catalysts. Furthermore, magnetic Ox‐CN‐Cu‐MOF demonstrated exceptional recyclability, as validated through repetitive continuous usage.

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Direction of theoretical and experimental investigation into the mechanism of n-HA/Si-PA-SC@Ag as a bio-based heterogeneous catalyst in the reduction reactions

Cited by 7 publications

References 63 publications

Unraveling High Chemoselectivity in Oxidative Dehydration of Glycerol into Acrylic Acid over a Bifunctional Metal–Organic Framework–Polyoxometalate Composite Catalyst

Unraveling High Chemoselectivity in Oxidative Dehydration of Glycerol into Acrylic Acid over a Bifunctional Metal–Organic Framework–Polyoxometalate Composite Catalyst

Elucidation of Active Sites and Mechanistic Pathways of a Heteropolyacid/Cu-Metal–Organic Framework Catalyst for Selective Oxidation of 5-Hydroxymethylfurfural via Ex Situ X-ray Absorption Spectroscopy and In Situ Attenuated Total Reflection-Infrared Studies

An efficient catalytic reduction of nitroarenes over metal‐organic framework‐derived magnetic graphitic carbon nitride nanosheet

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