Nitrogen-rich cobalt (II) MOFs as efficient bifunctional catalysts for single or tandem oxidation and CO2 conversion reactions

Valverde‐González, Antonio; Borrallo-Aniceto, M. Carmen; Díaz, Urbano; Maya, Eva M.; Gándara, Felipe; Sánchez, Félix; Iglesias, Marta

doi:10.1016/j.jcou.2022.102298

Cited by 18 publications

(19 citation statements)

References 67 publications

(74 reference statements)

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“…The lower yields may be because the large substrates cannot easily enter the channels of Mn-MOF-1a, and are also probably ascribed to the different electron-donating groups, leading to an increase in the electron cloud densities of the C-O bond of epoxides. Upon increasing the reaction time to 16 h, the yield after 16 h increased from 88 to 93% for phenyl glycidyl ether, from 79 to 83% for allyl glycidyl ether, from 81 to 83% for styrene oxide, and from 69 to 75% for epoxyhexane, which show that the yields of the tar- According to the previous reports [48][49][50][51][52][53][54]77 and the framework of Mn-MOF-1a, a possible catalytic mechanism was discussed as follows (Scheme 1). Firstly, the Lewis acid sites (Mn 2+ ions) activate the O atoms of epoxides through the coordination interaction.…”

Section: Dalton Transactions Papersupporting

confidence: 66%

“…According to the previous reports 48–54,77 and the framework of Mn-MOF- 1a , a possible catalytic mechanism was discussed as follows (Scheme 1). Firstly, the Lewis acid sites (Mn 2+ ions) activate the O atoms of epoxides through the coordination interaction.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, various MOFs with excellent catalytic activity in the cycloaddition of CO 2 with epoxide have been successively reported. 40–54 Previous reports showed that the unsaturated metal sites of MOFs as active Lewis acid centers could play a vital role in facilitating the cycloaddition of CO 2 with epoxides. 36,44–46 Dai et al 45 reported a [Zn 2 (iso) 2 (bpy) 2 ] n MOF with open metal sites, which exhibits exceptionally high catalytic activity for the cycloaddition of CO 2 and propylene oxide.…”

Section: Introductionmentioning

confidence: 99%

“…After treatment, the MOF with highly open metal sites can effectively catalyze the fixation of CO 2 with epoxides into cyclic carbonates under mild conditions. Besides Lewis acid sites, many Lewis base sites, like uncoordinated N imidazole , 55 N oxadiazole , 56 N tetrazole 48 and N pyridine 46 atoms, have been introduced into MOFs, which can enrich and activate CO 2 in the cycloaddition reaction of CO 2 with epoxides. In this context, creating unsaturated metal sites and introducing uncoordinated N atoms in organic ligands are an effective approach to this catalytic system, because they can enhance CO 2 capture, and functional sites (Lewis acid/base, etc .)…”

Section: Introductionmentioning

confidence: 99%

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Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Zhao

Chen

et al. 2023

Dalton Trans.

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Section: Dalton Transactions Papersupporting

confidence: 66%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Zhao

Chen

et al. 2023

Dalton Trans.

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“…The activity of Co-NDPhTz for the cycloaddition reaction between epichlorohydrin and CO 2 was high, achieving a TON value of 2555. [47]…”

Section: Bifunctional Acid/base Solidsmentioning

confidence: 99%

New Opportunities in Metal‐Organic Framework Catalysis: From Bifunctional to Frustrated Lewis Pairs Catalysis

Dhakshinamoorthy

Asiri

Garcı́a

2023

Chemistry A European J

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This article highlights novel prospects for metalorganic frameworks (MOFs) in heterogeneous catalysis as having frustrated Lewis acid-base pairs (FLPs) or as bifunctional acid-base solid catalysts able to activate molecular hydrogen. Starting from the extensive application MOFs as Lewis acid and Lewis base catalysts, this article uses catalytic hydrogenation to briefly summarize the efforts made to heterogenize boron and amine in MOFs to mimic molecular FLP systems. The core of this concept is based on recent findings which demonstrate the ability of two commonly used MOFs, namely UiO-66 and MIL-101, to catalyze the selective hydrogenation of polar double X=Y bonds at moderate H 2 pressures below 10 bar. The influence of electron-donating, the withdrawal of substituents on the linker, and the aniline poisoning effect highlight the significance of Lewis acid sites, while density-functional theory calculations indicate the heterolytic HÀ H bond cleavage at the MOF metal oxo clusters. It is expected that this new perspective on MOFs as solid FLP systems will spur further research to explore and define the potential of dual sites in the catalytic activation of small molecules.

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Phosphonium Salt/Al‐Porphyrin Copolymer as Bifunctional Heterogeneous Catalyst for CO₂ Conversion to Cyclic Carbonates

Valentino,

Célis,

Campisciano

et al. 2023

ChemCatChem

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The effective chemical valorization of CO2 by means of its conversion into valuable products is now more than ever a topic of considerable interest. It is on that basis that herein we have chosen the conversion of CO2 and epoxides to cyclic carbonates as a convenient route to achieve this goal. A new bifunctional (Lewis acid/nucleophile) heterogeneous material, TSP‐AlCl‐PhospBr, was designed in order to guarantee a close proximity between the two active sites that can cooperate to the activation and opening of the epoxide ring. The prepared copolymer has been extensively characterized using various spectroscopic and analytical techniques. As a heterogeneous catalyst, it enables efficient chemical conversion of CO2 and epoxides, even at low temperatures, down to 30 °C, without the use of solvents. In particular, the catalyst demonstrates high turnover numbers (TON) and frequency values (TOF). Recyclability studies on TSP‐AlCl‐PhospBr have shown its stability and reusability for consecutive cycles without the need of reactivation procedures.

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Nitrogen-rich cobalt (II) MOFs as efficient bifunctional catalysts for single or tandem oxidation and CO2 conversion reactions

Cited by 18 publications

References 67 publications

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

New Opportunities in Metal‐Organic Framework Catalysis: From Bifunctional to Frustrated Lewis Pairs Catalysis

Phosphonium Salt/Al‐Porphyrin Copolymer as Bifunctional Heterogeneous Catalyst for CO₂ Conversion to Cyclic Carbonates

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Nitrogen-rich cobalt (II) MOFs as efficient bifunctional catalysts for single or tandem oxidation and CO2 conversion reactions

Cited by 18 publications

References 67 publications

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO2 with epoxides and Knoevenagel condensation reactions

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO2 with epoxides and Knoevenagel condensation reactions

New Opportunities in Metal‐Organic Framework Catalysis: From Bifunctional to Frustrated Lewis Pairs Catalysis

Phosphonium Salt/Al‐Porphyrin Copolymer as Bifunctional Heterogeneous Catalyst for CO2 Conversion to Cyclic Carbonates

Contact Info

Product

Resources

About

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Thermally activated bipyridyl-based Mn-MOFs with Lewis acid–base bifunctional sites for highly efficient catalytic cycloaddition of CO₂ with epoxides and Knoevenagel condensation reactions

Phosphonium Salt/Al‐Porphyrin Copolymer as Bifunctional Heterogeneous Catalyst for CO₂ Conversion to Cyclic Carbonates