<i>para</i>-Aminobenzoic acid-capped hematite as an efficient nanocatalyst for solvent-free CO<sub>2</sub> fixation under atmospheric pressure

Mahalingam, Venkataramanan; Tudu, Gouri; Paliwal, Khushboo S.; Ghosh, Sourav; Biswas, Tanmoy; Koppsetti, Murthy; Mitra, Antarip

doi:10.1039/d1dt03821d

Cited by 15 publications

(13 citation statements)

References 60 publications

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“…The above-mentioned results clearly emphasize the importance of the guanidinium ion, which possesses free −NH 2 groups. 93,94 The interaction between NH 2 and CO 2 groups resulted in better catalytic efficiency, noted for Al−Gh. The abovementioned trend can also be traced from the CO 2 adsorption data where a 10 times increase in the CO 2 uptake volume is observed upon grafting N-rich guanidine hydrochloride on alumina (Al−Gh) compared to that of pristine γ-Al 2 O 3 (Figure 2d).…”

Section: ■ Results and Discussionmentioning

confidence: 98%

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

et al. 2022

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The quest toward sustainability and decarbonization demands the development of methods for efficient carbon dioxide capture and utilization. The nonreductive CO2 fixation into epoxides to prepare cyclic carbonates has gained attention in recent years. In this work, we report the development of guanidine hydrochloride-functionalized γ alumina (γ-Al2O3), prepared using green solvents, as an efficient bifunctional catalyst for CO2 fixation. The resulting guanidine-grafted γ-Al2O3 (Al–Gh) proved to be an excellent catalyst to prepare cyclic carbonates from epoxides and CO2 with high selectivity. The nitrogen-rich Al–Gh shows increased CO2 adsorption capacity compared to that of γ-Al2O3. The as-prepared catalyst was able to carry out CO2 fixation at 85 °C under atmospheric pressure in the absence of solvents and external additives (e.g., TBAI or KI). The material showed negligible loss of catalytic activity even after five cycles of catalysis. The catalyst successfully converted many epoxides into their respective cyclic carbonates under the optimized conditions. The gram-scale synthesis of commercially important styrene carbonates from styrene oxide and CO2 using Al–Gh was also achieved. Density functional theory (DFT) calculations revealed the role of alumina in activating the epoxide. This activation facilitated the chloride ion to open the ring to react with CO2. The DFT studies also validated the role of alumina in stabilizing the electron-rich intermediates during the course of the reaction.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

et al. 2022

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“…So, 7.49 mg (0.13 mmol) Fe is present in 100 mg Fe−L1 which effectively converted 90 % of 15 mmol epichlorohydrin. Based on the calculations, the TON for 90 % epichlorohydrin conversion was 104 (see details in Table 2 and Supporting Information) [62] . Moreover, to study the selectivity, the isolated yields of the cyclic carbonates of epichlorohydrin, styrene oxide and allyl glycidyl ethers were measured.…”

Section: Resultsmentioning

confidence: 99%

“…Based on the calculations, the TON for 90 % epichlorohydrin conversion was 104 (see details in Table 2 and Supporting Information). [62] Moreover, to study the selectivity, the isolated yields of the cyclic carbonates of epichlorohydrin, styrene oxide and allyl glycidyl ethers were measured. The results were comparable to the conversion measured from 1 H-NMR which further confirm the high selectivity of the catalyst and rule out the formation of side products like polycarbonates and diols (See details in Table S2, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Prudent Choice of Iron‐Based Metal‐Organic Networks for Solvent‐Free CO₂ Fixation at Ambient Pressure

et al. 2022

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The rising global warming and associated climate change demand efficient tactics to reduce CO2 concentration in the atmosphere. Conversion of epoxides to cyclic carbonates utilizing CO2 is a promising and sustainable approach towards CO2 fixation. However, the inert nature of CO2 and high activation energy requirement for the particular reaction necessitate the use of efficient catalysts. In this work, we have designed and developed a heterogeneous catalyst using catechol functionalized guanidinium based ligands (L1) and Fe(III) ions to perform the CO2 fixation reaction. The resulting amorphous material (Fe−L1) possesses metal‐organic network as revealed through different characterization methods. The optimized catalyst Fe−L1 is efficient for the conversion of a variety of epoxides into their corresponding cyclic carbonates in very good yield (>80 %). The reactions were performed under atmospheric pressure without solvent and external additives (e. g., TBAI or KI). The investigation of the mechanistic pathway indeed validates the synergistic effect of metal and halide ions that leads to the efficient conversion of different epoxides into cyclic carbonates. Furthermore, no significant loss in the catalytic activity of the Fe−L1 is noticed up to six cycles. The post catalytic analyses clearly indicate the robust nature of the catalyst. The developed one component bifunctional catalytic system can pave way towards transition to sustainable carbon capture and conversion.

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“…Nitrogen nucleophiles such as amines, , pyridines, triazoles, , alkanol amines, , Schiff bases, , DBU, and amino acids are regarded as a valuable and more sustainable alternative to halide nucleophiles for the synthesis of 5CCs. However, their application generally requires relatively harsh reaction conditions ( T = 100–120 °C, p = 10–20 bar) especially for systems in which the nucleophilic moieties are not assisted by HBDs.…”

Section: Monofunctional Polymersmentioning

confidence: 99%

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO₂ to Epoxides

et al. 2023

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The catalytic cycloaddition of CO2 to epoxides to afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field of investigation as a way to carry out the atom-economic conversion of CO2 to value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they are inexpensive, nontoxic, and readily available. Herein, we highlight and discuss key advances in the development of polymer-based organocatalytic materials that match these requirements of affordability and availability by considering their synthetic routes, the monomers, and the supports employed. The discussion is organized according to the number (monofunctional versus bifunctional materials) and type of catalytically active moieties, including both halide-based and halide-free systems. Two general synthetic approaches are identified based on the postsynthetic functionalization of polymeric supports or the copolymerization of monomers bearing catalytically active moieties. After a review of the material syntheses and catalytic activities, the chemical and structural features affecting catalytic performance are discussed. Based on such analysis, some strategies for the future design of affordable and readily available polymer-based organocatalysts with enhanced catalytic activity under mild conditions are considered.

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para-Aminobenzoic acid-capped hematite as an efficient nanocatalyst for solvent-free CO₂ fixation under atmospheric pressure

Abstract: Utilization of carbon dioxide by converting it into value-added chemicals is a sustainable remedy approach which stipulates abundant, cheap, non-toxic and efficient catalytic materials. In this study, we have demonstrated...

Cited by 15 publications

References 60 publications

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

Prudent Choice of Iron‐Based Metal‐Organic Networks for Solvent‐Free CO₂ Fixation at Ambient Pressure

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO₂ to Epoxides

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para-Aminobenzoic acid-capped hematite as an efficient nanocatalyst for solvent-free CO2 fixation under atmospheric pressure

Abstract: Utilization of carbon dioxide by converting it into value-added chemicals is a sustainable remedy approach which stipulates abundant, cheap, non-toxic and efficient catalytic materials. In this study, we have demonstrated...

Cited by 15 publications

References 60 publications

Alumina-Based Bifunctional Catalyst for Efficient CO2 Fixation into Epoxides at Atmospheric Pressure

Alumina-Based Bifunctional Catalyst for Efficient CO2 Fixation into Epoxides at Atmospheric Pressure

Prudent Choice of Iron‐Based Metal‐Organic Networks for Solvent‐Free CO2 Fixation at Ambient Pressure

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO2 to Epoxides

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Product

Resources

About

para-Aminobenzoic acid-capped hematite as an efficient nanocatalyst for solvent-free CO₂ fixation under atmospheric pressure

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

Alumina-Based Bifunctional Catalyst for Efficient CO₂ Fixation into Epoxides at Atmospheric Pressure

Prudent Choice of Iron‐Based Metal‐Organic Networks for Solvent‐Free CO₂ Fixation at Ambient Pressure

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO₂ to Epoxides