Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues

Deshpande

2017

J. Phys. Chem. C

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Borate-based compounds have been observed to be CO 2 capture agents in natural and synthetic setups. Carbon capture in such systems has been proposed to take place via hydration of CO 2 resulting in bicarbonate ion formation. Several experimental studies have reported borate-based catalysts for CO 2 hydration reaction, and the mechanism of the reaction has been proposed to follow the enzymatic carbonic anhydrase action. In view of the absence of detailed physical insights into the mechanistic aspects of borate-catalyzed CO 2 hydration, computational investigations were carried out in this study under the density functional theory framework to explain the mechanism of the reaction over borate-based systems. Three borate-based systems, namely, borate ions, triborate ions, and tetraborate ions, were tested as the catalysts for the aqueous phase carbon capture reaction. Free energy landscapes provided the details of the elementary steps of the reaction, concluding the mechanism of the reaction to be indeed biomimetic consisting of parallel and bent CO 2 complexation, intramolecular proton transfer, bicarbonate ion complex formation and displacement of bicarbonate ion by water molecule to form (poly)borate−water complexes. All three ions were found to be active for catalyzing the reaction. NMR and FTIR spectra of all the intermediates proposed during the biomimetic mechanism were computed and compared against the experimentally reported spectra. The comparative analyses proved the identities of the intermediates, thus further confirming the mechanism of the reaction.

Section: Computational Detailsmentioning

confidence: 99%

Computational Insights into Biomimetic CO₂ Hydration Activities of (Poly)borate Ions

Deshpande

2017

J. Phys. Chem. C

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“…Co and Ru metal clusters displayed the best catalytic activities in vacuum and in solvation, respectively. Later, Verma and Deshpande 206 designed metal doped heterofullerenes (C 59 M, M = Ru/Rh) as well as metal coordinated nitrogen doped heterofullerenes (C 56 N 3 M, M = Ru/Rh), as catalysts for hydration of CO 2 , in which the metal site of the doped heterofullerene was considered as the reaction site. C 56 N 3 M heterofullerene showed more enhanced catalytic activity than C 59 M with proton transfer (Lipscomb mechanism) as the rate limiting step for the CO 2 hydration reaction.…”

Section: Catalyzed Hydration Of Comentioning

confidence: 99%

Biomimetic Catalysis of CO₂ Hydration: A Materials Perspective

Bhaduri

Kumar

et al. 2021

Ind. Eng. Chem. Res.

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Rising temperatures and changing weather patterns have made the effect of climate change more evident setting up an alarm for the need of quick action for its mitigation. Carbon capture utilization and storage (CCUS) is an effective step in this direction. One of the key reactions in the heart of aqueous CCUS technologies is the reversible hydration of CO2. The reaction is catalyzed biologically by the enzymes of the carbonic anhydrase family, and for its industrial realization, catalysts including organometallic compounds and metallic nanoparticles have been widely investigated. These catalysts enhance the reaction rates at moderate conditions of temperature, pressure, and pH for suitable applications for CO2 separation and mineralization. However, the use of catalysts is limited by their industrial scale production costs and/or reusability. In this review, we present a materials perspective of different catalysts that have been developed worldwide for CO2 hydration with a specific emphasis on the biomimetic mechanism of the catalytic activity of the catalysts.

“…With this concern, preparation of biomimetic analogues of carbonic anhydrase enzyme has become a new strategy for carbon capture in power plants and studies reporting synthetic analogues of carbonic anhydrases have found good attention in the scientific literature in the recent past. [18][19][20][21][22][23][24] Transition metal oxides have been prominent candidates for large-scale heterogeneous catalytic reactions, and, therefore, exploring the activities of transition metal oxides for CO 2 hydration following the carbonic anhydrase mechanism can be a good strategy for catalyst development. Recently, Mino et al 18 reported CO 2 , carbonate, and bicarbonate adsorption over TiO 2 surfaces.…”

Section: Introductionmentioning

confidence: 99%

“…The development of synthetic analogues is important because carbonic anhydrases have a limited use in large‐scale CO 2 capture due to their poor stability and short lifetime. With this concern, preparation of biomimetic analogues of carbonic anhydrase enzyme has become a new strategy for carbon capture in power plants and studies reporting synthetic analogues of carbonic anhydrases have found good attention in the scientific literature in the recent past 18–24 …”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights into biomimetic CO₂ hydration activity of titania nanoclusters

Int J of Chemical Kinetics

Deshpande

2020

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Anatase TiO 2 , a widely used semiconductor metal oxide support, was tested for biomimetic carbonic anhydrase activity catalyzing the reversible hydration of CO 2 to bicarbonate ions. Owing to superior photocatalytic response of nanoclusters of TiO 2 and its apparent role in catalyzing CO 2 hydration, (TiO 2) 15 nanocluster was tested for the reaction using density functional theory calculations. Free energy landscape of the reaction was developed following the biological mechanism consisting of H 2 O adsorption, deprotonation, CO 2 complexation, CO 2 bending, intramolecular proton transfer, and bicarbonate ion displacement. The identity of the intermediates of the mechanistic cycle was further confirmed by computational nuclear magnetic resonance and infrared spectroscopic studies. A close correspondence of the computational and reported experimental spectroscopic analyses confirmed the identity of the intermediates and the presence of biomimesis over the TiO 2 cluster. K E Y W O R D S biomimetic catalyst, carbonic anhydrase enzyme, CO 2 hydration, density functional theory, (TiO 2) 15 cluster