Computational Insights into the Activity of Transition Metals for Biomimetic CO₂ Hydration

Abstract

Density functional theory (DFT) calculations were carried out on five transition metals (Co, Ni, Pd, Rh, Ru) to test their activities toward the biomimetic carbon dioxide hydration reaction. Periodic plane-wave calculations demonstrated the formation of surface species in accordance with the mechanism of the reaction known for α-carbonic anhydrase action. To determine different activation barriers for the different elementary steps involved in the reaction, DFT calculations using a cluster model of transition metals with Gaussian-type orbitals were carried out. The periodic and cluster calculations were found to correspond to a mechanism of the reaction constitituting seven steps, namely, surface adsorption of H2O, deprotonation and surface OH formation, adsorption of CO2, OH attack on adsorbed CO2, proton transfer, H2O attack on surface HCO3 – complex, and HCO3 – displacement by H2O. The behaviors of the metals were found to be different in a vacuum and in the solvated state, with Co being the best potential candidate for the biomimetic CO2 hydration reaction in a vacuum and Ru being the best candidate for the reaction in solution.

Photochemical Enhancement in Catalytic Activity of Nickel Nanoparticles for Hydration of CO2

“…They also observed that CO 2 hydration in DI water is an autocatalytic process catalysed by the H + ions generated by the dissociation of carbonic acid . The activity of NiNPs as a heterogeneous catalyst was also recently confirmed using DFT, showing that such biomimetic catalysts provide a robust substitute to CA . The heterogeneous NiNP catalyst is easily recovered due to its magnetic properties opening the possibility of developing cost effective mineralisation processes …”

Mechanistic insights into biomimetic CO2 hydration activity of titania nanoclusters

“…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.…”

“…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 …”

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

“…In an attempt to develop truly heterogeneous biomimetic CHR catalysts, Šiller and co‐workers recently reported the activity of inorganic nanoparticles . Our recent computational study on a series of transition metals showed the promising nature of ruthenium, along with the slightly inferior but still active nature of rhodium, for catalysis of the CHR . Immobilization of these metals onto a support can result in catalysts that could be utilized in industrial reactors with ease.…”

“…[16,17] Our recent computational study on as eries of transition metals showedt he promising nature of ruthenium, along with the slightly inferior but still active nature of rhodium, for catalysis of the CHR. [18] Immobilization of these metals onto as upport can result in catalysts that could be utilized in industrial reactorsw ith ease. Singleatom catalysis has been recently investigated by using experimental techniques in whichasingle-atom dispersion of an active metal on as upport was achieved, and such systems have been reported to be highly activef or the investigated reactions.…”