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The first row transition metal-corrole complexes as a single atom catalyst for electrochemical hydrogen evolution reaction: A DFT insight.

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Title: The first row transition metal-corrole complexes as a single atom catalyst for electrochemical hydrogen evolution reaction: A DFT insight.
Authors: Yaseen, Fatima1 (AUTHOR), Hashmi, Muhammad Ali1 (AUTHOR) muhammad.hashmi@ue.edu.pk, Ain, Qurat Ul1 (AUTHOR), Lakhani, Ahmed1,2 (AUTHOR) alakhani@ccsj.edu, Ayub, Khurshid3 (AUTHOR)
Source: International Journal of Hydrogen Energy. Feb2024, Vol. 57, p1389-1397. 9p.
Subjects: Atoms in molecules theory, Gibbs' free energy, Hydrogen economy, Catalysts, Density functional theory
Abstract: The electrocatalytic hydrogen evolution reaction, a half-cell reaction (reduction) in water splitting to produce H 2 gas, is considered a green and sustainable way to replace the conventional fossil fuels. Developing a highly conductive, robust, and efficient non-precious hydrogen evolution reaction (HER) catalyst is a key step in the hydrogen economy. Therefore, herein, we have evaluated metallocorroles as single-atom catalysts (SAC) for HER. All calculations of M-Corrole (M represents Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) have been carried out by using state-of-the-art density functional theory computations. The thermal and electrochemical stability of metallocorroles is manifested by the calculation of interaction energy and ionization potential (IP), respectively. Using the Gibbs free energy (ΔG H*) of adsorbed hydrogen as the primary descriptor, the efficiency of catalysts has been studied. According to the Sabatier principle (ΔG H* ≈ 0), titanium anchored in the corrole central cavity (Ti@Corrole) shows the best result having ΔG H* of −0.02 eV for Volmer step. This outcome is further analyzed by charge transfer analysis (NBO analysis), and interactions are studied using the quantum theory of atoms in molecules (QTAIM analysis), and noncovalent interactions (NCI analysis). Ab initio molecular dynamics (AIMD) calculations were done to check temperature stability and indicated that the structure is stable on a range of temperatures. In addition to this, mechanistic study is done, which indicates that Ti@corrole and Sc@corrole follow Volmer-Heyrovsky pathway, whereas Cr@corrole and Sc@corrole follow Volmer-Tafel step for hydrogen evolution process. [Display omitted] • DFT of the catalytic potential of M@Corrole (M = Sc, Ti, V, ..., Zn) for hydrogen evolution reaction (HER). • SAC (single atom catalysts) concept to achieve the maximum efficiency of the catalyst. • Interaction energies and Gibbs free energies of M@Corrole and adsorbed hydrogen (ΔG H*) have been calculated. • Results are examined based on Sabatier principle (ΔG H* ≈ 0). • Results also supported by the non-covalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analysis. [ABSTRACT FROM AUTHOR]
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Abstract:The electrocatalytic hydrogen evolution reaction, a half-cell reaction (reduction) in water splitting to produce H 2 gas, is considered a green and sustainable way to replace the conventional fossil fuels. Developing a highly conductive, robust, and efficient non-precious hydrogen evolution reaction (HER) catalyst is a key step in the hydrogen economy. Therefore, herein, we have evaluated metallocorroles as single-atom catalysts (SAC) for HER. All calculations of M-Corrole (M represents Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) have been carried out by using state-of-the-art density functional theory computations. The thermal and electrochemical stability of metallocorroles is manifested by the calculation of interaction energy and ionization potential (IP), respectively. Using the Gibbs free energy (ΔG H*) of adsorbed hydrogen as the primary descriptor, the efficiency of catalysts has been studied. According to the Sabatier principle (ΔG H* ≈ 0), titanium anchored in the corrole central cavity (Ti@Corrole) shows the best result having ΔG H* of −0.02 eV for Volmer step. This outcome is further analyzed by charge transfer analysis (NBO analysis), and interactions are studied using the quantum theory of atoms in molecules (QTAIM analysis), and noncovalent interactions (NCI analysis). Ab initio molecular dynamics (AIMD) calculations were done to check temperature stability and indicated that the structure is stable on a range of temperatures. In addition to this, mechanistic study is done, which indicates that Ti@corrole and Sc@corrole follow Volmer-Heyrovsky pathway, whereas Cr@corrole and Sc@corrole follow Volmer-Tafel step for hydrogen evolution process. [Display omitted] • DFT of the catalytic potential of M@Corrole (M = Sc, Ti, V, ..., Zn) for hydrogen evolution reaction (HER). • SAC (single atom catalysts) concept to achieve the maximum efficiency of the catalyst. • Interaction energies and Gibbs free energies of M@Corrole and adsorbed hydrogen (ΔG H*) have been calculated. • Results are examined based on Sabatier principle (ΔG H* ≈ 0). • Results also supported by the non-covalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analysis. [ABSTRACT FROM AUTHOR]
ISSN:03603199
DOI:10.1016/j.ijhydene.2024.01.135