Cyclo[16]carbon through the lens of density functional theory: Role of impurity decoration in hydrogen evolution reaction

• Published in: International journal of hydrogen energy Vol. 71; pp. 400 - 410
• Main Authors: Kanzariya, Ashvin, Vadalkar, Shardul, Saini, L.K., Jha, Prafulla K.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 19.06.2024
• Subjects: Cyclocarbon; Gibbs free energy; Hydrogen evolution reaction; Second-row transition metals; Volcano plot; Hydrogen evolution reaction; Gibbs free energy; Cyclocarbon; Second-row transition metals; Volcano plot
• ISSN: 0360-3199
• DOI: 10.1016/j.ijhydene.2024.05.236

The increasing global demand for sustainable energy sources has intensified the search for cost-effective catalysts in the hydrogen evolution reaction (HER). Single-atom catalysts (SACs) supported on suitable substrates have emerged as promising alternatives. In this study, we investigate the utilization of cyclo[16]carbon (C16 nanocluster) as a support for second-row transition metals (TMs) based SACs. The exploration focuses on analyzing the geometry, electronic properties, stability, and catalytic performance of TM@C16 SACs in the context of HER. Notably, highly negative binding energy values, structural modifications, and altered dipole moments collectively affirm the strong binding between the TMs and the C16 nanocluster. The incorporation of TMs onto the C16 nanocluster substantially enhances the conductivity of the latter. Studied SACs primarily showed H2 evolution via Volmer-Heyrovsky mechanisms. Notably, Pd@C16 and Rh@C16 displayed superior catalytic performance, with ΔGHV values of −0.007 eV and 0.05 eV, respectively. The determination of the exchange current via a volcano plot as a function of Gibbs free energy for hydrogen evolution over these designed SACs further validates their efficacy. Our findings establish Pd@C16 and Rh@C16 as highly stable and efficient SACs for the HER, underscoring their potential in advancing sustainable energy technologies. [Display omitted] •In this work, Cyclo [16]carbon (C16) is explored as a potential catalyst for hydrogen evolution reaction.•Although the Gibbs' free energy is pretty high for the pristine nanocluster of Cyclo [16]carbon.•Impurity decoration of second row transition metals is done by placing one atom over pristine C16 nanocluster.•The decorated nanoclusters show enhanced hydrogen evolution activity for the Heyrovsky reaction (particularly for Pd@C16 and Rh@C16).