General Directorate of Mineral Research and Exploration, Ankara, Turkey.
Turkish Energy, Nuclear and Mineral Research Agency, Rare Earth Elements Research Institute, Ankara, Turkey.
J Comput Chem. 2022 Oct 5;43(26):1793-1801. doi: 10.1002/jcc.26981. Epub 2022 Aug 24.
In this work, various precious and non-precious metals reported in the literature as the most effective catalysts for glucose electrooxidation reaction were investigated by the density functional theory (DFT) approach in order to reveal the mechanisms taking place over the catalysts in the fuel cell. The use of a single-atom catalyst model was adopted by insertion of one Au, Cu, Ni, Pd, Pt, and Zn metal atom on the pyridinic N atoms doped graphene surface (NG). β form of d-glucose in alkaline solution was used to determine the reaction mechanism and intermediates that formed during the reaction. DFT results showed that the desired glucono-lactone was formed on the Cu-3NG electrode in a single-step reaction pathway whereas it was produced via different two-step pathways on the Au and Pt-3NG electrodes. Although the interaction of glucose with Ni, Pd, and Zn-doped surfaces resulted in the deprotonation of the molecule, lactone product formation did not occur on these electrode surfaces. When the calculation results are evaluated in terms of energy content and product formation, it can be concluded that Cu, Pt, and especially Au doped graphene catalysts are effective for direct glucose oxidation in fuel cells reactor.
在这项工作中，通过密度泛函理论（DFT）方法研究了文献中报道的各种作为葡萄糖电氧化反应最有效催化剂的贵金属和非贵金属，以揭示在燃料电池中催化剂上发生的机制。通过在吡啶 N 原子掺杂石墨烯表面（NG）上插入一个 Au、Cu、Ni、Pd、Pt 和 Zn 金属原子，采用单原子催化剂模型。在碱性溶液中使用β形式的 d-葡萄糖来确定反应机制和反应过程中形成的中间体。DFT 结果表明，在 Cu-3NG 电极上，所需的葡糖酸内酯通过单步反应途径形成，而在 Au 和 Pt-3NG 电极上则通过不同的两步途径形成。尽管葡萄糖与 Ni、Pd 和 Zn 掺杂表面的相互作用导致分子去质子化，但在这些电极表面上没有形成内酯产物。当根据能量含量和产物形成来评估计算结果时，可以得出结论，Cu、Pt 特别是 Au 掺杂的石墨烯催化剂在燃料电池反应器中对直接葡萄糖氧化是有效的。
