Investigation of glucose electrooxidation mechanism over N‐modified metal‐doped graphene electrode by density functional theory approach

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. Electro‐oxidation of a glucose molecule to glucono‐lactone as an intermediate is investigated on metal‐doped nitrogen decorated graphene catalyst modeled as a single‐atom‐catalyst in an alkaline fuel cell reactor. Cu, Au, and Pt doped catalysts are the thermodynamically most favorite electrode surfaces and produce glucono‐lactone in the different pathways. Deprotonation of the glucose and water formation occurs on the Ni, Pd, and Zn‐doped catalysts, but the desired lactone product formation does not occur on these surfaces.