Electrocatalytic and Selective Oxidation of Glycerol to Formate on 2D 3d-Metal Phosphate Nanosheets and Carbon-Negative Hydrogen Generation

In the landscape of green hydrogen production, alkaline water electrolysis is a well-established, yet not-so-cost-effective, technique due to the high overpotential requirement for the oxygen evolution reaction (OER). A low-voltage approach is proposed to overcome not only the OER challenge by favorably oxidizing abundant feedstock molecules with an earth-abundant catalyst but also to reduce the energy input required for hydrogen production. This alternative process not only generates carbon-negative green H₂ but also yields concurrent value-added products (VAPs), thereby maximizing economic advantages and transforming waste into valuable resources. The essence of this study lies in a novel electrocatalyst material. In the present study, unique and two-dimensional (2D) ultrathin nanosheet phosphates featuring first-row transition metals are synthesized by a one-step solvothermal method, and evaluated for the electrocatalytic glycerol oxidation reaction (GLYOR) in an alkaline medium and simultaneous H₂ production. Co₃(PO₄)₂ (CoP), Cu₃(PO₄)₂ (CuP), and Ni₃(PO₄)₂ (NiP) exhibit 2D sheet morphologies, while FePO₄ (FeP) displays an entirely different snowflake-like morphology. The 2D nanosheet morphology provides a large surface area and a high density of active sites. As a GLYOR catalyst, CoP ultrathin (∼5 nm) nanosheets exhibit remarkably low onset potential at 1.12 V (vs RHE), outperforming that of NiP, FeP, and CuP around 1.25 V (vs RHE). CoP displays 82% selective formate production, indicating a superior capacity for C–C cleavage and concurrent oxidation; this property could be utilized to valorize larger molecules. CoP also exhibits highly sustainable electrochemical stability for a continuous 200 h GLYOR operation, yielding 6.5 L of H₂ production with a 4 cm² electrode and 98 ± 0.5% Faradaic efficiency. The present study advances our understanding of efficient GLYOR catalysts and underscores the potential of sustainable and economically viable green hydrogen production methodologies.