Kinetic Study and Simulation of Titanium Carbide-Supported, Platinum-Doped Tetrahedral Amorphous Carbon Electrodes for Hydrogen Evolution Reaction

This paper presents the kinetic study of titanium carbide (TiC)-supported, platinum-doped tetrahedral amorphous carbon (taC:Pt) referred to as TiC-taC, for the hydrogen evolution reaction (HER). This study employs the Volmer-Heyrovsky-Tafel (VHT) mechanism. A theoretical approach was utilized to investigate the kinetic properties of these materials for an HER in 0.5 M H₂SO₄. TiC-taC exhibited Volmer-dominated reactions with a Tafel slope of 40 mV/dec and the overpotential at 10 mA/cm² was 185 mV. In contrast, isolated TiC and taC:Pt recorded significantly higher Tafel slopes with 60-110 mV/dec and overpotentials of 871 mV and 1009 mV, respectively. The developed model was tested in one dimension (1D) for individual TiC and taC:Pt. The simulated kinetics parameters were determined for both TiC and taC:Pt, revealing that TiC follows the VHT steps, while taC:Pt follows the VH steps. The simulation results show excellent coherence with the experimental results. Further simulation of the hybrid TiC-taC electrocatalyst was conducted considering surface diffusion and edge effects in two (2D) and three dimensions (3D). To the best of our knowledge, this FEM simulation approach is the first to be reported due to the unique geometry of the TiC-taC catalyst enabling the assumption of surface diffusion and edge effect. The introduction of edge effects on the taC:Pt side of the TiC support significantly enhanced the current output, aligning closely with experimental results. The edge exhibited distinct kinetic properties compared to both TiC and taC:Pt. The kinetic parameters determined from the simulation demonstrated strong agreement with experimental findings. Adding the edge effects was essential to explaining the higher current output from the TiC-taC electrode. It exhibited unique kinetic properties not observed in either TiC or taC:Pt alone, acting as a pump where it absorbs <i>c_Hs</i> from neighbouring sites due to surface diffusivity and releases H2 via the Heyrovsky reaction. While surface diffusion had a lesser effect, the simulation indicated its positive influence on the HER.