Ligand removal dynamics. The dynamics of ligand removal from the nanocluster were investigated using the CP2K package (version 2023.1). The simulations employed the Perdew -Burke -Ernzerhof (PBE) functional within the generalized gradient approximation (GGA) in combination with the hybrid Gaussian/Plane-Wave (GPW) scheme. The computational domain was defined with a periodic lattice size of 23 × 23 × 28 Å 3 , including 192 water molecules to simulate the nanocluster's solvent environment. Molecular dynamics (MD) simulations were performed in the canonical (NVT) ensemble, using Nose-Hoover thermostats to maintain a constant temperature of 300 K. A time step of 1.0 fs was used throughout the simulations, which were run for a total of 10 ps. Dispersion corrections were applied using the DFT-D3 method to account for van der Waals interactions. The electronic structure was described by density functional theory (DFT) with spin-polarization and a mixed double-ζ Gaussian and plane-wave basis set, with an energy cutoff of 400 Ry. Thermodynamic calculations for HER and CO2RR. Spin-polarized DFT calculations were carried out using the Vienna Ab-initio Simulation Package (VASP, version 5.4.4). The exchange-correlation effects were described using the Perdew-Burke -Ernzerhof (PBE) functional within the generalized gradient approximation (GGA). The projector-augmented wave (PAW) method was employed to account for electron-ion interactions with a cutoff energy of 400 eV. For these calculations, the computational cell was set with a lattice size of 23 × 23 × 28 Å 3 , including 50 water molecules to adapt to the specific requirements of the reaction environments. The empirical DFT-D3 dispersion correction was applied to include van der Waals interactions. Brillouin zone integration was performed using a Gamma centered 1 × 1 × 1 k-point grid, with convergence criteria set at 0.05 eV/Å for forces and 10 -4 eV/cell for energy. The electrode potential was determined via tuning the work function (additional details are provided in Supporting Information).