First-principles modeling of the hydrogen evolution reaction and its application in electrochemical corrosion of Mg

Effective Descriptor for Designing High-Performance Catalysts for the Hydrogen Evolution Reaction

“…For the methods used in the TMs’ part, − ,− , the computational codes include VASP, Dacapo, and Quantum Espresso; the functionals include the RPBE functional, the BEEF-vdW, and PW91; the pseudopotentials include ultrasoft pseudopotential, projector-augmented wave (PAW) pseudopotential, and Vanderbilt pseudopotential . For the methods used in the alloys’ part, the data are calculated using the VASP code, Perdew–Burke–Ernzerhof (PBE) functional, and PAW pseudopotential . For the methods used in SACs’ part, ,− the computational codes contain VASP and Dmol; the functionals contain PBE and RPBE; the pseudopotentials contain PAW pseudopotential, and the basis set contains density functional theory (DFT) semicore pseudopots and double numerical plus polarization .…”

“…We focus on a model alloy, the Mg-based single-atom alloy, in which the TM atom replaces the position of the surface Mg atom. This concise model has been successfully employed in the research of electrochemical corrosion and the accompanying HER of Mg metal and alloys. , Here, the adsorption site of hydrogen is at the FCC hollow next to the dopant. In Figure a, the E ad of hydrogen on the Mg-based single-atom alloys shows the piecewise linear relationship with descriptor ψ.…”

“…Adsorption free energy and adsorption energy of hydrogen on the alloys as a function of descriptor ψ. (a) represents the adsorption free energies of H* on the Mg-based single-atom alloys . (b) represents the theoretical overpotential of HER vs descriptor ψ on the Mg-based single-atom alloys.…”

An electro-chemo-mechanical framework for predicting hydrogen uptake in metals due to aqueous electrolytes

“…It should be noted that the generalised model presented results in significantly more reaction constants relative to other models which only include either the acidic or non-acidic hydrogen reactions [12,[49][50][51]. Other simplifying assumptions for the hydrogen evolution reactions such as using a single rate-determining reaction [52], or assuming most backward reactions to be negligible [23,53,54] are also often made to reduce the number of constants needed. In contrast, by including both acidic and non-acidic reactions within a single scheme, and not assuming a single rate-determining reaction step, our model is valid for the complete range of electrolyte pH and electric overpotentials.…”

Modeling of the cathodic and anodic polarization curves of metals and alloys at an electronic level

“…20,21 Density functional theory (DFT) can provide insights into the corrosion process at the atomic and electronic levels. 9,[22][23][24] A lot of detailed information related to corrosion properties have been provided by DFT calculations, such as the interfacial structure, work function, electronegativity, and electronic chemical potential. 10,[25][26][27] These parameters, however, can neither be directly utilized to characterize the corrosion resistance, nor to explore ways to control the corrosion process.…”