Janus Mo₂P₃ Monolayer as an Electrocatalyst for Hydrogen Evolution

Abstract

The rational design of low-cost electrocatalysts with the desired performance is the core of the large-scale hydrogen production from water. Two-dimensional materials with high specific surface area and excellent electron properties are ideal candidates for electrocatalytic water splitting. Herein, we identify a hitherto unknown Mo2P3 monolayer with a Janus structure (i.e., out-of-plane asymmetry) through first-principle structure search calculations. Its inherent metallicity ensures good electrical conductivity. Notably, its catalytic activity is comparable to that of Pt and the density of active sites is up to 2.65 × 1015 site/cm2 owing to the Mo → P charge transfer enhancing the catalytic activity of P atoms and asymmetric structure exposing more active sites to the surface. The Mo2P3 monolayer can spontaneously produce hydrogen through the Volmer–Heyrovsky pathway. These excellent performances can be well maintained under strain. The coexistence of covalent and ionic bonds results in Mo2P3 having high stability. All these excellent properties make the Mo2P3 monolayer a promising candidate for electrocatalytic water splitting.

Heterointerface and Defect Dual Engineering in a Superhydrophilic Ni2P/WO2.83 Microsphere for Boosting Alkaline Hydrogen Evolution Reaction at High Current Density

“…Here, the experimentally observed WO 2.83 was simulated by WO 3 with oxygen vacancies (namely, WO 3– x ), and the Ni 2 P/WO 2.83 interface was modeled by connecting a Ni 2 P cluster on the WO 3– x surface (Figure S11a). Generally, the activity of H 2 O dissociation is closely associated with the adsorption energy (Δ E ad ) on the surface of the catalyst, while the ability of H* associative desorption is evaluated by the Gibbs free energy (Δ G H* ) of hydrogen adsorption on the catalyst. − The calculation results are shown in Figure a and 6b, and the optimal geometries are schematically shown in Figure c. It can be seen that the Ni 2 P/WO 3– x interface on the W site possessed much stronger adsorption energy of H 2 O (−0.83 eV) than pure Ni 2 P and WO 3– x , emphasizing the key role of WO 3– x of the Ni 2 P/WO 3– x interface in accelerating H 2 O dissociation.…”

Janus MoPC Monolayer with Superior Electrocatalytic Performance for the Hydrogen Evolution Reaction

“…Some metal-free catalysts have also shown excellent HER activity, e.g., β-PC, 24 C 3 N, 25 and g-C 3 N 4 . 26 In addition, the 2D transition-metal phosphides (TMPs) can also exhibit good HER performance, 27,28 for instance, the stable M 2 P monolayers (e.g., W 2 P and Fe 2 P) are reported to have metallicity and relatively lower overpotentials. 29 The MoP sheet was also found to have higher HER catalytic activity than MoS 2 and Mo 2 C sheets.…”

“…, β-PC, C 3 N, and g-C 3 N 4 . In addition, the 2D transition-metal phosphides (TMPs) can also exhibit good HER performance, , for instance, the stable M 2 P monolayers ( e.g. , W 2 P and Fe 2 P) are reported to have metallicity and relatively lower overpotentials .…”

Versatile transition metal monolayers with catalytic and superconducting properties: a computational study

“…Due to the occupation of d orbitals, the transition metals have valence electrons that not only may promote electron-phonon coupling and improve the superconducting temperature, according to the Bardeen-Cooper-Schrieffer (BCS) theory, 20 but also yield a better catalytic performance. [21][22][23][24][25][26] The distinct aromatic network structures also could endow this type of compound with novel properties, e.g., catalytic properties. This unique structural motif allows for great freedom to modulate the catalytic active sites and electronic features.…”