Revealing Activity Trends of Metal Diborides Toward pH‐Universal Hydrogen Evolution Electrocatalysts with Pt‐Like Activity

Abstract

Understanding of catalytic trends is an important prerequisite for providing rational guidance toward the prediction of advanced catalysts as well as the development of original materials design principles. A combined theoretical and experimental study that reveals the periodic trends in electrocatalytic activity for the hydrogen evolution reaction (HER) from Group IV B to Group VIII metal diborides is reported here. Theoretical results demonstrate a general linear relationship between the catalytic activity and d‐band center of metal diboride, meaning that the latter can serve as a descriptor of activity. And theoretical results also predict ruthenium diboride as the most competitive, nonplatinum candidate among metal diborides for HER because this material has a suitable d‐band center and a high density of efficient active sites. Furthermore, the experimental results validate the theoretical activity trends and identify ruthenium diboride as an efficient, pH‐universal electrocatalyst with Pt‐like activity for HER under both acidic and alkaline media.

Recent advances in transition metal-based electrocatalysts for alkaline hydrogen evolution

“…In doping strategies, the universally employed dopants include N, 24,243 P, 244,245 Ni, 246 and the combinations of these single elements. 90,246 Recently, Ji and co-authors prepared N, P-codoped Ni x B y , 94,252,253 Co x B y , 254 Fe x B y , 255 Ru x B y , 256 (Figure 21b).…”

Intermetallic borides: structures, synthesis and applications in electrocatalysis

“…Our group estimated the electrocatalytic activities for the HER on a family of twelve MB 2 (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Re, Ru and Os) both theoretically and experimentally. 38 According to the theoretical results, both metal-terminated and boron-terminated surfaces in these MB 2 catalysts possess a high density of efficient catalytic sites for the HER. However, only the metal-terminated surfaces comply well with the experimental activity trends, indicating that the metal-terminated surfaces are main catalytic sites in real samples.…”

“…ides. 38 They comprise 3D metallic frameworks and 2D boron layers as subunits, endowing diborides with high electrical conductivity. Boron layers in AlB 2 -type diborides are graphenelike borophene structures ( Fig.…”

“…Using the reaction between MgB 2 and anhydrous metal chloride (MCl x ), our group prepared a class of twelve MB 2 nanomaterials, covering many transition metals from Group IV B to Group VIII elements. 38 The reactions were very exothermic due to the formation of a thermodynamically stable by-product (i.e., MgCl 2 ), thus requiring a relatively low heating temperature of 850-950°C, with the exception of OsB 2 synthesized at 1100°C.…”

Phosphorus‐Doping‐Induced Optimization of Atomic Hydrogen Binding Energy in MoSe2 under High Coverage for Efficient Electrocatalytic Hydrogen Evolution Reactions

“…[1,2] The hydrogen evolution reaction (HER) via water electrocatalysis provides a carbon-neutral preparation method and consumption cycle. [3,4] Transitionmetal dichalcogenides (TMDCs) have attracted increasing attention owing to their efficient HER performance and abundancy. [5] Molybdenum diselenide (MoSe 2 ) is a representative lamellar TMDC, and two-dimensional (2D) or bulk MoSe 2 is formed by SeÀ MoÀ Se units via interlayer van der Waals forces.…”