Synthesis of nickel germanide (Ge₁₂Ni₁₉) nanoparticles for durable hydrogen evolution reaction in acid solutions

Abstract

Desigining advanced materials as electrochemical catalysts for the hydrogen evolution reaction (HER) has caught great attention owing to the growing demand for clean and renewable energy. Nickel (Ni)-based compounds and alloys are promising non-noble-metal electrocatalysts due to their low cost and high activity. However, in most cases, Ni-based compounds and alloys have low durability in acid electrolyte, which limits their application in the electrolytic processes. In this study, monoclinic Ge12Ni19 nanoparticles were synthesized and exhibited high electrocatalytic activity and stability for the HER in acidic solution. Ge12Ni19 nanoparticles achieve an overpotential of 190 mV at cathodic current density of 10 mA cm-2 and a Tafel slope of 88.5 mV per decade in 0.50 M H2SO4 electrolyte. Moreover, the performance is maintained after a 10 000-cycle CV sweep (-0.3 to +0.1 V vs. RHE) or under a static overpotential of -0.7 V vs. RHE for 24 hours. The reported electrocatalytic performance of the Ge12Ni19 nanoparticles sufficiently proves the excellent endurance at lower required active overpotentials in acidic solution, enabling the broad applications of the Ni-based electrocatalysts. Finally, a large-area (5 cm2) electrocatalyst for HER was demonstrated for the first time. The great efficiency of the energy conversion performance sufficiently represented the potential of Ge12Ni19 nanoparticles as electrocatalysts in commercial fuel cells.

P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview

“…Germanium (Ge) has been widely used in electrocatalysis as a semiconductor metal. [72][73][74] The broadening of the antibonding (1 π*) orbitals confirmed the strong hybridization of N 2 with GeSe, as shown by DOS calculations. This means that GeSe Small 2023, 19, 2206776 Li, l) DOS plot of dinitrogen adsorbed Al 12 Li @graphene complex, m) CDD plot of dinitrogen adsorbed Al 12 Li @graphene complex.…”

“…Germanium (Ge) has been widely used in electrocatalysis as a semiconductor metal. [ 72–74 ] The broadening of the antibonding (1 π*) orbitals confirmed the strong hybridization of N 2 with GeSe, as shown by DOS calculations. This means that GeSe provides a strong capability to absorb and activate N 2 by coupling antibonding orbitals.…”

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

“…Other binary and multinary group 10–14 intermetallics promise to be just as interesting. Germanides Ni 19 Ge 12 , Pt 3 Ge, and PtGe 2 catalyze the hydrogen evolution reaction (HER) under acidic conditions. , Pd 2 Ge nanoparticles are active in ethanol oxidation for fuel cell applications, where they are stable for up to 250 cycles. Nickel silicides have also received attention: for example, Ni 31 Si 12 , Ni 2 Si, NiSi 2 , and NiSi in hydrogenation reactions. − Ni 2 Si and Pd 2 Si were investigated for the HER and for selective phenylacetylene hydrogenation .…”

“…Germanides Ni 19 Ge 12 , Pt 3 Ge, and PtGe 2 catalyze the hydrogen evolution reaction (HER) under acidic conditions. 38,39 Pd 2 Ge nanoparticles are active in ethanol oxidation for fuel cell applications, 40 where they are stable for up to 250 cycles. Nickel silicides have also received attention: for example, Ni 31 Si 12 , Ni 2 Si, NiSi 2 , and NiSi in hydrogenation reactions.…”

Self‐Supporting Ni‐M (M = Mo, Ge, Sn) Alloy Nanosheets via Topotactic Transformation of Oxometallate Intercalated Layered Nickel Hydroxide Salts: Synthesis and Application for Electrocatalytic Hydrogen Evolution Reaction

“…This strict atomic ratio of bivalent and trivalent metal cations in LDHs limits the possible composition of multimetallic alloys. Given the reported excellent HER performance of Ni‐alloys such as NiSn, NiGe, and especially NiMo, there is an urgent need to develop a new method to produce self‐supporting Ni‐alloy nanostructures bypassing the trivalent metal restriction imposed by LDHs. Inspired by the tunable interlayer spacing of layered hydroxide salts (LHS), such as α‐Ni(OH) 2 , through intercalating anions adjustment, we speculate that a second metallic precursor in the form of oxometallate anions may be introduced into the interlayer gallery of LHS, which can then be further reduced to produce Ni‐alloy nanosheets, thus broadening the scope of the emerging LDHs derivatives.…”