RESUMEN
Herein, two Laves intermetallic series, ZrCo1.75M0.25 and NbCo1.75M0.25 (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt), were synthesized, and their hydrogen evolution reaction (HER) activities were examined to reveal the influence of d electrons to the corresponding HER activities. Owing to the different electronegativity between Zr and Nb (χZr = 1.33; χNb = 1.60), Co and/or M elements receive more electrons in ZrCo1.75M0.25 than that of the Nb one. This leads to the overall weak H adsorption energy (ΔGHad) of ZrCo1.75M0.25 series compared to that of NbCo1.75M0.25 and rationalizes well the superior HER activity of the Rh member compared to that of the Pt one in the ZrCo1.75M0.25 series. Under industrial conditions (333 K, 6.0 M KOH), ZrCo1.75Rh0.25 only requires an overpotential of 110 mV to reach the current density of 500 mA/cm2 and can be operated at high current density over 400 h. This work demonstrates that with a proper combination between elements in intermetallic phases, one can manipulate d electrons of the active metal to be closer to the sweet spot (ΔGHad = 0). The Pt member may no longer exhibit the best HER activity in series, and all elements exhibit the potential to outperform the Pt member in the HER with careful control of the d electron population.
RESUMEN
It is well known that the "iron" impurity will influence the oxygen evolution reaction (OER) in an alkaline electrolyte, especially for the Ni-based electrocatalyst. Many research studies have investigated the function of Fe in the OER active phase, such as M(OH)2/MOOH (M = Ni and/or Fe), while, surprisingly, very few studies have examined the function of Fe in the "precatalyst" system. Accordingly, in this work, the Ni3-xFexP (x = 0, 0.5, 1) series as an Ni-based precatalyst was employed to inspect the function of internal and external Fe in the Ni-based precatalyst system. It was realized that the sample with internal Fe (i.e., Ni2.5Fe0.5P and Ni2FeP) exhibits efficient OER activity compared to that of the Fe-free one (i.e., Ni3P) owing to the large amount of active M(OH)2/MOOH formed on the surface. This indicates that the internal Fe in the present system may have the ability to facilitate the phase transformation; it was later rationalized from electronic structural calculations that the d band center of the internal Fe (middle transition metal) and Ni (late transition metal) holds the key for this observation. Adding excessive ferrous chloride tetrahydrate (FeCl2·4H2O) as the external Fe in the electrolyte will greatly improve the OER performances for Ni3P; nevertheless, that the OER activity of Ni2FeP is still much superior than that of Ni3P corroborates the fact that the Fe impurity is not the only reason for the elevated OER activity of Ni2FeP and that internal Fe is also critical to the phase transformation as well as OER performance.
