Transition-metal selenides in hydrogen and oxygen electrocatalysis

doi:10.1016/j.metadv.2026.06.004

Abstract

Abstract:

Transition-metal selenides (TMSes) are attracting increasing interest as electrocatalysts owing to the covalent nature of the metal-Se bond and the polarizable Se sublattice, which collectively reshape charge distribution and adsorption energetics at working interfaces. This review summarizes the recent progress of TMSes as effective catalysts or pre-catalysts for hydrogen and oxygen electrocatalysis, including the hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), which are the core reactions for water electrolysis, fuel cells and metal-air batteries. Particular emphasis is placed on the correlations between electronic/interfacial structures and catalytic activity, selectivity, and stability to highlight recurring trends and existing limitations. Furthermore, the commonly employed regulation strategies, including chemical doping, heterointerface engineering and phase regulation, are summarized and their effectiveness compared. Practical concerns regarding stability/dissolution, selenium utilization and safety, as well as inconsistencies in benchmarking protocols, are also discussed. Finally, future perspectives on the development of TMSes as efficient, durable, and cost-competitive electrocatalysts are outlined.

Key words: Transition-metal selenides, Electrocatalysis, Hydrogen evolution reaction, Oxygen evolution reaction, Oxygen reduction reaction

Qiwen Fu, Yunzhu Du, Cheng Yan, Xiyu He, Qiaodan Hu, Junliang Zhang, Fan Yang. Transition-metal selenides in hydrogen and oxygen electrocatalysis[J]. Metals Advances, 2026, 48: 1-19.

Figures/Tables 10

Fig. 1. Schematic diagrams of electrochemical devices based on hydrogen and oxygen electrocatalysis. (a) An alkaline water electrolyzer, (b) an alkaline fuel cell and (c) a metal-air battery.

Fig. 2. (a) Schematic diagram of the HER, adapted with permission from Ref. [34]; (b) and (c) Schematic diagrams of the AEM and LOM mechanism for OER, respectively, adapted with permission from Ref. [35]; (d) Schematic diagram of the ORR, reproduced with permission from Ref. [36]; (e) Activity volcanoes for the 2e− and 4e− reduction of oxygen, reproduced with permission from Ref. [37].

Fig. 3. Literature compilation of electrocatalytic activity metrics for representative pristine or near-pristine TMSe electrocatalysts. (a) η10 of HER in 1.0 M KOH. (b) η10 of HER in 0.5 M H2SO4. (c) η10 of OER in 1.0 M KOH. (d) E1/2 of 4-electron ORR in 0.1 M KOH. Values are extracted from the references shown in Tables S1-S4.

Fig. 4. Effectiveness of various regulation strategies for enhancing activities of TMSe-based electrocatalysts in alkaline electrolyte. (a) HER; (b) OER. To minimize the impact of varying experimental conditions across different studies, the colors map the relative performance enhancement (Δη) compared to the pristine reference within the identical study.

Fig. 5. Family-level map of ORR performance for TMSe electrocatalysts. The upper panel summarizes representative 2e− ORR systems using H2O2 Faradaic efficiency (FE) as the selectivity metric, and the lower panel summarizes representative 4e− ORR systems using half-wave potential (E1/2) as activity metric. Shorthand labels within the squares are defined in the main text; grey cells indicate no data available. To minimize the impact of varying experimental conditions across different studies, the colors map the relative performance enhancement (FE improvement) compared to the pristine reference within the identical study.

Fig. 6. (a) Structural models of o-CoSe2 and c-CoSe2, S.G. represents space group; (b) and (c) Co K-edge X-ray absorption near-edge structure (XANES) spectra and fitting of Fourier-transform extended X-ray absorption fine structure (FT-EXAFS) spectra of different Co species; (d)-(f) Operando Raman spectra of o-CoSe2 in acidic HER, alkaline HER and alkaline OER, respectively; (g)-(i) Tafel plots of CoSe2 and S-doped CoSe2 for acidic HER, alkaline HER, and alkaline OER, respectively. Adapted with permission from Ref. [87].

Fig. 7. (a) Schematic illustration of the synthesis procedures for porous (Ni0.75Fe0.25)Se2 nanosheets; (b)-(e) low- and high-magnification scanning electron microscopy (SEM) images, high-resolution transmission electron microscopy (HRTEM) image, and energy-dispersive X-ray spectroscopy (EDS) elemental mapping of porous (Ni0.75Fe0.25)Se2 nanosheets, respectively; (f) iR-corrected OER polarization curves in 1 M KOH solution at 5 mV s−1; (g) Corresponding Tafel plots; (h) charging current density differences plotted vs scan rates. The linear slope is twice that of the double-layer capacitance (Cdl); (i) Chronopotentiometric curves of Ni-based nanosheet precursor and porous NiSe2 nanosheets at 15 mA cm−2, and NiFe-based precursor and porous (Ni0.75Fe0.25)Se2 nanosheets at 35 mA cm−2; (j) and (k) High-resolution XPS spectra for Ni 2p and Fe 2p for porous (Ni0.75Fe0.25)Se2 nanosheets, respectively. Adapted with permission from Ref. [119].

Fig. 8. Nonstoichiometric MoSex nanosheets for acidic HER. (a) Hydrothermal synthesis route and structure; the dominant phase evolves from 2H (x = 1.8, 2.0) to 1T′ (x = 2.2-2.4) with extra Se incorporation. (b, c) HER polarization curves and corresponding Tafel plots for MoSex (x = 1.8-2.4) versus Pt/C in H2-saturated 0.5 M H2SO4. (d, e) Proposed 1T′/2H structural models (A, B, C, C′) and calculated ΔG*H at TA sites. (f) Nudged elastic band (NEB)-calculated barrier for SeMo incorporation (initial/transition state/final). (g) Atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) of the basal plane confirming the lattice structure. Adapted from Ref. [137].

Fig. 9. (a)-(d) Crystal structure of 2D PdSe2, Pd4Se, Pd17Se15 and Pd7Se4, respectively. (e) The comparison of different Pd-Se phases (PdSe2, Pd4Se and Pd17Se15) at identical catalyst mass loading. The top solid traces represent the ring current density (normalized to the geometric area of the disk), and the bottom traces represent the disk current density. Dashed traces represent selectivity (right axis). (f)-(h) Number of electrons and kinetic currents observed for Pd17Se15, Pd7Se4 and Pd4Se phases, respectively. The electrolyte used is O2 saturated 0.1 M KOH and the scan rate used is 2 mV s−1. Adapted with permission from Ref. [186], [187].

Fig. 10. (a) Schematic diagram of preparation, morphology and crystal structure. Linear sweep voltammetry (LSV) curves, Tafel plots, and linear plots of capacitive current versus scan rate for NiFe carbonate hydroxide (NFCH)/NF, NiFeSe/NF, NiFeSe@NiFeOH/NF, and RuO2/NF at 5 mV s−1 for OER are shown below. (b)-(d) SEM images NFCH/NF, NiFeSe/NF, and NiFeSe@NiFeOH/NF; (e) HRTEM images of NiFeSe@NiFeOH/NF. Adapted with permission from Ref. [226]; (f) Charge density difference diagram (charge accumulation and depletion are denoted by yellow and blue colors, respectively); (g) BIEF schematic diagram of CoSe2@FeSe2 NC/NHC, where NC and NHC denote the N-doped carbon shell and N-doped honeycomb carbon support, respectively. Adapted with permission from Ref. [227].

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