Glycerol electrooxidation is an intriguing surrogate reaction for sluggish oxygen evolution in water electrolysis and can simultaneously produce value-added chemicals at the anode; however, the majority of non-precious catalysts suffer from large electrolytic voltage and poor stability for hydrogen production via hybrid water electrolysis at large current density. Here we present a hierarchical multi-level triphasic catalyst comprising bimetallic nitride nanoparticles in situ anchoring on biphasic metal sulfides with multilevel interfaces and multifunctional metal sites (Ni₃S₂/Co₉S₈/FeNiN). Benefiting from synergistic multi-metal sites and dynamic iron incorporation into the active species, this catalyst manifests extraordinary activity for both the oxygen evolution and glycerol electrooxidation in terms of ultralow potentials of 1.502/1.393 V at 300 mA cm⁻² and excellent Faradaic efficiency (95.2%) toward formate production, along with fabulous durability for over 1100/240 hours, placing it among the best non-noble metal-based electrocatalysts. Strikingly, by coupling with the NiMoN cathode, this catalyst can readily switch from traditional water electrolysis to hybrid water electrolysis with low cell voltages of 1.713/1.610 V to reach 1000 mA cm⁻² durably at an electricity-saving efficiency of 6.0%, outperforming nearly all the biomass upgrading assisted water electrolyzers reported hitherto. Operando Raman and X-ray photoelectron spectroscopic studies reveal the rapid switching from OH*-involved direct oxidation to oxyhydroxide-involved indirect oxidation for glycerol oxidation, which is in sharp contrast to the rapid generation of high-valence metal oxyhydroxide active species for oxygen evolution. Theoretical calculations further substantiate that the construction of dual heterojunction interfaces facilitates the C–C bond cleavage, dehydrogenation and oxygenation steps with much lower energy barriers, thereby promoting the selective oxidation of glycerol into formic acid.

Given the inherent potential of seawater, industrial wastewater, and residential water as inherent feedstocks for hydrogen production through water electrolysis, there is a critical demand for the exploration of robust and stable hydrogen-evolving catalysts that can operate effectively across a diverse range of pH conditions. However, the pursuit of hydrogen-evolving electrocatalysts that demonstrate both good stability and high efficiency over a wide pH range remains a formidable challenge. Here we report the rational design and synthesis of an outstanding nanoporous hybrid electrocatalyst consisting of intermetallic cobalt-molybdenum alloy particles anchoring on MoO₂ cuboid arrays, which demands very low overpotentials of 72, 123 and 134 mV to deliver a current density of −100 mA·cm⁻² for hydrogen evolution reaction under alkaline, neutral and acidic conditions, respectively. These catalytic activities are superior to most non-precious-metal-based catalysts documented in the literatures, and are even comparable to noble metal catalysts. In particular, this alloy electrocatalyst exhibits excellent stability at 50 or 300 mA·cm⁻² without obvious activity degradation, which is further supported by the undetectable changes in the surface chemical valence states on the basis of in-situ X-ray photoelectron spectroscopic studies. This study provides an innovative strategy for the design and synthesis of effective non-noble intermetallic catalysts for pH-universal hydrogen evolution over a wide pH range.