Electrocatalytic water splitting for hydrogen production is a crucial technology in achieving carbon neutrality. The development of efficient and stable hydrogen evolution reaction (HER) electrocatalysts is a core challenge in this field. This review systematically summarizes the latest research advancements in nanoporous transition metal-based catalysts, covering metal alloys and compounds. Through strategies such as compositional optimization, crystal structure modulation, interface engineering, and nanoporous structure design, these non-precious metal catalysts exhibit outstanding performance comparable to commercial platinum-carbon catalysts across a wide pH range. This paper thoroughly discusses the catalytic mechanisms of different material systems, including electronic structure regulation, active site exposure, and mass transport optimization. Finally, the challenges faced in current research are summarized, and future directions are projected, including scalable fabrication processes and performance validation in real electrolysis cell environments. This review provides significant insights into designing next-generation efficient and stable non-precious metal electrocatalysts.

Nanoporous Mo-doped Co ₂ P exhibits outstanding NITRR performance, as the introduction of electron-deficient Mo promotes H ₂ O dissociation to *H, enabling efficient NO hydrogenation with nearly 100% NH ₃ FE and 40.6% EE at −0.1 V vs. RHE.

Electrocatalytic nitrate reduction to ammonia (NO₃RR) is a promising approach to recycle nitrogen from nitrate pollutants, yet it remains challenged by low Faradaic efficiency and insufficient NH₃ production. Herein, Cu-doped nanoporous Co₂P (np-Co_2−xCu_xP) is reported as electrocatalyst for NO₃RR, achieving an ammonia yield rate of 30.6 mg h⁻¹ cm⁻² with a Faradaic efficiency of 93.4% at −0.3 V vs. RHE. In-situ spectroscopic analyses indicate that Cu incorporation modifies the surface electronic structure, resulting in the promotion of *H adsorption and *NO₂⁻ hydrogenation, thereby facilitating efficient ammonia generation.

Hydrogen production through water splitting is a promising path to develop renewable green energy. Effective, stable, and low-cost catalysts are the key to water splitting. In the present work, a series of self-supporting nanoporous alloys are prepared by using a dealloying process followed by electrooxidation. Among them, the np-AlFeNiO-4s sample exhibits remarkable activity (10 mA cm⁻² at 32 mV for the HER and 278 mV for the OER) and good long-term stability (100 h) in alkaline conditions for both the HER and the OER. It only requires 1.56 V to reach 10 mA cm⁻² current density for total water splitting performance. The very short time of electrooxidation can significantly improve the HER performance. Electrooxidation makes the metal and metal oxide sites on the electrode surface effectively coupled, which greatly enhances the kinetic rate of the Volmer and Heyrovsky steps. Appropriate electrooxidation is a rapid and easy way to improve the activity of the electrocatalyst, which has a broad application prospect in electrochemical water splitting.

N-doped Li₂ZrCl_6−3xN_x chloride solid electrolytes were synthesized via a mechanochemical method, and the effects of N incorporation on crystal structure, Li local environment, and Li⁺ transport were systematically investigated. X-ray diffraction suggested that the main Li₂ZrCl₆-related diffraction features were largely retained, while N introduction induced partial structural evolution toward C2/m-related features. 7Li MAS NMR revealed that N incorporation sharpened Li resonance peaks. Among the series, Li₂ZrCl_5.7N_0.1 exhibited the highest room-temperature ionic conductivity of 1.15 mS cm⁻¹, with the lowest activation energy of 0.237 eV, demonstrating a reduced Li⁺ migration barrier. All-solid-state batteries incorporating Li₂ZrCl_5.7N_0.1 showed stable rate capability and long-term cycling, retaining 85.9% capacity after 500 cycles at 1C and 77.4% after 3000 cycles at 3C. These results suggest that appropriate N modification can tune the Li₂ZrCl₆-based structure and Li local environment, thereby improving Li⁺ transport in all-solid-state lithium batteries. This work provides a feasible strategy for improving chloride-based solid electrolytes for next-generation energy storage.