Green hydrogen production by alkaline water electrolysis is an important technology in the decarbonization of the current industry. However

its large-scale application is limited by mediocre performance of conventional Raney Ni electrocatalysts. Herein

high-performance NiMoZn alloy catalysts of the Raney Ni type are developed by pulse electrodeposition for the hydrogen evolution reaction (HER). The optimized catalyst

NMZ-CA

exhibits an overpotential of 37 mV at 10 mA·cm

-2

and a Tafel slope of 27 mV·dec

-1

in 1 mol·L

-1

KOH. Tafel slope measurements

X-ray photoelectron spectroscopy

and H

2

temperature-programmed desorption experiments show that the incorporation of Mo and Zn in Ni weakens the binding of HER intermediate (H

ads

) on strongly adsorbing sites

leading to improved electrochemical kinetics. Electron microscopy and X-ray diffraction study reveals that a phase-pure Mo-doped Ni

2

Zn

11

intermetallic precatalyst formed

via

pulse electrodeposition and subsequent heat treatment is key to the structure integrity and performance of the catalyst after activation by alkaline leaching. Modification of NMZ-CA with PTFE enhances its HER performance by facilitating gas removal and improving structure integrity. A practical alkaline water electrolyzer built on the modified NMZ/PTFE-CA electrode delivers 2.0 A·cm

-2

at 1.92 V cell voltage and operates for 250 h without decay. This work provides insights into the synergy between Ni

Mo

and Zn in Raney Ni-type catalysts

and demonstrates the hydrophobic modification as an effective strategy for electrode development in high-performance alkaline water electrolysis.