An Active and Robust Catalytic Architecture of NiCo/GaN Nanowires for Light‐Driven Hydrogen Production from Methanol

Abstract On‐site hydrogen production from liquid organic hydrogen carriers e.g., methanol provides an emerging strategy for the safe storage and transportation of hydrogen. Herein, a catalytic architecture consisting of nickel‐cobalt nanoclusters dispersed on gallium nitride nanowires supported by silicon for light‐driven hydrogen production from methanol is reported. By correlative microscopic, spectroscopic characterizations, and density functional theory calculations, it is revealed that NiCo nanoclusters work in synergy with GaN nanowires to enable the achievement of a significantly reduced activation energy of methanol dehydrogenation by switching the potential‐limiting step from *CHO → *CO to *CH 3 O → *CH 2 O. In combination with the marked photothermal effect, a high hydrogen rate of 5.62 mol·gcat‐1·h‐1 with a prominent turnover frequency of 43,460 h‐1 is achieved at 5 Wcm‐2 without additional energy input. Remarkably, the synergy between Co and Ni, in combination with the unique surface of GaN, renders the architecture with outstanding resistance to sintering and coking. The architecture thereby exhibits a high turnover number of >16,310,000 over 600 h. Outdoor testing validates the viability of the architecture for active and robust hydrogen evolution under natural concentrated sunlight. Overall, this work presents a promising architecture for on‐site hydrogen production from CH 3 OH by virtually unlimited solar energy.