Recent years have witnessed an upsurge in the development of non-precious catalysts (NPCs) for alkaline water electrolysis (AWE), especially with the strides made in experimental and computational techniques. In this contribution, the most recent advances in NPCs for AWE were systematically reviewed, emphasizing the application of in situ/operando experimental methods and density functional theory (DFT) calculations in their understanding and development. First, we briefly introduced the fundamentals of the anode and cathode reaction for AWE, i.e., the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), respectively. Next, the most popular in situ/operando approaches for characterizing AWE catalysts, including hard and soft XAS, ambient-pressure XPS, liquid and identical location TEM, electrochemical mass spectrometry, and Raman spectroscopy were thoroughly summarized. Subsequently, we carefully discussed the principles, computational methods, applications, and combinations of DFT with machine learning for modeling NPCs and predicting the alkaline OER and HER. With the improved understanding of the structure–property–performance relationship of NPCs for AWE, we proceeded to overview their current development, summarising state-of-the-art design strategies to boost their activity. In addition, advances in various extensively investigated NPCs for AWE were evaluated. By conveying these methods, progress, insights, and perspectives, this review will contribute to a better understanding and rational development of non-precious AWE electrocatalysts for hydrogen production.

Single-atom catalysts have been widely investigated for several electrocatalytic reactions except electrochemical alcohol oxidation. Herein, we synthesize atomically dispersed platinum on ruthenium oxide (Pt₁/RuO₂) using a simple impregnation-adsorption method. We find that Pt₁/RuO₂ has good electrocatalytic activity towards methanol oxidation in an alkaline media with a mass activity that is 15.3-times higher than that of commercial Pt/C (6766 vs. 441 mA mg^‒1_Pt). In contrast, single atom Pt on carbon black is inert. Further, the mass activity of Pt₁/RuO₂ is superior to that of most Pt-based catalysts previously developed. Moreover, Pt₁/RuO₂ has a high tolerance towards CO poisoning, resulting in excellent catalytic stability. Ab initio simulations and experiments reveal that the presence of Pt‒O_3f (3-fold coordinatively bonded O)‒Ru_cus (coordinatively unsaturated Ru) bonds with the undercoordinated bridging O in Pt₁/RuO₂ favors the electrochemical dehydrogenation of methanol with lower energy barriers and onset potential than those encountered for Pt‒C and Pt‒Ru.