Zichen Xu

The high‐efficiency electrosynthesis of hydrogen peroxide (H ₂ O ₂ ) via two‐electron oxygen reduction reaction (2e ⁻ ORR) represents a promising alternative to the traditional anthraquinone process. However, achieving high selectivity, industrial‐grade stability, and on‐site utilization of H ₂ O ₂ remains a significant challenge. Here, we designed a single‐atom catalyst, CoNPC, featuring a Co–N/P co‐coordination structure, tailored for high‐current‐density H ₂ O ₂ electrosynthesis and relevant paired valorization of ethylene glycol. The P modulation optimized the electronic structure of Co centers, leading to enhanced selectivity (> 90%) and stable H ₂ O ₂ production for over 140 h at a high current density of −200 mA cm ⁻² . In situ spectroscopic studies and theoretical calculations revealed that the P heteroatom plays a critical role in optimizing *OOH binding energy, thereby facilitating the 2e ⁻ ORR process. The electrogenerated H ₂ O ₂ was further utilized in a Fenton‐like process to oxidize ethylene glycol to formic acid. By coupling this cathodic reaction with anodic EG electrooxidation, we demonstrated a paired electrolysis system that enables simultaneous value‐added products at both sides. This work not only offers a robust strategy for the design of single‐atom catalysts on industrial H ₂ O ₂ electrosynthesis but also pioneers an energy‐efficient paired electrolysis system for waste utilization.

The high‐efficiency electrosynthesis of hydrogen peroxide (H ₂ O ₂ ) via two‐electron oxygen reduction reaction (2e ⁻ ORR) represents a promising alternative to the traditional anthraquinone process. However, achieving high selectivity, industrial‐grade stability, and on‐site utilization of H ₂ O ₂ remains a significant challenge. Here, we designed a single‐atom catalyst, CoNPC, featuring a Co–N/P co‐coordination structure, tailored for high‐current‐density H ₂ O ₂ electrosynthesis and relevant paired valorization of ethylene glycol. The P modulation optimized the electronic structure of Co centers, leading to enhanced selectivity (> 90%) and stable H ₂ O ₂ production for over 140 h at a high current density of −200 mA cm ⁻² . In situ spectroscopic studies and theoretical calculations revealed that the P heteroatom plays a critical role in optimizing *OOH binding energy, thereby facilitating the 2e ⁻ ORR process. The electrogenerated H ₂ O ₂ was further utilized in a Fenton‐like process to oxidize ethylene glycol to formic acid. By coupling this cathodic reaction with anodic EG electrooxidation, we demonstrated a paired electrolysis system that enables simultaneous value‐added products at both sides. This work not only offers a robust strategy for the design of single‐atom catalysts on industrial H ₂ O ₂ electrosynthesis but also pioneers an energy‐efficient paired electrolysis system for waste utilization.

Proton exchange membrane water electrolysis (PEMWE) is a promising technology for green hydrogen production due to its high efficiency, compact design, and flexible operation. However, the reliance on noble metal‐based anode catalysts significantly increases hydrogen production costs. Transition metal oxides have emerged as alternatives for the acidic oxygen evolution reaction (OER) because of their diverse compositions, tunable structures, and lower cost. This review summarizes recent advances in transition metal oxide catalysts beyond pure IrO ₂ , RuO ₂ , and their mixtures. Fundamental OER mechanisms, including the adsorbate evolution mechanism, lattice oxygen mechanism, and oxide pathway mechanism, are introduced, with emphasis on their roles in regulating catalytic activity and stability. Representative catalyst systems such as spinels, perovskites, pyrochlores, dioxides, and high entropy oxides are systematically reviewed, highlighting performance enhancement strategies including heterostructure construction, elemental doping, and defect engineering. Emerging concepts such as reaction pathway engineering, corrosion suppression, and dynamic structural stability are discussed as effective approaches to overcoming the trade‐off between activity and stability. Finally, current challenges and future perspectives are outlined, with emphasis on artificial intelligence‐assisted catalyst design, characterization optimization, scalable synthesis, and standardized industrial evaluation, to accelerate the practical deployment of advanced acidic OER catalysts in sustainable hydrogen production.

The large‐scale implementation of electrocatalytic water splitting for green hydrogen production is hindered by the sluggish kinetics of the oxygen evolution reaction (OER), necessitating efficient and durable catalysts. Here, we report an innovative ultrafast synthesis strategy using pulsed laser irradiation for the one‐step fabrication of a nanoporous carbon‐coated FeCoNiCrZn multi‐element alloy (MEA) supported on carbon cloth (FeCoNiCrZn‐C@CC), with l ‐ascorbic acid as an auxiliary agent. This resulting catalyst shows exceptional OER performance, achieving an overpotential of only 233 mV at 10 mA cm ⁻² and remarkable stability for 94 h at 250 mA cm ⁻² . We attributed this enhanced activity to a unique active site architecture, enabled by in situ generation of M ^III ‐OOH (M=Fe, Co, and Ni) active species, partial Cr dissolution, and thermal dezincification. In situ differential electrochemical mass spectrometry combined with first‐principles calculations reveals that the OER follows an adsorbate evolution mechanism. This work not only presents an ultrafast laser‐processing route for constructing high‐performance catalysts but also offers atomic‐level insights into their rational design.

Understanding the reconstruction mechanism to rationally design cost‐effective electrocatalysts for oxygen evolution reaction (OER) is still challenging. Herein, a defect‐rich NiMoO ₄ precatalyst is used to explore its OER activity and reconstruction mechanism. In situ generated oxygen vacancies, distorted lattices, and edge dislocations expedite the deep reconstruction of NiMoO ₄ to form polycrystalline Ni (oxy)hydroxides for alkaline oxygen evolution. It only needs ≈230 and ≈285 mV to reach 10 and 100 mA cm ⁻² , respectively. The reconstruction boosted by the redox of Ni is confirmed experimentally by sectionalized cyclic voltammetry activations at different specified potential ranges combined with ex situ characterization techniques. Subsequently, the reconstruction route is presented based on the acid‐base electronic theory. Accordingly, the dominant contribution of the adsorbate evolution mechanism to reconstruction during oxygen evolution is revealed. This work develops a novel route to synthesize defect‐rich materials and provides new tactics to investigate the reconstruction.