Multiscale Catalyst Engineering for Stable, Selective, and Carbon‐Neutral Industrial Hydrogen Peroxide Electrosynthesis

ABSTRACT The electrocatalytic two‐electron oxygen reduction reaction (2e − ORR) has emerged as a pivotal strategy for sustainable hydrogen peroxide (H 2 O 2 ) synthesis, offering a carbon‐neutral alternative to the energy‐intensive anthraquinone process. This review critically synthesizes recent breakthroughs in catalyst design, mechanistic understanding, and system integration to address the persistent selectivity–stability trade‐off. Key advances include atomic‐level engineering of electronic modulation and surface functionalization and hydrophobicity control, which achieve > 95% H 2 O 2 selectivity by precisely tuning *OOH adsorption energy and suppressing 4e − pathways. Hierarchical architectures, such as flow‐through electrodes and catalytic membranes, extend operational stability beyond 500 h at industrial current densities (> 200 mA cm − 2 ) through confinement effects and interfacial engineering. Emerging operando characterization techniques coupled with machine learning‐accelerated simulations now enable dynamic mapping of active‐site evolution and degradation mechanisms. System‐level innovations integrating renewable energy input and circular carbon strategies demonstrate pilot‐scale feasibility for net‐negative emission H 2 O 2 production. However, persistent challenges in scalability, long‐term catalyst durability under fluctuating loads, and techno‐economic gaps between laboratory and industrial implementations require urgent attention. We propose a multidisciplinary roadmap combining materials genome initiatives, modular reactor design, and policy‐driven lifecycle assessment frameworks to accelerate the deployment of 2e − ORR systems. This work provides actionable guidance for advancing carbon‐neutral chemical manufacturing through electrochemical routes aligned with global net‐zero goals.