Solar‐Driven Ultrafast Production of Gram‐Per‐Litre Level Hydrogen Peroxide With 2.74% Solar‐to‐Chemical Efficiency via Synergistic Photothermal Catalysis by W‐Based Amorphous Metal–Organic Polymers

ABSTRACT Hydrogen peroxide (H 2 O 2 ) is a critical industrial chemical traditionally produced via the energy‐intensive anthraquinone process. Here, we report a low‐cost (<$0.6/g), hydroxyl‐functionalized metal‐organic polymer (MIL‐2OH‐W) featuring abundant undercoordinated [WO 6 ] 6 − centers for solar‐driven H 2 O 2 production. MIL‐2OH‐W achieves a record production rate of 11.25 mmol·g − 1 ·h − 1 in the first 10 min and becomes saturated to 3 mmol·g − 1 ·h − 1 in 1 h, reaching a concentration of 1.02 g·L − 1 (30 mmol·L − 1 ) with a 2.74% solar‐to‐chemical efficiency under mild conditions (40°C). Mechanistic studies from in ‐ situ transient absorption, in ‐ situ infrared, in ‐ situ electron paramagnetic resonance and density functional theory reveal a synergistic photothermal pathway, where aromatic hydroxyl linkers mimic anthraquinone‐like redox cycling, stabilize radical intermediates, and accelerate oxygen reduction. The catalyst exhibits exceptional stability (>40 days) and scalability, aligning with the United Nations decarbonization goals. This work provides a blueprint for sustainable H 2 O 2 synthesis by integrating photothermal catalysis with waste‐heat utilization.