Anchoring Pd Single Atoms on N‐Doped MOF‐Derived TiO 2 for Photocatalytic Hydrogen Evolution With an Ultra‐High Rate up to 185.8 mmol g −1 h −1

Photocatalytic hydrogen (H 2 ) evolution provides a sustainable pathway for clean energy production. However, conventional photocatalysts suffer from wide bandgaps and rapid charge recombination, leading to low photocatalytic efficiency. Herein, we construct an asymmetric N─Pd─O coordination environment by anchoring Pd single atoms (SAs) onto N‑doped MIL‑125‑derived TiO 2 . The optimized 1%PdN‑TiO 2 catalyst achieves a high H 2 evolution rate up to 185.8 mmol g −1 h −1 and an apparent quantum efficiency of 67.4% both measured under 365 nm monochromatic light irradiation. Synchrotron X‑ray absorption fine structure spectroscopy, ultrafast spectroscopy, and density functional theory calculations reveal that the asymmetric N─Pd─O coordination promotes directional charge transfer and lowers the H 2 evolution reaction (HER) barrier. This work offers insights into the rational design of heteroatom‑modulated asymmetric coordination microenvironments toward high‑efficiency MOF‑derived single‑atom photocatalysts for sacrificial‑agent‑assisted photocatalytic H 2 production.