Synergistic Contact‐Electro‐Catalysis and Photocatalysis via TiO ₂ @PTFE Composites for Efficient N ₂ to NH ₃ Conversion

Abstract Catalytic nitrogen fixation from N 2 and water under mild conditions offers a sustainable NH 3 synthesis route. Herein, we report a synergistic nitrogen fixation strategy combining contact‐electro‐catalysis (CEC) with photocatalysis via one‐step in situ hydrothermally synthesized TiO 2 @PTFE catalyst, and achieved an activity of 133.6 µmol g −1 h −1 . It represents 10.9‐fold and 7.5‐fold enhancements over pristine TiO 2 and PTFE, respectively, outperforming current CEC systems and many photocatalytic systems operating without sacrificial agents. Further characterization and theoretical calculations reveal the synergy: the composite catalyst enhances the CEC catalyst dispersion; the CEC‐generated electric fields promote photogenerated charge separation and elevate the semiconductor's Fermi level, bolstering photocatalytic N 2 reduction; conversely, the semiconductor boosts CEC efficiency via enhanced N 2 adsorption and supplemental electron donation. We anticipate that this work establishes a “two birds with one stone” strategy, providing novel insights into CEC‐photocatalysis synergy and a pathway for rational design of high‐performance nitrogen fixation catalysts.