The rational manipulation of electron transfer in photocatalysts are essential for the photocatalytic nitrogen fixation. In this study, a boron (B)-doping strategy is proposed for boosting the electron transfer of MOF-based photocatalysts. A series of B-doped Ti-MOFs, NH2/B-MIL-125 (NBM), were synthesized by a facile one-pot hydrothermal method, in which NH2-MIL-125, 2-aminoterephthalic acid (NH2-H2BDC) as the organic ligand, was chosen as the model material and the second ligand 4-carboxyphenylboronic acid (CPBA) was employed as the B source. The B element in CPBA is successfully incorporated into the MOF skeleton by forming the B-O-Ti bonds. The electron-deficient B atom can accommodate more photogenerated electrons, which acts as a “high-speed bridge” between the metal and ligand, thus effectively increasing the electron further transferring along the ligand-metal charge transfer (LMCT) path. Consequently, the recombination of photogenerated carriers is inhibited, greatly enhancing the photocatalytic nitrogen fixation performance. The optimal NBM sample exhibits an NH3 generation rate of 286.4 μmol g−1 L−1 under full spectrum, which is 2.9 times higher than that of pristine NH2-MIL-125 (73.4 μmol g−1 L−1). This study may provide a promising strategy to acquire high-efficiency photocatalysts via the electron-deficient element doping.
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