Incorporating Zinc Metal Sites in Aluminum-Coordinated Porphyrin Metal-Organic Frameworks for Enhanced Photocatalytic Nitrogen Reduction to Ammonia

Rationally designing photocatalysts is crucial for the solar-driven nitrogen reduction reaction (NRR) due to the stable N≡N triple bond. Metal-organic frameworks (MOFs) are considered promising candidates but suffer from insufficient active sites and inferior charge transport. Herein, it is demonstrated that incorporating 3d metal ions, such as zinc (Zn) or iron (Fe) ions, into Al-coordinated porphyrin MOFs (Al-PMOFs) enables the enhanced ammonia yield of 88.7 and 65.0 µg g_cat⁻¹ h⁻¹, 2.5- and 1.8-fold increase compared to the pristine Al-PMOF (35.4 µg g_cat⁻¹ h⁻¹), respectively. The origin of ammonia (NH₃) is verified via isotopic labeling experiments. Incorporating Zn or Fe into Al-PMOF generates active sites in Al-PMOF, that is, Zn-N₄ or Fe-N₄ sites, which not only facilitates the adsorption and activation of N₂ molecules but suppresses the charge recombination. Photophysical and theoretical studies further reveal the upshift of the lowest unoccupied molecular orbital (LUMO) level to a more energetic position upon inserting 3d metal ions (with a more significant shift in Zn than Fe). The promoted nitrogen activation, suppressed charge recombination, and more negative LUMO levels in Al-PMOF(3d metal) contribute to a higher photocatalytic activity than pristine Al-PMOF. This work provides a promising strategy for designing photocatalysts for efficient solar-to-chemical conversion.