The development of atmospheric pressure N₂ reduction to NH₃ is attracting much attention in green chemistry, yet it is still a challenge to obtain satisfactory activity under mild conditions. Herein, an efficient NIR photothermal catalysis reduction of N₂ constitutes an occurrence is reported. With or without V-substitute polyoxometalates (POMs) loaded on the surface of Fe-chelated polydopamine (Fe-PDA) photothermal support through the electrostatic interactions, NIR photothermal catalysts POMs@Fe-PDA are fabricated. The induction of “FeV” cofactor facilitates electron transfer between V(V)/V(IV)&Fe(III)/Fe(II) and N₂, thereby activating N₂ molecule. The synergy between the catalytic activity of V-POMs and the local NIR photothermal effect of Fe-PDA dramatically enhances N₂ reduction. Noticeably, PMo₁₀V₂@Fe-PDA exhibits a significantly enhanced NH₃ production rate of 181.1 μmol/L with a turnover frequency of 1006.1 mmol M⁻¹ h⁻¹ under 808 nm NIR laser radiation, being the highest values reported at atmospheric pressure. We expect that this work could provide an alternative approach for photothermal catalysis N₂ reduction under mild conditions.

As an important type of organic–inorganic hybrids, ionic and covalent polyoxometalate (POM) complexes with organic components have progressed rapidly over the past two decades. Due to the wide availability of organic building blocks and maneuverable combination styles, this field holds open opportunities now and in the near future. By abstracting the recent developments of POM complexes, some worthwhile topics are presented in this perspective. The important potentials of POM complexes are proposed to show in biological systems through ionic and covalent modification of biologically active molecules for immunosuppressive and therapeutic agents; in various functional materials with the incorporation of building and guest components for the construction of rigid/flexible nanostructures and frameworks; and in clean energy and environments via the combination of the photophysical and catalytic properties for chemical reactions with high efficiency.