One-Pot Photosynthesis of Cubic Fe@Fe₃O₄ Core-Shell Nanoparticle Well-Dispersed in N-Doping Carbonaceous Polymer...

Nanoscale zerovalent iron (NZVI) features potential application to biomedicine, (electro-/photo)catalysis, and environmental remediation. However, multiple-synthetic steps and limited ZVI content prompt the development of a novel strategy for efficient preparation of NZVI composites. Herein, a dinitrosyl iron complex [(N₃MDA)Fe(NO)₂] (1-NMDA) was explored as a molecular precursor for one-pot photosynthesis of a cubic Fe@Fe₃O₄ core-shell nanoparticle (ZVI% = 60%) well-dispersed in an N-doping carbonaceous polymer (NZVI@NC). Upon photolysis of 1-NMDA, photosensitizer Eosin Y, and sacrificial reductant TEA, the α-diimine N₃MDA and noninnocent NO ligands (1) enable the slow reduction of 1-NMDA into an unstable [(N₃MDA)Fe(NO)₂]^- species, (2) serve as a capping reagent for controlled nucleation of zerovalent Fe atom into Fe nanoparticle, and (3) promote the polymerization of degraded Eosin Y with N₃MDA yielding an N-doping carbonaceous matrix in NZVI@NC. This discovery of a one-pot photosynthetic process for NZVI@NC inspires continued efforts on its application to photolytic water splitting and ferroptotic chemotherapy in the near future.