One-Pot Photosynthesis of Cubic Fe@Fe3O4 Core–Shell Nanoparticle Well-Dispersed in N‑Doping Carbonaceous Polymer Using a Molecular Dinitrosyl Iron Precursor

• Published in: Inorganic chemistry 2022-12, Vol.61 (51), p.20719-20724
• Main Authors: Habib, Ibrahim, Lu, Tsai-Te, Sabbah, Amr, Chen, Kuei-Hsien, Tsai, Fu-Te, Liaw, Wen-Feng
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c03773

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-N 3 MDA) 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-N 3 MDA, photosensitizer Eosin Y, and sacrificial reductant TEA, the α-diimine N3MDA and noninnocent NO ligands (1) enable the slow reduction of 1-N 3 MDA 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.