4.8 Article

Ferric oxide nanoclusters with low-spin FeIII anchored g-C3N4 rod for boosting photocatalytic activity and degradation of diclofenac in water under solar light

Journal

APPLIED CATALYSIS B-ENVIRONMENTAL
Volume 317, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.apcatb.2022.121725

Keywords

Photocatalysis; Low -spin Fe-III; g-C3N4; D band center; Diclofenac

Funding

  1. National Key Research and Development Program of China [2021YFA1202500]
  2. Beijing Nova Program [Z191100001119054]
  3. National Natural Science Foundation of China (NSFC) [21906001, 52100069]
  4. Fundamental Research Funds for the Central Universities (2022 New Engineering Intersection Project of Peking University)
  5. China Postdoctoral Science Foundation [2021M700213]

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By using the nanocrystal size alteration strategy, a new photocatalyst FCN was developed by anchoring low-spin FeIII Fe2O3 nanoclusters on g-C3N4 rods. FCN showed high photocatalytic activity by enhancing the bonding state and promoting the production of reactive oxygen species, resulting in improved degradation efficiency of diclofenac under solar light.
Fe2O3, as an earth-abundant photocatalyst for water purification, has attracted great attention. However, the high-spin FeIII in traditional Fe2O3 restricts its catalytic performance. In this work, based on the nanocrystal size alteration strategy, cubic Fe2O3 nanoclusters (3-4 nm) with low-spin FeIII were successfully anchored on six-fold cavities of the supramolecular condensed g-C3N4 rod (FCN) through the impregnation-coprecipitation method. FCN showed high photocatalytic activity, as the d band center of Fe 3d orbital (-1.79 eV) in low-spin Fe-III shifted closer to Femi level, generating a weaker antibonding state. Then, the enhanced bonding state strengthened the interaction between Fe and O, further accelerating the charge carrier separation and enhancing its ability to capture OH- . Thus, low-spin FeIII enhanced the production of dominant reactive oxygen species (.OH/.O2(-)), promoting diclofenac photocatalytic degradation under solar light, with a kinetic rate constant (0.206 min(-1)) of similar to 5 times compared with that of pristine g-C3N4.

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