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The presence of oxygen vacancies and its role as a double-edged sword in anatase TiO2/polymerized carbon nitride composites for oxidative and reductive photocatalytic reactions

Article

Authorship
Manrique-Holguín, Manuela ; Murillo-Sierra, Juan C. ; Gil Rebaza, Arles V. ; Zuñiga, Julián A. ; Padró, Juan M. ; Ronco, Nicolas ; Contreras, David ; Pizzio, Luis R. ; RENGIFO HERRERA, JULIAN ANDRES
Date
2026
Publishing House and Editing Place
ELSEVIER SCIENCE SA
Magazine
MATERIALS CHEMISTRY AND PHYSICS, vol. 348 ELSEVIER SCIENCE SA
Summary Information provided by the agent in SIGEVA
In-depth characterization of TiO2@PCN composites (PCN, polymeric carbon nitride) prepared with a urea precursor (T/U30 % T/U80 %) and their photocatalytic activities in nitrobenzene (NB) reduction and malachite green dye (MGD) oxidation allowed to evaluate the role of oxygen vacancies in the photocatalytic activity.Materials T/U30 % and T/U80 % exhibited low amounts of PCN (<2.3 % wt.), a significant presence of Ti3+ sites related to deep electron traps and visible light absorption. Continuo... In-depth characterization of TiO2@PCN composites (PCN, polymeric carbon nitride) prepared with a urea precursor (T/U30 % T/U80 %) and their photocatalytic activities in nitrobenzene (NB) reduction and malachite green dye (MGD) oxidation allowed to evaluate the role of oxygen vacancies in the photocatalytic activity.Materials T/U30 % and T/U80 % exhibited low amounts of PCN (<2.3 % wt.), a significant presence of Ti3+ sites related to deep electron traps and visible light absorption. Continuous wave electron spin resonance (CW-ESR) spectra at 􀀀 196 ◦C during in-situ UV and visible light irradiation showed that the intensity of signals attributed to deep electron traps increased in the composites. Regarding photocatalytic activity, T/U30 % and T/U80 % materials were more efficient than pristine TiO2 and PCN in MGD oxidation, whereas their capacity to reduce NB was strongly affected under UVA- and blue-LED irradiation. We concluded that this synthetic method using urea as a PCN precursor led to the generation of TiO2@PCN composites with visible light absorption, direct Zschemes, low amounts of PCN, and high presence of oxygen vacancies acting as recombination centers, which caused a detrimental effect on the photocatalytic reductive properties of T/U30 % and T/U80 % composites. In addition, interaction with NB promoted the formation of nitrosobenzene and azoxybenzene instead of aniline, as occurred with pure PCN. Computational calculations demonstrated that NB interacts differently with PCN, TiO2, and oxygen-deficient TiO2. Finally, the visible-light absorption of T/U30 % and T/U80 % samples could not be exclusively attributed to PCN’s presence but also to oxygen vacancies generating midgap states.
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Key Words
TiO2Heterogeneous photocatalysisPCNHeterojunctions