Haijun Chen,Jie Liang,Li Li,Baozhan Zheng,Zhesheng Feng,Zhaoquan Xu,Yonglan Luo,Qian Liu,Xifeng Shi,Yang Liu,Shuyan Gao,Abdullah M. Asiri,Yan Wang,Qingquan Kong,Xuping Sun
Electrocatalytic nitrogen reduction reaction (NRR) enabled by introducing Ti3+ defect sites into TiO2 through a doping strategy has recently attracted widespread attention. However, the amount of Ti3+ ions is limited due to the low concentration of dopants. Herein, we propose Ti2O3 nanoparticles as a pure Ti3+ system that performs efficiently toward NH3 electrosynthesis under ambient conditions. This work has suggested that Ti3+ ions, as the main catalytically active sites, significantly increase the NRR activity. In an acidic electrolyte, Ti2O3 achieves extraordinary performance with a high NH3 yield and a Faradaic efficiency of 26.01 μg h–1 mg–1 cat. and 9.16%, respectively, which are superior to most titanium-based NRR catalysts recently reported. Significantly, it also demonstrates a stable NH3 yield in five consecutive cycles. Theoretical calculations uncovered that the enhanced electrocatalytic activity of Ti2O3 originated from Ti3+ active sites and significantly lowered the overpotential of the potential-determining step.
Ultrathin TiO 2 nanosheet (NST) with abundant Ti 3+ sites is developed as a photocatalyst which exhibits a high yield (147.2 μmol g −1 h −1 ) and selectivity (96.8%) for CO 2 to CH 4 . The results of in situ FTIR, in situ EPR and density functional theory (DFT) calculation suggest that CO 2 would be selectively activated on NST surface via forming the bridging Ti···CO 2 − ···Ti coordination species which not only lowers the activation energy barrier, but also determines the selectivity of CH 4 . Additionally, NST with the better separation and transfer ability for photogenerated electrons-holes can fleetly supply the electrons to CO 2 molecules for high efficiently producing CH 4 via the Ti-C coordination bond. Finally, a possible mechanism of the synergistic effect about coordination-activation and photocatalysis is discussed at a molecule level. This work would offer a perspective for designing an effective photocatalyst and tailoring the selectivity of products by coordination activation.
Ultrathin TiO 2 nanosheets (NST) containing Ti 3+ sites are developed as a photocatalyst that exhibits high degradation efficiencies (98.6%) for the degradation of enrofloxacin (ENR) under visible light. The increment of degradation efficiencies for ENR over NST is mainly due to the increase of Ti 3+ and oxygen vacancies (OVs). Ti 3+ sites on the surface of NST can be associated with ENR molecules through the formation of surface coordination species -COO∙∙∙Ti- intermediates, resulting in the activation of ENR. OVs on NST can adsorb and activate more O 2 molecules to accelerate the generation of O 2 - by photogenerated electrons reduction. The photogenerated holes quickly transfer to the surface of the catalyst to directly degrade the activated ENR. Finally, a possible mechanism about the synergistic effect of coordination activation and photocatalysis is proposed over NST at a molecule level. This study highlights the significant role of coordination activation in the photocatalytic degradation of antibiotics.
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