Semiconductor photocatalytic technology has great potential for the removal of dilute gaseous NO in indoor and outdoor atmospheres but suffers from unsatisfactory NO-removal selectivity due to undesirable NO2 byproduct generation. In this study, we demonstrate that the 99% selectivity of photocatalytic NO oxidation toward nitrate can be achieved over blue TiO2 bearing oxygen vacancies (OVs) under visible-light irradiation. First-principles density functional theory calculation and experimental results suggested that the OVs of blue TiO2 with localized electrons could facilitate the molecular oxygen activation through single-electron pathways to generate ·O2- and simultaneously promote the photogenerated hole annihilation. The generated ·O2- directly converted NO to nitrate, while the hole annihilation inhibited the side-reaction between holes and NO to avoid toxic NO2 byproduct formation, resulting in the highly selective removal of NO. This study reveals the dual functions of OVs in defective photocatalysts and also provides fundamental guidance for the selective purification of NO with photocatalytic technology.

Oxygen Vacancies Promoted the Selective Photocatalytic Removal of NO with Blue TiO2 via Simultaneous Molecular Oxygen Activation and Photogenerated Hole Annihilation.

Creatively constructing Z-scheme composites is a promising and common strategy for designing effective photocatalyst systems. Herein, we synthesized Z-scheme Fe2O3@Ag-ZnO@C heterostructures from the Fe-MOFs and applied it to photodegradation of tetracycline and methylene blue pollutants in wastewater. The optimized sample exhibits a remarkable performance as well as stability under visible light irradiation. The calculating and experimental results demonstrate that the Fe2O3@ZnO nanointerface and carbon sheath together boost the transfer efficiency of photogenerated carriers and absorption ability, thereby improving the photocatalytic activity. Furthermore, detailed mechanism investigation reveals the pivotal role of reactive oxygen species (•OH and •O2-) generated, resulting in remarkable performance. In addition, cell biology experiments reveal that the wastewater after photocatalytic treatment has good biological compatibility, which is important for applications. This work provides valuable information for constructing high-performance Z-scheme photocatalysts from MOFs for environmental treatment.

Constructing Fe-MOF-Derived Z-Scheme Photocatalysts with Enhanced Charge Transport: Nanointerface and Carbon Sheath Synergistic Effect

MXenes as noble-metal-alternative co-catalysts in photocatalysis

In this work, an efficient nanoporous BiVO4 composite photoelectrode with high photocurrent and low onset potential for photoelectrochemical water splitting is achieved through modification of BiVO4 with a stable heterometallic CoNi-MOF layer. Compared with pristine BiVO4 anode, the formation of CoNi-MOFs/BiVO4 increases the photocurrent density by about 260 %. In addition, the CoNi-MOFs/BiVO4 photoanode is of greater steadiness for water oxidation, without insignificant activity attenuation within 3 reaction hours at 1.23 V vs. RHE. It is postulated that bimetal-organic framework CoNi-MOFs could supply more open sites which account for the impressively enhanced PEC performance of BiVO4 photoanodes toward water splitting under illumination. The results demonstrate a new method to fabricate dual metal nanoparallelepiped-like MOF for steady hydrolysis photoanode material.

Preparation of heterometallic CoNi-MOFs-modified BiVO4: a steady photoanode for improved performance in photoelectrochemical water splitting

Carbon deposit during the catalytic oxidation of volatile organic compounds (VOCs) is a key factor to restrict long-term stability of catalysts. Herein, a modified ordered porous catalyst with high coke-resistance performance was developed by introducing oxygen vacancies (OVs) into CeO2 through simple redox and steam treatment (ARCeO2), and applied in efficiently photothermocatalytic degradation of VOCs. Abundant OVs in ARCeO2 leads to enhanced light absorption, improved charge separation and increased reactive oxygen generation, and then promote its photothermocatalytic performance. Moreover, no obvious decrease was observed in the photothermocatalytic activity of ARCeO2 at 200 °C for 25 h reaction. Its superior photothermocatalytic stability can be attributed to the less intermediates and limited coke accumulation onto ARCeO2. This work provides a facile and cost-effective strategy for the design and fabrication of CeO2 catalyst with strong coke-resistance potential and highlights the significance of OVs engineering for improving the photothermocatalytic performance of VOCs degradation.

Introduce oxygen vacancies into CeO2 catalyst for enhanced coke resistance during photothermocatalytic oxidation of typical VOCs

The status of defects of TiO2 are of fundamental importance in determining its physicochemical properties. Here we report a simple chemical deposition method for controllable synthesis of defective anatase TiO2 nanocrystals under various calcination atmospheres. XPS and ESR analysis reveals that both the oxygen vacancies ( VO) and the trivalent titanium (Ti3+) defects exist in TiO2 after N2 treatment (N-TiO2). Meanwhile, mainly VO defects can be obtained in TiO2 with air calcination (A-TiO2). ESR spectra for reactive oxygen species determination, clearly show that the visible light catalytic activity is mainly caused by the efficient activation of oxygen molecules to •O2- species for A-TiO2, which play an important role in hindering the accumulation of intermediates during p-chlorophenol (4-CP) photodegradation process. However, the oxygen molecules cannot be activated for N-TiO2 even with superior visible light absorption and thus the photogenerated electron are reductant, which participated in the transformation of BQ to HQ via electron shuttle mechanism. Moreover, A-TiO2 exhibits higher separation efficiency of photogenerated carriers than that of N-TiO2, showing the critical role of VO with a suitable concentration in transferring photogenerated charges.

Wei Li

Papers

Unveiling the Role of Defects on Oxygen Activation and Photodegradation of Organic Pollutants.