从结构到改性:TiO_2基光催化剂的研究进展及大气污染防治应用

国内外关于TiO_2基光催化剂的设计有着广泛的研究,应用驱动式的光催化剂设计本质是从结构设计到改性设计的过程。首先综述了目前TiO_2基体结构的形态和制备方法,完整阐述了TiO_2纳米管的优势和阳极氧化过程,进而综述了TiO_2纳米管的改性方式,特别说明了表面等离子体光催化技术的原理和应用潜力,介绍了大气污染防治中挥发性有机化合物(VOCs)降解对TiO_2基光催化剂的需求和应用案例,最后指出表面等离子体TiO_2纳米管在大气污染防治过程中作为技术革新点的可能性和工业应用前景。

Recent developments in visible-light photocatalytic degradation of antibiotics

With the significant discharge of antibiotic wastewater into the aquatic and terrestrial ecosystems, antibiotic pollution has become a serious problem and presents a hazardous risk to the environment. To address such issues, various investigations on the removal of antibiotics have been undertaken. Photocatalysis has received tremendous attention owing to its great potential in removing antibiotics from aqueous solutions via a green, economic, and effective process. However, such a technology employing traditional photocatalysts suffers from major drawbacks such as light absorption being restricted to the UV spectrum only and fast charge recombination. To overcome these issues, considerable effort has been directed towards the development of advanced visible light-driven photocatalysts. This mini review summarises recent research progress in the state-of-the-art design and fabrication of photocatalysts with visible-light response for photocatalytic degradation of antibiotic wastewater. Such design strategies involve the doping of metal and non-metal into ultraviolet light-driven photocatalysts, development of new semiconductor photocatalysts, construction of heterojunction photocatalysts, and fabrication of surface plasmon resonance-enhanced photocatalytic systems. Additionally, some perspectives on the challenges and future developments in the area of photocatalytic degradation of antibiotics are provided.

SPR effect of bismuth enhanced visible photoreactivity of Bi_2WO_6 for NO abatement

Bi2WO6 is a typical visible-light-responsive semiconductor photocatalyst with a layered structure.However,the relatively large bandgap(2.6–2.8 eV)and quick recombination of photo-generated carriers result in its low quantum efficiency.In this paper,Bi-nanospheres-modified flower-like Bi2WO6 was successfully prepared by solvothermal treatment of Bi2WO6 powders in Bi(NO3)3 solution using ethylene glycol as reductant.The photoreactivity of this photocatalyst was evaluated by the oxidation of NO in a continuous-flow reactor under irradiation by a visible LED lamp(λ>400 nm).It was found that both Bi nanospheres and flower-like Bi2WO6 precursor exhibit very poor photocatalytic activity with NO removal rates of only 7.7%and 8.6%,respectively.The photoreactivity of Bi/Bi2WO6 was found to steadily increase from 12.3%to 53.1%with increase in the amount of Bi nanospheres from 0 to 10 wt%.However,with further increase in the loading amount of Bi nanospheres,the photoreactivity of Bi/Bi2WO6 hybridized photocatalyst begins to decrease,possibly due to the light filtering by the Bi nanospheres.The enhanced visible photoreactivity of Bi/Bi2WO6 towards NO abatement was attributed to surface plasmon resonance driven interfacial charge separation.The excellent stability of Bi/Bi2WO6 hybridized photocatalyst towards NO oxidation demonstrates its potential for applications such as air purification.

Synergistic integration of metallic Bi and defects on BiOI: Enhanced photocatalytic NO removal and conversion pathway

Surface plasmon resonance(SPR)of metals may provide a way to improve light absorption and utilization of semiconductors,achieving better solar light conversion and photocatalysis efficiency.This study uses the advantages of SPR in metallic Bi and artificial defects to cooperatively enhance the photocatalytic performance of BiOI.The catalysts were prepared by partial reduction of BiOI to form Bi@defective BiOI,which showed highly enhanced visible photocatalytic activity for NOx removal.The effects of reductant quantity on the photocatalytic performance of Bi@defective BiOI were investigated.The as-prepared photocatalyst(Bi/BiOI-2)using 2 mmol of reductant NaBH4 showed the most efficient visible light photocatalytic activity.This enhanced activity can be ascribed to the synergistic effects of metallic Bi and oxygen vacancies.The electrons from the valence band tend to accumulate at vacancy states;therefore,the increased charge density would cause the adsorbed oxygen to transform more easily into superoxide radicals and,further,into hydroxyl radicals.These radicals are the main active species that oxidize NO into final products.The SPR effect of elemental Bi enables the improvement of visible light absorption efficiency and the promotion of charge carrier separation,which are crucial factors in boosting photocatalysis.NO adsorption and reaction processes on Bi/BiOI-2 were dynamically monitored by in situ infrared spectroscopy(FT-IR).The Bi/BiOI photocatalysis mechanism co-mediated by elemental Bi and oxygen vacancies was proposed based on the analysis of intermediate products and DFT calculations.This present work could provide new insights into the design of high-performance photocatalysts and understanding of the photocatalysis reaction mechanism for air-purification applications.

Decorating non-noble metal plasmonic Al on a TiO2/Cu2O photoanode to boost performance in photoelectrochemical water splitting

Designing low-cost and high-performance photoelectrodes with improved light harvesting and charge separation rates is significant in photoelectrochemical water splitting.Here,a novel TiO2/Cu2O/Al/Al2O3 photoelectrode is manufactured by depositing plasmonic nanoparticles of the non-noble metal Al on the surface of a TiO2/Cu2O core/shell heterojunction for the first time.The Al nanoparticles,which exhibit a surface plasmon resonance(SPR)effect and are substantially less expensive than noble metals such as Au and Ag,generate hot electron-hole pairs and amplify the electromagnetic field at the interface under illumination.The as-prepared TiO2/Cu2O/Al/Al2O3 photoelectrodes have an extended absorption range and enhanced carrier separation and transfer.Their photocurrent density of 4.52 mA·cm^-2 at 1.23 V vs.RHE represents an 1.84-fold improvement over that of TiO2/Cu2O.Specifically,the ultrathin Al2O3 passivation layer spontaneously generated on the surface of Al in air could act as a protective layer to significantly increase its stability.In this work,the synergistic effect of the heterojunctions and the SPR effect of the non-noble metal Al significantly improve the photoelectrode performance,providing a novel concept for the design of electrodes with good properties and high practicability.

Microwave-assisted hydrothermal synthesis of cube-like Ag-Ag_2MoO_4 with visible-light photocatalytic activity

Cube-like Ag-Ag2MoO4 composite has been successfully prepared in the presence of PVP （potyvinylpyrrolidone） via a facile microwave-assisted hydrothermal process. Studies of its photocatalytic performance in the decomposition of RhB indicate that the cube-like Ag-Ag2MoO4 composite exhibits good catalytic activities under visible-light irradiation. The face that Ag pro- motes the absorption of visible light may be attributed to the surface plasmon resonance. Further XRD characterization after recycle photocatalytic tests confirms that partial Ag~ ions in Ag2MoO4 have been reduced to metallic Ag. Reaction temperature, reaction time and the amount of PVP have also been studied and found to play crucial roles in the formation of the cube-like microstructures.

Synthesis of novel CaCO_3/Ag_2CO_3/Ag I/Ag plasmonic photocatalyst with enhanced visible light photocatalytic activity.

In this work, novel CaCO3/Ag2CO3/AgI/Ag plasmonic photocatalysts were successfully synthesized by a two-step in situ ion exchange process and their photocatalytic properties were studied. The morphology, crystal structure and optical properties of the as-prepared CaCO3/Ag2CO3/AgI/Ag nanocomposites were characterized by transmission electron microscopy （TEM）, X- Ray diffraction （XRD）, and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the obtained nanocomposites was evaluated by the photodegradation of methyl orange （MO） under visible light irradiation. It was found that the as-prepared CaCO3/Ag2CO3/AgI/Ag plasmonic photocatalyst exhibits high visible light photocatalytic activity. With an optimized composition, MO dye can be decomposed by more than 94% within 15 min under visible light irradiation. Moreover, the photocatalytic stability could be greatly improved upon the addition of Na2CO3 into the photocatalytic system. From the proposed photocatalytic mechanism, the strong surface plasmon resonance effect of Ag nanoparticles and the efficient separation of photogenerated electrons and holes can effectively enhance the photocatalytic performance of the CaCO3/Ag2COj AgI/Ag composites.