Photocatalytic degradation of tetracycline hydrochloride with visible light-responsive bismuth tungstate/conjugated microporous polymer

Conjugated microporous polymer(CMP)is an emerging organic semiconductor withπ-conjugated skeletons,and the bandgap of CMP can be flexibly modulated to harvest visible light.Based on the diversity and adjustability of monomers in CMP,we designed and synthesized donor-accepter(D-A)type BTNCMP through Sonogashira-Hagihara cross-coupling polymerization,further in-situ constructing series of inorganic/organic Z-scheme BW/BTN-n composite in the presence of Bi_(2)WO_(6).After optimization,the tetracycline hydrochloride(C0=10 mg·L^(-1))degradation efficiency reached 84%with BW/BTN-2 as catalyst in 90 min under visible light irradiation,the apparent rate constant k1 is 0.017 min^(-1),which is 1.7 and 5.7 times higher than bare Bi_(2)WO_(6) and BTN-CMP.X-ray photoelectron spectra and UV-Vis diffuse spectra showed that the enhanced photocatalytic activity originated from the tight heterojunction between Bi_(2)WO_(6) and BTN-CMP,which can extend the light absorption range and facilitate the separation and transport of photogenerated charges in the interface of heterojunction.The active species trapping experiments and electron spin resonance technique revealed that h+was the dominant active species during the photodegradation process of tetracycline hydrochloride(TCH).The present study demonstrated the feasibility to construct inorganic/organic composite for the photocatalytic degradation of environmental pollutants.

The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO_(2) thin film

The effects of radio frequency(RF)atmospheric pressure(AP)He/H_(2)plasma and thermal treatment on the hydrogenation of TiO_(2)thin films were investigated and compared in this work.The color of the original TiO_(2)film changes from white to black after being hydrogenated in He/H_(2)plasma at160 W(gas temperature~381℃)within 5 min,while the color of the thermally treated TiO_(2)film did not change significantly even in pure H_(2)or He/H_(2)atmosphere with higher temperature(470℃)and longer time(30 min).This indicated that a more effective hydrogenation reaction happened through RF AP He/H_(2)plasma treatment than through pure H_(2)or He/H_(2)thermal treatment.The color change of TiO_(2)film was measured based on the Commission Internationale d’Eclairage L*a*b*color space system.Hydrogenated TiO_(2)film displayed improved visible light absorption with increased plasma power.The morphology of the cauliflower-like nanoparticles of the TiO_(2)film surface remained unchanged after plasma processing.X-ray photoelectron spectroscopy results showed that the contents of Ti3+species and Ti-OH bonds in the plasma-hydrogenated black TiO_(2)increased compared with those in the thermally treated TiO_(2).X-ray diffraction(XRD)patterns and Raman spectra indicated that plasma would destroy the crystal structure of the TiO_(2)surface layer,while thermal annealing would increase the overall crystallinity.The different trends of XRD and Raman spectra results suggested that plasma modification on the TiO_(2)surface layer is more drastic than on its inner layer,which was also consistent with transmission electron microscopy results.Optical emission spectra results suggest that numerous active species were generated during RF AP He/H_(2)plasma processing,while there were no peaks detected from thermal processing.A possible mechanism for the TiO_(2)hydrogenation process by plasma has been proposed.Numerous active species were generated in the bulk plasma region,accelerated in the sheath region,and bumped toward the TiO_(2)film,which will react with the TiO_(2)surface to form OVs and disordered layers.This leads to the tailoring of the band gap of black TiO_(2)and causes its light absorption to extend into the visible region.

Template-free large-scale synthesis of g-C3N4 microtubes for enhanced visible light-driven photocatalytic H2 production

A template-free hydrothermal-assisted thermal polymerization method has been developed for the large-scale synthesis of one-dimensional （1D） graphitic carbon nitride （g-C3N4） microtubes. The g-C3N4 microtubes were obtained by simple thermal polymerization of melamine-cyanuric acid complex microrods under N2 atmosphere, which were synthesized by hydrothermal treatment of melamine solution at 180℃ for 24 h. The as-obtained g-C3N4 microtubes exhibited a large surface area and a unique one-dimensional tubular structure, which provided abundant active sites for proton reduction and also facilitated the electron transfer processes. As such, the g-C3N4 microtubes showed enhanced photocatalytic H2 production activity in lactic acid aqueous solutions under visible light irradiation （A 〉 420 nm）, which was - 3.1 times higher than that of bulk g-C3N4 prepared by direct thermal polymerization of the melamine precursor under the same calcination conditions.

Visible Light and Temperature Regulated Reflection Colors in Self-supporting Cholesteric Liquid Crystal Physical Gels

Photo-responsive cholesteric liquid crystals(CLCs)have attracted much attention in recent years due to their wide applications in filters,tun able optical lasers,dyn amic display devices,etc.However,UV light is usually used as the exter nal stimulus source,which is not envir on ment-frie ndly enough.On the other hand,the mecha nical properties of CLCs are not strong eno ugh for these practical applications.Therefore,it still remains a challenge to endow the CLCs with visible light response and high mechanical properties at the same time.Herein,an axially chiral tetra-fluorinated binaphthyl azobenzene gelator(S-4F-AG)is synthesized.Upon 550 and 450 nm light irradiations,S-4F-AG exhibits excellent photo-switchable behaviors.Notably,the maximum con tent of c/s-isomer and its half-life are as high as 35%and 89 h in acet on itrile,respectively.A self-supporting CLC physical gel with a storage modulus around 104 Pa can be obtained when 3wt%S-4F-AG and 12wt%binaphthyl azobenzene derivative(dopant 2)are co-doped into a nematic LC host P0616A.This CLC physical gel exhibits a temperature-driven blue,green,and red reflection colors reversibly.Importantly,such three primary RGB colors can also be realized by adjusting the exposure time of 550 nm green light.This work lays a solid foundation for the applications ranging from information storage to high-tech anticounterfeit.

In situ preparation of visible-light-driven carbon quantum dots/NaBiO3 hybrid materials for the photoreduction of Cr(Ⅵ)

In this study,different carbon quantum dots(CQDs)/NaBiO3 hybrid materials were synthesized as photocatalysts to effectively utilize visible light for the photocatalytic degradation of contaminants effectively.These hybrid materials exhibit an enhanced photocatalytic reduction of hexavalent chromium(Cr(Ⅵ))in the aqueous medium.Zero-dimensional nanoparticles of CQDs were embedded within the two-dimensional NaBiO3 nanosheets by the hydrothermal process.Compared with that of the pure NaBiO3 nanosheets,the photocatalytic performance of the hybrid catalysts was significantly high and 6 wt.%CQDs/NaBiO3 catalyst exhibited better photocatalytic performance.We performed the first-principles density functional theory calculations to study the interfacial properties of pure NaBiO3 nanosheets and hybrid photocatalysts,and confirmed the CQDs played an important role in the CQDs/NaBiO3 composites.The experimental results indicated that the enhanced reduction of Cr(Ⅵ)was probably due to the high loading of CQDs(electron acceptor)on NaBiO3,which made NaBiO3 nanomaterials to respond in visible light and significantly improved their electron-hole separation efficiency.

Visible light responsive photocatalysts developed by substitution with metal cations aiming at artificial photosynthesis

To solve resource,energy,and environmental issues,development of sustainable clean energy system is strongly required.In recent years,hydrogen has been paid much attention to as a clean energy.Solar hydrogen production by water splitting using a photocatalyst as artificial photosynthesis is a promising method to solve these issues.Efficient utilization of visible light comprised of solar light is essential for practical use.Three strategies,i.e.,doping,control of valence band,and formation of solid solution are often utilized as the useful methods to develop visible light responsive photocatalysts.This minireview introduces the recent work on visible-light-driven photocatalysts developed by substitution with metal cations of those strategies.

Charge transfer between biogenic jarosite derived Fe^3＋ and TiO2 enhances visible light photocatalytic activity of TiO2

In this work, we have shown that mining waste derived Fe^3＋can be used to enhance the photocatalytic activity of TiO2. This will allow us to harness a waste product from the mines, and utilize it to enhance TiO2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO2 and biogenic jarosite. Evidence of Fe／O／Ti bonding in the TiO2/jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO2, biogenic jarosite and mechanically mixed sample of jarosite and TiO2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO2 and jarosite derived Fe^3＋as was shown from the EELS and ELNEFS. Generation of OHU was supported by photoluminesence（PL） experiments.