Detection of intermediates in the TiO_2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.

Roughness Control of Layer-by-Layer and Alternative Spray Films from Congo Red and PAH via Laser Light Irradiation

Films from congo red (CR) alternated with poly(allylamine hydrochloride), PAH, were prepared by layer-by-layer and alternative spray techniques. In order to investigate the change of roughness induced by laser light irradiation (532 nm), both kinds of films were characterized by using UV-visible spectroscopy and atomic force microscopy (AFM). At dif- ferent irradiation times, layer-by-layer, LbL, films showed small changes in the roughness and irregular behavior, whereas spray films exhibited higher and a regular decreasing of roughness with increasing irradiation time. The higher roughness of spray films as compared with the LbL ones was attributed to different formation mechanisms of the films. The decreasing of the roughness as a function of the irradiation time (exhibited by the spray films) was associated to surface relaxation due to the interplay between photoisomerization of congo red dye and the heating of the sample during the laser light irradiation. The results suggested that the alternative spray technique is the best choose to control of roughness of the films by using light irradiation.

Enhanced pitting corrosion resistance of a Zr-based metallic glass by ultraviolet light irradiation

The influence of ultraviolet light irradiation on the pitting corrosion performance of a Zr_(2)Ni metallic glass was examined using electrochemical methods and immersion test in 0.05 mol/L NaCl solution.From the results of potentiostatic polarization,the pitting potential of the ultraviolet light-irradiated sample shifted positively with a value of~300 mV,revealing the enhanced pitting corrosion resistance of the samples.The corrosion morphology after the immersion test also demonstrated lower degree of corrosion damage and improved pitting resistance of the sample with ultraviolet light irradiation.X-ray photoelectron spectroscopy analysis revealed more zirconium enrichment in the passive film and no chloride ions adsorption for the samples with ultraviolet irradiation,accounting for the suppression of the pit generation and growth.Our findings indicate that ultraviolet light irradiation improves the pitting corrosion resistance of the Zr-based metallic glasses,which are promising structural materials to be used in corrosion environments with high ultraviolet irradiation.

Embedding ultrasmall Ag nanoclusters in Luria-Bertani extract via light irradiation for enhanced antibacterial activity

Ultrasmall silver nanoclusters(Ag NCs)with rich surface chemistry and good biocompatibility are promising in antibacterial application,however,further development of Ag NCs for practical settings has been constrained by their relatively weak antibacterial activity.Using the nutritionally-rich medium for bacteria(e.g.,Luria-Bertani(LB)medium)to coat active Ag NCs could further improve their antibacterial activity.Here,we provide a delicate design of a highly efficient Ag NCs@ELB antibacterial agent(ELB denotes the extract of LB medium)by anchoring Ag NCs inside the ELB species via light irradiation.The as-designed Ag NCs with bacterium-favored nutrients on the surface can be easily swallowed by the bacteria,boosting the production of the intracellular reactive oxygen species(ROS,about 2-fold of that in the pristine Ag NCs).Subsequently,a higher concentration of ROS generated in Ag NCs@ELB leads to enhanced antibacterial activity,and enables to reduce the colony forming units(CFU)of both gram-positive and gram-negative bacteria with 3–4 orders of magnitude less than that treated with the pristine Ag NCs.In addition,the Ag NCs@ELB also shows good biocompatibility.This study suggests that surface engineering of active species(e.g.,Ag NCs)with nutritionally-rich medium of the bacteria is an efficient way to improve their antibacterial activity.

Nonylphenol photodegradation by novel ternary MIL-100(Fe)/ZnFe_(2)O_(4)/PCN composite under visible light irradiation via double charge transfer process

Nonylphenol(NP)residues,as a typical endocrine disrupting chemical(EDC),frequently exist in sewage,surface water,groundwater and even drinking water,which poses a serious threat to human health due to its bioaccumulation.In order to remove NP,a series of MIL-100(Fe)/Zn Fe_(2)O_(4)/flake-like porous carbon nitride(MIL/ZC)was synthesized through in-situ synthesis at room temperature.High performance of ternary MIL/ZC is used to degrade NP under visible light irradiation.The results show that 30MIL/ZC2(20 wt.%Zn Fe_(2)O_(4))ternary composite had the best photocatalytic activity(99.84%)when the dosage was 30 mg.Further mechanism analysis shows that the excellent photocatalytic activity of 30MIL/ZC2could be ascribed to the double charge transfer process between flake-like porous carbon nitride(PCN)and other catalysts in the ternary heterojunction,and the separation of photogenerated electron-hole pairs was more effective.In addition,the 30MIL/ZC2 also showed high stability after five cycles of the photodegradation reaction.Furthermore,the active substance(·O_(2)^(-))was considered to be the main active substance in the NP degradation process.Based on the research results,the possible photocatalytic reaction mechanism of 30MIL/ZC2ternary composite was proposed and discussed in detail.

Visible light-driven oxidant-free dehydrogenation of alcohols in water using porous ultrathin g-C_(3)N_(4)nanosheets

Graphitic carbon nitride(g-C_(3)N_(4)) is a fascinating photocatalyst for solar energy utilization in photo-catalysis.Nevertheless,it often suffers from moderate photo-catalytic activity due to its low specific surface area and fast recombination rate of photogenerated electrons upon photo-excitation.Herein,we overcome the bottlenecks by constructing a porous g-C_(3)N_(4) nanosheet(PCNS)through a simple thermal oxidation etching method.Benefited from its porous layer structure,the obtained PCNS exhibits large specific surface area,efficient separation of photogenerated charge carriers,as well as high exposure of active sites.As a result,it is robust and universal in visible light-driven dehydrogenation of alcohols in water under oxidant-free condition.Almost quantitative yields(>99%)of various valuable carbonyl compounds were obtained over PCNS,while bulk g-C_(3)N_(4) was far less efficient.Moreover,the photo-catalyst was highly stable and could be facilely recovered from the aqueous system for efficient reuse.The easy preparation and excellent performance made PCNS a promising and competitive photocatalyst for the solar applications.

ELECTROCHEMISTRY OF POLYANILINE UNDER LIGHT

The electrochemistry of polyaniline synthesized electrochemically in acidic solution under light irradiation has been studied as a function of the applied potentials, the concentration and acidity of electrolyte as well as pH at applied potentials in the rang+0.40 to-0.5V vs. SCE. It is concluded that under selected experimental conditions the reduced repeat groups in polyaniline are oxidized by air in the dark and that this oxidation process can be strongly photocatalyzed.

2,5-Diformylfuran production by photocatalytic selective oxidation of 5-hydroxymethylfurfural in water using MoS_(2)/CdIn_(2)S_(4) flower-like heterojunctions

The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.

Effect of pH Values on Photocatalytic Properties of Bi_2WO_6 Synthesized by Hydrothermal Method

Highly crystalline orthorhombic Bi2WO6 powders were hydrothermally synthesized from aqueous solutions of Na2WO4 · 2H2O and Bi （NO3）3 · 5H2O over a wide range of pH. The effect of pH on morphologies, sizes and properties of the Bi2WO6 crystals was investigated. The band gaps of the as-prepared Bi2WO6 were determined from the onset of the absorption edge of UV-vis diffuse reflectance spectra. The methyl orange photodegradation was employed as a probe reaction to test the photocatalytic activity of the as-prepared samples under visible light irradiation. The photocatalytic activities of methyl orange degradation under visible light irradiation are strongly dependent on the pH used in the synthesis. The highest efficiency is observed at pH=7.

Facile Synthesis of Gold Nanoplates by Citrate Reduction of AuCl_(4)^(-) at Room Temperature

Single-crystalline, regular-edged gold nanoplates are synthesized through chemical reduction of AuCl4^- by a suitable amount of citrate at room temperature, without additional capping agents or surfactants. The suitable molar ratio of sodium citrate to HAuCl4, low reaction temperature and the presence of natural light are critical factors for the formation of the regularly shaped nanoplates.

Calculation of the Average Irradiance and the Microalgae Growth for a Year at CUET, Bangladesh

The light is one of the important factors for the microalgae growth in the biofuel technology. As biofuel project is large and expensive thus before setting a microalgae based biofuel project in any geographical location, it is important to investigate the suitability of all important parameters involving with the system. This paper aims to investigate the sunlight availability and the microalgae growth for a photobioreactor at Chittagong University of Engineering and Technology (CUET). A computational growth model related to the average irradiance is proposed to calculate the growth of microalgae. We observed that average irradiance is the highest in June and is the lowest in December. From our simulation it is found that the growth of microalgae varies with the average irradiance in a year.

A time-dependent luminescent phosphor of Na_(2)Ba_(2)Si_(2)O_(7):Eu for multi-level encryption and dynamic information display

Photo-stimuli responsive materials show great potential in the fields of information encryption and storage due to their distinctive spatial or temporal color changes.However,the conventional single or multi-color static outputs by light stimulus difficulty meet practical requirements for high-security optical storage technologies.Here,a novel dynamic irradiation-responsive phosphor of Na_(2)Ba_(2)Si_(2)O_(7):Eu is demonstrated,exhibiting high storage stability and convenient readout behaviors.The inherent Eu^(2+)luminescence can be dynamically tuned,instantly read out,and conveniently erased by controlling irradiation duration of a portable diode laser(365 nm).The modulation mechanism is unraveled by optically induced oxidation reactions of Eu^(2+)→Eu^(3+)and defects as killer centers.The excellent luminescence modulation degree(ΔR_(t)=89.5%)and the accompanying larger color contrast enable the creation of invisible optical codes with multi-level encryption in bright or dark field.These results indicate potential applications of Na_(2)Ba_(2)Si_(2)O_(7):-based materials in information encryption and invisible optical storage,and are expected to expand more investigations on optically induced PL modulation behaviors based on mixed valences and defects.

Visible light response ZnO-C_(3)N_(4) thin film photocatalyst

Nanoflower-like ZnO-C_(3)N_(4) thin film with a porous net structure was successfully synthesized by a simple chemical corrosion method.The prepared ZnOC_(3)N_(4) thin films presented remarkable photocatalytic activities for the degradation of methyl orange under visible light irradiation,and more than 90%methyl orange was removed from water by ZnO-C_(3)N_(4) composite.Meanwhile,the ZnO-C_(3)N_(4) composite presented an enhanced photocatalytic stability.The loading content of C_(3)N_(4) had a great effect on the photocatalytic performance.Moreover,the photocatalytic activities were higher in acidic media than those in alkaline conditions.The adsorption of methyl orange was enhanced,and the recombination of photogenerated electrons and holes was suppressed with a suitable content of C_(3)N_(4).However,too much loading content of C_(3)N_(4) resulted in a poor dispersion of C_(3)N_(4) as the aggregated C_(3)N_(4) can behave as recombination centers.In addition,the prepared ZnO-C_(3)N_(4) thin film can be used for the water splitting in water-methanol system under simulated solar light irradiation.

Degradation of Reactive Yellow 86 with photo-Fenton process driven by solar light

The decolorization of Reactive Yellow 86 （RY 86）, one of reactive azo dyes, was investigated in the presence of Fenton reagent under solar light irradiation. The decolorization rate was strongly influenced by pH, initial concentrations of H202 and Fe（II）, and so on. An initial concentration of 40 mg/L was decolored more than 90% after 20 min under optimum conditions. The activation energy of the solar photo-Fenton reaction was 1.50 kJ/mol for RY 86 in the temperature range of 10-60℃. In the kinetic study, the rate constant of RY 86 with OH- radicals could be estimated to be 1.7 × 10^10 L/（mol.sec）. The decolorization efficiency of RY 86 under solar light irradiation was comparable to the artificial light irradiation. The decrease of TOC as a result of mineralization of RY 86 was observed during photo-Fenton process. The rate of RY 86 mineralization was about 83% under UV irradiation after 24 hr. The formation of chloride, sulfate, nitrate and ammonium ions as end-products was observed during the photocatalytic process. The decomposition of RY 86 gave two kinds of intermediate products. The degradation mechanism of RY 86 was proposed on the base of the identified intermediates.

High efficiency visible-light-driven Fe_2O_3-xS_x/S-doped g-C_3N_4 heterojunction photocatalysts: Direct Z-scheme mechanism

Several nanoporous Fe2 O3-xSx/S-doped g-C3 N4（CNS） Z-scheme hybrid heterojuctions have been successfully synthesized by one-pot in situ growth of the Fe2O3-xSx particles on the surface of CNS. The characterization results show that S-doping in the g-C3 N4 backbone can greatly enhance the charge mobility and visible light harvesting capability. In addition, porous morphology of hybrid composite provides available open pores for guest molecules and also improves light absorbing property due to existence of multiple scattering effects. More importantly, the Fe2 O3-xSx nanoparticles formed intimate heterojunction with CNS and developed the efficient charge transfer by extending interfacial interactions occurred at the interfaces of both components. It has been found that the Fe2 O3-xSx/CNS composites have an enhanced photocatalytic activity under visible light irradiation compared with isolated Fe2 O3 and CNS components toward the photocatalytic degradation of methylene blue（MB）. The optimal loaded Fe2 O3-xSx value obtained is equal to 6.6 wt% that provided 82% MB photodegradation after 150 min with a reaction rate constant of 0.0092 min（-1） which was faster than those of the pure Fe2 O3（0.0016 min（-1））and CNS（0.0044 min（-1）） under the optimized operating variables acquired by the response surface methodology. The specific surface area and the pore volume of Fe2 O3（6.6）/CNS hybrid are 33.5 m2/g and0.195 cm3/g, which are nearly 3.8 and 7.5 times greater compared with those of the CNS, respectively. The TEM image of Fe2 O3（6.6）/CNS nanocomposite exhibits a nanoporous morphology with abundant uniform pore sizes of around 25 nm. Using the Mott-Schottky plot, the conduction and valence bands of the CNS are measured（at pH = 7） equal to-1.07 and 1.48 V versus normal hydrogen electrode（NHE）, respectively.Trapping tests prove that ·OH-and ·O2-radicals are major active species in the photocatalytic reaction.It has been established that formation of the Z-scheme Fe2 O3（6.6）/CNS heterojunction between CNS and Fe2 O3 directly produces ·OH as well as ·O2-radicals which is consistent with the results obtained from trapping experiments.

Light-induced variation in environmentally persistent free radicals and the generation of reactive radical species in humic substances

Environmentally persistent free radicals(EPFRs)in humic substances play an essential role in soil geochemical processes.Light is known to induce EPFRs formation for dissolved organic matter in aquatic environments;however,the impacts of light irradiation on the variation of EPFRs in soil humic substances remain unclear.In this study,humic acid,fulvic acid,and humin were extracted from peat soil and then in situ irradiated using simulated sunlight.Electron paramagnetic resonance spectroscopy results showed that with the increasing irradiation time,the spin densities and g-factors of humic substances rapidly increased during the initial 20 min and then gradually reached a plateau.After irradiation for 2h,the maximum spin density levels were up to 1.63×10^17,2.06×10^17,and 1.77×10^×10^17 spins/g for the humic acid,fulvic acid,and humin,respectively.And the superoxide radicals increased to 1.05×10^l4-1.46×10^14spins/g while the alkyl radicals increased to 0.47×10^14-1.76×10^14 spins/g.The light-induced EPFRs were relatively unstable and readily returned back to their original state under dark and oxic conditions.Significant positive correlations were observed between the concentrations of EPFRs and reactive radical species(R2=0.65-0.98,/?<0.05),which suggested that the newly produced EPFRs contributed to the formation of reactive radical species.Our findings indicate that under the irradiation humic substances are likely to be more toxic and reactive in soil due to the formation of EPFRs.

Facile synthesis and enhanced visible-light photocatalytic activity of Ti3 ＋-doped Ti02 sheets with tunable phase composition

Ti3＋-doped TiO2 nanosheets with tunable phase composition （doped TiO2 （A/R）） were synthesized via a hydrothermal method with high surface area anatase TiO2 nanosheets TiO2 （A） as a substrate, structure directing agent, and inhibitor; the activity was evaluated using a probe reaction-photocatalytic CO2 conversion to methane under visible light irradiation with H2 as an electron donor and hydrogen source. High-resolution transmission electron microscope （HRTEM）, field emission scanning electron microscope, UV-Vis diffuse reflectance spectra, and X-ray diffraction （XRD） etc., were used to characterize the photocatalysts. XRD and HRTEM measurements confirmed the existence of anatase-rutile phase junction, while Ti3-and single-electron-trapped oxygen vacancy in the doped TiO2 （A/R） photocatalyst were revealed byelectron paramagnetic resonance （EPR） measurements. Effects of hydrothermal synthesis temperature and the amount of added anatase TiO2 on the photocatalytic activity were elucidated. Significantly enhanced photo- catalytic activity of doped TiO2 （A/R） was observed; under the optimized synthesis conditions, CH4 generation rate of doped TiO2 （A/R） was 2.3 times that of Ti3＋-doped rutile TiO2.

Metal-Free-Mediated Oxidation Aromatization of 1,4-Dihydropyridines to Pyridines Using Visible Light and Air

A metal-free and environmentally friendly aerobic aromatization photosensitized by organic dye eosin Y bis(tetrabutyl ammonium salt)(TBA-eosinY)has been developed.With the aid of K_(2)CO_(3),the aerobic catalytic system converts 1,4-dihydropyridines to their corresponding pyridine derivatives efficiently under visible light irradiation(λ=450 nm)at room temperature.

Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2

In the present study, the decomposition rates of carbon tetrachloride （CC14） and 2,4-dichlorophenol （2,4- DCP） in water by the ultraviolet （UV） light irradiation alone and H2O2AYV were experimentally investigated. The detailed experimental studies have been conducted for examining treatment capacities of the two different ultraviolet light sources （low and medium pressure Hg arc） in H2O2/UV processes. The low or medium UV lamp alone resulted in a 60%-90% decomposition of 2,4-DCP while a slight addition of H2O2 resulted in a drastic enhancement of the 2,4-DCP decomposition rate. The decomposition rate of 2,4-DCP with the medium pressure UV lamp alone was about 3-6 times greater than the low pressure UV lamp alone. In the direct photolysis of aqueous CC14, the medium pressure UV lamp had advantage over the low pressure UV lamp because the molar extinction coefficient of CC14 at shorter wavelength （210-220 nm） is about 20 to 50 times higher than that at 254 nm. However, adding H202 to the medium pressure UV lamp system rendered a negative oxidation rate because H202 acted as a UV absorber being competitive with CC14 due to negligible reaction between CC14 and OH radicals. The results fi：om the present study indicated significant influence of the photochemical properties of the target contaminants on the photochemical treatment characteristics for designing cost-effective UV-based degradation of toxic contaminants.

Synthesis and characterization of Gd-doped PbMoO_(4) nanoparticles used for UV-light-driven photocatalysis

Gd-doped PbMoO_(4) nanoparticles were prepared by a refluxing method at 80℃ for 2 h.Effect of molar content of Gd dopant on phase,morphology and optical properties was studied.The as-prepared Gddoped PbMoO_(4) samples can be indexed to pure tetragonal PbMoO_(4) phase.The particles size of PbMoO_(4) is decreased with increasing in the molar content of Gd dopant from 15.20±3.04 nm for pure PbMoO_(4) to 8.72±1.53 nm for 5 mol% Gd-doped PbMoO_(4).The absorption of 5 mol% Gd-doped PbMoO_(4) nanoparticles shows red-shift caused by lattice distortion of PbMoO_(4).The photocatalytic performance of 5 mol% Gddoped PbMoO_(4) nanoparticles shows the highest degradation of rhodamine B(RhB) of 97.92% under UV radiation and 67.65% under visible radiation because Gd^(3+) dopant as an electron acceptor plays the role in enhancing the separation of electron-hole pair.