Selective photocatalytic aerobic oxidative cleavage of lignin C–O bonds over sodium lignosulfonate modified Fe_(3)O_(4)/TiO_(2)

Lignocellulose shows significantly potential in sustainable conversion to high-quality fuel and valueadded chemicals with the demands for realizing the rapid cycle of carbon resources and helping to reach carbon neutrality in nature.Selective tailoring of α-O-4,β-O-4,etc.linkages in lignin has always been viewed as "death blow" for its depolymerization.Herein,novel sodium lignosulfonate(SL) modified Fe_(3)O_(4)/TiO_(2)(SL-Fe_(3)O_(4)/TiO_(2)) spherical particles have been developed and used as catalysts for selectively photocatalytic oxidative cleavage of organosolv lignin.As expected,80% selective conversion of lignin in C2-C4 esters has been achieved,while C-O bonds in lignin model compounds can be effectively cleaved.Other than normal hydroxyl radical-mediated photocatalytic depolymerization of lignin over TiO_(2)-based materials,in this contribution,mechanism studies indicate that photogenerated holes and superoxide anion radicals are main active species,which trigger the cleavage of α/β-O-4 bond,and the isotopelabeling study confirms the crucial factor of C_β-H dehydrogenation in cleavage of β-O-4 bonds.

Introducing oxygen vacancies in TiO_(2) lattice through trivalent iron to enhance the photocatalytic removal of indoor NO

The synthesis of oxygen vacancies(OVs)-modified TiO_(2)under mild conditions is attractive.In this work,OVs were easily introduced in TiO_(2)lattice during the hydrothermal doping process of trivalent iron ions.Theoretical calculations based on a novel charge-compensation structure model were employed with experimental methods to reveal the intrinsic photocatalytic mechanism of Fe-doped TiO_(2)(Fe-TiO_(2)).The OVs formation energy in Fe-TiO_(2)(1.12 eV)was only 23.6%of that in TiO_(2)(4.74 eV),explaining why Fe^(3+)doping could introduce OVs in the TiO_(2)lattice.The calculation results also indicated that impurity states introduced by Fe^(3+)and OVs enhanced the light absorption activity of TiO_(2).Additionally,charge carrier transport was investigated through the carrier lifetime and relative mass.The carrier lifetime of Fe-TiO_(2)(4.00,4.10,and 3.34 ns for 1at%,2at%,and 3at%doping contents,respectively)was longer than that of undoped TiO_(2)(3.22 ns),indicating that Fe^(3+) and OVs could promote charge carrier separation,which can be attributed to the larger relative effective mass of electrons and holes.Herein,Fe-TiO_(2)has higher photocatalytic indoor NO removal activity compared with other photocatalysts because it has strong light absorption activity and high carrier separation efficiency.

Synergetic effect between non-thermal plasma and photocatalytic oxidation on the degradation of gas-phase toluene: Role of ozone

In this study, a hybrid process using non‐thermal plasma (NTP) and photocatalytic oxidation (PCO) was adopted for the degradation of gas‐phase toluene using TiO2 as the photocatalyst. To discover the synergetic effect between NTP and PCO, the performances of both sole (O3, UV, NTP, and PCO) and combined (O3 + TiO2, O3 + UV, NTP + UV, O3 + PCO, and NTP + PCO) processes were investigated from different perspectives, such as the toluene removal efficiency, selectivity of COx, mineralization rate, ozone utilization, and the generation of by‐products. The toluene removal efficiency of the combined NTP + PCO process was 80.2%, which was much higher than that of a sole degradation process such as NTP (18.8%) and PCO (13.4%). The selectivity of CO2 and the ozone utilization efficiency also significantly improved. The amount of by‐products in the gas phase and the carbon‐ based intermediates adsorbed on the catalyst surface dramatically reduced. The improvement in the overall performances of the combined NTP + PCO process was mainly ascribed to the efficient utilization of ozone in the photocatalytic oxidation, and the ozone further acting as an electron acceptor and scavenger, generating more hydroxyl radicals and reducing the recombination of electron‐ hole pairs.

S-scheme Sb2WO6/g-C3N4 photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance

Normal photocatalysts cannot effectively remove low-concentration NO because of the high recombination rate of the photogenerated carriers.To overcome this problem,S-scheme composites have been developed to fabricate photocatalysts.Herein,a novel S-scheme Sb2WO6/g-C3N4 nanocomposite was fabricated by an ultrasound-assisted method,which exhibited excellent performance for photocatalytic ppb-level NO removal.Compared with the pure constituents of the nanocomposite,the as-prepared 15%-Sb2WO6/g-C3N4 photocatalyst could remove more than 68%continuous-flowing NO(initial concentration:400 ppb)under visible-light irradiation in 30 min.The findings of the trapping experiments confirmed that•O2^–and h+were the important active species in the NO oxidation reaction.Meanwhile,the transient photocurrent response and PL spectroscopy analyses proved that the unique S-scheme structure of the samples could enhance the charge separation efficiency.In situ DRIFTS revealed that the photocatalytic reaction pathway of NO removal over the Sb2WO6/g-C3N4 nanocomposite occurred via an oxygen-induced route.The present work proposes a new concept for fabricating efficient photocatalysts for photocatalytic ppb-level NO oxidation and provides deeper insights into the mechanism of photocatalytic NO oxidation.

Solvothermal fabrication of Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies and excellent photocatalytic oxidation performance in quinoline production and antibiotics degradation

Novel Bi_(2)MoO_(6) nanocrystals with tunable oxygen vacancies have been developed via a facile low-cost approach with the assistance of a glyoxal reductant under solvothermal conditions.With the introduction of oxygen vacancies,the optical absorption of Bi_(2)MoO_(6) is extended and its bandgap narrowed.Oxygen vacancies not only lead to the appearance of a defect band level in the forbidden band but can also result in a minor up-shift of the valence band maximum,promoting the mobility of photogenerated holes.Moreover,oxygen vacancies can act as electron acceptors,temporarily capturing electrons excited by light and reducing the recombination of electrons and holes.At the same time,oxygen vacancies help to capture oxygen,which reacts with the captured photogenerated electrons to generate more superoxide radicals(·O_(2)-)to participate in the reaction,thereby significantly promoting the redox performance of the photocatalyst.From Bi_(2)MoO_(6) containing these oxygen vacancies(OVBMO),excellent photocatalytic performance has been obtained for the oxidation of 1,2,3,4-tetrahydroquinoline to produce quinoline and cause antibiotic degradation.The reaction mechanism of the oxidation of 1,2,3,4-tetrahydroquinoline to quinoline over the OVBMO materials is elucidated in terms of heterogeneous Catal.via a radical pathway.

Photocatalytic Oxidation Kinetics of Thiophene with Nano-F^-/Fe^(3+)/TiO_2

Photocatalytic oxidation kinetics of thiophene in n-octane/water extraction system was studied with fluorine and ferric ion codoped nano-TiO_2(nano-F^-/Fe^(3+)/TiO_2) powders used as the photocatalyst.Effects of initial concentration of thiophene and additional dosage of F^-/Fe^(3+)/TiO_2 on the reaction rate constant and half-life were investigated.The results showed that the appropriately added dosage of F^-/Fe^(3+)/TiO_2 was 0.1 g in the 100-mL reaction system and the photooxidative kinetics of thiophene in the presence of F^-/Fe^(3+)/TiO_2 catalyst was of first-order with a rate constant of 0.6508 h^(-1) and a half-life of 1.0651 h.The desulfurization rate of thiophene was 98.1%in 5 h and the sulfur content could be reduced from 800 ppm to 15 ppm.The reaction rate constant increased with a decreasing initial concentration of thiophene.

Photocatalytic Oxidation of NO_ x with Porous TiO_2 Nanometer Thin Film

A new kind of porous nano-'IiO_2 composite films was prepared on the glasssubstrate with the water glass as binders and the sodium fluorosilicate as solidifying reagent. Themorphologies of the films were studied by scanning electron microscope(SEM).The UV-Visspcctiophotometer was also used to investigate the absorption of the films. The gas-phasephotocatalytic oxidation of nitrogen oxides on the composite film was carried out in Ti0_2/UVsystem, and some important factors affecting the photocatalytic oxidation were also studied such asthe catalyst concentration, vapor pressure and the presence of oxygen. The results showed theconversion of NO_x reached 97.5% alter 2 h UV-irradiation. The final product of photo-oxidation wasdetected to be HNO_3 by FT-IR. The way of photocatalytic oxidation of NO_x was possibly useful inthe practical application.

Advanced Treatment of Biologically Treated Chemical Comprehensive Wastewater by Nano-TiO2 Photocatalytic Oxidation

Nano-TiO2 photocatalytic oxidation was used to perform the advanced treatment of biologically treated chemical comprehensive wastewater. The effects of reaction time,nano-TiO2 dosage and initial p H of the wastewater on the removal rate of COD were tested. The GC/MS and EEM techniques were used to qualitatively analyze organic compounds in the wastewater before and after treatment. The result showed that after the biologically treated chemical comprehensive wastewater was treated by nano-TiO2 photocatalytic oxidation under the conditions of reaction time 3 h,nano-TiO2 dosage 8 g/L,and pH 8. 0,the effluent COD was 61. 9 mg/L and its removal rate was 63. 8%. Additionally,the species of organic pollutants reduced from 12 to 6. Meanwhile,the content of humic-like and fulvic-like substances dropped dramatically.

Experimental studies on photocatalytic oxidation of nitric oxides using titanium dioxide

In order to remove nitric oxides （NO） from flue gas, experimental studies on the photocatalytic oxidation （PCO） of NO are carried out in an efficient laboratory-scale reactor. Nano-sized TiO2 particles loading on quartz sand are prepared and used as the photocatalyst. Effects of several key operating parameters on NO conversion are investigated, including operating temperature, NO inlet concentration, oxygen percentage, relative humidity and residence time. The results illustrate that the NO inlet concentration, the oxygen percentage and the relative humidity play an important role in the oxidation of NO. A lower NO inlet concentration and a higher oxygen percentage result in a higher NO conversion efficiency. When the relative humidity is 8%, the maximum value of NO conversion efficiency is achieved. In addition, the operating temperature and the residence time have a little effect on the conversion efficiency of NO.

Octahedral Cu_2O-modified TiO_2 nanotube arrays for efficient photocatalytic reduction of CO_2

A photocatalyst composed of TiO 2 nanotube arrays（TNTs） and octahedral Cu2 O nanoparticles was fabricated,and its performance in the photocatalytic reduction of CO2 under visible and simulated solar irradiation was studied. The average nanotube diameter and length was 100 nm and 5 μm,respectively. The different amount of octahedral Cu2 O modified TNTs were obtained by varying electrochemical deposition time. TNTs modified with an optimized amount of Cu2 O nanoparticles exhibited high efficiency in the photocatalysis,and the predominant hydrocarbon product was methane. The methane yield increased with increasing Cu2 O content of the catalyst up to a certain deposition time,and decreased with further increase in Cu2 O deposition time. Insufficient deposition time（5 min） resulted in a small amount of Cu2 O nanoparticles on the TNTs,leading to the disadvantage of harvesting light. However,excess deposition time（45 min） gave rise to entire TNT surface being most covered with Cu2 O nanoparticles with large sizes,inconvenient for the transport of photo-generated carriers. The highest methane yield under simulated solar and visible light irradiation was observed for the catalysts prepared at a Cu2 O deposition time of 15 and 30 min respectively. The morphology,crystallization,photoresponse and electrochemical properties of the catalyst were characterized to understand the mechanism of its high photocatalytic activity. The TNT structure provided abundant active sites for the adsorption of reactants,and promoted the transport of photogenerated carriers that improved charge separation. Modifying the TNTs with octahedral Cu2 O nanoparticles promoted light absorption,and prevented the hydrocarbon product from oxidation. These factors provided the Cu2O-modified TNT photocatalyst with high efficiency in the reduction of CO2,without requiring co-catalysts or sacrificial agents.

Enhanced visible-light photocatalytic oxidation capability of carbon-doped TiO_2 via coupling with fly ash

A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.

Characterization of metal doped-titanium dioxide and behaviors on photocatalytic oxidation of nitrogen oxides

A series of nanosized ion-doped TiO2 catalysts with different ion content （between 0.1 at.% and 1.0 at.%） have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide. The catalytic activity was correlated with structural, electronic and surface examinations of the catalysts using X-ray diffraction analysis （XRD）, ultraviolet-visible （UV-Vis） absorption spectroscopy, transmission electron microscopy （TEM）, energy disperse spectrometer （EDS） and high resolution-transmission electron microscopy （HR-TEM） techniques. An enhancement of the photocatalytic activity was observed for Zn2＋ doping catalyst ranged from 0.1 at.% to 1.0 at.% which was attributed to the lengthened lifetime of electrons and holes. The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr^3＋ （0.1 at.%）. However, the doping of Fe^3＋, Mo^6＋, Mn^2＋ and the high doping concentration of Cr^3＋ had no contribution to photocatalytic activity of nitric oxide.

Synthesis of Ni^2+cation modified TS-1 molecular sieve nanosheets as effective photocatalysts for alcohol oxidation and pollutant degradation

lmprovement of the charge separation of titanosilicate molecular sieves is critical to their use asphotocatalysts for oxidative organic transformations.In this work,MFI TS-1 molecular sievenanosheets(TS-1 NS)were synthesized by a low-temperature hydrothermal method using a tai-lored diquaternary ammonium surfactant as the structure-directing agent.Introducing Ni^2+cationsat the ion-exchange sites of the TS-1 NS framework significantly enhanced its photoactivity in aero-bic alcohol oxidation.The optimized Ni cation-functionalized TS-1 NS(Ni/TS-1 NS)provide impres-sive photoactivity,with a benzyl alcohol(BA)conversion of 78.9%and benzyl aldehyde(BAD)se-lectivity of 98.8%using O as the only oxidant under full light irradiation;this BAD yield is approx-imately six times greater than that obtained for bulk TS-1,and is maintained for five runs.The ex-cellent photoactivity of Ni/TS-1 NS is attributed to the significantly enlarged surface area of thetwo-dimensional morphology TS-1 NS,extra mesopores,and greatly improved charge separation.Compared with bulk TS-1,Ni/TS-1 NS has a much shorter charge transfer distance.Theas-introduced Ni species could capture the photoelectrons to further improve the charge separa-tion.This work opens the way to a class of highly selective,robust,and low-cost titanosilicate mo-lecular sieve-based photocatalysts with industrial potential for selective oxidative transformationsand pollutant degradation.

Properties of TiO_2-SiO_2 Mixed Oxides and Photocatalytic Oxidation of Heptane and Sulfur Dioxide

A series of TiO 2-XSiO 2[X denotes the molar fraction(%) of silica in the mixed oxides] with different \{n(Ti)\}/n(Si) ratios was prepared with ammonia water as a hydrolysis catalyst. The photocatalysts prepared were characterized by XRD, thermal analysis, FTIR, UV-Vis and SPS. The characterization results of FTIR and UV-Vis spectra show that Ti atoms were gradually changed from octahedral coordination to tetrahedral coordination with the addition of silica, which is not beneficial for obtaining strong Brnsted acidity and higher photocatalytic activity. The photocatalytic activity experiments, which were conducted by using heptane(or SO 2) as the model reactant, showed that TiO 2-SiO 2 containing a suitable amount of silica can exhibit much higher photocatalytic activity than pure TiO 2. The enhanced photocatalytic activity can be attributed to three following factors: (1) smaller crystalline size; (2) higher thermal stability; (3) the new strong Brnsted acidity.

Intrinsic photocatalytic water oxidation activity of Mn-doped ferroelectric BiFeO3

The development of stable and efficient visible light-absorbing oxide-based semiconductor photocatalysts is a desirable task for solar water splitting applications.Recently,we proposed that the low photocurrent density in film-based BiFeO_(3)(BFO)is due to charge recombination at the interface of the domain walls,which could be largely reduced in particulate photocatalyst systems.To demonstrate this hypothesis,in this work we synthesized particulate BFO and Mn-doped BiFeO_(3)(Mn-BFO)by the sol-gel method.Photocatalytic water oxidation tests showed that pure BFO had an intrinsic photocatalytic oxygen evolution reaction(OER)activity of 70μmol h^(-1) g^(-1),while BFO-2,with an optimum amount of Mn doping(0.05%),showed an OER activity of 255μmol h^(-1) g^(-1) under visible light(λ≥420 nm)irradiation.The bandgap of Mn-doped BFO could be reduced from 2.1 to 1.36 eV by varying the amount of Mn doping.Density functional theory(DFT)calculations suggested that surface Fe(rather than Mn)species serve as the active sites for water oxidation,because the overpotential for water oxidation on Fe species after Mn doping is 0.51 V,which is the lowest value measured for the different Fe and Mn species examined in this study.The improved photocatalytic water oxidation activity of Mn-BFO is ascribed to the synergistic effect of the bandgap narrowing,which increases the absorption of visible light,reduces the activation energy of water oxidation,and inhibits the recombination of photogenerated charges.This work demonstrates that Mn doping is an effective strategy to enhance the intrinsic photocatalytic water oxidation activity of particulate ferroelectric BFO photocatalysts.

Iron-Doped Titania Nanoparticles for the Photocatalytic Oxidative Degradation of Nitrite

Iron-doped titania nanoparticles exhibit a higher photocatalytic activity than pure TiO_2 for the degradation of nitrite. The optimum Fe-doped content in terms of activity is approximately 0.5%. The increase in photoactivity is probably due to the higher adsorption and the inhibition of electron-hole recombination. The photocatalytic oxidation reaction of nitrite over the Fe-doped TiO_2 catalyst follows zero-order kinetics, which is different from that over pure TiO_2. The reaction rate decreases linearly with the increase of the pH of the solution.

REMOVAL OF ORGANIC POLLUTANTS USING TITANIUM DIOXIDE MEDIATED PHOTOCATALYTIC OXIDATION

A simple and effective method of removing polluted organics in water is reported here.Titanium dioxide is a catalyst in photo-oxidation of monocrotophos.The mechanism of photocatalytic oxidation and the kinetics of the reaction were studied. This same principle also leads to the construction of instrument of PTR-FIA analysis for monitoring organic phosphorus and phosphate in water.

Photocatalytic oxidation of nitric oxide from simulated flue gas by wet scrubbing using ultraviolet/TiO_2/H_2O_2 process

Nitric oxide(NO) from flue gas is hard to remove because of low solubility and reactivity. A new technology for photocatalytic oxidation of NO using ultraviolet(UV)/TiO2/H2O2 process is studied in an efficient laboratory-scale reactor. Effects of several key operational parameters on NO removal efficiency are studied, including TiO2 content, H2O2 initial concentration, UV lamp power, NO initial content, oxygen volume fraction and TiO2/H2O2 solution volume. The results illustrate that the NO removal efficiency increases with the increasing of H2O2 initial concentration or UV lamp power. Meanwhile, a lower NO initial content or a higher TiO2/H2O2 solution volume will result in higher NO removal efficiency. In addition, oxygen volume fraction has a little effect.The highest NO removal efficiency is achieved at the TiO2 content of 0.75 g/L, H2O2 initial concentration of 2.5 mol/L, UV lamp power of 36 W, NO initial content of 206×10-6 and TiO2/H2O2 solution volume of 600 m L. It is beneficial for the development and application of NO removal from coal-fired flue gas with UV/TiO2/H2O2 process.

Gas-phase photocatalytic oxidation of benzene over titanium dioxide loaded on Bi_(12)TiO_(20)

TiO2 was prepared by sol-gel method using tetrabutyl titanate as precursor. TiO2 was loaded on Bi12TiO20. The photocatalyst with different TiO2 loading was calcined at 723 K. The photocatalytic activity of decomposition gaseous benzene was investigated in a batch reactor. The prepared photocatalyst was characterized by UV-vis diffuse reflectance. The result showed that TiO2/Bi12TiO20 absorbed much more ultraviolet light than Ti02 in the ultraviolet light region and showed red shift. The results indicated that the prepared photocatalyst can greatly promote the photocatalytic activity. The 2.0% TiO2/Bi12TiO20 system exhibited the highest photocatalytic activity.

A Proposed Mechanism of Photocatalytic Oxidation of Trichloroethylene in Gas Phase

GC/MS has been used to identify gas phase products and intermediates formed during the gas phase photocatalytic oxidation of trichloroethylene (TCE) on TiO(2) with low BET surface area. A new byproduct, oxalyl choloride (ClCOCOCl) was detected together with other byproducts such as COCl(2), CHCl(3), DCAC and C(2)HCl(5). Firstly the method of perturbation on the reaction system was conducted. Very little amount of water was carried into the feed gas and subsequent changes were observed. The discussion based on the product distribution changes led to a postulated mechanism consisting of two stages.