This research focuses on the evaluation of diverse approaches for removing formaldehyde from indoor environments,which is a significant concern for indoor air quality.The study systematically examines physical,chemica...This research focuses on the evaluation of diverse approaches for removing formaldehyde from indoor environments,which is a significant concern for indoor air quality.The study systematically examines physical,chemical,and biological methods to ascertain their effectiveness in formaldehyde mitigation.Physical methods,including air circulation and adsorption,particularly with activated carbon and molecular sieves,are assessed for their efficiency in various concentration scenarios.Chemical methods,such as photocatalytic oxidation using titanium dioxide and plasma technology,are analyzed for their ability to decompose formaldehyde into non-toxic substances.Additionally,biological methods involving plant purification and microbial transformation are explored for their eco-friendly and sustainable removal capabilities.The paper concludes that while each method has its merits,a combined approach may offer the most effective solution for reducing indoor formaldehyde levels.The study underscores the need for further research to integrate these methods in a practical,cost-effective,and environmentally sustainable manner,highlighting their potential to improve indoor air quality significantly.展开更多
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 photocat...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.展开更多
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 wer...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.展开更多
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 b...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.展开更多
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 th...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.展开更多
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 decompositi...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.展开更多
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 cholori...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.展开更多
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 ...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.展开更多
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.Theore...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.展开更多
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 neutr...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.展开更多
The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction wa...The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.展开更多
Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to p...Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.展开更多
Partial oxidation of methane into primary oxidation products with high value remains a challenge.In this work,photocatalytic oxidation of methane(CH_(4))with high methyl hydroperoxide(CH_(3)OOH)selectivity is achieved...Partial oxidation of methane into primary oxidation products with high value remains a challenge.In this work,photocatalytic oxidation of methane(CH_(4))with high methyl hydroperoxide(CH_(3)OOH)selectivity is achieved using pure titanium oxide(TiO_(2))without any cocatalyst at room temperature and atmospheric pressure.The CH_(3)OOH production rate can reach up to 2050±88μmol·g^(-1)·h^(-1) at pH≈7.0 with 100%selectivity in the liquid product.The stable reaction cycle can reach more than 30 times.This low-cost system achieves superior CH_(4) conversion activity and selectivity compared with similar work.The energy of hydrogen peroxide(H_(2)O_(2))to adsorbed hydroperoxyl radical(^(*)OOH)has a significantly lower reaction energy than conversion to adsorbed hydroxyl radical(*OH)on the(210)surface of the TiO_(2).The^(*)OOH preferentially combines with methyl radical(·CH_(3))to form the most energetically favorable CH_(3)OOH.The mild oxidative environment of this system prevents the reduction of CH_(3)OOH to CH_(3)OH or over-oxidation of CH_(4),which ensures the final CH_(3)OOH with high selectivity and stability.This work provided a low-cost but highly efficient method to achieve partial oxidation with superior selectivity,i.e.,to convert CH_(4) into high-value chemicals.展开更多
The degradation of fulvic acid(FA) by nanoparticle TiO2 in a submerged membrane photocatalysis(SMPC) reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuou...The degradation of fulvic acid(FA) by nanoparticle TiO2 in a submerged membrane photocatalysis(SMPC) reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuous air supplier provided O2 for the photocatalytical reaction and mixed the solution through an airflow controller. The particle TiO2 could automatically settle due to gravity without particle agglomeration so it could be easily separated by microfiltration(MF) membrane. It was efficient to maintain high flux of membranes. The effects of operational parameters on the photocatalytic oxidation rate of FA were investigated. Results indicated that photocatalyst at 0.5 g/L and airflow at 0.06 m^3/h were the optimum condition for the removal of fulvic acid, the removal efficiency was higher in acid media than that in alkaline media. The effects of different filtration duration on permeate flux rate of MF with P25 powder and with nanoparticle TiO2 were compared. Experimental results indicated that the permeate flux rate of MF was improved and the membrane fouling phenomenon was reduced with the addition of nanoparticle TiO2 catalyst compared with conventional P25 powder. Therefore, this submerged membrane photocatalysis reactor can faciliate potential application of photocatalytic oxidation process in drinking water treatment.展开更多
A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS...A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS).Keggin-type polyoxometallate ionic liquid[TTPh]_(3)PW_(12)O_(40) was prepared and used as catalyst to enhance the EDS capacity by means of photocatalytic oxidative process.Both of the DESs and[TTPh]_(3)PW_(12)O_(40) ionic liquid catalyst were characterized in detail by Fourier transform infrared spectroscopy spectra(FT-IR),elemental analysis,and X-ray photoelectron spectroscopy(XPS).It was found that the molar ratios of Ch Cl:HCOOH had a major impact on desulfurization performance,and the optimal desulfurization capacity 96.5%was obtained by ChCl/5 HCOOH.Besides dibenzothiophene(DBT),the desulfurization efficiencies of 4-methylbenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT),two kinds of DBT derivatives,were also investigated under the same experimental conditions.Moreover,the free radical scavenging experiments manifested that superoxide radical(·O_(2)^(-)) and hole(h^(+)) played important roles in the desulfurization system.After further analysis of the oxidation products by gas chromatography-mass spectrometry(GC–MS),the possible reaction mechanism was proposed.Thus,photocatalytic oxidative has been proved to be one of the efficient approaches for enhancing the extractive desulfurization performance in DES.展开更多
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 photoa...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.展开更多
This work reported the lanthanide ion(Gd^(3+))doped tungsten trioxide(Gd-WO_(3))nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H_(2)O_(2)production.With d...This work reported the lanthanide ion(Gd^(3+))doped tungsten trioxide(Gd-WO_(3))nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H_(2)O_(2)production.With doped lanthanide ion(Gd^(3+)),Gd-WO_(3)showed a much broad and enhanced solar light absorption,which not only promoted the photocatalytic degradation efficiency of organic compounds,but also provided a suitable bandgap for direct reduction of oxygen to H_(2)O_(2).Additionally,the isolated Gd^(3+)on WO_(3)surface can efficiently weaken the*OOH binding energy,increasing the activity and selectivity of direct reduction of oxygen to H_(2)O_(2),with a rate of 0.58 mmol L^(-1)g^(-1)h^(-1).The in-situ generated H_(2)O_(2)can be subsequently converted to·OH based on Fenton reaction,further contributed to the overall removal of organic pollutants.Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.展开更多
This paper generalized the structure characteristics of three different configuration photoreactors: annular type irradiated by lamp, solar shallow pond and solar flat plate and compared their performance efficiency a...This paper generalized the structure characteristics of three different configuration photoreactors: annular type irradiated by lamp, solar shallow pond and solar flat plate and compared their performance efficiency at the same reaction condition level which was determined by the first order rate constant in photocatalytic decolorization of methyl orange in TiO 2 suspension. It was demonstrated that solar could be considered as an alternative light source in photoreactors not only for low running and construction cost but also for their successful performance. The evidence has proved the feasibility of solar photocatalytic oxidation as an additional or alternative advantage stage of wastewater treatment process.展开更多
( CdS/ TiO2 )/ MCM-41 loaded nanometer photocatalyst was prepared by the sol-gel method and dipping process, the photocatalytic degradation of methyl thionine chloride in water was investigated by using the photocat...( CdS/ TiO2 )/ MCM-41 loaded nanometer photocatalyst was prepared by the sol-gel method and dipping process, the photocatalytic degradation of methyl thionine chloride in water was investigated by using the photocatalyst. The experimental results show that the optimum concentration of CdS over TiO2 was 3% ( molar ratio ), the photocatalytic activity was enhanced when making TiO2 the anatase ptase with a rise of the roasting temperature, and the carrier, mesoporous molecular sieve MCM-41, was beneficial to improving the photocatalytic activity of TiO2 for photocatalytic degradation of methyl thionine chloride. The morphology and the crystalline phase of the photocatalyst were discussed by means of XRD and SEM techniques, and the reaction mechanism of catalytic properties was also discussed.展开更多
In the process of methane(CH_(4))oxidation to methanol(CH3OH),CH3OH is more easily oxidized than CH_(4),resulting in inevitable peroxide phenomenon.In this work,we innovatively proposed a tandem reaction pathway to ob...In the process of methane(CH_(4))oxidation to methanol(CH3OH),CH3OH is more easily oxidized than CH_(4),resulting in inevitable peroxide phenomenon.In this work,we innovatively proposed a tandem reaction pathway to obtain a photocatalytic oxidation process of CH_(4) with high activity and selectivity.This work confirms that the methyl hydrogen peroxide(CH3OOH),the first product of CH_(4) oxidation by H_(2)O_(2),is then completely reduced to CH3OH in an electron-rich environment.Under irradiation,H_(2)O_(2) was excited into hydroxyl radicals(·OH)and hydroperoxyl radicals(·OOH)on brookite TiO_(2) photocatalyst.The·OH oxidized CH_(4) to form methyl radicals(·CH3),which then reacted with·OOH to form CH3OOH.CH3OOH gained electrons on Pt nanoparticles(NPs)and was reduced to CH3OH.At this point,low concentration of·OH was difficult to further oxidize CH3OH,so that it can exist stably.Under the conditions of room temperature(25°C)and atmospheric pressure,the productivity of CH3OH was 883μmol/(g·h),which was 4 times more than the reported photocatalytic CH_(4) oxidation system with the same reaction conditions,and the selectivity was 100%in liquid products(98.77%for all products).The photocatalyst showed excellent stability and maintained>85%product activity after 9 catalytic cycles.This work contributed to the development of highly efficient and selective CH_(4) photooxidation system under mild conditions.展开更多
文摘This research focuses on the evaluation of diverse approaches for removing formaldehyde from indoor environments,which is a significant concern for indoor air quality.The study systematically examines physical,chemical,and biological methods to ascertain their effectiveness in formaldehyde mitigation.Physical methods,including air circulation and adsorption,particularly with activated carbon and molecular sieves,are assessed for their efficiency in various concentration scenarios.Chemical methods,such as photocatalytic oxidation using titanium dioxide and plasma technology,are analyzed for their ability to decompose formaldehyde into non-toxic substances.Additionally,biological methods involving plant purification and microbial transformation are explored for their eco-friendly and sustainable removal capabilities.The paper concludes that while each method has its merits,a combined approach may offer the most effective solution for reducing indoor formaldehyde levels.The study underscores the need for further research to integrate these methods in a practical,cost-effective,and environmentally sustainable manner,highlighting their potential to improve indoor air quality significantly.
基金Porject supported by the New Century Excellent Scholar Program of Ministry of Education of China(No.NCET-04-0549)the China Postdoctoral Science Foundation(No.20060401047).
文摘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.
基金Supported by the National Natural Science Foundation of China(No.2 0 2 770 15 )
文摘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.
基金Supported by the Key Technologies Research and Development Programme of the Ninth Five year Plan of China (96 554 03 01)
文摘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.
文摘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.
文摘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.
文摘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.
文摘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.
基金supported by the BJAST High-level Innovation Team Program (No.BGS202001)the Beijing Postdoctoral Research Foundation (No.2022-ZZ-046)+3 种基金the National Natural and Science Foundation of China (No.51972026)the Japan Society for the Promotion of Science (JSPS)Grant-in-Aid for the Scientific Research (KAKENHI,Nos.16H06439 and 20H00297)the Dynamic Alliance for Open Innovations Bridging Human,Environment and Materials,the Cooperative Research Program of“Network Joint Research Center for Materials and Devices.”the scholarship granted to a visiting Ph.D.student of the Inter-University Exchange Project by the China Scholarship Council (CSC,No.201906460113)。
文摘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.
基金the financial support of the Natural Science Foundation of China (21736003, 22178130 and 22005106)the Natural Science Foundation of Guangdong Province, China (2020A0505100008)the Science and Technology Program of Guangzhou (202206010024)。
文摘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.
基金supported by National Natural Science Foundation of China(22369022)Technology Innovation Leading Program of Shaanxi(2022QFY07-03)。
文摘The efficiency of photocatalytic overall water splitting was mainly limited by the slow reaction kinetics of water oxidation.How to design effective surface active site to overcome the slow water oxidation reaction was a major challenge.Here,we propose a strategy to accelerate surface water oxidation through the fabrication spatially separated double active sites.FeCoPi/Bi_(4)NbO_(8)Cl-OVs photocatalyst with spatially separated double active site was prepared by hydrogen reduction photoanode deposition method.Due to the high matching of the spatial loading positions of FeCoPi and OVs with the photogenerated charge distribution of Bi_(4)NbO_(8)Cl and corresponding reaction mechanisms of substrate,the FeCoPi and OVs on the(001)and(010)crystal planes of Bi_(4)NbO_(8)Cl photocatalyst provided surface active site for water oxidation reaction and electron shuttle reaction(Fe^(3+)/Fe^(2+)),respectively.Under visible light irradiation,the evolution O_(2)rate of FeCoPi/Bi_(4)NbO_(8)Cl OVs was 16.8μmol h^(-1),as 32.9 times as Bi_(4)NbO_(8)Cl.Furthermore,a hydrogen evolution co-catalyst PtRu@Cr_(2)O_(3)was prepared by sequential photodeposition method.Due to the introduction of Ru,the Schottky barrier between PbTiO_(3)and Pt was effectively reduced,which promoted the transfer of photogenerated electrons to PtRu@Cr_(2)O_(3)thermodynamically,the evolution H_(2)rate on PtRu@Cr_(2)O_(3)/PbTiO_(3)increased to 664.8 times.On based of the synchronous enhancement of the water oxidation performance on FeCoPi/Bi_(4)NbO_(8)Cl-OVs and water reduction performance on PtRu@Cr_(2)O_(3)/PbTiO_(3),a novel Z-Scheme photocatalytic overall water splitting system(FeCoPi/Bi_(4)NbO_(8)Cl-OVs)mediated by Fe^(3+)/Fe^(2+)had successfully constructed.Under visible light irradiation,the evolution rates of H_(2)and O_(2)were 2.5 and 1.3μmol h^(-1),respectively.This work can provide some reference for the design of active site and the controllable synthesis of OVs spatial position.On the other hand,the hydrogen evolution co catalyst(PtRu@Cr_(2)O_(3))and the co catalyst FeCoPi for oxygen evolution contributed to the construction of an overall water splitting system.
基金supported by the National Natural Science Foundation of China(21731002,21975104,22101099,22150004,22271120)Guangdong Major Project of Basic and Applied Research(2019B030302009)+1 种基金the Outstanding Innovative Talents Cultivation Funded Programs for Doctoral Students of Jinan University(2022CXB007)the Fundamental Research Funds for the Central Universities and Jinan University(21621035)。
文摘Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.
基金support by the National Natural Science Foundation of China(No.21972028)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000).
文摘Partial oxidation of methane into primary oxidation products with high value remains a challenge.In this work,photocatalytic oxidation of methane(CH_(4))with high methyl hydroperoxide(CH_(3)OOH)selectivity is achieved using pure titanium oxide(TiO_(2))without any cocatalyst at room temperature and atmospheric pressure.The CH_(3)OOH production rate can reach up to 2050±88μmol·g^(-1)·h^(-1) at pH≈7.0 with 100%selectivity in the liquid product.The stable reaction cycle can reach more than 30 times.This low-cost system achieves superior CH_(4) conversion activity and selectivity compared with similar work.The energy of hydrogen peroxide(H_(2)O_(2))to adsorbed hydroperoxyl radical(^(*)OOH)has a significantly lower reaction energy than conversion to adsorbed hydroxyl radical(*OH)on the(210)surface of the TiO_(2).The^(*)OOH preferentially combines with methyl radical(·CH_(3))to form the most energetically favorable CH_(3)OOH.The mild oxidative environment of this system prevents the reduction of CH_(3)OOH to CH_(3)OH or over-oxidation of CH_(4),which ensures the final CH_(3)OOH with high selectivity and stability.This work provided a low-cost but highly efficient method to achieve partial oxidation with superior selectivity,i.e.,to convert CH_(4) into high-value chemicals.
文摘The degradation of fulvic acid(FA) by nanoparticle TiO2 in a submerged membrane photocatalysis(SMPC) reactor was studied. In this reactor, photocatalytic oxidation and membrane separation co-occured. The continuous air supplier provided O2 for the photocatalytical reaction and mixed the solution through an airflow controller. The particle TiO2 could automatically settle due to gravity without particle agglomeration so it could be easily separated by microfiltration(MF) membrane. It was efficient to maintain high flux of membranes. The effects of operational parameters on the photocatalytic oxidation rate of FA were investigated. Results indicated that photocatalyst at 0.5 g/L and airflow at 0.06 m^3/h were the optimum condition for the removal of fulvic acid, the removal efficiency was higher in acid media than that in alkaline media. The effects of different filtration duration on permeate flux rate of MF with P25 powder and with nanoparticle TiO2 were compared. Experimental results indicated that the permeate flux rate of MF was improved and the membrane fouling phenomenon was reduced with the addition of nanoparticle TiO2 catalyst compared with conventional P25 powder. Therefore, this submerged membrane photocatalysis reactor can faciliate potential application of photocatalytic oxidation process in drinking water treatment.
基金financially supported by the National Natural Science Foundation of China(No.21808091)Natural Science Foundation of Jiangsu Province(Nos.BK20200896,BK20190243)+2 种基金Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education,Hainan Normal University(20150376)China Postdoctoral Foundation(No.2020M671365)the Student Innovation and Entrepreneurship Training Program(202010299457X)。
文摘A series of novel binary deep eutectic solvents(DESs)composed of choline chloride(ChCl)and formic acid(HCOOH)with different molar ratios have been successfully synthesized and applied in extractive desulfurization(EDS).Keggin-type polyoxometallate ionic liquid[TTPh]_(3)PW_(12)O_(40) was prepared and used as catalyst to enhance the EDS capacity by means of photocatalytic oxidative process.Both of the DESs and[TTPh]_(3)PW_(12)O_(40) ionic liquid catalyst were characterized in detail by Fourier transform infrared spectroscopy spectra(FT-IR),elemental analysis,and X-ray photoelectron spectroscopy(XPS).It was found that the molar ratios of Ch Cl:HCOOH had a major impact on desulfurization performance,and the optimal desulfurization capacity 96.5%was obtained by ChCl/5 HCOOH.Besides dibenzothiophene(DBT),the desulfurization efficiencies of 4-methylbenzothiophene(4-MDBT)and 4,6-dimethyldibenzothiophene(4,6-DMDBT),two kinds of DBT derivatives,were also investigated under the same experimental conditions.Moreover,the free radical scavenging experiments manifested that superoxide radical(·O_(2)^(-)) and hole(h^(+)) played important roles in the desulfurization system.After further analysis of the oxidation products by gas chromatography-mass spectrometry(GC–MS),the possible reaction mechanism was proposed.Thus,photocatalytic oxidative has been proved to be one of the efficient approaches for enhancing the extractive desulfurization performance in DES.
基金the National Natural Science Foundation of China.
文摘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.
基金supported by Natural Science Foundation of Zhejiang Province(No.LR21B07002)National Natural Science Foundation of China(Nos.22176170,21976152)the Open Research Program of Key Laboratory of 3D Micro/Nano Fabrication and Characterization of Zhejiang Province,Westlake University。
文摘This work reported the lanthanide ion(Gd^(3+))doped tungsten trioxide(Gd-WO_(3))nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H_(2)O_(2)production.With doped lanthanide ion(Gd^(3+)),Gd-WO_(3)showed a much broad and enhanced solar light absorption,which not only promoted the photocatalytic degradation efficiency of organic compounds,but also provided a suitable bandgap for direct reduction of oxygen to H_(2)O_(2).Additionally,the isolated Gd^(3+)on WO_(3)surface can efficiently weaken the*OOH binding energy,increasing the activity and selectivity of direct reduction of oxygen to H_(2)O_(2),with a rate of 0.58 mmol L^(-1)g^(-1)h^(-1).The in-situ generated H_(2)O_(2)can be subsequently converted to·OH based on Fenton reaction,further contributed to the overall removal of organic pollutants.Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.
文摘This paper generalized the structure characteristics of three different configuration photoreactors: annular type irradiated by lamp, solar shallow pond and solar flat plate and compared their performance efficiency at the same reaction condition level which was determined by the first order rate constant in photocatalytic decolorization of methyl orange in TiO 2 suspension. It was demonstrated that solar could be considered as an alternative light source in photoreactors not only for low running and construction cost but also for their successful performance. The evidence has proved the feasibility of solar photocatalytic oxidation as an additional or alternative advantage stage of wastewater treatment process.
基金Funded by Special Fund of Education Department of ShaanxiProvince(No.03JK144)
文摘( CdS/ TiO2 )/ MCM-41 loaded nanometer photocatalyst was prepared by the sol-gel method and dipping process, the photocatalytic degradation of methyl thionine chloride in water was investigated by using the photocatalyst. The experimental results show that the optimum concentration of CdS over TiO2 was 3% ( molar ratio ), the photocatalytic activity was enhanced when making TiO2 the anatase ptase with a rise of the roasting temperature, and the carrier, mesoporous molecular sieve MCM-41, was beneficial to improving the photocatalytic activity of TiO2 for photocatalytic degradation of methyl thionine chloride. The morphology and the crystalline phase of the photocatalyst were discussed by means of XRD and SEM techniques, and the reaction mechanism of catalytic properties was also discussed.
基金support by the National Natural Science Foundation of China(No.21972028)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000).
文摘In the process of methane(CH_(4))oxidation to methanol(CH3OH),CH3OH is more easily oxidized than CH_(4),resulting in inevitable peroxide phenomenon.In this work,we innovatively proposed a tandem reaction pathway to obtain a photocatalytic oxidation process of CH_(4) with high activity and selectivity.This work confirms that the methyl hydrogen peroxide(CH3OOH),the first product of CH_(4) oxidation by H_(2)O_(2),is then completely reduced to CH3OH in an electron-rich environment.Under irradiation,H_(2)O_(2) was excited into hydroxyl radicals(·OH)and hydroperoxyl radicals(·OOH)on brookite TiO_(2) photocatalyst.The·OH oxidized CH_(4) to form methyl radicals(·CH3),which then reacted with·OOH to form CH3OOH.CH3OOH gained electrons on Pt nanoparticles(NPs)and was reduced to CH3OH.At this point,low concentration of·OH was difficult to further oxidize CH3OH,so that it can exist stably.Under the conditions of room temperature(25°C)and atmospheric pressure,the productivity of CH3OH was 883μmol/(g·h),which was 4 times more than the reported photocatalytic CH_(4) oxidation system with the same reaction conditions,and the selectivity was 100%in liquid products(98.77%for all products).The photocatalyst showed excellent stability and maintained>85%product activity after 9 catalytic cycles.This work contributed to the development of highly efficient and selective CH_(4) photooxidation system under mild conditions.