Efficiently and thoroughly degrading organic dyes in wastewater is of great importance and challenge.Herein,vertically oriented mesoporous a-Fe_(2)O_(3)nanorods array(a-Fe_(2)O_(3)-NA)is directly grown on fluorine-dop...Efficiently and thoroughly degrading organic dyes in wastewater is of great importance and challenge.Herein,vertically oriented mesoporous a-Fe_(2)O_(3)nanorods array(a-Fe_(2)O_(3)-NA)is directly grown on fluorine-doped tin oxide(FTO)glass and employed as the photoanode for photoelectrocatalytic degradation of methylene blue simulated dye wastewater.The Ovsites on the a-Fe_(2)O_(3)-NA surface are the active sites for methylene blue(MB)adsorption.Electrons transfer from the adsorbed MB to Fe-O is detected.Compared with electrocatalytic and photocatalytic degradation processes,the photoelectrocatalytic(PEC)process exhibited the best degrading performance and the largest kinetic constant.Hydroxyl,superoxide free radicals,and photo-generated holes play a jointly leading role in the PEC degradation.A possible degrading pathway is suggested by liquid chromatography-mass spectroscopy analysis.This work demonstrates that photoelectrocatalysis by a-Fe_(2)O_(3)-NA has a remarkable superiority over photocatalysis and electrocatalysis in MB degradation.The in-depth investigation of photoelectrocatalytic degradation mechanism in this study is meaningful for organic wastewater treatment.展开更多
As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective...As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.展开更多
The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrie...The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.展开更多
A significant promotion effect of low-molecular hydroxyl compounds(LMHCs) was found in the nano-photoelectrocatalytic(NPEC) degradation of fulvic acid(FA),which is a typical kind of humic acid existing widely in natur...A significant promotion effect of low-molecular hydroxyl compounds(LMHCs) was found in the nano-photoelectrocatalytic(NPEC) degradation of fulvic acid(FA),which is a typical kind of humic acid existing widely in natural water bodies,and its influence mechanism was proposed.A TiO_2 nanotube arrays(TNAs) material is served as the photoanode.Methanol,ethanediol,and glycerol were chosen as the representative of LMHCs in this study.The adsorption performance of organics on the surface of TNAs was investigated by using the instantaneous photocurrent value.The adsorption constants of FA,methanol,ethanediol,and glycerol were 43.44,19.32,7.00,and 1.30,respectively,which indicates that FA has the strongest adsorption property.The degradation performance of these organics and their mixture were observed in a thin-layer reactor.It shows that FA could hardly achieve exhausted mineralization alone,while LMHCs could be easily oxidized completely in the same condition.The degradation degree of FA,which is added LMHCs,improves significantly and the best promotion effect is achieved by glycerol.The promotion effect of LMHCs in the degradation of FA could be contributed to the formation of a tremendous amount of hydroxyl radicals in the NPEC process.The hydroxyl radicals could facilitate the complete degradation of both FA and its intermediate products.Among the chosen LMHCs,glycerol molecule which has three hydroxyls could generate the most hydroxyl radicals and contribute the best effective promotion.This work provides a new way to promote the NPEC degradation of FA and a direction to remove humus from polluted water.展开更多
CdS quantum dots sensitized platelike WO_3 photoelectrodes were successfully synthesized by a facile hydrothermal method and a modified chemical bath deposition(CBD) technique.To further improve the stability of the p...CdS quantum dots sensitized platelike WO_3 photoelectrodes were successfully synthesized by a facile hydrothermal method and a modified chemical bath deposition(CBD) technique.To further improve the stability of the photoelectrodes in alkaline environment,the platelike WO_3 films were treated with TiCl_4 to form a nano-TiO_2 buffer layer on the WO_3 plate surface before loading CdSQDs.The resulting electrodes were characterized by using XRD,SEM,HR-TEM and UV-vis spectrum.The photocatalytic activity of the resulting electrodes was investigated by degradation of methyl orange(MO) in aqueous solution.The photoelectrochemical(PEC) property of the resulting electrodes was also characterized by the linear sweep voltammetry.The results of both the degradation of MO and photocurrent tests indicated that the as-prepared CdSQDs sensitized WO_3 platelike photoelectrodes exhibit a significant improvement in photocatalytic degradation and PEC activity under visible light irradiation,compared with unsupported CdSQDs electrodes.Significantly,coating the WO_3 plates with nano-TiO_2 obviously facilitate the charge separation and retards the charge-pair recombination,and results in a highest activity for QDsCdS/TiO_2/WO_3 photoelectrodes.展开更多
A titanium dioxide loaded tremella-like mesoporous calcium silicate hydrate(TiO_(2)@CSH)with both adsorption and photocatalytic degradation activity was successfully prepared by a hydrothermal method combined with sol...A titanium dioxide loaded tremella-like mesoporous calcium silicate hydrate(TiO_(2)@CSH)with both adsorption and photocatalytic degradation activity was successfully prepared by a hydrothermal method combined with sol-gel strategy in two steps in this work.Tremella-shaped CSH provides abundant active sites for accommodating of TiO_(2),thus the corresponding TiO_(2)@CSH achieved a high loading ratio of 36.73%.Such a special shaped TiO_(2)@CSH exhibits excellent pre-enrichment capacity and photocatalytic degradation capacity for organic pollutants.Bisphenol A(BPA)removal experiments show that TiO_(2)@CSH can remove 91.17%of BPA from aqueous solutions.Studies on removal mechanism suggest that BPA tends to bind on the interface between CSH and TiO_(2) and the pre-enrichment process conforms to the intraparticle diffusion model;and then,it is decomposed to harmless substances of CO_(2) and H_(2)O during the photocatalytic process.The experimental results show that loading functional nanoparticles such as TiO_(2) on the surface of inorganic porous materials can endow inert porous materials with new functions such as photocatalytic degradation,which effectively expands the application range of inorganic porous materials.展开更多
Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization...Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization of FC structure showed that Cu_(2)O in cubic crystals was loaded with circular sheets of Fe_(2)O_(3).Owing to this structure,FC showed efficient PEC degradation of BTA when exposed to ultraviolet light.The experimental results demonstrated that FC efficiently degraded BTA.When the PEC degradation continued for 60 min,100%degradation of BTA was achieved because FC enhanced the photoelectron-hole separation and the separation and transfer of articulated carriers.High per-formance liquid chromatography-mass spectrometry showed that intermediates formed during the PEC degradation of BTA.Finally,various pathways for degradation of BTA were postulated.This FC-based PEC system provides a harmless and effective method for degradation of BTA.展开更多
Layered double hydroxide(LDH)with special layered structure has been proved to have excellent hole transport capacity and good stability.Herein,we report a high efficient composite photocatalyst of CoAlLDH and BiPO4pr...Layered double hydroxide(LDH)with special layered structure has been proved to have excellent hole transport capacity and good stability.Herein,we report a high efficient composite photocatalyst of CoAlLDH and BiPO4prepared by hydrothermal and che mical adsorption(denoted as CoAl-LDH/BiPO_(4)).Phenol can be entirely degraded by 1%CoAl-LDH/BiPO_(4)under 30 min ultraviolet(UV)light irradiation,and the degradation rate constants k are 3 times and 39 times higher than that of pure BiPO_(4)and CoAl-LDH,respectively.The enhanced photocatalytic activity can be attributed to effective holes transfer from BiPO4to CoAl-LDH,which hinders the recombination of photo genera ted charge carriers.In addition,the combination of BiPO4and CoAl-LDH avoids the agglomeration of BiPO4and improves the stability of BiPO_(4).Active species capture experiments indicate that superoxide radicals(·O-_(2))are the main active species responsible for the degradation of phenol.This work provides technical approaches and research ideas for solving the photogenerated charge carrier recombination problem of photocatalyst.展开更多
In this study,biochar(BC)derived from pomelo was prepared via a high-temperature calcination method to modify the graphitic carbon nitride(g-C_(3)N_(4))to synthesize the BC/g-C_(3)N_(4)composite for the degradation of...In this study,biochar(BC)derived from pomelo was prepared via a high-temperature calcination method to modify the graphitic carbon nitride(g-C_(3)N_(4))to synthesize the BC/g-C_(3)N_(4)composite for the degradation of the tetracycline(TC)antibiotic under visible light irradiation.The experimental results exhibit that the optimal feeding weight ratio of biochar/urea is 0.03:1 in BC/g-C_(3)N_(4)composite could show the best photocatalytic activity with the degradation rate of tetracycline is 83%in 100 min irradiation.The improvement of photocatalytic activity is mainly attributed to the following two points:(i)the strong bonding with π-π stacking between BC and g-C_(3)N_(4)make the photogenerated electrons of light-excited g-C_(3)N_(4)transfer to BC,quickly and improve the separation efficiency of carriers;(ii)the introduction of BC reduces the distance for photogenerated electrons to migrate to the surface and increases the specific surface area for providing more active sites.This study provides a sustainable,economical and promising method for the synthesis of photocatalytic materials their application to wastewater treatment.展开更多
The metal-doping into the photocatalyst was evaluated for the photocatalytic degradation of bisphenol A in aqueous solution with ZnO powder. Au/ZnO, Ag/ZnO and Cu/ZnO were tested in the present work. Ag-doping ZnO was...The metal-doping into the photocatalyst was evaluated for the photocatalytic degradation of bisphenol A in aqueous solution with ZnO powder. Au/ZnO, Ag/ZnO and Cu/ZnO were tested in the present work. Ag-doping ZnO was effective for the improvement of efficiency for the photocatalytic degradation of bisphenol A in water. The optimum doping concentration of silver was found to be 3 wt%. The pseudo first-order rate constant with 3 wt% Ag/ZnO was 1.3 times better compared with bare ZnO. The photocatalytic degradation of treatment for the wastewater containing bisphenol A is simple, easy handling and low cost.展开更多
TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron micro...TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photo electron spectroscopy (XPS), BET surface area, FTIR and diffuse reflectance spectra (DRS). The results showed that the prepared catalysts are anatase type and nanosized par-ticles. The catalysts exhibited stronger absorption in the visible light region with a red shift in the adsorption edge. The photocatalytic activity of TCNS photocatalysts was evaluated by the photocatalytic degradation of isoproturon pesticide in aqueous solution. In the present study the maximum activity was achieved for TCNS5 catalyst at neutral pH with 1 g L-1 catalyst amount and at 1.14 x 10-4 M concentration of the pesticide solution. The TCNS photocatalysts showed higher phtocatalytic activity under solar light irradiation. This is attributed to the synergetic effects of red shift in the absorption edge, higher surface area and the inhibition of charge carrier recombination process.展开更多
Kinetics of photocatalytic degradation of methylene blue(MB) over Ca Ti O3 was studied. Effects of the solution p H, the MB concentration, the Ca Ti O3 dosage, and the type of light source on photocatalytic degradatio...Kinetics of photocatalytic degradation of methylene blue(MB) over Ca Ti O3 was studied. Effects of the solution p H, the MB concentration, the Ca Ti O3 dosage, and the type of light source on photocatalytic degradation rate of MB over Ca Ti O3 were investigated in detail. The results show that photocatalytic degradation of MB over Ca Ti O3 followed the first-order reaction. The apparent rate constant(kobs) of MB significantly increased with increasing solution p H while it greatly decreased with increasing MB concentration. The kobs of MB increased with increasing Ca Ti O3 dosage from 0.05 to 0.1 g, whereas it slightly decreased with increasing Ca Ti O3 dosage in the range of 0.1-0.4 g. The kobs of MB under UV-visible light irradiation was larger by factors of 2.2 than that under visible light irradiation. The kobs of MB was(4.8±0.3)×10-1h-1 under optimal conditions with the solution p H of 11, the MB concentration of 1 ppm, the Ca Ti O3 dosage of 0.1 g, and UV-visible light irradiation.展开更多
The suppression of the recombination of electrons and holes(e–h) and the enhancement of the light absorption of semiconductors are two key points toward efficient photocatalytic degradation.Here,we report a few-layer...The suppression of the recombination of electrons and holes(e–h) and the enhancement of the light absorption of semiconductors are two key points toward efficient photocatalytic degradation.Here,we report a few-layer g-C_3N_4/α-MoO_3 nanoneedles(flg-C_3N_4/α-MoO_3 NNs) all-solid-state Z-scheme mechanism photocatalyst synthesized via a typical hydrothermal method in a controlled manner.The recombination of the photo-induced e–h pairs could be effectively restrained by the Z-scheme passageway between the flg-C_3N_4 and α-MoO_3 NNs in the composite,which could also promise a high redox ability to degrade pollutants.And it became possible for the prepared photocatalyst to absorb light in a wide range of wavelengths.The detailed mechanism was studied by electron spin-resonance spectroscopy(ESR).The low-dimensional nanostructure of the two constituents(α-MoO_3 NNs with one-dimensional structure and flg-C_3N_4 with two-dimensional structure) endowed the composite with varieties of excellent physicochemical properties,which facilitated the transfer and diffusion of the photoelectrons and increased the specific surface area and the active sites.The 10 wt% flg-C_3N_4/α-MoO_3 NNs showed the best photocatalytic performance toward RhB degradation,the rate of which was 71.86%,～2.6 times higher than that ofα-MoO_3 NNs.展开更多
Perovskite type oxides LaCoO 3 was prepared by citrate method in granula of 20～30 nm. Using a fluorescent Hg lamp or sunlight as irradiator, the degradation experiments of various water soluble dyes were carried out ...Perovskite type oxides LaCoO 3 was prepared by citrate method in granula of 20～30 nm. Using a fluorescent Hg lamp or sunlight as irradiator, the degradation experiments of various water soluble dyes were carried out in the suspension system of LaCoO 3. The results show that the perovskite type oxide LaCoO 3 has good photocatalytic activity. With the study of X ray photoelectron spectroscopy and photoacoustic spectra, its photocatalytic activity is mainly related with the factors such as the d electron structure of ion Co 3+ , Co O binding energy and adsorbed oxygen on the surface etc.展开更多
The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on...The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on gaseous organic-pollutant photocatalytic degradation, we synthesized a series of TiO_2 nanoparticles with controllable phase ratios. We explored the role of the TiO_2 phase ratio on the photocatalytic activity and degradation pathway in the photodegradation of 2-propanol(IPA). We estimated the crystallite size and crystal proportions of anatase and rutile by X-ray diffraction. We used the Brunauer-Emmett-Teller method to calculate the specific surface area and Fourier transform infrared spectroscopy to characterize the surface chemistry of the samples. Our results show the photocatalytic activities of pure anatase and the sample with 8.6% rutile to be much better than those of the samples with a phase junction and pure rutile. As such, anatase is the better option for the study of photodegradation design and preparation of gas-phase organic pollutants.展开更多
Silicotungstic acid and phosphotungstic acid were prepared and characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the prepared catalysts possess classi...Silicotungstic acid and phosphotungstic acid were prepared and characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the prepared catalysts possess classical Keggin structure. The factors on the degradation of methyl orange, such as the kind of catalyst, the amount of catalyst, the original concentration of dye and illumination time were investigated under metal halide lamp. The degradation of methyl orange is up to 93.6% with phosphotungstic acid at the best reaction conditions at 8.89 g/L concentration of phosphotungstic acid, 5.56 mg/L concentration of methyl orange and 80 min illumination time.展开更多
To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence ...To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.展开更多
The crosslinked gelatin/CuS/PVA nanocomposite catalyst prepared using gamma irradiation as initiator was extensively characterized using several techniques including transmission electron microscopy (TEM), UV-Vis spec...The crosslinked gelatin/CuS/PVA nanocomposite catalyst prepared using gamma irradiation as initiator was extensively characterized using several techniques including transmission electron microscopy (TEM), UV-Vis spectroscopy, infrared spectroscopy (IR) and X-ray diffraction (XRD). We chose Rhodamine B (RhB) dye as a model contaminant in order to investigate its Photocatalytic activity under solar light irradiation. The effects of pH, catalyst concentration and RhB concentration on degradation reaction were also investigated. Similar to the observed trend for the photocatalytic oxidation of other organic compounds, the efficiency of photocatalytic degradation of RhB tended to decrease with increasing the concentration of RhB. The degradation efficiency of RhB is found to increase as pH is increased up to pH of 10, then starts decreasing at pH values higher than 10. The degradation efficient of RhB is found to increase as the amount of the catalyst dosage increases up to an optimum value of 0.25 g. Increasing the concentrations of photocatalyst beyond 0.25 g was found to decrease the photocatalytic activity of RhB. It was proven that the degradation process of RhB reaction rate obeyed a pseudo-first-order reaction of the catalyst concentration of gelatin/CuS/PVA nanocomposite. The degradation kinetics was found to fit well Langmuir-Hinshelwood rate law. The results obtained showed that after using the catalyst five times repeatedly, the catalyst retained its efficiency and the rate of the degradation process was still above 80%.展开更多
Two isomers of nitrochlorobenzene (o-, and p-NCB) were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines ...Two isomers of nitrochlorobenzene (o-, and p-NCB) were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines (CAN) first through an amination process, and then rapidly dechlorinated to become aniline (AN) and Cl?, without the involvement of any other inter-mediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene (o-, and p-NCB) in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy (correlation with the activation energy) of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.展开更多
In this study,the sulfur-doped porous g-C_(3)N_(4) nanosheets(CN-T-U 1.75)were synthesized successfully by onestep calcination utilizing urea and thiourea as precursors.Under visible light irradiation,CN-T-U 1.75 show...In this study,the sulfur-doped porous g-C_(3)N_(4) nanosheets(CN-T-U 1.75)were synthesized successfully by onestep calcination utilizing urea and thiourea as precursors.Under visible light irradiation,CN-T-U 1.75 showed remarkable photocatalytic activity for Rhodamine B(RhB)degradation with a kinetic reaction rate constant of 0.01838 min^(-1).The characterization analysis indicated that CN-T-U 1.75 had a higher specific surface area and the doping altered the energy band structure.This work offers a new viewpoint on modifying the band structure of a photocatalyst using a doping strategy,as well as new insights into the generation routes of active species involved in the photocatalytic process.展开更多
基金financially supported by the National Natural Science Foundation of China (22005097)the State Key Laboratory of Physical Chemistry of Solid Surfaces,Xiamen University,Xiamen 361005,P.R.China (201815)。
文摘Efficiently and thoroughly degrading organic dyes in wastewater is of great importance and challenge.Herein,vertically oriented mesoporous a-Fe_(2)O_(3)nanorods array(a-Fe_(2)O_(3)-NA)is directly grown on fluorine-doped tin oxide(FTO)glass and employed as the photoanode for photoelectrocatalytic degradation of methylene blue simulated dye wastewater.The Ovsites on the a-Fe_(2)O_(3)-NA surface are the active sites for methylene blue(MB)adsorption.Electrons transfer from the adsorbed MB to Fe-O is detected.Compared with electrocatalytic and photocatalytic degradation processes,the photoelectrocatalytic(PEC)process exhibited the best degrading performance and the largest kinetic constant.Hydroxyl,superoxide free radicals,and photo-generated holes play a jointly leading role in the PEC degradation.A possible degrading pathway is suggested by liquid chromatography-mass spectroscopy analysis.This work demonstrates that photoelectrocatalysis by a-Fe_(2)O_(3)-NA has a remarkable superiority over photocatalysis and electrocatalysis in MB degradation.The in-depth investigation of photoelectrocatalytic degradation mechanism in this study is meaningful for organic wastewater treatment.
基金supported by the National Key Research and Development Program of China(2019YFA0210302)the National Natural Science Foundation of China(21878009).
文摘As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.
基金National Natural Science Foundation of China(No.12075037)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX21_2873)Research and Application Service Platform Project of API Manufacturing Environmental Protection and Safety Technology in China(No.2020-0107-3-1).
文摘The effect of N_(2)discharge products on cyclohexane degradation over a MnO_(2)/γ-Al_(2)O_(3)catalyst has been evaluated by feeding N_(2)discharge products to the catalyst using a specially designed dielectric barrier discharge reactor.At a reaction temperature of 100℃,the cyclohexane conversion increased from 2.46%(without N_(2)discharge products)to 26.3%(with N_(2)discharge products).N-and O-containing by-product(3,4-dehydroproline)was found on the catalyst surface using gas chromatograph-mass spectrometry identification,in which C=N–C and C=N–H bonds were also confirmed from x-ray photoelectron spectroscopy analysis results.Operando analysis results using diffuse reflectance infrared Fourier transform spectroscopy revealed that N atoms can react with surface H_(2)O possibly to NH and OH reactive species that have reactivities to promote CO oxidation to CO_(2).The mechanism of N-atom-driven cyclohexane degradation to CO and CO_(2)is proposed.
基金the National High Technology Research and Development Program of China(Grant No.2009AA063003)the National Nature Science Foundation of China(Grant No.20677039) for financial support
文摘A significant promotion effect of low-molecular hydroxyl compounds(LMHCs) was found in the nano-photoelectrocatalytic(NPEC) degradation of fulvic acid(FA),which is a typical kind of humic acid existing widely in natural water bodies,and its influence mechanism was proposed.A TiO_2 nanotube arrays(TNAs) material is served as the photoanode.Methanol,ethanediol,and glycerol were chosen as the representative of LMHCs in this study.The adsorption performance of organics on the surface of TNAs was investigated by using the instantaneous photocurrent value.The adsorption constants of FA,methanol,ethanediol,and glycerol were 43.44,19.32,7.00,and 1.30,respectively,which indicates that FA has the strongest adsorption property.The degradation performance of these organics and their mixture were observed in a thin-layer reactor.It shows that FA could hardly achieve exhausted mineralization alone,while LMHCs could be easily oxidized completely in the same condition.The degradation degree of FA,which is added LMHCs,improves significantly and the best promotion effect is achieved by glycerol.The promotion effect of LMHCs in the degradation of FA could be contributed to the formation of a tremendous amount of hydroxyl radicals in the NPEC process.The hydroxyl radicals could facilitate the complete degradation of both FA and its intermediate products.Among the chosen LMHCs,glycerol molecule which has three hydroxyls could generate the most hydroxyl radicals and contribute the best effective promotion.This work provides a new way to promote the NPEC degradation of FA and a direction to remove humus from polluted water.
基金Project(2014FJ3041)supported by the Research Funds of Science and Technology Agency of Hunan Provincial,ChinaProject(14A076)supported by the Research Funds of Education Agency of Hunan Provincial,ChinaProject supported by the Postdoctoral Science Foundation of Central South University,China
文摘CdS quantum dots sensitized platelike WO_3 photoelectrodes were successfully synthesized by a facile hydrothermal method and a modified chemical bath deposition(CBD) technique.To further improve the stability of the photoelectrodes in alkaline environment,the platelike WO_3 films were treated with TiCl_4 to form a nano-TiO_2 buffer layer on the WO_3 plate surface before loading CdSQDs.The resulting electrodes were characterized by using XRD,SEM,HR-TEM and UV-vis spectrum.The photocatalytic activity of the resulting electrodes was investigated by degradation of methyl orange(MO) in aqueous solution.The photoelectrochemical(PEC) property of the resulting electrodes was also characterized by the linear sweep voltammetry.The results of both the degradation of MO and photocurrent tests indicated that the as-prepared CdSQDs sensitized WO_3 platelike photoelectrodes exhibit a significant improvement in photocatalytic degradation and PEC activity under visible light irradiation,compared with unsupported CdSQDs electrodes.Significantly,coating the WO_3 plates with nano-TiO_2 obviously facilitate the charge separation and retards the charge-pair recombination,and results in a highest activity for QDsCdS/TiO_2/WO_3 photoelectrodes.
基金Funded by the Beijing Natural Science Foundation(No.2192016)the Beijing Natural Science Foundation and the Key Scientific Project of Beijing Municipal Education Commission(No.KZ202110011018)。
文摘A titanium dioxide loaded tremella-like mesoporous calcium silicate hydrate(TiO_(2)@CSH)with both adsorption and photocatalytic degradation activity was successfully prepared by a hydrothermal method combined with sol-gel strategy in two steps in this work.Tremella-shaped CSH provides abundant active sites for accommodating of TiO_(2),thus the corresponding TiO_(2)@CSH achieved a high loading ratio of 36.73%.Such a special shaped TiO_(2)@CSH exhibits excellent pre-enrichment capacity and photocatalytic degradation capacity for organic pollutants.Bisphenol A(BPA)removal experiments show that TiO_(2)@CSH can remove 91.17%of BPA from aqueous solutions.Studies on removal mechanism suggest that BPA tends to bind on the interface between CSH and TiO_(2) and the pre-enrichment process conforms to the intraparticle diffusion model;and then,it is decomposed to harmless substances of CO_(2) and H_(2)O during the photocatalytic process.The experimental results show that loading functional nanoparticles such as TiO_(2) on the surface of inorganic porous materials can endow inert porous materials with new functions such as photocatalytic degradation,which effectively expands the application range of inorganic porous materials.
基金supported by the Open Program of the Tianjin Key Laboratory of Green Chemical Engineering Process Engineering,Tiangong University,Tianjin(Grant No.GCEPE20190108)the Inner Mongolia Natural Science Foundation(Grant No.2020MS02015)the Regional Science Foundation Project of the National Natural Science Foundation of China(Grant No.42167029)
文摘Given the difficulties of degrading benzotriazole(BTA),this study used a one-pot hydrothermal method to prepareα-Fe_(2)O_(3)/Cu_(2)O(FC)composites for photoelectrocatalytic(PEC)degradation of BTA.The characterization of FC structure showed that Cu_(2)O in cubic crystals was loaded with circular sheets of Fe_(2)O_(3).Owing to this structure,FC showed efficient PEC degradation of BTA when exposed to ultraviolet light.The experimental results demonstrated that FC efficiently degraded BTA.When the PEC degradation continued for 60 min,100%degradation of BTA was achieved because FC enhanced the photoelectron-hole separation and the separation and transfer of articulated carriers.High per-formance liquid chromatography-mass spectrometry showed that intermediates formed during the PEC degradation of BTA.Finally,various pathways for degradation of BTA were postulated.This FC-based PEC system provides a harmless and effective method for degradation of BTA.
基金supported by the National Key Research and Development Program of China [2019YFC1904500]National Natural Science Foundation of China [52270115, 21878331, 21777080]Science Foundation of China University of Petroleum, Beijing [2462019QNXZ05, 2462020YXZZ018]
文摘Layered double hydroxide(LDH)with special layered structure has been proved to have excellent hole transport capacity and good stability.Herein,we report a high efficient composite photocatalyst of CoAlLDH and BiPO4prepared by hydrothermal and che mical adsorption(denoted as CoAl-LDH/BiPO_(4)).Phenol can be entirely degraded by 1%CoAl-LDH/BiPO_(4)under 30 min ultraviolet(UV)light irradiation,and the degradation rate constants k are 3 times and 39 times higher than that of pure BiPO_(4)and CoAl-LDH,respectively.The enhanced photocatalytic activity can be attributed to effective holes transfer from BiPO4to CoAl-LDH,which hinders the recombination of photo genera ted charge carriers.In addition,the combination of BiPO4and CoAl-LDH avoids the agglomeration of BiPO4and improves the stability of BiPO_(4).Active species capture experiments indicate that superoxide radicals(·O-_(2))are the main active species responsible for the degradation of phenol.This work provides technical approaches and research ideas for solving the photogenerated charge carrier recombination problem of photocatalyst.
基金the founding support from the National Natural Science Foundation of China (21906072, 22006057 and 31971616)the Natural Science Foundation of Jiangsu Province (BK20190982)+4 种基金“Doctor of Mass Entrepreneurship and Innovation” Project in Jiangsu ProvinceHenan Postdoctoral Foundation (202003013)the Science and Technology Research Project of the Department of Education of Jilin Province (JJKH20200039KJ)the Science and Technology Research Project of Jilin City (20190104120, 201830811)the Project of Jilin Provincial Science and Technology Development Plan (20190201277JC, 20200301046RQ, YDZJ202101ZYTS070)
文摘In this study,biochar(BC)derived from pomelo was prepared via a high-temperature calcination method to modify the graphitic carbon nitride(g-C_(3)N_(4))to synthesize the BC/g-C_(3)N_(4)composite for the degradation of the tetracycline(TC)antibiotic under visible light irradiation.The experimental results exhibit that the optimal feeding weight ratio of biochar/urea is 0.03:1 in BC/g-C_(3)N_(4)composite could show the best photocatalytic activity with the degradation rate of tetracycline is 83%in 100 min irradiation.The improvement of photocatalytic activity is mainly attributed to the following two points:(i)the strong bonding with π-π stacking between BC and g-C_(3)N_(4)make the photogenerated electrons of light-excited g-C_(3)N_(4)transfer to BC,quickly and improve the separation efficiency of carriers;(ii)the introduction of BC reduces the distance for photogenerated electrons to migrate to the surface and increases the specific surface area for providing more active sites.This study provides a sustainable,economical and promising method for the synthesis of photocatalytic materials their application to wastewater treatment.
文摘The metal-doping into the photocatalyst was evaluated for the photocatalytic degradation of bisphenol A in aqueous solution with ZnO powder. Au/ZnO, Ag/ZnO and Cu/ZnO were tested in the present work. Ag-doping ZnO was effective for the improvement of efficiency for the photocatalytic degradation of bisphenol A in water. The optimum doping concentration of silver was found to be 3 wt%. The pseudo first-order rate constant with 3 wt% Ag/ZnO was 1.3 times better compared with bare ZnO. The photocatalytic degradation of treatment for the wastewater containing bisphenol A is simple, easy handling and low cost.
文摘TiO2 doped with C, N and S (TCNS photocatalyst) was prepared by hydrolysis process using titanium iso-propoxide and thiourea. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photo electron spectroscopy (XPS), BET surface area, FTIR and diffuse reflectance spectra (DRS). The results showed that the prepared catalysts are anatase type and nanosized par-ticles. The catalysts exhibited stronger absorption in the visible light region with a red shift in the adsorption edge. The photocatalytic activity of TCNS photocatalysts was evaluated by the photocatalytic degradation of isoproturon pesticide in aqueous solution. In the present study the maximum activity was achieved for TCNS5 catalyst at neutral pH with 1 g L-1 catalyst amount and at 1.14 x 10-4 M concentration of the pesticide solution. The TCNS photocatalysts showed higher phtocatalytic activity under solar light irradiation. This is attributed to the synergetic effects of red shift in the absorption edge, higher surface area and the inhibition of charge carrier recombination process.
基金Funded by the National Natural Science Foundation of China(No.21407020)the Fundamental Research Fund for the Central Universities(No.N130302004)
文摘Kinetics of photocatalytic degradation of methylene blue(MB) over Ca Ti O3 was studied. Effects of the solution p H, the MB concentration, the Ca Ti O3 dosage, and the type of light source on photocatalytic degradation rate of MB over Ca Ti O3 were investigated in detail. The results show that photocatalytic degradation of MB over Ca Ti O3 followed the first-order reaction. The apparent rate constant(kobs) of MB significantly increased with increasing solution p H while it greatly decreased with increasing MB concentration. The kobs of MB increased with increasing Ca Ti O3 dosage from 0.05 to 0.1 g, whereas it slightly decreased with increasing Ca Ti O3 dosage in the range of 0.1-0.4 g. The kobs of MB under UV-visible light irradiation was larger by factors of 2.2 than that under visible light irradiation. The kobs of MB was(4.8±0.3)×10-1h-1 under optimal conditions with the solution p H of 11, the MB concentration of 1 ppm, the Ca Ti O3 dosage of 0.1 g, and UV-visible light irradiation.
基金supported by National Natural Science Foundation of China (21476097,21776118,21507046)Six Talent Peaks Project in Jiangsu Province (2014-JNHB-014)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘The suppression of the recombination of electrons and holes(e–h) and the enhancement of the light absorption of semiconductors are two key points toward efficient photocatalytic degradation.Here,we report a few-layer g-C_3N_4/α-MoO_3 nanoneedles(flg-C_3N_4/α-MoO_3 NNs) all-solid-state Z-scheme mechanism photocatalyst synthesized via a typical hydrothermal method in a controlled manner.The recombination of the photo-induced e–h pairs could be effectively restrained by the Z-scheme passageway between the flg-C_3N_4 and α-MoO_3 NNs in the composite,which could also promise a high redox ability to degrade pollutants.And it became possible for the prepared photocatalyst to absorb light in a wide range of wavelengths.The detailed mechanism was studied by electron spin-resonance spectroscopy(ESR).The low-dimensional nanostructure of the two constituents(α-MoO_3 NNs with one-dimensional structure and flg-C_3N_4 with two-dimensional structure) endowed the composite with varieties of excellent physicochemical properties,which facilitated the transfer and diffusion of the photoelectrons and increased the specific surface area and the active sites.The 10 wt% flg-C_3N_4/α-MoO_3 NNs showed the best photocatalytic performance toward RhB degradation,the rate of which was 71.86%,～2.6 times higher than that ofα-MoO_3 NNs.
文摘Perovskite type oxides LaCoO 3 was prepared by citrate method in granula of 20～30 nm. Using a fluorescent Hg lamp or sunlight as irradiator, the degradation experiments of various water soluble dyes were carried out in the suspension system of LaCoO 3. The results show that the perovskite type oxide LaCoO 3 has good photocatalytic activity. With the study of X ray photoelectron spectroscopy and photoacoustic spectra, its photocatalytic activity is mainly related with the factors such as the d electron structure of ion Co 3+ , Co O binding energy and adsorbed oxygen on the surface etc.
基金supported by the National Natural Science Foundation of China (Nos.21406164,21466035,51203111)the National Basic Research Program of China("973" program,Nos.2012CB720100,2014CB239300)
文摘The crystal form of TiO_2 is a crucial focus of research on the photocatalytic degradation of gaseous pollutants by TiO_2-based composite photocatalysts. To explore the synergistic effect of mixed crystalline TiO_2 on gaseous organic-pollutant photocatalytic degradation, we synthesized a series of TiO_2 nanoparticles with controllable phase ratios. We explored the role of the TiO_2 phase ratio on the photocatalytic activity and degradation pathway in the photodegradation of 2-propanol(IPA). We estimated the crystallite size and crystal proportions of anatase and rutile by X-ray diffraction. We used the Brunauer-Emmett-Teller method to calculate the specific surface area and Fourier transform infrared spectroscopy to characterize the surface chemistry of the samples. Our results show the photocatalytic activities of pure anatase and the sample with 8.6% rutile to be much better than those of the samples with a phase junction and pure rutile. As such, anatase is the better option for the study of photodegradation design and preparation of gas-phase organic pollutants.
文摘Silicotungstic acid and phosphotungstic acid were prepared and characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The results showed that the prepared catalysts possess classical Keggin structure. The factors on the degradation of methyl orange, such as the kind of catalyst, the amount of catalyst, the original concentration of dye and illumination time were investigated under metal halide lamp. The degradation of methyl orange is up to 93.6% with phosphotungstic acid at the best reaction conditions at 8.89 g/L concentration of phosphotungstic acid, 5.56 mg/L concentration of methyl orange and 80 min illumination time.
文摘To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.
文摘The crosslinked gelatin/CuS/PVA nanocomposite catalyst prepared using gamma irradiation as initiator was extensively characterized using several techniques including transmission electron microscopy (TEM), UV-Vis spectroscopy, infrared spectroscopy (IR) and X-ray diffraction (XRD). We chose Rhodamine B (RhB) dye as a model contaminant in order to investigate its Photocatalytic activity under solar light irradiation. The effects of pH, catalyst concentration and RhB concentration on degradation reaction were also investigated. Similar to the observed trend for the photocatalytic oxidation of other organic compounds, the efficiency of photocatalytic degradation of RhB tended to decrease with increasing the concentration of RhB. The degradation efficiency of RhB is found to increase as pH is increased up to pH of 10, then starts decreasing at pH values higher than 10. The degradation efficient of RhB is found to increase as the amount of the catalyst dosage increases up to an optimum value of 0.25 g. Increasing the concentrations of photocatalyst beyond 0.25 g was found to decrease the photocatalytic activity of RhB. It was proven that the degradation process of RhB reaction rate obeyed a pseudo-first-order reaction of the catalyst concentration of gelatin/CuS/PVA nanocomposite. The degradation kinetics was found to fit well Langmuir-Hinshelwood rate law. The results obtained showed that after using the catalyst five times repeatedly, the catalyst retained its efficiency and the rate of the degradation process was still above 80%.
基金Project (No. 20407015) supported by the National Natural ScienceFoundation of China
文摘Two isomers of nitrochlorobenzene (o-, and p-NCB) were treated by a Pd/Fe catalyst in aqueous solutions through catalytic amination and dechlorination. Nitrochlorobenzenes are rapidly converted to form chloroanilines (CAN) first through an amination process, and then rapidly dechlorinated to become aniline (AN) and Cl?, without the involvement of any other inter-mediate reaction products. The amination and dechlorination reaction are believed to take place predominantly on the surface site of the Pd/Fe catalysts. The dechlorination rate of the reductive degradation of the two isomers of nitrochlorobenzene (o-, and p-NCB) in the presence of Pd/Fe as a catalyst was measured experimentally. In all cases, the reaction rate constants were found to increase with the decrease in the Gibbs free energy (correlation with the activation energy) of NCBs formation; the activation energy of each dechlorination reaction was measured to be 95.83 and 77.05 kJ/mol, respectively for o- and p-NCB. The results demonstrated that p-NCBs were reduced more easily than o-NCBs.
基金supported by the Liaoning Provincial Natural Fund Mentoring Program Project (2019-ZD-0057)
文摘In this study,the sulfur-doped porous g-C_(3)N_(4) nanosheets(CN-T-U 1.75)were synthesized successfully by onestep calcination utilizing urea and thiourea as precursors.Under visible light irradiation,CN-T-U 1.75 showed remarkable photocatalytic activity for Rhodamine B(RhB)degradation with a kinetic reaction rate constant of 0.01838 min^(-1).The characterization analysis indicated that CN-T-U 1.75 had a higher specific surface area and the doping altered the energy band structure.This work offers a new viewpoint on modifying the band structure of a photocatalyst using a doping strategy,as well as new insights into the generation routes of active species involved in the photocatalytic process.
