CN104549395A - Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst - Google Patents

Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst Download PDF

Info

Publication number
CN104549395A
CN104549395A CN201410577824.5A CN201410577824A CN104549395A CN 104549395 A CN104549395 A CN 104549395A CN 201410577824 A CN201410577824 A CN 201410577824A CN 104549395 A CN104549395 A CN 104549395A
Authority
CN
China
Prior art keywords
sic
cdla
catalyst
sample
composite photo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410577824.5A
Other languages
Chinese (zh)
Other versions
CN104549395B (en
Inventor
李慧泉
崔玉民
苗慧
陶栋梁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ANHUI JINSENYUAN ENVIRONMENTAL ENGINEERING Co.,Ltd.
Original Assignee
Fuyang Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuyang Normal University filed Critical Fuyang Normal University
Priority to CN201410577824.5A priority Critical patent/CN104549395B/en
Publication of CN104549395A publication Critical patent/CN104549395A/en
Application granted granted Critical
Publication of CN104549395B publication Critical patent/CN104549395B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Catalysts (AREA)

Abstract

The invention discloses a compound photocatalyst for treating wastewater pollution as well as a preparation method and application of the compound photocatalyst for treating the wastewater pollution. According to the preparation method, a matrix substance CdLa2S4of the compound photocatalyst is compounded once by virtue of a hydrothermal method and is prepared into the compound photocatalyst with a regular shape by virtue of a calcining method. The compound photocatalyst can be utilized for catalytically degrading organic dyes under ultraviolet irradiation, and particularly the efficiency for catalytically degrading azo organic dyes is high.

Description

A kind of composite photo-catalyst and preparation and application thereof of administering contaminated wastewater
Technical field
The invention belongs to photocatalysis field, relate to a kind of composite photo-catalyst and preparation and application thereof, particularly administer the composite photo-catalyst SiC/CdLa of contaminated wastewater 2s 4and preparation and application.
Background technology
In recent years, along with industrial fast development, problem of environmental pollution is subject to the common concern of people always.Along with administering improving constantly of industrial pollution technology, photocatalysis technology, namely utilizes sun power to carry out the research of Photocatalyst in environmental improvement to pollutent more and more deep.
Another thinking of research photocatalyst finds novel photocatalyst.At present, be no longer the semiconductor compound finding occurring in nature existence to the exploitation that can be used for light-catalysed semiconductor compound, but trend towards synthetic semiconductor compound, as CdLa 2s 4deng, but, not high as the photocatalysis efficiency of photocatalyst using this compound merely.
Therefore, need a kind of existing good photochemical catalysis of exploitation badly and reduce organic photocatalyst staining thing effect.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: with Cd (NO 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide, as initial action raw material, prepare CdLa by hydrothermal method single step reaction 2s 4, to obtained product after simple process, then by the CdLa after silicon carbide (SiC) and process 2s 4powder mixes, and fully grinds, and at high temperature calcines, obtained composite photo-catalyst, and this obtained composite photo-catalyst both can organic dye pollutant, particularly azo organic dye in catalyzed degradation water under illumination condition.
The object of the present invention is to provide following aspect:
First aspect, a kind of composite photo-catalyst SiC/CdLa 2s 4, it is characterized in that, this composite photo-catalyst comprises SiC and CdLa 2s 4, wherein, based on CdLa 2s 4weighing scale, the weight fraction of SiC is 0.1% ~ 20%;
Its X-ray diffraction spectrum (XRD) is about 18.03 ° at diffraction angle 2 θ, 20.74 °, 24.72 °, 26.50 °, 27.97 °, 30.29 °, 43.91 °, 52.05 °, 53.95 °, 35.65 °, 41.46 °, 59.98 ° and 75.26 ° of place's existence (111) respectively, (200), (120), (121), (220), (300), (303), (422), (501), (111), (200), (220), (203) crystallographic plane diffraction peak.
Second aspect, the invention provides a kind of method preparing above-mentioned composite photo-catalyst, the method comprises the following steps:
(1) CdLa 2s 4preparation, comprise following sub-step:
(1-1) by Cd (NO 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide are placed in water, at high temperature isothermal reaction, obtained throw out;
(1-2) separated from reaction system by throw out obtained in step (1-1), washing, drying, obtain CdLa 2s 4sample;
(2) composite photo-catalyst SiC/CdLa 2s 4preparation, comprise following sub-step:
(2-1) CdLa of preparation in step (1) is taken respectively 2s 4carry out mixed grinding with SiC, the mixed powder after grinding is placed in the container filling solvent;
(2-2) remove solvent, drying, more at high temperature calcine, after calcining, cooling, obtains composite photo-catalyst.
The third aspect, the present invention also provides above-mentioned composite photo-catalyst at improvement sewage, the particularly application of dye wastewater aspect, and wherein, described dyestuff is preferably azo dyes.
Accompanying drawing explanation
Fig. 1 illustrates XRD spectra in experimental example 1, wherein
A represents that comparative example 1 obtains the XRD spectra of sample;
B represents that embodiment 1 obtains the XRD spectra of sample;
C represents that embodiment 2 obtains the XRD spectra of sample;
D represents that embodiment 3 obtains the XRD spectra of sample;
E represents that embodiment 4 obtains the XRD spectra of sample;
F represents that comparative example 2 obtains the XRD spectra of sample;
Fig. 2 a illustrates that comparative example 1 obtains the scanning electron microscope (SEM) photograph of sample;
Fig. 2 b illustrates that comparative example 2 obtains the scanning electron microscope (SEM) photograph of sample;
Fig. 2 c illustrates that embodiment 2 obtains the scanning electron microscope (SEM) photograph of sample;
Fig. 3 illustrates that comparative example 1 and embodiment 2 obtain sample photoluminescence spectra, wherein,
A represents that comparative example 1 obtains the photoluminescence spectra figure of sample;
B represents that embodiment 2 obtains the photoluminescence spectra figure of sample;
Fig. 4 illustrates that comparative example 1, comparative example 2 and embodiment 2 obtain the impedance spectrum of sample, wherein,
A represents that comparative example 2 obtains the impedance spectrum of sample;
B represents that comparative example 1 obtains the impedance spectrum of sample;
C represents that embodiment 2 obtains the impedance spectrum of sample;
Fig. 5 illustrates that embodiment 1 ~ 4, comparative example 1 and comparative example 2 obtain the ultraviolet catalytic activity of sample, wherein,
A represents that comparative example 1 obtains the ultraviolet catalytic activity of sample;
B represents that embodiment 1 obtains the ultraviolet catalytic activity of sample;
C represents that embodiment 2 obtains the ultraviolet catalytic activity of sample;
D represents that embodiment 3 obtains the ultraviolet catalytic activity of sample;
E represents that embodiment 4 obtains the ultraviolet catalytic activity of sample;
F represents that comparative example 2 obtains the ultraviolet catalytic activity of sample;
Fig. 6 illustrates that scavenging agent obtains the UV-light activity influence of the degraded methyl orange solution of sample to embodiment 2, wherein,
No scavenget represents and does not add scavenging agent;
IPA represents and adds Virahol;
AO represents and adds ammonium oxalate;
BQ represents and adds para benzoquinone;
CAT represents and adds catalase;
NO 3 -represent and add NaNO 3.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
The present inventor finds, by with Cd (NO through research 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide, as initial action raw material, prepare CdLa by hydrothermal method single step reaction 2s 4, after obtained product process, then by pretreated silicon carbide (SiC) and above-mentioned CdLa 2s 4powder mixes, and fully grinds, and at high temperature calcines, obtained composite photo-catalyst, this composite photo-catalyst not only at catalyze and degrade organic pollutants under UV-irradiation, can may be used for the sewage that improvement dye wastewater, particularly organic dye cause as azo dyes.
Below illustrate the present invention.
According to a first aspect of the invention, provide a kind of composite photo-catalyst, this composite photo-catalyst comprises CdLa 2s 4and SiC, wherein, based on CdLa 2s 4weighing scale, the weight fraction of SiC is 0.1% ~ 20%, is preferably 0.3% ~ 15%, is more preferably 0.5% ~ 10%, more preferably 0.8% ~ 5%, is further preferably 1% ~ 3%.
The X-ray diffraction spectrum of this composite photo-catalyst is about 18.03 ° at diffraction angle 2 θ, 20.74 °, 24.72 °, 26.50 °, 27.97 °, 30.29 °, 43.91 °, 52.05 °, 53.95 °, 35.65 °, 41.46 °, 59.98 ° and 75.26 ° of place's existence (111) respectively, (200), (120), (121), (220), (300), (303), (422), (501), (111), (200), (220), (203) crystallographic plane diffraction peak.
Fig. 2 c illustrates that embodiment 2 obtains the scanning electron microscope (SEM) photograph of sample, and its pattern is regular club shaped structure, with CdLa 2s 4obviously different with SiC, illustrate that photocatalyst provided by the invention is mixture, instead of the physical mixed that two kinds of materials are simple.
The trans cis photoisomerization of this composite photo-catalyst as shown in Figure 3, is show similar fignal center equally within the scope of 515-530nm at wavelength, but peak intensity will comparatively CdLa 2s 4weak many, that is, the recombination probability of photo-generated carrier (electron-hole pair) is lower, and photocatalytic activity is higher.
As shown in Figure 4, its Nyquist radius of circle is significantly less than SiC and CdLa to the electrochemical impedance performance of this composite photo-catalyst 2s 4nyquist radius of circle, that is, the specific conductivity of this composite photo-catalyst is large.
The ultraviolet catalytic activity of this composite photo-catalyst as shown in Figure 5, compares CdLa 2s 4or SiC significantly strengthens.
According to a second aspect of the invention, provide a kind of method preparing above-mentioned composite photo-catalyst, the method comprises the following steps:
Step 1, CdLa 2s 4preparation, comprise following sub-step:
(1-1) by Cd (NO 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide are placed in water, at high temperature isothermal reaction, obtained throw out;
In the present invention, Cd (NO 3) 24H 2the molar weight of O with the molar amount of Cd element wherein, La (NO 3) 36H 2the molar weight of O is with the molar amount of La element wherein, and the molar weight of thiocarbamide, with the molar amount of S element wherein, makes Cd (NO 3) 24H 2the molar weight of O, La (NO 3) 36H 2the ratio of the molar weight of O and the molar weight of thiocarbamide is Cd (NO 3) 24H 2o:La (NO 3) 36H 2o: thiocarbamide=1:(2 ~ 3): (4 ~ 8), are preferably Cd (NO 3) 24H 2o:La (NO 3) 36H 2o: thiocarbamide=1:(2 ~ 3): (4 ~ 5).
Selection hydrothermal method of the present invention prepares one of component CdLa in mixture 2s 4, Cd (NO 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide can reach molecular level in aqueous other fully mixes, then in High Temperature High Pressure, preferably 100 ~ 170 DEG C, more preferably 120 ~ 165 DEG C, most preferably react under 140 ~ 160 DEG C and corresponding pressure, can obtain the CdLa of homogeneous phase 2s 4, can by water-fast solid product CdLa by the method for solid-liquid separation 2s 4separate, with this CdLa 2s 4body material as mixture contributes to the lifting of composite photo-catalyst performance.
(1-2) separated from reaction system by throw out obtained in step (1-1), washing, drying, obtain CdLa 2s 4sample.
After step (1-1) reaction, in system, naturally separate out CdLa 2s 4solid, after cooling, its amount of precipitation increases, therefore, to the CdLa in system after the present invention preferably lowers the temperature 2s 4be separated, the present invention is not particularly limited to the method be separated, and laboratory or industrial any one can be adopted to carry out the method for solid-liquid separation, as suction filtration, centrifugal etc.
Washing being separated the solid that obtains, washing or alcohol wash can be adopted, preferably select ethanol to wash, organism residual in most solid can be washed on the one hand, on the other hand can the drying of accelerating solid.
The CdLa that the present invention obtains 2s 4have good resistance to elevated temperatures, can adopt the method for constant pressure and dry or drying under reduced pressure, drying temperature can select 50 ~ 200 DEG C, is preferably 60 ~ 150 DEG C, is more preferably 70 ~ 120 DEG C.
Optionally, the present invention, after step 1, can also comprise the following steps:
The pre-treatment of (1 ') SiC, this step comprises following sub-step:
SiC powder is at high temperature calcined by (1 '-1), then floods in HF solution, obtained SiC suspension liquid.
The present invention SiC used can be commercially available SiC powder, and the order number produced as rich abrasive material Nai Cai factory of unit of Dengfeng City is 320 object silicon carbide.The present inventor finds after deliberation, and the photocatalytic activity of photocatalyst strengthens along with the reduction of its particle, and therefore, the present invention preferably selects particle is little, order number is large silicon carbide powder as raw material.
According to the preferred embodiment of the present invention, before use SiC, pre-treatment can be carried out according to above step to SiC.The benefit done like this is, the impurity such as the organism generally containing minute quantity in commercial carbonized silicon and silicon-dioxide, thus can reduce the activity of composite photo-catalyst to a certain extent.Therefore, preferably pre-treatment is carried out to SiC, to remove the impurity that wherein may contain.
Preferably, high-temperature calcination process can be carried out to commercially available SiC, with the organic substance decomposing that will wherein exist for water and carbonic acid gas, although the present invention is not particularly limited to calcining temperature, but be all decomposed into preferably to make organic substance wherein, as selected calcining temperature to be 300 DEG C ~ 900 DEG C, being preferably 400 DEG C ~ 800 DEG C, being more preferably 500 DEG C ~ 800 DEG C.
Because silicon-dioxide etc. can react with hydrofluoric acid solution, generate the compound of solubility and soluble in water, and SiC react with hydrofluoric acid, therefore, commercially available SiC powder is preferably flooded in a solution of hydrofluoric acid by the present invention.
Because hydrofluoric acid has stronger corrodibility, therefore, the present invention uses the concentration of hydrofluoric acid solution be greater than 0.1% and be less than 5%, namely 0.1% ~ 5%, when hydrofluoric acid solution concentration is greater than 5%, hydrogen fluoride gas wherein is easily overflowed reaction system, and corrode plant and instrument, even threaten operator safety, and when the concentration of hydrofluoric acid solution is less than 0.1%, its concentration is too small and the impurity such as the silicon-dioxide in SiC powder can not be eliminated, the concentration of the preferred hydrofluoric acid solution of the present invention is 1% ~ 4%, be more preferably 1.5% ~ 3%, as 2%.
The present invention is not particularly limited to the time to dipping, so that the whole soluble compounds that are converted into being difficult to be removed by calcining wherein can be made to be preferred, as selected dipping time to be 1 ~ 20 hour, being preferably 2 ~ 15 hours, being more preferably 3 ~ 10 hours.
SiC suspension liquid obtained for step (1 '-1) is separated by (1 '-2), and to be separated obtain solids wash, drying, obtained SiC sample.
Because SiC exists in solid form after treatment in system, impurity is then converted into soluble compounds and is dissolved in reaction system, therefore, the SiC suspension liquid obtained in step (1 '-1) is carried out solid-liquid separation by the present invention, the present invention is not particularly limited to the mode be separated, laboratory or industrial any one can be adopted to carry out the method for solid-liquid separation, as suction filtration, centrifugal etc.
The present invention is not also particularly limited to washings, can adopt laboratory or any one or a few available washings industrial, as distilled water, deionized water or ethanol etc.
The present invention selects to carry out drying treatment to the product that obtains after washing, and the SiC after process can be disperseed effectively, thus can with obtained CdLa in step 1 2s 4homogeneous phase mixing.
The present invention is not particularly limited to drying temperature, if preferred drying temperature is 50 DEG C ~ 300 DEG C, is preferably 70 DEG C ~ 250 DEG C, is more preferably 90 DEG C ~ 200 DEG C.
Step 2, composite photo-catalyst SiC/CdLa 2s 4preparation, comprise following sub-step:
(2-1) CdLa of preparation in step 1 is taken respectively 2s 4the SiC pretreated with step 2 carries out mixed grinding, and the mixed powder after grinding is placed in the container filling solvent.
According to CdLa in composite photo-catalyst 2s 4weight ratio with SiC, takes CdLa respectively 2s 4and SiC, for making the photocatalysis effect of the composite photo-catalyst obtained more excellent, the present invention selects SiC and CdLa 2s 4weight ratio be 0.1% ~ 20%, be preferably 0.3% ~ 15%, be more preferably 0.5% ~ 10%, more preferably 0.8% ~ 5%, be further preferably 1% ~ 3%.
Due to CdLa obtained in the present invention 2s 4with SiC in pretreatment process all through washing drying and other steps, therefore, inevitably form the material of some inclusions, for making CdLa 2s 4can mix fully with SiC, form the mixture of regular appearance in subsequent step, the present invention selects CdLa 2s 4grind with the mixture of SiC, and disperse grinding the mixed powder obtained in water, form uniform dispersion system.
In the present invention, preferably adopt ultrasonic method to process dispersion system, make CdLa 2s 4disperse with SiC more even in water, make it in subsequent calcination recombination process, form the regular mixture of appearance.
In the present invention, the preferably ultrasonic time is 1 ~ 200 minute, and be preferably 10 ~ 150 minutes, be more preferably 20 ~ 100 minutes, preferably ultrasonic power is 20KHz ~ 500MHz, is more preferably 50KHz ~ 100MHz, more preferably 100KHz ~ 1000KHz.
(2-2) remove solvent, drying, more at high temperature calcine, after calcining, cooling, obtains composite photo-catalyst.
The present invention adopts calcination method to prepare mixture, therefore, first remove the solvent in above-mentioned dispersion system and drying, the present invention is not particularly limited to the method removing solvent, laboratory or industrial any one can be adopted can to remove the method for solvent, as methods such as filtration, evaporations; The method of the present invention to drying is not also particularly limited to, and laboratory or industrial any one can be adopted can to carry out dry method, as constant pressure and dry or drying under reduced pressure etc. to said mixture.
For making SiC and CdLa 2s 4compound obtains more abundant, and the present invention selects calcining temperature to be 300 DEG C ~ 800 DEG C, and be preferably 350 DEG C ~ 600 DEG C, as 450 DEG C, calcination time is 1 ~ 10 hour, is preferably 2 ~ 8 hours, is more preferably 3 ~ 6 hours, as 5 hours.
According to a third aspect of the present invention, provide above-mentioned composite photo-catalyst at improvement organic dye sewage, the particularly application of azo dyes sewage aspect.
Azoic dyestuff is a kind of dyestuff that in existing Dyestuff Market, kind is quantitatively maximum, gains the name containing azo-group by dye molecule.In its production process, topmost chemical process is diazotization and coupled reaction, and its reaction process is also by the impact of multiple reaction conditions.The advantages such as azoic dyestuff has because synthesis technique is simple, with low cost in application, dyeing behavior is outstanding, but reduction reaction can be there is form carcinogenic aromatic amine compound in it, and therefore part azoic dyestuff is forbidden.
The present invention take tropeolin-D as the model compound of light-catalyzed reaction, measures as probe molecule with terephthalic acid to the ultraviolet liquid-phase catalysis activity of Mn-BiOCl photocatalyst and ultraviolet solid catalysis activity.
Because tropeolin-D is typical azo dyes using tropeolin-D as model compound, and its stable chemical nature, can not decompose under the action of uv light, deduction can be avoided during experiment blank, reduce error, improve the efficiency of experiment; And tropeolin-D by absorbancy and concentration curve, directly can calculate rate of decomposition, calculates reliably easy; In addition, tropeolin-D experiment is comparatively ripe, and degree of recognition is high, and result is easily accepted.
The photocatalytic activity to organic pollutant of composite photo-catalyst provided by the invention is with SiC and CdLa 2s 4the increase of weight ratio first increase and reduce again, as SiC and CdLa 2s 4quality ratio when being 1.0% the degradation rate of photocatalyst reach the highest, but the ultraviolet catalytic of composite photo-catalyst is active all higher than simple CdLa 2s 4or SiC.
By adding scavenging agent experiment, known composite photo-catalyst provided by the invention can form the free radical that catalysis organic dye, particularly azo dyes decompose under UV-irradiation on its surface, thus the decomposition of catalysis organic dye.
Based on above experimental result, under not being bound by any theory, the present inventor thinks, is more than or equal to the rayed SiC/CdLa of its conductor energy gap with energy 2s 4photocatalyst, the electronics be in valence band will be excited on conduction band, and valence band produces hole (h +), thus at SiC/CdLa 2s 4photocatalyst surface produces the electron-hole pair with high activity, and this electron-hole pair is the active centre of light-catalyzed reaction, has very strong oxidation capacity, can will be adsorbed in SiC/CdLa 2s 4oH-and H of photocatalyst surface 2o is oxidized, and produces the OH free radical with strong oxidizing property.
The reaction of OH free radical can be 402.8MJ/mol, it can be destroyed C-C, C-H, C-O and N-H key in pollutent by the hydroxyl adduction, replacement, transfer transport etc. between pollutent, there is the ability of efficient-decomposition pollutent, make pollutent all or close to whole mineralising, contaminant degradation is the innoxious substance such as carbonic acid gas, water the most at last, meanwhile, hole itself also can will be adsorbed in SiC/CdLa 2s 4the organism direct oxidation of photocatalyst surface is decomposed, in addition, and SiC/CdLa 2s 4the high reactivity electronics that photocatalyst surface produces has very strong reducing power, when having O in solution 2when existing, light induced electron meeting and O 2effect generates O 2 -, O 2 -again with H +effect generates HO 2, final generation OH free radical, oxidative degradation organism.
Embodiment
The order number that in the present embodiment and comparative example, SiC sample used is produced purchased from rich abrasive material Nai Cai factory of unit of Dengfeng City is 320 object silicon carbide.
embodiment 1
(1) CdLa 2s 4the preparation of sample
(1-1) by 2.3799g Cd (NO 3) 24H 2o, 6.6896g La (NO 3) 36H 2the thiocarbamide of O and 2.5365g is placed in 60mL distilled water, and gained solution joins in the stainless steel autoclave of the polytetrafluoroethylsubstrate substrate of 100mL capacity, and isothermal reaction 72h under 433K (about 160 DEG C), obtains yellow mercury oxide,
(1-2) with yellow mercury oxide obtained in dehydrated alcohol rinsing step (1-1), and vacuum-drying under 333K (about 60 DEG C), obtain CdLa 2s 4sample;
The pre-treatment of (1 ') SiC
3h calcined by the retort furnace that SiC powder is placed in 973K (about 700 DEG C) by (1 '-1), be placed in 2%HF solution and flood 5h,
Solution is carried out suction filtration by (1 '-2), and with distilled water drip washing 3 times, finally obtains SiC sample at 393K (about 120 DEG C) dry 12h;
(2) SiC/CdLa 2s 4the preparation of catalyst sample
(2-1) CdLa of preparation in 0.5000g step (1) is accurately taken respectively 2s 4mix with pretreated 0.0025gSiC, be placed in agate mortar grinding 20min, the mixed powder after grinding transferred in the small beaker filling 30mL distilled water, supersound process 30min,
(2-2) anhydrate in the water-bath of 383K (about 110 DEG C), evaporate to dryness, 723K (about 450 DEG C) retort furnace calcining 2h, naturally cooling, obtains composite catalyst sample SiC/CdLa 2s 4, in this sample, the weight fraction of SiC is 0.5%.
embodiment 2
The present embodiment method therefor is identical with embodiment 1, and difference is only to add 0.005g SiC in step (2-1), obtained composite catalyst sample SiC/CdLa 2s 4the weight fraction of middle SiC is 1.0%.
embodiment 3
The present embodiment method therefor is identical with embodiment 1, and difference is only to add 0.010g SiC in step (2-1), obtained composite catalyst sample SiC/CdLa 2s 4the weight fraction of middle SiC is 2.0%.
embodiment 4
The present embodiment method therefor is identical with embodiment 1, and difference is only to add 0.020g SiC in step (2-1), obtained composite catalyst sample SiC/CdLa 2s 4the weight fraction of middle SiC is 4.0%.
embodiment 5
(1) CdLa 2s 4the preparation of sample
(1-1) by 2.3799g Cd (NO 3) 24H 2o, 10.0376g La (NO 3) 36H 2the thiocarbamide of O and 3.5346g is placed in 60mL distilled water, and gained solution joins in the stainless steel autoclave of the polytetrafluoroethylsubstrate substrate of 100mL capacity, and isothermal reaction 60h under 443K (about 170 DEG C), obtains yellow mercury oxide,
(1-2) with yellow mercury oxide obtained in dehydrated alcohol rinsing step (1-1), and vacuum-drying under 473K (about 200 DEG C), obtain CdLa 2s 4sample;
The pre-treatment of (1 ') SiC
3h calcined by the retort furnace that SiC powder is placed in 873K (about 600 DEG C) by (1 '-1), be placed in 0.2%HF solution and flood 10h,
Solution is carried out suction filtration by (1 '-2), and with distilled water drip washing 3 times, finally obtains SiC sample at 373K (about 100 DEG C) dry 12h;
(2) SiC/CdLa 2s 4the preparation of catalyst sample
(2-1) CdLa of preparation in 0.5000g step (1) is accurately taken respectively 2s 4mix with pretreated 0.0030gSiC, be placed in agate mortar grinding 20min, the mixed powder after grinding transferred in the small beaker filling 30mL distilled water, supersound process 30min,
(2-2) anhydrate in the water-bath of 383K (about 110 DEG C), evaporate to dryness, 723K (about 450 DEG C) retort furnace calcining 2h, naturally cooling, obtains composite catalyst sample SiC/CdLa 2s 4, in this sample, the weight fraction of SiC is 0.6%.
Recording this composite catalyst to Photocatalytic Degradation of Methyl Orange rate by the method for experimental example 5 is 32.5%.
embodiment 6
(1) CdLa 2s 4the preparation of sample
(1-1) by 2.3650g Cd (NO 3) 24H 2o, 8.3264g La (NO 3) 36H 2the thiocarbamide of O and 4.6756g is placed in 60mL distilled water, and gained solution joins in the stainless steel autoclave of the polytetrafluoroethylsubstrate substrate of 100mL capacity, and isothermal reaction 68h under 538K (about 165 DEG C), obtains yellow mercury oxide,
(1-2) with yellow mercury oxide obtained in dehydrated alcohol rinsing step (1-1), and vacuum-drying under 423K (about 150 DEG C), obtain CdLa 2s 4sample;
The pre-treatment of (1 ') SiC
3h calcined by the retort furnace that SiC powder is placed in 1073K (about 800 DEG C) by (1 '-1), be placed in 4%HF solution and flood 5h,
Solution is carried out suction filtration by (1 '-2), and with distilled water drip washing 3 times, finally obtains SiC sample at 323K (about 50 DEG C) dry 12h;
(2) SiC/CdLa 2s 4the preparation of catalyst sample
(2-1) CdLa of preparation in 0.5000g step (1) is accurately taken respectively 2s 4mix with pretreated 0.0075gSiC, be placed in agate mortar grinding 20min, the mixed powder after grinding transferred in the small beaker filling 30mL distilled water, supersound process 30min,
(2-2) anhydrate in the water-bath of 383K (about 110 DEG C), evaporate to dryness, 723K (about 450 DEG C) retort furnace calcining 2h, naturally cooling, obtains composite catalyst sample SiC/CdLa 2s 4, in this sample, the weight fraction of SiC is 1.5%.
Recording this composite catalyst to Photocatalytic Degradation of Methyl Orange rate by the method for experimental example 5 is 43.6%.
embodiment 7
(1) CdLa 2s 4the preparation of sample
(1-1) by 2.3650g Cd (NO 3) 24H 2o, 9.9872g La (NO 3) 36H 2the thiocarbamide of O and 2.9312g is placed in 60mL distilled water, and gained solution joins in the stainless steel autoclave of the polytetrafluoroethylsubstrate substrate of 100mL capacity, and isothermal reaction 84h under 393K (about 120 DEG C), obtains yellow mercury oxide,
(1-2) with yellow mercury oxide obtained in dehydrated alcohol rinsing step (1-1), and vacuum-drying under 393K (about 120 DEG C), obtain CdLa 2s 4sample;
The pre-treatment of (1 ') SiC
4h calcined by the retort furnace that SiC powder is placed in 573K (about 300 DEG C) by (1 '-1), be placed in 3%HF solution and flood 3h,
Solution is carried out suction filtration by (1 '-2), and with distilled water drip washing 3 times, finally obtains SiC sample at 473K (about 200 DEG C) dry 12h;
(2) SiC/CdLa 2s 4the preparation of catalyst sample
(2-1) CdLa of preparation in 0.5000g step (1) is accurately taken respectively 2s 4mix with pretreated 0.0125gSiC, be placed in agate mortar grinding 20min, the mixed powder after grinding transferred in the small beaker filling 30mL distilled water, supersound process 30min,
(2-2) anhydrate in the water-bath of 383K (about 110 DEG C), evaporate to dryness, 723K (about 450 DEG C) retort furnace calcining 2h, naturally cooling, obtains composite catalyst sample SiC/CdLa 2s 4, in this sample, the weight fraction of SiC is 2.5%.
Recording this composite catalyst to Photocatalytic Degradation of Methyl Orange rate by the method for experimental example 5 is 35.2%.
Comparative example
comparative example 1
This comparative example only carries out step (1) in embodiment 1, obtained CdLa 2s 4sample.
comparative example 2
This comparative example only carries out step (2) in embodiment 1, obtains pretreated SiC.
Experimental example
the XRD spectrum of experimental example 1 sample measures
This experimental example specimen in use is preparation in embodiment 1 ~ 4 and comparative example 1 and comparative example 2, and test condition is:
Bruker D8Advance type X-ray diffractometer (XRD), copper target (Cu K α, λ=0.154nm) ray, Ni spectral filter, operating voltage 40kV, electric current 40mA, sweep limit 2 θ=15 ° ~ 80 °.
Sample XRD spectra result as shown in Figure 1, as shown in Figure 1:
CdLa 2s 4the diffraction peak that 18.03 °, 20.74 °, 24.72 °, 26.50 °, 27.97 °, 30.29 °, 43.91 °, 52.05 °, 53.95 ° places exist (111), (200), (120), (121), (220), (300), (303), (422), (501) crystal face is respectively about at diffraction angle 2 θ.(curve a)
SiC is about 2 θ at diffraction angle 2 θ and is about the diffraction peak that 35.65 °, 41.46 °, 59.98 °, 71.81 °, 75.26 ° places exist (111), (200), (220), (311), (203) crystal face respectively.(curve f)
The SiC/CdLa that embodiment 1 ~ 4 is obtained 2s 4composite photo-catalyst sample is about at diffraction angle 2 θ the diffraction peak that 18.03 °, 20.74 °, 24.72 °, 26.50 °, 27.97 °, 30.29 °, 43.91 °, 52.05 °, 53.95 ° places exist (111), (200), (120), (121), (220), (300), (303), (422), (501) crystal face respectively, and these peaks are CdLa 2s 4diffraction peak; In addition, be about 35.65 °, 41.46 °, 59.98 °, 75.26 ° places at diffraction angle 2 θ and there is (111), (200), (220), (203) crystallographic plane diffraction peak respectively, these are SiC diffraction peak, and above-mentioned diffraction peak can absolutely prove SiC and CdLa 2s 4obtain sufficient compound.
the scanning electron microscope (SEM) photograph of experimental example 2 sample
This experimental example specimen in use is preparation in embodiment 1 ~ 4 and comparative example 1 and comparative example 2, and test condition is:
Nova Nano 230 electron microscope, scanning acceleration voltage 0.1 ~ 30KV, the vacuum tightness of sample chamber is less than 2.7 × 10 -5pa.
The result of the scanning electron microscope of sample as shown in Fig. 2 a ~ 2c,
From Fig. 2 a, the CdLa that comparative example 1 is obtained 2s 4it is aggregate;
From Fig. 2 b, the SiC that comparative example 2 obtains is granular pattern;
From Fig. 2 c, SiC/CdLa 2s 4composite catalyst is regular club shaped structure, and SiC and CdLa is described 2s 4obtain the more uniform material of compound, instead of the physical mixed that two kinds of materials are simple.
the trans cis photoisomerization figure of experimental example 3 sample
Photoluminescence spectra (PL) is a kind of effective ways of research semiconductor nano material electronic structure and optical property, the structural performance such as surface imperfection and Surface Oxygen room of semiconductor nano material can be disclosed, and the information such as the separation of photo-generated carrier (electron-hole pair) and compound, thus for preparing and utilizing high-performance semiconductor material to provide strong foundation.
This experimental example specimen in use is preparation in embodiment 2 and comparative example 1, and test condition is:
Instrument is the model that Edinburgh company produces is FL/FS920 fluorescence spectrophotometer, and detector is photomultiplier, and sample carries out stable state and transient photoluminescence (PL) test by compressing tablet pattern.
Wherein, stable state PL measures at normal temperatures, and photoluminescent light source is xenon lamp; Transient state PL measures under 77K (liquid nitrogen) condition, and photoluminescent light source is millisecond flashing lamp, and excitation wavelength is 325nm.
The trans cis photoisomerization figure of sample as shown in Figure 3, as shown in Figure 3:
CdLa 2s 4catalyst sample is show stronger luminous signal within the scope of 515-530nm at wavelength; The obtained composite catalyst sample of embodiment 2 is show similar fignal center equally within the scope of 515-530nm at wavelength, but peak intensity will comparatively CdLa 2s 4weak many, and it is generally acknowledged, fluorescent signal is stronger, and the recombination probability of photo-generated carrier (electron-hole pair) is higher, and photocatalytic activity is lower, that is, the activity of the composite catalyst that embodiment 2 is obtained is significantly better than the obtained CdLa of comparative example 1 2s 4sample, the composite photo-catalyst activity order that this experimental result and previous experiments record is consistent.
the electrochemical impedance performance measurement of experimental example 4 sample
This experimental example uses the sample of preparation in embodiment 2 and comparative example 1 and comparative example 2, and test condition is:
Electrochemical impedance (EIS) is tested on Zennium electrochemical workstation, and this experimental example adopts drop-coating Kaolinite Preparation of Catalyst sample thin film electrode, and adopt the three-electrode system of standard to test the photoelectrochemical behaviour of catalyzer, electrolytic solution is 0.2molL -1na 2sO 4solution, visible light source is produced by " combination of xenon lamp+420nm spectral filter ", and concrete grammar is as follows:
(1) conducting surface of a 0.5 × 0.5cm is cooked up at FTO conductive glass (2 × 1cm) the conducting surface adhesive tape cleaned.By 0.0500g catalyzer ultrasonic disperse in 800 μ lDMF, and pipette 20 μ l and be suspended drop and be coated on the conducting surface planned, dry under room temperature, electrode is kept in closed enclosure for subsequent use.
(2) in three-electrode system, Pt sheet as to electrode, Ag/AgCl (3molL -1) as reference electrode, sample electrode, as working electrode, in test process, adopts the incident mode of backlight photograph to eliminate even the brought experimental error of non-uniform film thickness.
The electrochemical impedance performance of sample as shown in Figure 4, as shown in Figure 4:
The SiC/CdLa that embodiment 2 is obtained 2s 4the SiC that the Nyquist radius of circle of composite photo-catalyst and comparative example 2 obtain and the CdLa that comparative example 1 obtains 2s 4compare, obviously reduce, show that SiC is at CdLa 2s 4after load, the specific conductivity of sample obtains certain increase, and impedance is also little to some extent.Be not bound by any theory, the present inventor thinks, composite photo-catalyst is conducive to separation and the interfacial migration of current carrier, thus suppress the compound of current carrier, and then improving the UV degradation ability of composite photo-catalyst, above-mentioned conclusion also can be verified (specifically see experimental example 5) from the experiment of catalyzer photo-catalytic degradation of methyl-orange.
the ultraviolet catalytic of experimental example 5 sample is active
This experimental example specimen in use is preparation in embodiment 1 ~ 4 and comparative example 1 and comparative example 2, and testing method is:
Accurately take the sample that 0.0500g comparative example 1, embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 2 is obtained respectively, put into 6 silica tubes respectively, be numbered a ~ f, in above-mentioned 6 fragmented silica tubes, add 40mL concentration respectively is successively 5.00mgL -1methyl orange solution, and add a magneton.
Silica tube is put into photochemical reaction instrument, under continuous stirring, dark reaction process 30min, samples centrifugal, surveys its absorbance A 0 respectively.Turn on lamp power supply, carry out photo-irradiation treatment 1h, sample centrifugal, survey its absorbance A t respectively, 1 calculate degradation rate according to the following formula:
W (%)=(A0-At)/A0 × 100% formula I
And degradation rate is depicted as histogram, as shown in Figure 5.As shown in Figure 5:
The photocatalytic activity to organic pollutant of composite photo-catalyst is with SiC and CdLa 2s 4the increase of weight ratio first increase and reduce again, as SiC and CdLa 2s 4quality ratio when being 1.0% the degradation rate of photocatalyst reach the highest, be 49.9%; The ultraviolet catalytic of composite photo-catalyst is active all higher than simple CdLa 2s 4or SiC.
experimental example 6 scavenging agent is on the impact of photocatalyst photocatalytic activity
The sample that this experimental example uses sample to prepare for embodiment 2, testing method is:
Accurately take six parts of 0.0500g SiC-CdLa 2s 4(1%) catalyst fines is placed in six silica tubes respectively, numbering 1,2,3,4,5 and 6, and all adding 40mL concentration is successively 5.00mgL -1methyl orange solution, do not add any scavenging agent in No. 1 pipe, in No. 2 pipes, add 0.0040g ammonium oxalate, 0.0040g para benzoquinone is added in No. 3 pipes, add 3.800 μ L catalases in No. 4 pipes, add 5.000 μ L Virahols in No. 5 pipes, in No. 6 pipes, add 0.0040g NaNO 3add a magneton at each Guan Zhongjun again, above-mentioned each silica tube is put into photochemical reaction instrument, under continuous stirring, carry out dark reaction process 30min, sample centrifugal, survey its absorbance A 0 respectively, turn on lamp power supply, carry out ultraviolet lighting process 1h, sample centrifugal, survey its absorbance A t respectively, I calculates degradation rate according to the following formula:
W (%)=(A0-At)/A0 × 100% formula I
According to the experimental data recorded, calculate the degradation rate of each sample when adding different scavenging agent, draw out each catalyst sample by gained degradation rate and add histogram to 40mL methyl orange solution (5.00mg/L) degradation rate after scavenging agent, as shown in Figure 6.
Wherein, added scavenging agent Virahol can catch the OH in system;
NaNO 3the unbound electron e in system can be caught -,
Catalase can H in catalyst system 2o 2decomposition;
Ammonium oxalate can catch the hole in system;
Para benzoquinone can catch the O in system 2 -.
As shown in Figure 6, Virahol (IPA) and NaNO 3add the impact of catalyzer UV active very little, can ignore, and not add compared with scavenging agent, when other conditions are identical, under UV-irradiation photo-catalytic degradation of methyl-orange process in OH and be not main active specy;
After adding catalase (CAT), ammonium oxalate (AO) and para benzoquinone (BQ), the activity of catalyzer all has and comparatively significantly reduces, particularly the activity of catalyzer is had reduce more significantly adding of para benzoquinone (BQ), that is, H 2o 2, h +and O 2 -all work, particularly O 2 -play a major role in photocatalytic process.
More than in conjunction with embodiment and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.

Claims (8)

1. administer the composite photo-catalyst SiC/CdLa of contaminated wastewater for one kind 2s 4, it is characterized in that, this composite photo-catalyst comprises SiC and CdLa 2s 4, based on CdLa 2s 4weighing scale, the weight fraction of SiC is 0.1% ~ 20%.
2. composite photo-catalyst according to claim 1, it is characterized in that, according to X-ray diffraction analysis, it is about 18.03 ° at diffraction angle 2 θ, 20.74 °, 24.72 °, 26.50 °, 27.97 °, 30.29 °, 43.91 °, 52.05 °, 53.95 °, 35.65 °, 41.46 °, 59.98 ° and 75.26 ° of place's existence (111) respectively, (200), (120), (121), (220), (300), (303), (422), (501), (111), (200), (220), (203) crystallographic plane diffraction peak.
3. prepare a method for composite photo-catalyst according to claim 1, it is characterized in that, the method comprises the following steps:
(1) CdLa 2s 4preparation, comprise following sub-step:
(1-1) by Cd (NO 3) 24H 2o, La (NO 3) 36H 2o and thiocarbamide are placed in water, at high temperature isothermal reaction, obtained throw out;
(1-2) separated from reaction system by throw out obtained in step (1-1), washing, drying, obtain CdLa 2s 4sample;
(2) composite photo-catalyst SiC/CdLa 2s 4preparation, comprise following sub-step:
(2-1) CdLa of preparation in step (1) is taken respectively 2s 4carry out mixed grinding with SiC, the mixed powder after grinding is placed in the container filling solvent;
(2-2) remove solvent, drying, calcining, after calcining, cooling, obtains composite photo-catalyst.
4. method according to claim 3, is characterized in that, after step (1), before step (2), further comprising the steps of:
The pre-treatment of (1 ') SiC, this step comprises following sub-step:
SiC powder is at high temperature calcined by (1 '-1), then floods in HF solution, obtained SiC suspension liquid;
SiC suspension liquid obtained for step (1 '-1) is separated by (1 '-2), and to be separated obtain solids wash, drying, obtained SiC sample.
5. the method according to claim 3 or 4, is characterized in that, in step (1-1),
Cd (NO 3) 24H 2the molar weight of O with the molar amount of Cd element wherein, La (NO 3) 36H 2the molar weight of O is with the molar amount of La element wherein, and the molar weight of thiocarbamide, with the molar amount of S element wherein, makes Cd (NO 3) 24H 2the molar weight of O, La (NO 3) 36H 2the ratio of the molar weight of O and the molar weight of thiocarbamide is Cd (NO 3) 24H 2o:La (NO 3) 36H 2o: thiocarbamide=1:(2 ~ 3): (4 ~ 8); And/or
Temperature is 100 ~ 170 DEG C, preferably 120 ~ 165 DEG C, more preferably 140 ~ 160 DEG C.
6. the method according to claim 4 or 5, is characterized in that, in step (1 '-1), calcining temperature is 300 DEG C ~ 900 DEG C; And/or the concentration of hydrofluoric acid solution is 0.1% ~ 5%.
7. according to the method one of claim 3 to 6 Suo Shu, it is characterized in that, in step (2-2), calcining temperature is 300 DEG C ~ 900 DEG C.
8. composite photo-catalyst according to claim 1 and 2 or the composite photo-catalyst prepared according to the method one of claim 3 to 7 Suo Shu are at improvement organic dye sewage, the particularly application of azo dyes sewage aspect.
CN201410577824.5A 2014-10-24 2014-10-24 Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst Active CN104549395B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410577824.5A CN104549395B (en) 2014-10-24 2014-10-24 Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410577824.5A CN104549395B (en) 2014-10-24 2014-10-24 Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst

Publications (2)

Publication Number Publication Date
CN104549395A true CN104549395A (en) 2015-04-29
CN104549395B CN104549395B (en) 2017-01-18

Family

ID=53067100

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410577824.5A Active CN104549395B (en) 2014-10-24 2014-10-24 Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst

Country Status (1)

Country Link
CN (1) CN104549395B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109534696A (en) * 2019-01-25 2019-03-29 重庆化工职业学院 Load the preparation method of the glass fiber material of silicon carbide
CN111250128A (en) * 2018-12-03 2020-06-09 阜阳师范学院 Composite photocatalyst CNB-CdLa2S4, and preparation and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000170078A (en) * 1998-12-08 2000-06-20 Nippon Soda Co Ltd Method for producing photocatalyst supporting structure and photocatalyst supporting structure obtained thereby
CN101386409A (en) * 2008-10-16 2009-03-18 昆明理工大学 Method for preparing silicon carbide nano line

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000170078A (en) * 1998-12-08 2000-06-20 Nippon Soda Co Ltd Method for producing photocatalyst supporting structure and photocatalyst supporting structure obtained thereby
CN101386409A (en) * 2008-10-16 2009-03-18 昆明理工大学 Method for preparing silicon carbide nano line

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHRISTIAN GÓMEZ-SOLÍS ET AL.: ""Photodegradation of indigo carmine and methylene blue dyes in aqueous solution by SiC-TiO2 catalysts prepared by sol-gel"", 《JOURNAL OF HAZARDOUS MATERIALS》 *
JUNGANG HOU ET AL.: ""Hydrothermal synthesis of CdS/CdLa2S4 heterostructures for efficient visible-light-driven photocatalytic hydrogen production"", 《RSC ADVANCES》 *
李金望等: ""Si3N4/SiC纳米复合陶瓷的制备、结构和性能"", 《功能材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111250128A (en) * 2018-12-03 2020-06-09 阜阳师范学院 Composite photocatalyst CNB-CdLa2S4, and preparation and application thereof
CN109534696A (en) * 2019-01-25 2019-03-29 重庆化工职业学院 Load the preparation method of the glass fiber material of silicon carbide

Also Published As

Publication number Publication date
CN104549395B (en) 2017-01-18

Similar Documents

Publication Publication Date Title
Rao et al. Defect chemistry of Er3+-doped TiO2 and its photocatalytic activity for the degradation of flowing gas-phase VOCs
CN101653728B (en) Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst
CN104607230A (en) Composite photocatalyst Bi2O3/g-C3N4 as well as preparation method and application of composite photocatalyst
CN101020143A (en) Use of bismuth oxyhalide
CN101024188A (en) Halogen-oxide photocatalytic material and preparing method
CN105107505A (en) Magnetic TiO2-porous carbon-Fe3O4 composite visible light photocatalyst and preparation method thereof
Tian et al. Pyrite nanotube array films as an efficient photocatalyst for degradation of methylene blue and phenol
CN106044842A (en) Preparation method and application of sector hydroxyl zinc fluoride
CN108940300A (en) A kind of polynary Cu2O@CQDs/Bi2WO6The Preparation method and use of composite photo-catalyst
CN110368968A (en) NiFe-LDH/Ti3C2/Bi2WO6Nano-chip arrays and preparation method and application
Zhang et al. Synthesis of visible‐light‐driven g‐C3N4/PPy/Ag ternary photocatalyst with improved photocatalytic performance
CN108339544A (en) Photochemical catalyst/super-hydrophobic film composite material of fullerene carboxy derivatives modification
CN111659455B (en) Preparation method and application of Co-CDs @ NM photocatalyst
CN112495400B (en) SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI)
Gao et al. Electronic properties and photodegradation ability of V–TiO2 for aniline
CN104549395A (en) Compound photocatalyst for treating wastewater pollution as well as preparation method and application of compound photocatalyst
CN111359676B (en) MOF-based composite material and preparation method and application thereof
CN104785282A (en) New type trivalent titanium and nonmetallic element nitrogen co-doped titanium dioxide nano photocatalyst preparation
CN104874401B (en) Nd3-xCoxTaO7The preparation and application of the compound porous nano catalytic material of zeolite
CN104549396B (en) Composite photocatalyst for photocatalytic water splitting for hydrogen generation and preparation method and application of composite photocatalyst
CN103894178B (en) Bi 0.5na 0.5tiO 3preparation method and application in photocatalysis
CN114573086B (en) Method for catalytically degrading low-concentration antibiotics in water body by SEP @ CTFs composite material under visible light
CN113871631B (en) Photocatalytic fuel cell for treating azo dye wastewater and preparation method thereof
CN108993501A (en) A kind of silver-silver oxide-zinc oxide photocatalysis material preparation method
CN109772381B (en) FTO surface-based bismuth oxyhalide/calcium bismuthate composite material, preparation method and application of FTO surface-based bismuth oxyhalide/calcium bismuthate composite material in photocatalytic degradation of dye in water body

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20200811

Address after: 236000 Xingye Road, Xinhua Street Office, Yingdong District, Fuyang City, Anhui Province

Patentee after: ANHUI JINSENYUAN ENVIRONMENTAL ENGINEERING Co.,Ltd.

Address before: 236037 No. 100 Qinghe West Road, Anhui, Fuyang

Patentee before: FUYANG NORMAL College

TR01 Transfer of patent right