CN105195194A - Photocatalyst composition CNB-BiVO4 and preparation method and application thereof - Google Patents
Photocatalyst composition CNB-BiVO4 and preparation method and application thereof Download PDFInfo
- Publication number
- CN105195194A CN105195194A CN201510494640.7A CN201510494640A CN105195194A CN 105195194 A CN105195194 A CN 105195194A CN 201510494640 A CN201510494640 A CN 201510494640A CN 105195194 A CN105195194 A CN 105195194A
- Authority
- CN
- China
- Prior art keywords
- cnb
- containing compound
- bismuth
- calcining
- boron
- 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.)
- Pending
Links
Abstract
The invention provides a photocatalyst composition CNB-BiVO4. According to the photocatalyst composition CNB-BiVO4, nitrogen-containing organic matter serves as a raw material, boron-doped graphite-phase carbon nitride (abbreviated as CNB) is prepared through a hydrothermal method, a boron-containing compound and a vanadium-containing compound serve as raw materials and react in an acidic solution, then solids obtained through reaction are calcined to obtain BiVO4, and then the prepared CNB and the BiVO4 are mixed and prepared into the photocatalyst composition CNB-BiVO4 through a hydrothermal method. The prepared photocatalyst composition has a good catalytic degradation effect on organic dye and particularly azo type organic dye under ultraviolet light and can be used for treating sewage containing the organic dye.
Description
Technical field
The present invention relates to and a kind ofly administer Photocatalyst Composite of organic dyestuff sewage and preparation method thereof, particularly a kind of light Photocatalyst Composite CNB-BiVO
4and preparation method thereof.
Background technology
Graphite phase carbon nitride, good stability, cost of material higher with its photocatalytic activity are cheap, especially not this outstanding advantages of containing metal, make it become a kind of novel catalysis material, but, the g-C of single-phase
3n
4catalyst makes its photocatalysis performance show usually because quantum efficiency is low not ideal enough.In addition, g-C
3n
4material photo-generate electron-hole recombination rate is higher, causes its catalytic efficiency lower, thus limits its application in photocatalysis.
In order to improve g-C
3n
4catalytic activity, recent years, people have studied a lot of method of modifying.
One is to g-C with nonmetalloid
3n
4carry out modification, described nonmetalloid comprises S, N, F, P etc., it is generally acknowledged that these nonmetalloids instead of C, N, H element in 3-s-triazine structural units, thus forms g-C
3n
4lattice defect makes photo-generate electron-hole to being effectively separated, and effectively improves its photocatalysis performance.As by dicyandiamide and BmimPF
6(ionic liquid) mixes, and obtains P doping g-C after high-temperature calcination
3n
4through XPS analysis, catalyst, shows that P element instead of C in construction unit, although a small amount of P doping can not change g-C
3n
4structure, but it obviously changes g-C
3n
4electronic structure, photogenerated current is also apparently higher than undoped g-C
3n
4.
For another example, by g-C
3n
4at H
2prepare in 450 DEG C of calcinings in S atmosphere and there is unique electronic structure S element doping g-C
3n
4cNS catalyst, XPS analysis display S instead of g-C
3n
4n in structure, as λ > 300 and 420nm, S adulterates g-C
3n
4photocatalysis Decomposition aquatic products hydrogen catalysis efficiency is respectively than single-phase g-C
3n
4improve 7.2 and 8.0 times.
For another example, NH is used
4f obtains F element doping g-C as F source and DCDA
3n
4catalyst (CNF), F element mixes g-C
3n
4skeleton in, define C-F key, make wherein a part of sp
2c is converted into sp
3c, thus cause g-C
3n
4planar structure irregularity; In addition, along with F element doping increasing number, the absorption region of CNF in visible region also expands thereupon, and the band-gap energy of its correspondence drops to 2.63eV by 2.69eV.
But above-mentioned preparation method not only complicated operation, cost of material is high, and obtained its photocatalysis efficiency of modified catalyst increases limitation, can not meet industrial requirements.
Therefore, need exploitation one badly and there is high catalytic efficiency, and preparation method is simple, photochemical catalyst easy to use or Photocatalyst Composite.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: with itrogenous organic substance as raw material, boron doped graphite phase carbon nitride (being abbreviated as CNB) is made by hydro-thermal method, be that raw material is first with boron-containing compound and vanadium-containing compound again to react in acid solution, then the solid be obtained by reacting is carried out calcining obtained BiVO
4, and then by obtained CNB and BiVO
4mixing, makes Photocatalyst Composite CNB-BiVO by hydro-thermal method
4, obtained Photocatalyst Composite is under ultraviolet light to organic dyestuff, and particularly azo organic dyestuff has good catalytic degradation effect, can be used in administering the sewage containing above-mentioned organic dyestuff, thus completes the present invention.
The object of the present invention is to provide following aspect:
First aspect, the invention provides one and prepares Photocatalyst Composite CNB-BiVO
4method, it is characterized in that, the method comprises the following steps:
(1) mixed with boron-containing compound by itrogenous organic substance, heat up calcining, optionally cools calcined product and pulverize after calcining, obtained CNB;
(2) bismuth-containing compound and vanadium-containing compound are dissolved in acid solution, regulation system pH, heat up, reaction terminates the solid that rear separation obtains, then washs solid, optionally carries out drying after washing, calcine again, optionally pulverize after calcining, obtained BiVO
4;
(3) BiVO that CNB step 1 obtained and step 2 obtain
4mix, optionally, mixture is pulverized, then mixture is calcined, obtained Photocatalyst Composite CNB-BiO
4.
Second aspect, the invention provides a kind of Photocatalyst Composite CNB-BiO that method is obtained according to above-mentioned first aspect
4, it is characterized in that, according to its infrared spectrum, be 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak.
The third aspect, the present invention also provides the CNB-BiO of the Photocatalyst Composite described in above-mentioned second aspect
4at improvement dye wastewater, particularly administer the application of the sewage aspect containing azo dyes.
Accompanying drawing explanation
Fig. 1 illustrates the infrared spectrogram of the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 is obtained;
Fig. 2 illustrates the photoluminescence spectra figure of the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 is obtained;
Fig. 3 illustrates the UV-Vis diffuse reflection spectroscopy figure of the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 is obtained;
Fig. 4 illustrates the sample ultraviolet catalytic determination of activity result that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 is obtained;
Fig. 5 illustrates that scavenger obtains the ultraviolet catalytic activity influence result of sample to embodiment 1.
Detailed description of the invention
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.
Below in detail the present invention is described in detail.
According to a first aspect of the invention, one is provided to prepare Photocatalyst Composite CNB-BiVO
4method, it is characterized in that, the method comprises the following steps:
Step 1, mixes itrogenous organic substance with boron-containing compound, and heat up calcining, optionally cools calcined product and pulverize after calcining, obtained CNB.
In the present invention, described itrogenous organic substance refers to the small organic molecule simultaneously containing nitrogen element and carbon, refer to the nitrogenous small organic molecule that can decompose in a heated condition especially, it is being prepared in graphite phase carbon nitride not only as nitrogen source but also as carbon source material.
The present inventor finds, use the itrogenous organic substance of the small-molecular-weight that carbon-nitrogen ratio is 1:3 ~ 3:1 as raw material, the small-molecular-weight itrogenous organic substance that preferred use carbon-nitrogen ratio is 1:2, as raw material, as cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride etc., is preferably urea.
The boron-containing compound that the present invention selects is selected from boron oxide, boric acid and/or boracic salt, is preferably selected from boron oxide, boric acid, Boratex, potassium borate, potassium tetraphenylboron and/or sodium tetraphenylborate etc., is preferably sodium tetraphenylborate.
The present invention selects the weight ratio of itrogenous organic substance and boron-containing compound to be the weight of itrogenous organic substance: weight=(1.0 ~ 20.0) g:(0.5 ~ 50.0 of boron-containing compound) mg, be preferably (3.0 ~ 18.0) g:(1.0 ~ 45.0) mg, be more preferably (5.0 ~ 15.0) g:(1.5 ~ 40.0) mg, more preferably (8.0 ~ 12.0) g:(2.0 ~ 35.0) mg, again more preferably (9.0 ~ 11.0) g:(2.0 ~ 30.0) mg, as 10.0g:2.5mg, 10.0g:5.0mg, 10.0g:9.0mg and 10.0g:20.0mg, wherein, highly preferred is 10.0g:5.0mg.
The present inventor finds, itrogenous organic substance and boron-containing compound is placed in liquid-phase system and mixes, and can make above-mentioned two kinds of materials mixing fully, and the boron doping carbonitride pattern that calcining obtains is homogeneous.
The solvent of the present invention to itrogenous organic substance and boron-containing compound place liquid-phase system is not particularly limited to, and preferably uses pure water, deionized water and/or distilled water, is preferably distilled water.
The present inventor finds, the solvent removed in itrogenous organic substance and boron-containing compound mixture place liquid-phase system significantly can shorten calcination time, therefore, the present invention selects the solvent removed before calcination in itrogenous organic substance and boron-containing compound mixture place liquid-phase system, the present invention is not particularly limited to the mode except desolventizing, in prior art, any one all can use except the mode of desolventizing, as normal temperature volatilization, normal heating, decompression distillation etc., the present invention is not also particularly limited to except temperature during desolventizing, be decomposed into preferably not make itrogenous organic substance and boron-containing compound, as 30 DEG C ~ 200 DEG C, be more preferably 50 DEG C ~ 150 DEG C, more preferably 60 DEG C ~ 120 DEG C, as 80 DEG C.
Optionally, carry out drying by except the mixture after desolventizing, the present inventor finds, dried mixture its more easily react under the condition of high-temperature calcination, can obvious Reaction time shorten.
The mixture of itrogenous organic substance and boron-containing compound can generate boron and to adulterate carbonitride when calcining at 400 DEG C ~ 800 DEG C, i.e. CNB, and obtained product morphology is homogeneous, and preferred calcination temperature of the present invention is 450 DEG C ~ 700 DEG C, be more preferably 400 DEG C ~ 600 DEG C, as 550 DEG C.
The present inventor finds further, and calcination time is can fully react for 1 ~ 5 hour, and therefore, the present invention preferably selected calcination time to be 1.5 ~ 4 hours, is more preferably 2 ~ 3.5 hours, as 2 hours.
In the present invention, optionally, the material after calcining is cooled, and pulverizes.
In step 1 of the present invention, the mode of cooling is not particularly limited to, the mode that in prior art, any one cools pressed powder can be adopted, as natural cooling and artificial pressure cooling method etc., preferably adopt natural cooling.
In step 1 of the present invention, preferably the material after above-mentioned calcining is cooled to 10 DEG C ~ 50 DEG C, is more preferably 15 DEG C ~ 40 DEG C, more preferably 20 DEG C ~ 35 DEG C, as 25 DEG C.
In step 1 of the present invention, the method pulverized is not particularly limited to, the mode that in prior art, any one solid is pulverized can be used, as grinding etc., the present invention is not particularly limited to the particle diameter of particle after pulverizing, and with by after strong base solution process, its modification is fully preferred.
Step 2, is dissolved in acid solution by bismuth-containing compound and vanadium-containing compound, regulation system pH, heats up, reaction terminates the solid that rear separation obtains, then washs solid, optionally carries out drying after washing, calcine again, optionally pulverize after calcining, obtained BiVO
4.
In the present invention, described bismuth-containing compound is preferably soluble bismuth salt, as bismuth nitrate and hydrate, bismuth sulfate and hydrate thereof, bismuth chloride and hydrate thereof etc., be preferably bismuth nitrate and hydrate thereof, be more preferably the composition of bismuth nitrate, five water bismuth nitrates and arbitrary proportion thereof.
The present inventor finds, above-mentioned bismuth-containing compound can in the acid solution of its correspondence stable existence, form the solution of stable homogeneous, and in solution system, do not produce precipitation, thus enable bismuth-containing compound and vanadium-containing compound in liquid-phase system, reach fully mixing of molecule rank.
In the present invention, the acid ion of acid in described acid solution is identical with the acid ion forming bismuth-containing compound.The present inventor finds, bismuth-containing compound can stable existence in the acid solution of its relative acid, but also can not introduce other foreign ion, is convenient to subsequent treatment.
In the present invention, described vanadium-containing compound is preferably solubility metavanadate, is preferably ammonium metavanadate and/or potassium metavanadate etc., is more preferably ammonium metavanadate.The present inventor finds, metavanadate can carry out combination reaction with described bismuth-containing compound in described acid solution, generation pucherite precipitates, and the accessory substance of reaction has good solubility in preparation system, it can not separate out in preparation system, therefore, it is possible to be comparatively easy to obtain target product pucherite.
In the present invention, the weight ratio of bismuth-containing compound and vanadium-containing compound is (15 ~ 25): (3 ~ 8), is preferably (18 ~ 22): (4 ~ 6), as 20:5 etc.
In the present invention, the concentration of described acid solution selects (0.5 ~ 4) mol/L, is preferably (1 ~ 3) mol/L, and as 2mol/L, wherein, the mole of acid is with the molar amount of the molecule of described acid.The present inventor finds, in the acid solution of above-mentioned concentration, bismuth-containing compound can stable existence, form stable solution, and, along with the increase of acid solutions, bismuth-containing compound stability wherein strengthens, after the concentration of acid solution reaches 4mol/L, bismuth-containing compound stability wherein no longer significantly strengthens, but, acid solutions is larger, acid required for preparating acid solution is then more, excessive acid adds production cost on the one hand, on the other hand, also need regulation system pH to alkalescent preparing in pucherite process, the concentration of acid solution is excessive, needs to consume a large amount of conditioning agent, too increase production cost from another point of view, therefore, the present invention selects the concentration of acid solution for (0.5 ~ 4) mol/L.
In the present invention, the w/v of bismuth-containing compound and acid solution is (15 ~ 25) weight portion: 1000 parts by volume, is preferably (18 ~ 22) weight portion: 1000 parts by volume, as 20 weight portions: 1000 parts by volume.The present inventor finds, when bismuth-containing compound mixes according to above-mentioned w/v with acid solution, can be mixed with the solution of stable homogeneous, and the side reactions such as hydrolysis can not occur bismuth-containing compound.
In the present invention, bismuth-containing compound with containing after vanadium chemical combination mix in acid solution, regulation system pH, makes reaction system present alkalescent, makes to generate pucherite in system, and the pucherite generated can with the precipitation of the form of precipitation in weakly alkaline environment.
The present inventor find, system pH is adjusted to 7 ~ 9, be preferably 7.5 ~ 8.5, as 7.5 time, the pucherite in system can be precipitated out.
In the present invention, the reagent of regulation system pH is not particularly limited to, can be in prior art any one for regulating the alkaline reagent of above-mentioned reaction system pH, its state can be solid, also can be its solution, in the present invention, specifically can select NaOH and the aqueous solution, KOH and the aqueous solution thereof, urea and the aqueous solution or ammoniacal liquor etc., be preferably urea.
After the pH of reaction system is adjusted to alkalescent, reaction system is heated up, can reaction rate be increased on the one hand, impel pucherite rapid precipitation, on the other hand, increase the amount of pucherite precipitation, reaction is carried out more fully.
The present inventor finds, when the temperature of reaction system reaches 70 DEG C ~ 100 DEG C, is preferably 80 DEG C ~ 95 DEG C, during as 90 DEG C, react comparatively stable, when temperature is lower than 70 DEG C, reaction rate is little, needs the reaction time of consumption long, when temperature is higher than 100 DEG C, need on the one hand to be reacted by specific autoclave, on the other hand, reaction rate is too fast, the process of wayward reaction, product may be caused uneven, poor performance.
In the present invention, after system being heated up, make reaction system react 15 ~ 30h within the scope of said temperature, be preferably 18 ~ 28h, be more preferably 20 ~ 26h, as 24h.The present inventor finds, after reaction system reacts 15 ~ 30h within the scope of said temperature, vanadium-containing compound and bismuth-containing compound can fully react generation pucherite, and meanwhile, the pucherite of generation also fully can be precipitated out in reaction system.
In the present invention, optionally, first reduce temperature of reaction system and be separated obtained pucherite precipitation again, preferably system temperature is reduced to 5 DEG C ~ 30 DEG C, is more preferably 10 DEG C ~ 25 DEG C, as 20 DEG C etc.
In the present invention, be not particularly limited to obtained pucherite is precipitated the method separated from reaction system, the method for any one Separation of Solid and Liquid in prior art can be adopted, as natural filtration, filtration under diminished pressure etc., be preferably filtration under diminished pressure.
In the present invention, washing being separated the solid obtained, removing the soluble impurity that its surface may be adhered to, select water and alcohol for the cleaning solution washing solid, wherein, alcohol is preferably methyl alcohol, ethanol etc., is more preferably ethanol.
In the present invention, preferably first washing being separated the solid obtained with water, removing the water-solubility impurity on its surface, then carrying out washing to remove its alcohol dissolubility impurity that may remain on the surface with alcohol.
Optionally, after the solid obtained separation washs, drying is carried out to it, the mode of the present invention to drying is not particularly limited to, the method of any one solid drying in prior art can be adopted, as normal pressure heating, heating under diminished pressure, naturally volatilize method etc., preferably use normal heating method to carry out drying, preferred baking temperature is (40 ~ 80) DEG C, be more preferably (50 ~ 70) DEG C, as 60 DEG C, drying time is 6h ~ 15h, be preferably 8h ~ 12h, as 10h.
Pucherite solid through above-mentioned process is calcined, the present inventor finds, barium bismuth solid after above-mentioned process is carried out calcining and can significantly improve end-product Photocatalyst Composite activity, in the present invention, calcining heat selects 350 DEG C ~ 550 DEG C, is preferably 400 DEG C ~ 500 DEG C, as 450 DEG C, calcination time selects 5 ~ 25min, is preferably 10 ~ 20min, as 15min.
Optionally, by calcining after solid pulverize, make its particle diameter more even, meanwhile, follow-up react with CNB time, its structure of the product of generation is also more even.
Step 3, the BiVO that the CNB obtained by step 1 and step 2 obtain
4mix, optionally, mixture is pulverized, then mixture is calcined, obtained Photocatalyst Composite CNB-BiO
4.
In the present invention, the CNB that step 1 the is obtained and BiVO that step 2 obtains
4weight ratio select (0.1 ~ 0.9): (0.9 ~ 0.1), as 0.1:0.9,0.2:0.8,0.5:0.5,0.8:0.2 or 0.9:0.1 etc.The present inventor finds, described CNB and described BiVO
4carry out composite according to above-mentioned weight ratio, through the Photocatalyst Composite that the method for calcining is obtained, to organic dyestuff under ultraviolet light existent condition, particularly azo organic dyestuff has good photocatalytic Degradation, degradation efficiency is high, can reach more than 78%.
The present inventor finds, the BiVO that the CNB obtained by step 1 and step 2 obtain
4be placed in liquid-phase system to mix, can make above-mentioned two kinds of materials mixing fully, the Photocatalyst Composite pattern that calcining obtains is more homogeneous.
The present invention is to the obtained CNB of the step 1 and obtained BiVO of step 2
4the solvent of place liquid-phase system is not particularly limited to, and preferably uses pure water, deionized water and/or distilled water, is preferably distilled water.
Preferably, the BiVO will the obtained CNB of step 1 be comprised obtaining with step 2
4liquid-phase system heat up, the BiVO that the CNB making step 1 obtained obtains with step 2
4be mixed to get more abundant, then the solvent in removing system, the present invention is not particularly limited to the method except desolventizing, any one can be adopted in prior art except the method for desolventizing, as normal pressure heating, heating under diminished pressure etc.
After the solvent removing in system, the mixture obtained is pulverized, makes the particle diameter of each component in mixture comparatively close, thus it is more abundant to make it be mixed to get, and then make the Photocatalyst Composite pattern that obtains and structure more homogeneous, photocatalysis performance is stablized, and photocatalysis efficiency is high.
The present invention is not particularly limited to milling time, to make two kinds of component particle diameters be close to preferably, as 10 ~ 30min, is preferably 15 ~ 20min.
Calcined by sufficient for above-mentioned mixing mixture, calcining heat selects 350 DEG C ~ 550 DEG C, is preferably 400 DEG C ~ 500 DEG C, and as 450 DEG C, calcination time selects 1 ~ 3h, is preferably 1.5 ~ 2.5h, as 2h.
In step 3 of the present invention, obtained Photocatalyst Composite CNB-BiO
4, according to its infrared spectrum, be 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak.
Second aspect, the invention provides a kind of Photocatalyst Composite CNB-BiO that method is obtained according to above-mentioned first aspect
4, it is characterized in that, according to its infrared spectrum, be 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak.
The third aspect, the present invention also provides the CNB-BiO of the Photocatalyst Composite described in above-mentioned second aspect
4at improvement dye wastewater, particularly administer the application of the sewage aspect containing azo dyes.
According to Photocatalyst Composite CNB-BiO provided by the invention
4and its preparation method and application, there is following beneficial effect:
(1) method is simple to prepare described Photocatalyst Composite, and condition is easy to control, and raw material sources are extensive, and easily obtain, preparation cost is low;
(2) described preparation method's environmental protection, the raw material used and intermediate product all can not produce environmental pollution;
(3) obtained Photocatalyst Composite CNB-BiO
4there is good photocatalytic activity under ultraviolet light, to organic dyestuff, there is stronger degradation;
(4) described Photocatalyst Composite CNB-BiO
4itself not easily decomposes, and it has lasting degradation in dye wastewater.
Embodiment
embodiment 1
(1) tetraphenylboron sodium of 10.0g urea and 5.0mg is taken, be placed in the small beaker of clean dried, add 20mL distilled water, mixed dissolution is even, then small beaker is put into 80 DEG C of water-baths (being preheated to 80 DEG C), evaporate to dryness water, obtain solid, the solid obtained is moved in crucible, puts into Muffle furnace, under 550 DEG C of conditions, calcine 2h, CNB sample can be obtained;
(2) 19.4gBi (NO is taken with electronic balance
3)
35H
2o and 4.68gNH
4vO
3be dissolved in respectively in 500mL salpeter solution (2mol/L), mix, mixed solution is moved in the large beaker of 1000mL, obtain saffron solution, then in mixed solution, add 7.5g urea, regulate the pH value to 7.5 of mixed solution,
Mixed solution is placed in the oil bath magnetic stirring apparatus fully stirring reaction 24h of 90 DEG C, jonquilleous crystalline solid is had to generate gradually, the solid suction filtration will generated after abundant reaction, the solid distilled water washing that suction filtration obtains once, three times are fully washed again with absolute ethyl alcohol, by the solid dry 10h under 60 DEG C of conditions obtained after washing, dried solid is placed in crucible, move in Muffle furnace and calcine 15min at 450 DEG C, after calcining, by product porphyrize, be 50 μm to D50 particle diameter, obtained BiVO
4sample;
(3) BiVO that the obtained CNB powder of 0.1g step 1 obtains with 0.9g step 2 is accurately taken
4powder, is placed in dried beaker, adds distilled water, after mixed dissolution is even, is placed on by beaker in 80 DEG C of water-baths, evaporate to dryness.Then mixed solid is moved in agate mortar and grind 15min, mix, catalyst sample is moved in crucible, be placed in roasting 2h at Muffle furnace 450 DEG C, required catalyst sample CNB-BiVO can be obtained
4, this identified as samples is designated as 10%CNB-BiVO
4(namely CNB is at carbon monoxide-olefin polymeric CNB-BiVO for catalyst
4in quality percentage be 10%).Same method obtains 20%CNB-BiVO
4, 50%CNB-BiVO
4, 80%CNB-BiVO
4, 90%CNB-BiVO
4photochemical catalyst.
embodiment 2 ~ 5
Embodiment 2 ~ 5 method therefor is similar to embodiment 1, and difference is only, in step (3), takes the BiVO that the obtained CNB powder of step 1 obtains with step 2
4the weight of powder respectively is 0.2g and 0.8g (embodiment 2), 0.5g and 0.5g (embodiment 3), 0.8g and 0.2g (embodiment 4), 0.9g and 0.1g (embodiment 5).
Comparative example
comparative example 1
This comparative example specimen in use is CNB powder obtained in embodiment 1 step 1.
comparative example 2
This comparative example specimen in use is BiVO obtained in embodiment 1 step 2
4powder.
Experimental example
the infrared spectrum measurement of experimental example 1 sample
Infrared spectrum is used to measure sample when being subject to the Infrared irradiation of consecutive variations frequency, the radiation of some frequency of molecule absorption, and the change of dipole moment is caused by its oscillating movement or bending motion, cause the transition of energy level from ground state to excitation state, thus form molecular absorption spectrum.
This experimental example specimen in use is the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 obtains.
Method of operating: get above-mentioned catalyst sample, add enough KBr white powders, fully be ground to agate mortar and mix, then move in mould, pelleting press is utilized manually catalyst to be pressed into thin slice pellucidly, infrared spectrometer measures, and setup parameter scanning is 30 times, and resolution ratio is 2cm
-1, with FTIS, infrared spectrum characterization is carried out to catalyst, result as shown in Figure 1, wherein,
Curve a illustrates that comparative example 1 obtains the infrared spectrum curve of sample;
Curve b illustrates that embodiment 5 obtains the infrared spectrum curve of sample;
Curve c illustrates that embodiment 3 obtains the infrared spectrum curve of sample;
Curve d illustrates that embodiment 2 obtains the infrared spectrum curve of sample;
Curve e illustrates that embodiment 1 obtains the infrared spectrum curve of sample;
Curve f illustrates that comparative example 2 obtains the infrared spectrum curve of sample.
As shown in Figure 1,
The sample obtained by embodiment 1,2,4,5 is 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak, wherein,
In curve a, 1385cm
-1neighbouring broad peak corresponds to the stretching vibration absworption peak of B-N singly-bound, at 1250cm
-1neighbouring peak is the stretching vibration absworption peak of end group C-N key, and wave number is 1648cm
-1the neighbouring absworption peak existed corresponds to sp
2c=N stretching vibration absworption peak, wave number is 3415cm
-1near there is small absworption peak, show catalyst surface may exist trace adsorbed water.
In curve b ~ e, 1648cm
-1neighbouring absworption peak corresponds to sp
2c=N stretching vibration absworption peak;
3415cm
-1near there is small absworption peak, show carbon monoxide-olefin polymeric surface may exist trace adsorbed water.
In curve f, wave number is 618cm
-1the neighbouring peak existed is owing to v3 (VO
4 3-) stretching vibration absworption peak, and be 810cm in wave number
-1v1 (the VO that the neighbouring peak existed is corresponding
4 3-) stretching vibration absworption peak, wave number is 3415cm
-1the neighbouring peak existed may be BiVO
4the micro-water of adsorption produces.
To sum up, in the carbon monoxide-olefin polymeric of above-mentioned different ratio, 10%CNB-BiVO
4type carbon monoxide-olefin polymeric is at 810cm
-1near and 1385cm
-1near the absworption peak that occurs comparatively strong, be not bound by any theory, the present inventor thinks that this may to have relatively high photocatalytic activity relevant with it.
the photoluminescence spectra of experimental example 2 sample measures
Photoluminescence spectrum (PL) is a kind of effective ways of research semiconductor nano material electronic structure and Optical Properties, being separated and the information such as compound of the blemish that can disclose semiconductor nano material and Surface Oxygen room isostructuralism matter and photo-generated carrier (electron-hole pair), thus provide strong foundation by carrying out photoluminescence spectra analysis to semi-conducting material for developing and preparing high performance semiconductor functional material.
It is generally acknowledged, fluorescence signal is stronger, and the recombination probability of photo-generated carrier (electron-hole pair) is higher, and photocatalytic activity is lower.
This experimental example specimen in use is the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5 and comparative example 1 obtains.
Method of operating: get above-mentioned catalyst sample (powder) and be placed in sample cell on a small quantity, with pelleting press, surface is flattened, as far as possible sample is pressed fine and close, to keep the smooth of sample surfaces, utilize XRF to detect the photoluminescence performance of various catalyst sample, excitation wavelength is 400nm, and result as shown in Figure 2, wherein
Curve a illustrates that comparative example 1 obtains the photoluminescence spectra curve of sample;
Curve b illustrates that embodiment 5 obtains the photoluminescence spectra curve of sample;
Curve c illustrates that embodiment 3 obtains the photoluminescence spectra curve of sample;
Curve d illustrates that embodiment 2 obtains the photoluminescence spectra curve of sample;
Curve e illustrates that embodiment 1 obtains the photoluminescence spectra curve of sample.
As shown in Figure 2,
Be that CNB catalyst sample (CNB) (pulverulence) that within the scope of 450 ~ 550nm, comparative example 1 is obtained shows not only strong but also wide luminous signal at wavelength.
Sample (the 90%CNB-BiVO that embodiment 5 is obtained
4type carbon monoxide-olefin polymeric) and the obtained sample (50%CNB-BiVO of embodiment 3
4type carbon monoxide-olefin polymeric) (being pulverulence) be also show stronger luminous signal within the scope of 450 ~ 550nm at wavelength.
Sample (the 20%CNB-BiVO that embodiment 2 is obtained
4type carbon monoxide-olefin polymeric) (pulverulence) is show similar signal peak equally within the scope of 450 ~ 550nm at wavelength, but the intensity at peak is weak compared with former three many.
For the sample (10%CNB-BiVO that embodiment 1 is obtained
4type carbon monoxide-olefin polymeric) (pulverulence), be that within the scope of 450 ~ 550nm, signal peak is the most weak at wavelength.
The above results shows, the activity order of catalyst is 10%CNB-BiVO
4type carbon monoxide-olefin polymeric activity is the strongest, 20%CNB-BiVO
4type carbon monoxide-olefin polymeric takes second place, and is minimum with the activity of CNB catalyst.
the UV-Vis diffuse reflection spectroscopy of experimental example 3 sample measures
UV-Vis diffuse reflection spectroscopy to detect in semi-conducting material electronic state and can with a kind of effective ways at interval.
This experimental example specimen in use is the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 obtains.
Method of operating: get above-mentioned catalyst sample and put into sample cell, flattened on surface with pelleting press, first proofreads with blank reference, then utilize UV-Vis diffuse reflection spectroscopy instrument to characterize each catalyst sample, scanning wavelength is 200 ~ 800nm, and result as shown in Figure 3, wherein
Curve a illustrates that comparative example 1 obtains the UV-Vis diffuse reflection spectroscopy curve of sample;
Curve b illustrates that embodiment 5 obtains the UV-Vis diffuse reflection spectroscopy curve of sample;
Curve c illustrates that embodiment 3 obtains the UV-Vis diffuse reflection spectroscopy curve of sample;
Curve d illustrates that embodiment 2 obtains the UV-Vis diffuse reflection spectroscopy curve of sample;
Curve e illustrates that embodiment 1 obtains the UV-Vis diffuse reflection spectroscopy curve of sample;
Curve f illustrates that comparative example 2 obtains the UV-Vis diffuse reflection spectroscopy curve of sample.
As shown in Figure 3:
Embodiment 1 obtains sample (10%CNB-BiVO
4type Photocatalyst Composite) very strong in UV light region absorbability, along with increasing of CNB load capacity, the absorption of carbon monoxide-olefin polymeric to visible ray weakens, and be not bound by any theory, the present inventor thinks, this may be because a large amount of CNB hampers BiVO
4to the absorption of visible ray;
Pure BiVO
4except having except strong absorption at ultra-violet (UV) band (<380nm), it is very strong in visible region absorbability;
Pure CNB ratio is dispersed in BiVO
4on CNB there is more weak ultraviolet-visible absorption ability.
the ultraviolet catalytic determination of activity of experimental example 4 sample
This experimental example specimen in use is the sample that embodiment 1, embodiment 2, embodiment 3, embodiment 5, comparative example 1 and comparative example 2 obtains.
Method of operating: accurately take each 0.0500g of above-mentioned catalyst fines in quartz ampoule, number consecutively 1,2,3,4,5 and 6 is 5.00mgL respectively to adding 40mL concentration in quartz ampoule
-1methyl orange solution, and respectively add a little magneton, quartz ampoule is put into photochemical reaction instrument, under continuous stirring, dark reaction 30min, samples centrifugal, surveys its absorbance A respectively
0, open light source, photo-irradiation treatment 1h, sample centrifugal, survey its absorbance A
t, calculate degradation rate W according to following formula,
W(％)＝(A
0－A
t)/A
0×100％，
According to the UV active figure calculating gained degradation rate and draw out different catalysts sample, result as shown in Figure 4, wherein,
A illustrates that comparative example 1 obtains the ultraviolet catalytic activity of sample;
B illustrates that embodiment 5 obtains the ultraviolet catalytic activity of sample;
C illustrates that embodiment 3 obtains the ultraviolet catalytic activity of sample;
D illustrates that embodiment 2 obtains the ultraviolet catalytic activity of sample;
E illustrates that embodiment 1 obtains the ultraviolet catalytic activity of sample;
F illustrates that comparative example 2 obtains the ultraviolet catalytic activity of sample.
As shown in Figure 4,
In Photocatalyst Composite, its degraded takes the lead in the minimizing of CNB load capacity and reduces, and when the load capacity of CNB is 50%, the degradation rate of photochemical catalyst touches the bottom.Then its ultraviolet catalytic activity increases with the minimizing of the load capacity of CNB again.
In addition, at carbon monoxide-olefin polymeric CNB-BiVO
4in, the photocatalytic activity of the sample (10%CNB-BiVO4 type carbon monoxide-olefin polymeric) obtained with embodiment 1 is the highest, and when after UV-irradiation 1h, it is 78.3% to the photocatalytic activity of methyl orange solution.
experimental example 5 scavenger is on the impact of sample photocatalytic activity
This experiment take methyl orange as model compound, by introducing various free radical scavenger, and the photocatalysis mechanism of research Photocatalyst Composite.
Add isopropyl alcohol (IPA) and play the effect that in inhibition system degradation process, OH produces,
Add ammonium oxalate (AO) and play h in inhibition system degradation process
+the effect produced,
Add 1,4-benzoquinone (BQ) and play O in inhibition system degradation process
2 -the effect produced,
Add catalase (CAT) and play H in inhibition system degradation process
2o
2the effect produced.
This experimental example specimen in use is the carbon monoxide-olefin polymeric that embodiment 1 obtains.
Method of operating: accurately take catalyst composition powder described in 5 parts of 0.050g and be placed in 5 quartz ampoules respectively, number consecutively is 1,2,3,4 and 5, is 5.00mgL respectively to adding 40mL concentration in quartz ampoule
-1methyl orange solution.
Scavenger is not added in No. 1 pipe,
5.000 μ L isopropyl alcohols are added in No. 2 pipes,
0.004g ammonium oxalate is added in No. 3 pipes,
0.004g 1,4-benzoquinone is added in No. 4 pipes,
3.800 μ L catalases are added in No. 5 pipes,
Each Guan Zhongjun adds a little magneton, quartz ampoule is put into photochemical reaction instrument, and under continuous stirring, dark reaction 30min, samples centrifugal, surveys its absorbance A respectively
0, open light source, ultraviolet lighting process 1h, samples centrifugal, surveys its absorbance A t, calculates degradation rate W according to following formula,
W(％)＝(A
0－A
t)/A
0×100％，
According to result of calculation drafting pattern, result as shown in Figure 5, wherein,
Noscavenger represents and does not add scavenger,
IPA represents and adds isopropyl alcohol,
AO represents and adds ammonium oxalate,
BQ represents and adds 1,4-benzoquinone,
CAT represents and adds catalase.
As shown in Figure 5, when other condition is constant,
(1) with do not add compared with scavenger, after adding scavenger, the activity of carbon monoxide-olefin polymeric all decreases;
(2) after adding isopropyl alcohol (IPA), catalase (CAT), ammonium oxalate (AO) and 1,4-benzoquinone (BQ), the activity of catalyst all has and comparatively significantly reduces, adding of isopropyl alcohol (IPA) makes the activity of catalyst fall minimum, that is, OH, H
2o
2, h+ and O
2-in Photocatalytic Degradation Process, play obvious effect, especially OH plays main effect in photocatalytic process.
More than in conjunction with detailed description of the invention 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 (10)
1. prepare Photocatalyst Composite CNB-BiVO for one kind
4method, it is characterized in that, the method comprises the following steps:
(1) mixed with boron-containing compound by itrogenous organic substance, heat up calcining, optionally cools calcined product and pulverize after calcining, obtained CNB;
(2) bismuth-containing compound and vanadium-containing compound are dissolved in acid solution, regulation system pH, heat up, reaction terminates the solid that rear separation obtains, then washs solid, optionally carries out drying after washing, calcine again, optionally pulverize after calcining, obtained BiVO
4;
(3) BiVO that CNB step 1 obtained and step 2 obtain
4mix, optionally, mixture is pulverized, then mixture is calcined, obtained Photocatalyst Composite CNB-BiO
4.
2. method according to claim 1, is characterized in that, in step 1,
Described itrogenous organic substance refers to the small organic molecule simultaneously containing nitrogen element and carbon, being preferably carbon-nitrogen ratio is that the itrogenous organic substance of the small-molecular-weight of 1:3 ~ 3:1 is as raw material, the small-molecular-weight itrogenous organic substance that preferred use carbon-nitrogen ratio is 1:2 is as raw material, as cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride etc., be preferably urea; And/or
Boron-containing compound is selected from boron oxide, boric acid and/or boracic salt, is preferably selected from boron oxide, boric acid, Boratex, potassium borate, potassium tetraphenylboron and/or sodium tetraphenylborate etc., is preferably sodium tetraphenylborate; And/or
The weight ratio of itrogenous organic substance and boron-containing compound is the weight of itrogenous organic substance: weight=(1.0 ~ 20.0) g:(0.5 ~ 50.0 of boron-containing compound) mg, be preferably (3.0 ~ 18.0) g:(1.0 ~ 45.0) mg, be more preferably (5.0 ~ 15.0) g:(1.5 ~ 40.0) mg, more preferably (8.0 ~ 12.0) g:(2.0 ~ 35.0) mg, again more preferably (9.0 ~ 11.0) g:(2.0 ~ 30.0) mg, as 10.0g:2.5mg, 10.0g:5.0mg, 10.0g:9.0mg and 10.0g:20.0mg, wherein, highly preferred is 10.0g:5.0mg.
3. method according to claim 1 and 2, is characterized in that, in step 1,
Itrogenous organic substance and boron-containing compound are placed in liquid-phase system mix; And/or
The temperature of calcining is 450 DEG C ~ 700 DEG C, is more preferably 400 DEG C ~ 600 DEG C, as 550 DEG C; And/or
The time of calcining is 1 ~ 5 hour, is preferably 1.5 ~ 4 hours, is more preferably 2 ~ 3.5 hours, as 2 hours; And/or
Material after above-mentioned calcining is cooled to 10 DEG C ~ 50 DEG C, is more preferably 15 DEG C ~ 40 DEG C, more preferably 20 DEG C ~ 35 DEG C, as 25 DEG C.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterized in that, in step 2,
Described bismuth-containing compound is preferably soluble bismuth salt, as bismuth nitrate and hydrate, bismuth sulfate and hydrate thereof, bismuth chloride and hydrate thereof etc., is preferably bismuth nitrate and hydrate thereof, is more preferably the composition of bismuth nitrate, five water bismuth nitrates and arbitrary proportion thereof; And/or
The acid ion of acid in described acid solution is identical with the acid ion forming bismuth-containing compound; And/or
Described vanadium-containing compound is preferably solubility metavanadate, is preferably ammonium metavanadate and/or potassium metavanadate etc., is more preferably ammonium metavanadate; And/or
The weight ratio of bismuth-containing compound and vanadium-containing compound is (15 ~ 25): (3 ~ 8), is preferably (18 ~ 22): (4 ~ 6), as 20:5 etc.; And/or
The concentration of described acid solution selects (0.5 ~ 4) mol/L, is preferably (1 ~ 3) mol/L, and as 2mol/L, wherein, the mole of acid is with the molar amount of the molecule of described acid; And/or
The w/v of bismuth-containing compound and acid solution is (15 ~ 25) weight portion: 1000 parts by volume, is preferably (18 ~ 22) weight portion: 1000 parts by volume, as 20 weight portions: 1000 parts by volume.
5., according to the method one of Claims 1 to 4 Suo Shu, it is characterized in that, in step 2,
System pH is adjusted to 7 ~ 9, is preferably 7.5 ~ 8.5, as 7.5; And/or
The reagent of regulation system pH is selected from NaOH and the aqueous solution, KOH and the aqueous solution thereof, urea and the aqueous solution or ammoniacal liquor etc., is preferably urea; And/or
System temperature is increased to 70 DEG C ~ 100 DEG C, is preferably 80 DEG C ~ 95 DEG C, as 90 DEG C; And/or
After system being heated up, reaction 15 ~ 30h, is preferably 18 ~ 28h, is more preferably 20 ~ 26h, as 24h; And/or
Be water and alcohol for washing the cleaning solution of solid, wherein, alcohol is preferably methyl alcohol and ethanol etc., is more preferably ethanol; And/or
The temperature of calcining is 350 DEG C ~ 550 DEG C, is preferably 400 DEG C ~ 500 DEG C, as 450 DEG C; And/or
The time of calcining is 5 ~ 25min, is preferably 10 ~ 20min, as 15min.
6., according to the method one of Claims 1 to 5 Suo Shu, it is characterized in that, in step 3, the CNB that step 1 the is obtained and BiVO that step 2 obtains
4weight ratio select (0.1 ~ 0.9): (0.9 ~ 0.1), as 0.1:0.9,0.2:0.8,0.5:0.5,0.8:0.2 or 0.9:0.1 etc.
7., according to the method one of Claims 1 to 5 Suo Shu, it is characterized in that, in step 3,
The temperature of calcining is 350 DEG C ~ 550 DEG C, is preferably 400 DEG C ~ 500 DEG C, as 450 DEG C; And/or
The time of calcining is 1 ~ 3h, is preferably 1.5 ~ 2.5h, as 2h.
8., according to the method one of claim 1 ~ 7 Suo Shu, it is characterized in that, in step 3, obtained Photocatalyst Composite CNB-BiO
4, according to its infrared spectrum, be 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak.
9. the Photocatalyst Composite CNB-BiO obtained according to the described method of one of claim 1 ~ 8
4, it is characterized in that, according to its infrared spectrum, be 810cm in wave number
-1, 1385cm
-1, 1648cm
-1and 3415cm
-1near there is absworption peak.
10. Photocatalyst Composite CNB-BiO according to claim 9
4at improvement dye wastewater, particularly administer the application of the sewage aspect containing azo dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510494640.7A CN105195194A (en) | 2015-08-12 | 2015-08-12 | Photocatalyst composition CNB-BiVO4 and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510494640.7A CN105195194A (en) | 2015-08-12 | 2015-08-12 | Photocatalyst composition CNB-BiVO4 and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105195194A true CN105195194A (en) | 2015-12-30 |
Family
ID=54943353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510494640.7A Pending CN105195194A (en) | 2015-08-12 | 2015-08-12 | Photocatalyst composition CNB-BiVO4 and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105195194A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006850A (en) * | 2016-05-25 | 2016-10-12 | 安徽普氏生态环境工程有限公司 | Method for performing electrochemical oxidative degradation on sewage COD (chemical oxygen demand) by using boron-doped graphene electrode |
| CN109012725A (en) * | 2018-07-19 | 2018-12-18 | 中国科学院东北地理与农业生态研究所 | The graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification |
| CN109529810A (en) * | 2019-01-24 | 2019-03-29 | 重庆化工职业学院 | The preparation method of composite bismuth vanadium photocatalyst |
| CN111364080A (en) * | 2020-03-05 | 2020-07-03 | 中国空间技术研究院 | C for photo-anodexNy/BiVO4Material, preparation method and application thereof |
| CN115814837A (en) * | 2023-01-06 | 2023-03-21 | 太原理工大学 | Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst and process for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806915A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Composite bismuth vanadium photocatalyst supported by cobalt oxide and preparation method thereof |
| CN104549404A (en) * | 2014-12-09 | 2015-04-29 | 阜阳师范学院 | Composite photocatalyst-In2O3/CNB and preparation method and application thereof |
| CN104549403A (en) * | 2014-11-28 | 2015-04-29 | 阜阳师范学院 | Composite photocatalyst-DyVO4/g-C3N4 and preparation method thereof |
-
2015
- 2015-08-12 CN CN201510494640.7A patent/CN105195194A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806915A (en) * | 2006-02-23 | 2006-07-26 | 上海交通大学 | Composite bismuth vanadium photocatalyst supported by cobalt oxide and preparation method thereof |
| CN104549403A (en) * | 2014-11-28 | 2015-04-29 | 阜阳师范学院 | Composite photocatalyst-DyVO4/g-C3N4 and preparation method thereof |
| CN104549404A (en) * | 2014-12-09 | 2015-04-29 | 阜阳师范学院 | Composite photocatalyst-In2O3/CNB and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| MAN OU ET AL.: "Synthesis and characterization of g-C3N4/BiVO4 composite photocatalysts with improved visible-light-driven photocatalytic performance", 《J SOL-GEL SCI TECHNOL》 * |
| S. C. YAN ET AL.: "Photodegradation of Rhodamine B and Methyl Orange over Boron-Doped g-C3N4 under Visible Light Irradiation", 《LANGMUIR》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006850A (en) * | 2016-05-25 | 2016-10-12 | 安徽普氏生态环境工程有限公司 | Method for performing electrochemical oxidative degradation on sewage COD (chemical oxygen demand) by using boron-doped graphene electrode |
| CN109012725A (en) * | 2018-07-19 | 2018-12-18 | 中国科学院东北地理与农业生态研究所 | The graphite phase carbon nitride and preparation method thereof of base metal base nickel borides modification |
| CN109529810A (en) * | 2019-01-24 | 2019-03-29 | 重庆化工职业学院 | The preparation method of composite bismuth vanadium photocatalyst |
| CN111364080A (en) * | 2020-03-05 | 2020-07-03 | 中国空间技术研究院 | C for photo-anodexNy/BiVO4Material, preparation method and application thereof |
| CN111364080B (en) * | 2020-03-05 | 2021-11-16 | 中国空间技术研究院 | C for photo-anodexNy/BiVO4Material, preparation method and application thereof |
| CN115814837A (en) * | 2023-01-06 | 2023-03-21 | 太原理工大学 | Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst and process for producing the same |
| CN115814837B (en) * | 2023-01-06 | 2024-02-20 | 太原理工大学 | Hollow flower-ball-shaped Z-shaped heterojunction BCN/Bi 2 O 2 [BO 2 (OH)]Photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105195196A (en) | Photocatalyst Co3O4-CNI and preparation method and application thereof | |
| CN105195193A (en) | Photocatalyst alkaline CNB and preparation method and application thereof | |
| CN105195194A (en) | Photocatalyst composition CNB-BiVO4 and preparation method and application thereof | |
| CN106492854B (en) | There is the composite nano Ag of photocatalysis performance using two-step method preparation3PO4/TiO2Material and methods and applications | |
| CN106540734A (en) | Compound CNB photocatalysts of a kind of transition metal oxide and preparation method thereof | |
| CN103551201B (en) | A kind of preparation method of copper hydroxyphosphate catalyst | |
| CN107774294A (en) | A kind of novel photochemical catalyst K g C3N4And its prepare and apply | |
| CN105056973B (en) | Efficient Bi2S3-BiFeO3 composite visible-light-driven photocatalyst prepared through in-situ growth with chemical corrosion method and application of Bi2S3-BiFeO3 composite visible-light-driven photocatalyst | |
| CN101791548A (en) | Visible light catalyst BiVO4 and preparation method thereof | |
| CN106582760A (en) | Metal element doped CNB photocatalyst and preparation method thereof | |
| CN105195221A (en) | Composite photocatalyst SiO2/g-C3N4 as well as preparation method and application thereof | |
| CN105195190A (en) | Heterojunction photocatalyst SnS2/g-C3N4 as well as preparation method and application thereof | |
| CN103191725A (en) | BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof | |
| CN105964250A (en) | Ag10Si4O13 photocatalyst with visible-light response and preparation method and application thereof | |
| CN105032397A (en) | Method for synthesizing bismuth vanadate photocatalyst through starch self-combustion | |
| CN104549403A (en) | Composite photocatalyst-DyVO4/g-C3N4 and preparation method thereof | |
| CN106732508A (en) | A kind of photochemical catalyst alkali metal CNB and preparation method thereof | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN103785425B (en) | A kind of flower-shaped Bi 2o (OH) 2sO 4the preparation method of photochemical catalyst and application | |
| CN105435763A (en) | Composite photocatalyst SiO2/CNI and preparation method and application thereof | |
| CN104495922A (en) | Bismuth yttrate nanorod as well as preparation method and application thereof | |
| CN108212187B (en) | Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst and process for producing the same | |
| CN104148100A (en) | Novel vanadium phosphate photocatalytic material as well as preparation method and application thereof | |
| CN103466584A (en) | Method for preparing silver phosphate nanometer material by solid phase chemical reaction | |
| CN106076374A (en) | A kind of Fe3o4c@Bi2o3biOI photocatalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151230 |
|
| RJ01 | Rejection of invention patent application after publication |