CN107876080A - A kind of novel photochemical catalyst Ag/g C3N4B and its preparation and application - Google Patents
A kind of novel photochemical catalyst Ag/g C3N4B and its preparation and application Download PDFInfo
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- CN107876080A CN107876080A CN201711147646.2A CN201711147646A CN107876080A CN 107876080 A CN107876080 A CN 107876080A CN 201711147646 A CN201711147646 A CN 201711147646A CN 107876080 A CN107876080 A CN 107876080A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 22
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
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- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 cyanogen Amine Chemical class 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
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- 238000012805 post-processing Methods 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 15
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 14
- 229940012189 methyl orange Drugs 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 5
- 238000002441 X-ray diffraction Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 abstract 1
- 238000002189 fluorescence spectrum Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 18
- 239000011941 photocatalyst Substances 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
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- 238000010521 absorption reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000009102 absorption Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
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- 238000002329 infrared spectrum Methods 0.000 description 4
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- 235000011194 food seasoning agent Nutrition 0.000 description 3
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- 239000004809 Teflon Substances 0.000 description 2
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- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
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- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The present invention relates to a kind of photochemical catalyst Ag/g C3N4B preparation method, using itrogenous organic substance and the aqueous solution of boron source as presoma, dry in a water bath, be calcined and g C are made3N4B, by g C3N4Ag/g C are made with silver salt solution reaction in B3N4B, and by X-ray diffraction (XRD), FTIR spectrum (FT IR), fluorescence spectrum (PL), UV-vis DRS spectrum (UV), laser particle analyzer etc. to Ag/g C3N4B is characterized, and the invention further relates to the application of obtained catalyst, the model compound using methyl orange as light-catalyzed reaction, have rated its photocatalytic activity.
Description
Technical field
The present invention relates to a kind of novel composite photo-catalyst for administering waste water from dyestuff pollution and preparation method thereof, belong to light and urge
Change field.
Background technology
g-C3N4With its photocatalytic activity is higher, stability is good, cost of material is cheap, especially without metal this protrusion
Advantage, a kind of new catalysis material is made it, however, single phase catalyst generally urges its light because quantum efficiency is low
It is not ideal enough to change performance.Because of g-C3N4Material photo-generate electron-hole recombination rate is higher, causes its catalytic efficiency relatively low, from
And limit its application in terms of photocatalysis.In order to improve g-C3N4Catalytic activity, recent years, people have studied very
More method of modifying.To g-C3N4The nonmetalloid being modified is including S, N, C, B, F, P, B etc., it is considered that these are nonmetallic
Element instead of C, N in 3-s- triazine structural units, H element, so as to form g-C3N4Lattice defect causes light induced electron-sky
Cave effectively improves its photocatalysis performance to being efficiently separated.
Metallic element doping and change g-C3N4The important means of electronic band structure.But up to the present, relevant Ag+
Adulterate g-C3N4Performance study but has no report in terms of B photochemical catalysts.
The content of the invention
In order to solve the above problems, the present inventor is used as forerunner by research using itrogenous organic substance and the aqueous solution of boron source
Body, solid is dried after heating solvent flashing, calcine and g-C is made3N4B, then by it with after silver salt solution post-reaction treatment, being made
Ag/g-C3N4B composite photo-catalysts, so as to complete the present invention.
Present disclosure includes following aspect：
In a first aspect, the invention provides one kind to prepare photochemical catalyst Ag/g-C3N4The method of B compounds, this method include
Following steps：
(1) itrogenous organic substance and boron source are dissolved in water, heating evaporation is to separating out white solid；
(2) solid is dried, optionally crushed, then calcined, g-C is made3N4B；
(3) by g-C3N4B, distilled water, silver salt solution and methanol mixing, are reacted, post-treated, and Ag/g- is finally made
C3N4B。
Second aspect, the present invention also provide the photochemical catalyst according to made from the above method or its application, the photochemical catalyst
For Ag/g-C3N4B, Ag and g-C3N4B quality ratios are 0.5%~1.7%, when excitation wavelength is 369nm or so, its photic hair
Absworption peak at 450nm be present in light spectrum；Available for degradable organic pollutant, particularly dye wastewater, azo of especially degrading
Benzene class dyestuff.
Brief description of the drawings
Fig. 1 shows catalyst sample X-ray diffractogram；
Fig. 2 shows catalyst photoluminescence spectra figure；
Fig. 3 shows catalyst infrared spectrogram；
Fig. 4 shows UV-Vis DRS spectrogram；
Fig. 5 (1) shows catalyst (g-C3N4) granularity measure；
Fig. 5 (2) shows catalyst (g-C3N4B) the measure of granularity；
Fig. 5 (3) shows catalyst (Ag t.%=1.073% Ag/g-C3N4B) the measure of granularity；
Fig. 6 (1) is shown as the visible light catalysis activity block diagram of photocatalyst for degrading methyl orange；
Fig. 6 (2) is shown as the visible light catalysis activity figure of photocatalyst for degrading methyl orange.
Embodiment
A kind of composite photo-catalyst Ag/g-C3N4B preparation method, this method comprise the following steps：
Step (1), itrogenous organic substance and boron source be dissolved in water, heating evaporation is to separating out white solid.
In the present invention, the itrogenous organic substance is selected from cyanamide, dicyanodiamine, melamine, urea and guanidine hydrochloride, excellent
Elect urea as.
The inventors discovered that the use of carbon-nitrogen ratio is 1:3~3:The itrogenous organic substance of 1 small-molecular-weight is as raw material, preferably
The use of carbon-nitrogen ratio is 1:2 small-molecular-weight itrogenous organic substance can be made as raw material after being calcined in 300 DEG C~800 DEG C environment
Obtain the g-C of network structure3N4, such as cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride, preferably urea.
In the present invention, the boron source is water-soluble boron source, preferably tetraphenylboron sodium.Tetraphenylboron sodium is cheap and easily-available, can be with
Itrogenous organic substance is dissolved in water jointly.
Research shows that chemical doping modification can change g-C well3N4Electronic structure, so as to improve its photocatalysis performance.
The heteroatomic introducings of B make g-C3N4Electron potential redistribute, redox site isolation, catalytic performance significantly improves.Miscellaneous original
The introducing of son necessarily causes the uneven change for causing electronic structure of electronics in the entire network, and band gap reduces, so as to improve
G-C3N4Photocatalysis performance.
In the present invention, the amount ratio of itrogenous organic substance, tetraphenylboron sodium and water is 10.0000g： 10.0mg：20.00mL contain
Nitrogen organic and tetraphenylboron sodium separate out simultaneously again after being dissolved in water, reach complete mixing, so that the structure of product is more equal
It is even.
In the present invention, itrogenous organic substance and boron source solution evaporation water, heating-up temperature 70 under thermostat water bath heating
~90 DEG C, preferably 80.0 DEG C.Heating can accelerate the evaporation of water, beneficial to the quick precipitation of solid.When heating-up temperature is less than 70
DEG C when, water evaporation is slower, uses overlong time；When temperature is more than 90 DEG C, temperature is too high, and water evaporation is very fast, the white solid of precipitation
Crystal structure is uneven.
Step (2), solid dried, optionally crushed, then calcined, g-C is made3N4B。
In the present invention, white solid is dried in an oven, oven temperature is 70~90 DEG C, preferably 80.0 DEG C.It is dry
The dry time is 18~30h, preferably 24h.
The material being dried to obtain is crushed, the method for crushing is not specially limited, existing crushing side can be selected
Any one in method, for example grind.The inventors discovered that being ground crushing to the material being dried to obtain, be advantageous to follow-up
The abundant progress of reaction, calcining obtained product, evenly performance is more stable.
In a preferred embodiment of the invention, the roasting that selection is carried out to raw material in confined conditions, avoids original
Material too contacts with oxygen, so as to the significant loss for reducing raw material complete oxidation and bringing.
Scientific research personnel does not have found natural g-C also so far3N4Crystal structure, so the research application to him needs laboratory
Synthesis.Currently used synthetic method has：High temperature and high pressure method, sedimentation, solvent-thermal method and thermal polymerization etc..Due to thermal polymerization
G-C can be adjusted conveniently by adding other materials or changing reaction condition3N4Crystal structure, so as to improve g-C3N4Light
Catalytic performance, at present conventional thermal polymerization calcining synthesis.
In the present invention, the calcining is carried out under the conditions of 300~800 DEG C, preferably 500~600 DEG C, more preferably
550.0℃。
In calcination process of the present invention, it is 10~30 DEG C of min to select heating rate-1, preferably 15~25 DEG C of min-1, such as 20 DEG C of min-1。
The inventors discovered that when heating rate is more than 30 DEG C of min-1When, obtained product morphology is uneven；When heating speed
Rate is less than 10 DEG C of min-1When, the reaction time is long, and has accessory substance generation.
In the present invention, it is 1~3 hour to select calcination time, preferably 1.5~2.5 hours, such as 2 hours.Upon calcination
Between when being less than 1 hour, calcination time is too short, and reaction is insufficient, still has the complete raw material of unreacted remaining in reaction system；When forging
After burning the time more than 3 hours, raw material fully reacts, the no longer showed increased of the product in system, continues to extend calcination time
The waste of the energy and the increase of time cost can only be caused.
Research finds g-C made from laboratory3N4, actually incomplete cross-linking products of linear polymer chain.Heating
During, urea is condensed to form linear polymer chain through deamination first, and then further crosslinking linear chain polymerisation obtains boron
The g-C of doping3N4。
Obtained material is subjected to cooling down, the present invention is not specially limited to the method for cooling down, can used
Any one method that solid can be cooled down in the prior art, such as natural cooling, preferably artificial cooling method, natural cooling
Method.
Step (3), by g-C3N4B, distilled water, silver salt solution and methanol mixing, are reacted, post-treated, final to be made
Ag/g-C3N4B。
The inventors discovered that in g-C3N4The electronics filling of non-bonding on a large amount of nitrogen holes and hybridized orbit in B structure be present
In nitrogen hole, therefore g-C3N4B is that a kind of host material, silver ion well can be combined into nitrogen hole with unpaired electron, is formed
Metal-doped, doped rear sample shows excellent performance.
In the present invention, the silver salt is water soluble silver salt, preferably silver nitrate.Add g-C3N4B and silver salt solution ratio
For 1.0000g:0.05~0.15mmol (concentration 0.0100mol/L).Selecting response mixes under dark condition, is due to
Silver ion is unstable under light illumination, and after being doped into semi-conducting material, its catalytic activity and stability are all improved.
The present invention is not specially limited to the mode of mixing, can use in the prior art any one, as mechanical agitation,
Sonic oscillation, magnetic agitation etc., preferably using magnetic agitation method.Magnetic agitation 20~40min of selection of time, it is preferably
30min。
In the present invention, dark condition mixes, and is reacted after mixing, and the reaction is to be reacted under illumination, described
Illumination is ultraviolet lighting, and the illumination stirring reaction time is 3.0~7.0h, preferably 5.0h.The ultraviolet lighting causes Ag+Ion
Generation photo catalytic reduction reaction generation metal Ag atoms, so that metal Ag is preferably deposited on g-C3N4B surfaces, so as to improve
Ag/g-C3N4B photocatalysis performance.
Last handling process includes：Separation of solid and liquid, precipitation is collected, wash drying, and grind.
The method that any one separation of solid and liquid in the prior art can be used, as volatilized naturally, is filtered under diminished pressure, the side such as centrifugation
Method, the method preferably centrifuged；After the completion of illumination reaction, centrifugation 15min is carried out with supercentrifuge, will be clear after centrifugation terminates
Liquid is poured out, and collects solid precipitation.
Optionally obtained solid is dried, in the present invention, dry mode is not specially limited, can be made
It is excellent with any one drying mode in the prior art, such as natural seasoning, high-temperature pressure seasoning, high-temperature pressure-reduction seasoning
Choosing heating atmosphere pressure desiccation is more preferably heat blowing drying.Drying temperature selection is 80~120 DEG C, preferably 100 DEG C；Dry
Time is 12~36h, preferably 24.0h,
Detailed process is：Solution is transferred in centrifuge tube after the completion of stirring reaction, centrifuged on supercentrifuge
15min, after centrifugation terminates, liquid is poured out, solid is in 100 DEG C of dry 24.0h of air dry oven, the obtained Ag/ of taking-up after cooling
g-C3N4B。
Above method obtains composite photo-catalyst Ag/g-C3N4B, wherein Ag and g-C3N4B quality ratios be 0.5%~
1.7%, when excitation wavelength is 369nm or so, there is absworption peak in its photoluminescence spectra at 450nm.
Product Ag/g-C3N4In B XRD, diffraction peak intensity at 2 θ=27.5 ° with silver content be continuously increased
It is significantly reduced, or even being continuously increased with silver content of the diffraction maximum at 2 θ=13.6 °, this feature summit are gradually dropped
It is low, or even disappear.This shows that Ag causes g-C3N4Some defects in B layers be present, periodic structure is by a certain degree of destruction.
In addition, the g-C with pure phase3N4Contrast discovery, Ag/g-C3N4In B XRD, at 2 θ=38.1 ° and 2 θ=44.1 °
In the presence of two weaker diffraction maximums, the two diffraction maximums are to belong to Ag (111) crystal faces and (220) crystal face respectively.This also says
Understand that Ag is successfully loaded to g-C3N4B surface, and certain influence each other be present in both.
Therefore, it is dirty for organic pollutants of degrading, particularly dyestuff also to provide above-mentioned composite photo-catalyst by the present invention
Water, azobenzene dyestuff of especially degrading.
Ag/g-C3N4B photochemical catalyst photocatalytic activity methods for measuring are as follows：
Each 0.0500g of photochemical catalyst sample accurately is weighed in Boiling tube, then adds 40.00mL's in Boiling tube
5.000mg/L methyl orange solutions, it is put into Teflon stir；Start dark reaction in photochemical reaction instrument；Dark reaction
After 30min, take out part solution and centrifuge 10min under supercentrifuge in centrifuge tube, test tube is taken out, by supernatant liquid
Be transferred in the test tube of another clean dried, again with supercentrifuge centrifuge 15min after, with supernatant liquid it is ultraviolet can
See in spectrophotometer and measure its absorbance A0And record related data；After dark reaction terminates, first open recirculated cooling water and
Bellows and then opening mercury lamp, start timing optical response time, after 30min, repeat aforesaid operations, survey its absorbance At
And related data is recorded, terminate experiment.Calculate degradation rate W (%)=(A0-At)/A0× 100%.
According to composite photo-catalyst Ag/g-C provided by the invention3N4B and its preparation method and application, have beneficial below
Effect：
(1) photochemical catalyst belongs to metal-silver-doped composite photo-catalyst under visible light catalytic, to sewage, particularly
Dye wastewater has very strong degradation；
(2) method for preparing the composite photo-catalyst is simple and feasible, is advantageously implemented industrialized production；
(3) composite photo-catalyst and preparation method thereof is green, non-environmental-pollution.
Embodiment 1
Precise urea 10.0000g and 10.0mg tetraphenylboron sodium are added in 100mL beaker, add 20.00mL steamings
Distilled water, stir to urea and tetraphenylboron sodium and be completely dissolved；Beaker is placed in 80.0 DEG C of thermostat water baths, evaporated until there is white
When solid separates out, take out beaker and 24h is dried in 80.0 DEG C of baking oven, obtain white solid.
Then white solid is ground to powdered and be transferred into the porcelain crucible of closing, be placed in chamber type electric resistance furnace
It is interior, 550.0 DEG C of temperature are heated to 20.0 DEG C/min speed, after being calcined 2h, chamber type electric resistance furnace is closed, it is cold to open one of gap
But to after room temperature；Taking-up sample is ground in agate mortar obtains buff powder.
By obtained g-C in above-mentioned steps3N4B weighs 1.0000g sample in Boiling tube, is put into stirrer, adds
35.00mL distilled water, and add 0.0100 mol/L AgNO3Solution 5.00mL is finally added in test tube
5.00mL absolute methanol is in Boiling tube；Test tube is placed under dark condition and stirs 30min, then opens 500W mercury lamp illumination
Under the conditions of stir 5.0h after, solution is transferred in centrifuge tube, with 15.0min is centrifuged on supercentrifuge, centrifugation terminates
Liquid is poured out afterwards, takes out solid, is put into the small beaker of cleaning, 24.0h is dried in 100.0 DEG C of electric drying oven with forced convections,
After taking out sample, ground with agate mortar, then obtain the Ag/g-C that Ag quality ratios are 0.537%3N4B samples, product are designated as
0.537%Ag/g-C3N4B。
Embodiment 2
Precise urea 10.0000g and 10.0mg tetraphenylboron sodium are added in 100mL beaker, add 20.00mL steamings
Distilled water, stir to urea and tetraphenylboron sodium and be completely dissolved；Beaker is placed in 80.0 DEG C of thermostat water baths, evaporated until there is white
When solid separates out, take out beaker and 24h is dried in 80.0 DEG C of baking oven, obtain white solid.
Then white solid is ground to powdered and be transferred into the porcelain crucible of closing, be placed in chamber type electric resistance furnace
It is interior, 550.0 DEG C of temperature are heated to 20.0 DEG C/min speed, after being calcined 2h, chamber type electric resistance furnace is closed, it is cold to open one of gap
But to after room temperature；Taking-up sample is ground in agate mortar obtains buff powder.
By obtained g-C in above-mentioned steps3N4B weighs 1.0000g sample in Boiling tube, is put into stirrer, adds
35.00mL distilled water, and add 0.0100 mol/L AgNO3Solution 10.00mL is finally added in test tube
5.00mL absolute methanol is in Boiling tube；Test tube is placed under dark condition and stirs 30min, then opens 500W mercury lamp light
After stirring 5.0h according under the conditions of, solution is transferred in centrifuge tube, with 15.0min is centrifuged on supercentrifuge, centrifugation is tied
Liquid is poured out after beam, takes out solid, is put into the small beaker of cleaning, is dried in 100.0 DEG C of electric drying oven with forced convections
24.0h, after taking out sample, ground with agate mortar, then obtain the Ag/g-C that Ag quality ratios are 1.073%3N4B samples,
Product is designated as 1.073% Ag/g-C3N4B。
Embodiment 3
Precise urea 10.0000g and 10.0mg tetraphenylboron sodium are added in 100mL beaker, add 20.00mL steamings
Distilled water, stir to urea and tetraphenylboron sodium and be completely dissolved；By beaker, it is placed in 80.0 DEG C of thermostat water baths, is evaporated white until having
When color solid separates out, take out beaker and 24h is dried in 80.0 DEG C of baking oven, obtain white solid.
Then white solid abrasive flour shape is placed in chamber type electric resistance furnace in the porcelain crucible of closing is transferred to, with
20.0 DEG C/min speed is heated to 550.0 DEG C of temperature, after being calcined 2h, closes chamber type electric resistance furnace, opens one of gap and is cooled to
After room temperature；Taking-up sample is ground in agate mortar obtains buff powder.
By obtained g-C in above-mentioned steps3N4B weighs 1.0000g sample in Boiling tube, is put into stirrer, adds
35.00mL distilled water, and add 0.0100 mol/L AgNO3Solution 15.00mL is finally added in test tube
5.00mL absolute methanol is in Boiling tube；Test tube is placed under dark condition and stirs 30min, then opens 500W mercury lamp light
After stirring 5.0h according under the conditions of, solution is transferred in centrifuge tube, with 15.0min is centrifuged on supercentrifuge, centrifugation is tied
Liquid is poured out after beam, takes out solid with clean small beaker, drying 24.0h in 100.0 DEG C of electric drying oven with forced convections, taking
After going out sample, ground with agate mortar, then obtain the Ag/g-C that Ag quality ratios are 1.609%3N4B samples, product are designated as
1.609%Ag/g-C3N4B。
Comparative example
20g urea is weighed, is put it into the crucible of dried and clean, is moved into crucible tongs in Muffle furnace, in 550 DEG C of temperature
Lower roasting 2h, smalls is ground after cooling, you can g-C is made3N4。
Experimental example
Experimental example 1：X-ray powder diffraction (XRD) characterizes
X-ray diffraction analysis are to carry out structure of matter analysis, Mei Zhongjie using diffraction effect of the X ray in crystalline solid
Eutectic substance, there are its specific crystal structure, including the parameter such as lattice type, interplanar distance.By determining diffraction Angle Position (peak
Position) qualitative analysis of compound can be carried out, quantitative analysis can be carried out by determining the integrated intensity (peak intensity) of spectral line, and be determined
The intensity of spectral line can carry out the detection of the size and shape of crystal grain with the variation relation of angle.
Operating method：
Using Bruker D8 Advance types X-ray diffractometers (XRD), copper target (Cu K α (λ=0.154nm)) ray,
Ni optical filters, operating voltage 40kV, electric current 40mA, 2 θ of scanning range=10-70 °, analyze the crystal phase structure of sample.(a)g-
C3N4, (b) g-C3N4B (c) 0.537%Ag/g-C3N4B, (d) 1.073%Ag/g-C3N4B, (e) 1.609%Ag/g-C3N4B。
As a result it is as shown in Figure 1.
In Fig. 1, for the g-C of pure phase3N4For, the diffraction maximum in 2 θ=13.6 ° belongs to crystal face (100), can be by crystalline substance
Stacking between face illustrates；Very strong characteristic diffraction peak belongs to crystal face (002) at 2 θ=27.5 °, can be by gripping fragrance altogether
The stacking of system is explained.
Examine Ag/g-C3N4B XRD, find Ag/g-C3N4Diffraction peak intensities of the B at its 2 θ=27.5 ° with
Being continuously increased for silver content is significantly reduced, or even the diffraction maximum at 2 θ=13.6 °, with being continuously increased for silver content,
This feature summit gradually reduces, or even disappears, and this shows that Ag causes g-C3N4Some defects in B layers be present, periodic structure by
Destruction to a certain extent.
With the g-C of pure phase3N4Contrast, it can be seen that figure d and scheme e in spectral line in, deposited at 2 θ=38.1 ° and 2 θ=44.1 °
In two weaker diffraction maximums, the two diffraction maximums are to belong to Ag (111) crystal faces and (220) crystal face respectively.This also illustrates
Ag is successfully loaded to g-C3N4B surface, and certain influence each other be present in both.
Experimental example 2：Photoluminescence spectra characterizes
Photoluminescence spectra (PL) is to study semiconductor nano material electronic structure and the effective ways of optical property, its energy
Enough disclose architectural characteristic and the photo-generated carrier (electron-holes such as surface defect and the surface Lacking oxygen of semiconductor nano material
It is right) separation and the information such as compound, so as to provide strong foundation to develop and preparing high performance semiconductor functional material.
Operating method：
Take a small amount of g-C3N4、g-C3N4B, 0.537%Ag/g-C3N4B, 1.073% Ag/g-C3N4B, 1.609%Ag/g-
C3N4B catalyst samples (powder), the photoluminescence performance of various catalyst samples is tested using XRF.Excitation wavelength
400nm, scanning range 400-600nm.In experiment, with slide sample should be pressed fine and close as far as possible, to keep sample surfaces
It is smooth, and a sample at least twice, should ensure the validity of data by parallel testing.Various catalysis are detected using XRF
The photoluminescence performance of agent sample.(a)g-C3N4, (b) g-C3N4B, (c) 0.537%Ag/g-C3N4B, (d) 1.073%Ag/g-
C3N4B, (e) 1.609%Ag/g-C3N4B.As shown in Figure 2.
The wavelength of excitation source is 369.0nm in Fig. 2.With the C of pure phase3N4Compare, g-C3N4B, Ag/g-C3N4B's is compound
The fluorescence intensity of photochemical catalyst has the decline of highly significant, illustrates to be supported on g-C3N4B and Ag on surface inhibit certain journey
Degree glazing excites the compound of caused electron-hole pair, and this will be advantageous to improve its photocatalysis efficiency.
This is primarily due to nano particle Ag can be in g-C3N4Surface forms electronics capture trap, promotes light induced electron not
Migration of the disconnected ground to Ag surfaces, thus inhibit the compound of hole and light induced electron；So as to improve Ag/g-C3N4B compounds
Photocatalysis efficiency.
It is generally believed that fluorescence signal is stronger, the recombination probability of photo-generated carrier (electron-hole pair) is higher, and photocatalysis is lived
Property it is just corresponding lower.In this regard, Ag/g- C3N4B composite photo-catalysts have higher electron hole separative efficiency, carry
The high catalytic activity of catalyst.
Experimental example 3：Infrared spectrum characterization
In compound molecule, the atom for forming chemical bond and the functional group of compound etc. is in the state constantly vibrated,
Its vibration frequency is suitable with the vibration frequency of infrared light.When Infrared irradiation organic molecule, chemical bond or official in molecule
Can roll into a ball can occur absorption of vibrations, and the absorption frequency of different chemical bonds is different, and can analyzes compound from infrared spectrogram
Chemical bond or functional group's information in molecule.
Operating method：
Take a small amount of g-C3N4、g-C3N4B, 0.537%Ag/g-C3N4B, 1.073% Ag/g-C3N4B, 1.609%Ag/g-
C3N4B catalyst samples, a small amount of potassium bromide powder is separately added into, is ground to well mixed, be pressed into thin slice, it is red with Fourier transformation
External spectrum instrument carries out infrared spectrum characterization to catalyst.(a)g-C3N4, (b) g-C3N4B, (c) 0.537%Ag/g-C3N4B, (d)
1.073%Ag/g-C3N4B, (e) 1.609%Ag/g-C3N4B.As shown in Figure 3.
The infrared spectrum and g-C of all samples in Fig. 33N4Infrared spectrum it is substantially the same.In the 810cm of the figure-1Place
Absworption peak correspond to the flexural vibrations peak of ring；In the 1250-1750cm of the figure-1There are a series of stronger absorptions in wave-length coverage
Peak, and corresponding to these peaks be g-C3N4The characteristic peak of heteroaromatic in structure；In the 3000-3300cm of the figure-1Width
It is O-H vibration peaks and N-H stretching vibrations corresponding to absworption peak, this may is that is total to by the urea not decomposed completely on a small quantity and absorption water
Result caused by same-action.
As can be seen that g-C from FT-IR spectrograms3N4B in the composite only destroyed by part, but it still remains
g-C3N4B basic structure, the infared spectrum of different silver-colored compound quantities are substantially the same.
These phenomenons obtain that result is consistent, and this illustrates that we have successfully prepared g-C with XRD analysis in Fig. 13N4B and
Ag/g-C3N4B composite photocatalysts.
Experimental example 4：The UV-Vis DRS spectrum of catalyst
The structure of catalyst is characterized using UV-Vis spectrum.Above-mentioned sample (pulverulence) is taken, utilizes dual-beam
Ultraviolet-visible spectrophotometer (UV-vis spectrophotometer, UV-1901 Beijing Pu Xi all purpose instruments Co., Ltd)
The absorption spectrum of determination sample, using barium sulfate as reference, wavelength scanning range 200-700nm, sweep speed is quick, step
A length of 1.0nm, as a result as shown in Figure 4.
In Fig. 4, (a) g-C3N4, (b) g-C3N4B, (c) 0.537%Ag/g-C3N4B, (d) 1.073%Ag/g-C3N4B,
(e) 1.609%Ag/g-C3N4B。
A, b, c, d and e UV-Vis DRS abosrption spectrogram are followed successively by Fig. 4 along the direction of arrow.Can from figure
To find out, the g-C of pure phase3N4There is precipitous absorption band edge at 450nm or so places.According to energy gap calculation formula：
Eg (eV)=1240/ λ (nm)
In formula, Eg is semiconductor energy gap, and λ is its Absorption edge value.Understand g-C obtained in this experiment3N4
Energy gap be 2.75eV, obtained g-C3N4B energy gap is 2.715eV.With g-C3N4Compare, g-C3N4B and Ag/
g-C3N4Absorption peak strengths of the B at less than 450nm substantially increases, and shows B and Ag load, improves g-C3N4To ultraviolet light
Utilization ratio.
As we can clearly see from the figure, g-C3N4B and Ag/g-C3N4B has a wide absworption peak at 450-750nm,
This is mainly corresponding to nano particle Ag surface plasmon absorption peak, this explanation Ag/g-C3N4B application can open up
Open up visible region.
In the case where both contrast, either visible region or ultra-violet (UV) band, Ag/g-C3N4B occupies advantage well, can be with
Predict its catalytic performance than simple g-C3N4And g-C3N4B will get well.
It can be seen that UV-Vis DRS spectrogram shape before and after doping loads is almost similar, change is not
It is it is obvious that not producing new collection of illustrative plates phenomenon. Ag/g-C3N4Type B photochemical catalyst and g-C3N4、g-C3N4B catalyst exists
There is obvious absworption peak between wavelength 225-450nm, and as Ag dopings increase, what light absorption value presentation gradually increased becomes
Gesture.It can significantly find out the composite catalyst after doping load in ultraviolet and visibility region all than simple g-C3N4Or g-
C3N4B catalyst has stronger absorption light ability, and this shows greatly to improve in ultra-violet (UV) band and visual field photocatalytic degradation capability
.
It can also be seen that and pure sample g-C from Fig. 43N4Or g-C3N4B is compared, Ag/g-C3N4The absorption band edge of B catalyst
Along red shift occurs, absorption band edge generation red shift is bigger, and catalyst activity is higher, and this is basically identical with catalyst activity.
Experimental example 5：The sign of laser particle analyzer
Each catalyst sample is characterized successively using laser particle analyzer, after opening laser particle analyzer instrument, waits instrument
After device self-test, the associated sample that will be tested gradually is added, ensures that concentration within scope of experiment, preserves related data,
Repeat；In experiment, ensure the validity of data, sample should at least parallel testing be twice.As shown in Fig. 5.
In Fig. 5, (a) g-C3N4, (b) g-C3N4B, (c) 0.537%Ag/g-C3N4B, (d) 1.073%Ag/g-C3N4B,
(e) 1.609%Ag/g-C3N4B。
Fig. 5 (1) is catalyst (g-C3N4) granularity measure；Fig. 5 (2) catalyst (g-C3N4B) the measure of granularity；Fig. 5
(3) catalyst (Ag t.%=1.073% Ag/g-C3N4B) the measure of granularity.According to the grain that each photochemical catalyst is understood in Fig. 5
Footpath distribution map.
It can be obtained in Fig. 5 (1), g-C3N4Particle diameter be mainly distributed between 20-30um, its D50=16.55um；
By the way that g-C can be obtained in Fig. 5 (2)3N4B particle diameter is mainly distributed between 20-30um, its D50=
16.35um；
By the Ag/g-C that Ag wt.%=1.073% can be obtained in Fig. 5 (3)3N4B particle diameter is mainly distributed on 3-
Between 10um, its D50=5.501um；
It can be seen that g-C3N4, g-C3N4It is identical that both B particle diameter mainly distributes section, but its D50Size is but not
Together, respectively 16.55um, 16.35um.Under normal circumstances, D50Smaller, the specific surface area of photochemical catalyst is bigger, with connecing for degraded
Contacting surface is also bigger, and degrading activity is also higher.
Experimental example 6：The active testing experiment of catalyst
G-C is accurately weighed respectively3N4B and Ag quality ratios are respectively 0.537%, 1.073%, 1.609% Ag/g-
C3N4Each 0.0500g of B photochemical catalyst samples is separately added into 40.00mL's in 4 Boiling tubes, then in 4 Boiling tubes
5.000mg/L methyl orange solutions, respectively it is put into 1 Teflon stir；Start dark reaction in photochemical reaction instrument；It is dark anti-
After answering 30min, take out part solution and centrifuge 10 min under supercentrifuge in centrifuge tube, take out test tube, upper strata is clear
Clear liquid is transferred in the test tube of another clean dried, after centrifuging 15min with supercentrifuge again, with supernatant liquid in purple
Its absorbance A is measured in outer visible spectrophotometer0And record related data；After dark reaction terminates, circulating cooling is first opened
Water and bellows and then opening mercury lamp, start timing optical response time, after 30min, repeat aforesaid operations, survey its extinction
Spend AtAnd related data is recorded, until three groups of experiments have all been surveyed, terminate experiment.
Calculate degradation rate W (%)=(A0- At)/A0× 100%, inequality Ag doping g- is drawn out according to gained degradation rate
C3N4The visible activity figure of B methyl orange catalyst sample.Such as Fig. 6（1）And Fig. 6（2）It is shown.
Fig. 6（1）And Fig. 6（2）In, (a) g-C3N4, (b) g-C3N4B, (c) 0.537%Ag/g-C3N4B, (d) 1.073%
Ag/g-C3N4B, (e) 1.609%Ag/g-C3N4B。
Fig. 6 (1) is the visible light catalysis activity block diagram of photocatalyst for degrading methyl orange.
Fig. 6 (2) is the visible light catalysis activity figure of photocatalyst for degrading methyl orange.
According to Fig. 6 (1), it can be seen that methyl orange degradation rate of the degradation rate of a methyl orange substantially than b in figure is low in figure
A lot, this is also to illustrate that B element can be with g-C3N4The g-C obtained after compound3N4B significantly improves former g-C3N4Photocatalysis
Activity；Methyl orange degradation rate in figure corresponding to d is highest, but the degradation rate and d of the methyl orange corresponding to the f in figure
Carrying out contrast has apparent reduction, silver-colored compound obtained Ag/g-C of this explanation in excess3N4B composite photo-catalyst light is lived
Property can reduce；
As can be seen that the degradation rate of cloudy, turbid phase catalysis is extremely low, in photoreaction stage over time from Fig. 6 (2)
Be constantly increasing, the degradation rate of catalyst little by little becomes big by small.Meanwhile for Visible Light Induced Photocatalytic rate that different catalysts obtain
It is different, compound catalyst is substantially than pure g-C3N4Catalyst degradation effect is good.After light reaction 1.5h, pure phase g-C3N4
The degradation rate of catalyst is 65.6%, and 1.073%Ag/g-C3N4The degradation rate of B composite catalysts is maximum, can reach
89.4%.And g-C3N4B, 0.537%Ag/g-C3N4B and 1.609%Ag/g-C3N4The degradation rate difference of B composite catalysts
For 80.4%, 83.0%, 84.5%.
With reference to Fig. 6 (1), Fig. 6 (2) analysis result, thereby it is assumed that, with Ag materials amount be continuously increased it is compound
The degraded of catalyst takes the lead in increasing and reduced again, in Ag wt.%=1.073% Ag/g-C3N4B nearby reaches most degradation rate,
This and figure (5) in D50The result that the analysis of size obtains is consistent.
The present invention is using the aqueous solution of urea and tetraphenylboron sodium as presoma, after being dried to solid in a water bath, by solid
In roasting so as to obtaining g-C3N4B, then by itself and the different amounts of silver nitrate of concentration of the same race (0.010mol/L AgNO3) solution reaction
Ag/g-C is made3N4B composite photo-catalyst.By the photocatalytic degradation of the dyestuffs such as methyl orange, Ag/g-C have rated3N4B's
Visible light catalysis activity.
As a result show：With pure g-C3N4Or g-C3N4B is compared, Ag/g-C3N4B photochemical catalysts have in 225-450nm regions
There are stronger absorbing properties, and absorb band edge and moved to long wave direction.In all Ag/g-C3N4In B samples, 1.073%
Ag/g-C3N4B composite catalysts have highest visible light catalysis activity, under the optimal conditions, it is seen that light irradiation 1.5h,
1.073%Ag/g-C3N4B photo-catalytic degradation of methyl-orange degradation rates reach 89.4%.
The present invention is described in detail above in association with embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
A variety of equivalencing, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is determined by the appended claims.
Claims (10)
- A kind of 1. photochemical catalyst Ag/g-C3N4B preparation method, it is characterised in that this method comprises the following steps：(1) itrogenous organic substance and boron source are dissolved in water, heating evaporation is to separating out white solid；(2) solid is dried, optionally crushed, then calcined, g-C is made3N4B；(3) by g-C3N4B, distilled water, silver salt solution and methanol mixing, are reacted, post-treated, and Ag/g- is finally made C3N4B。
- 2. preparation method according to claim 1, it is characterised in that in step (1), the itrogenous organic substance is selected from single cyanogen Amine, dicyanodiamine, melamine, urea and guanidine hydrochloride, preferably urea.
- 3. preparation method according to claim 1 or 2, it is characterised in that in step (1), the boron source is water-soluble boron Source, preferably tetraphenylboron sodium,Preferably, the amount ratio of itrogenous organic substance, tetraphenylboron sodium and water is 10.0000g：10.0mg：20.00mL.
- 4. the preparation method according to one of claims 1 to 3, it is characterised in that in step (1), itrogenous organic substance and boron Source solution evaporates under thermostat water bath heating, and heating-up temperature is 70~90 DEG C, preferably 80.0 DEG C.
- 5. the preparation method according to one of Claims 1 to 4, it is characterised in that in step (2), in an oven by white Solid is dried, and oven temperature is 70~90 DEG C, preferably 80.0 DEG C；Drying time is 18~30h, preferably 24h.
- 6. the preparation method according to one of Claims 1 to 5, it is characterised in that in step (2), calcining heat be 300~ 800 DEG C, preferably 500~600 DEG C, more preferably 550.0 DEG C；Programming rate is 20.0 DEG C/min；Calcination time is 1~3h, preferably 2h.
- 7. the preparation method according to one of claim 1~6, it is characterised in that in step (3), the silver salt solution is Silver nitrate；g-C3N4B and silver salt amount ratio are 1.0000g:0.05~0.15mmol, the silver salt are concentration 0.0100mol/L silver Salting liquid.
- 8. the preparation method according to one of claim 1~7, it is characterised in that in step (3),g-C3N4B, distilled water, silver salt solution and methanol mix under dark condition, and incorporation time is 20~40min, are preferably 30min,g-C3N4B, after distilled water, silver salt solution and methanol mixing, reacted under light illumination, the illumination is ultraviolet lighting, light Mixing time is 3.0~7.0h, preferably 5.0h according under the conditions of；The post processing includes：Separation of solid and liquid, precipitation is collected, washed, dried, and grind.
- 9. preparation method according to claim 8, it is characterised in that in step (3),Drying condition is：Drying temperature is 80~120 DEG C, preferably 100 DEG C；Drying time is 12~36h, preferably 24.0h.
- 10. according to photochemical catalyst made from one of claim 1~9 preparation method or its application, it is characterised in that：It is described Photochemical catalyst is Ag/g-C3N4B, Ag and g-C3N4B quality ratios are 0.5%~1.7%, are 369nm or so in excitation wavelength When, absworption peak at 450nm be present in its photoluminescence spectra；Available for organic pollutants of degrading, particularly dye wastewater, Especially degraded azobenzene dyestuff.
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