CN105817244B - A kind of AgI/ β Bi2O3‑Bi2O2CO3Photochemical catalyst and its preparation method and application - Google Patents
A kind of AgI/ β Bi2O3‑Bi2O2CO3Photochemical catalyst and its preparation method and application Download PDFInfo
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- CN105817244B CN105817244B CN201610230892.3A CN201610230892A CN105817244B CN 105817244 B CN105817244 B CN 105817244B CN 201610230892 A CN201610230892 A CN 201610230892A CN 105817244 B CN105817244 B CN 105817244B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 230000004044 response Effects 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 9
- 235000015165 citric acid Nutrition 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000010010 raising Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
- B01J27/236—Hydroxy carbonates
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of AgI/ β Bi2O3‑Bi2O2CO3Photochemical catalyst and its preparation method and application, preparation method include：(1) by Bi (NO3)3·5H2O is dissolved in HNO3In, citric acid is then added, then pH is adjusted to the laggard water-filling thermal response of faintly acid, reaction is centrifuged after terminating and takes precipitation, and Bi is obtained after scrubbed, drying and milled processed2O2CO3；(2) by Bi2O2CO3It is scattered in AgNO3The aqueous solution in, be then added dropwise KI solution, reaction terminate after through centrifuging, drying, grinding to obtain AgI/Bi2O2CO3；(3) by AgI/Bi2O2CO3Calcining at constant temperature obtains AgI/ β Bi2O3‑Bi2O2CO3Photochemical catalyst.The preparation method of photochemical catalyst of the present invention is simple, cost is low, visible light-responded degree improves, photocatalysis performance is good, to, the processing of the waste water containing paranitroanilinum, non-secondary pollution.
Description
Technical field
The present invention relates to catalysis material technical field, especially visible light catalytic material technical field, and in particular to one
Kind AgI/ β-Bi2O3-Bi2O2CO3The preparation method and applications of photochemical catalyst.
Background technology
Catalysis material is due to using sunshine, carrying out organic pollutant degradation, heavy metal reduction, and recyclable profit
With widely studied in recent years.With conventional TiO2Exemplified by, greater band gap, it can only absorb and account for ultraviolet light of the solar energy less than 5%,
It is very low to solar energy utilization ratio.Thus, it is necessary to research and develop the photochemical catalyst of high visible response.
For example, Publication No. CN 102962078A Chinese invention patent application document disclose it is a kind of visible light-responded
Photochemical catalyst and preparation method thereof.By analytically pure silver nitrate, cupric oxide, niobium pentaoxide, tantalum pentoxide according to
AgCuNb1-xTaxO4(wherein 0≤x≤1) is put into autoclave after weighing, using potassium hydroxide as mineralizer, using Hydrothermal Synthesiss work
Skill obtains the composite oxides with good visible light photocatalysis characteristic.
Publication No. CN 104014325A Chinese invention patent application document discloses a kind of visible-light response nano two
Titanium oxide catalyst, it is combined by nano titanium oxide, nano bismuth oxide and graphene oxide, it is titanium dioxide, nano oxidized
The mass ratio of bismuth and graphene oxide is 1: 0.05-1: 1-2.
Photochemical catalyst using bismuth system as representative, can produce photo-generate electron-hole pair, in degraded and ore deposit under ultraviolet light
While changing organic pollution, the heavy metal ion in environment is removed/reclaims by reduction reaction.Wherein, Bi2O3Band-gap energy is
2.8eV, absorbing wavelength is longer, there is certain utilization rate to visible ray.Bi2O2CO3Band-gap energy is 3.4eV, greater band gap, pair can
See that light absorbs are weak, but its broad-band gap is easily modified, so as to improve the response to visible ray.In addition, AgI is as light-sensitive material, it is right
Visible ray has very high response, but deficient in stability under illumination condition.
Semiconductors coupling is to improve a kind of visible light-responded important method of photochemical catalyst, can be with exploitation value band, energy level
Difference, promote electron transmission in photochemical catalyst, reduce compound, the life in promotion light induced electron and hole in light induced electron and hole
Into so as to improve treatment effect of the photochemical catalyst to the waste water containing paranitroanilinum.
The content of the invention
The present invention provides a kind of AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst and its preparation method and application, photochemical catalyst
Preparation method is simple, cost is low, visible light-responded degree improves, photocatalysis performance is good, for the place of the waste water containing paranitroanilinum
Reason, non-secondary pollution.
A kind of AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst with the atomic ratio represented with formula (I) characterized in that, form：
AgI/β-Bi2O3-Bi2O2CO3 (Ⅰ)。
The present invention also provides a kind of AgI/ β-Bi2O3-Bi2O2CO3The preparation method of photochemical catalyst, it is described to have with formula (I)
The photochemical catalyst of the atomic ratio composition of expression is preferably prepared using the preparation method, and the preparation method comprises the following steps：
(1) by Bi (NO3)3·5H2O is dissolved in HNO3In, citric acid is then added, then adjust pH to the laggard water-filling of faintly acid
Thermal response, reaction are centrifuged after terminating and take precipitation, and Bi is obtained after scrubbed, drying and milled processed2O2CO3；
(2) by Bi2O2CO3It is scattered in AgNO3The aqueous solution in, be then added dropwise KI solution, reaction passed through after terminating from
The heart, drying, grind to obtain AgI/Bi2O2CO3；
(3) by AgI/Bi2O2CO3Calcining at constant temperature obtains AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst.
It is of the invention mainly to use the method for semiconductors coupling to Photocatalyst.Semiconductors coupling is to improve photochemical catalyst
A kind of visible light-responded important method, electron transmission in photochemical catalyst can be promoted with the difference of exploitation value band, energy level, reduced
Wide raw electronics and compound, promotion light induced electron and the Holes buffer layer, so as to improve photochemical catalyst to containing paranitroanilinum in hole
The treatment effect of waste water.
AgI/ β-the Bi of the present invention2O3-Bi2O2CO3Photochemical catalyst, it is with Bi2O2CO3Based on, on the one hand utilize
Bi2O2CO3β-Bi can be generated by calcining2O3-Bi2O2CO3Straightforward procedure, structure β-Bi2O3With Bi2O2CO3Compound light
Catalyst, improve visible light-responded.On the other hand, based on Bi2O3Compound photosensitive materials A gI, can prepare high performance catalyst, be
To the reproducibility for improving photochemical catalyst.Therefore, it is of the invention, flower-shaped Bi is prepared for first2O2CO3(white), and it is multiple on this basis
AgI is closed, by exploring optimum calcinating temperature, prepares AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst, realize the performance of catalyst most
Optimization.AgI、β-Bi2O3、Bi2O2CO3The band gap of three kinds of catalyst, conduction band, valence band relative position are as shown in fig. 7, radiation of visible light
Afterwards, AgI and β-Bi2O3Electron transition in valence band is to conduction band, due to conduction band positions difference, and AgI (N-type semiconductor) and β-
Bi2O3(P-type semiconductor), and β-Bi2O3With Bi2O2CO3(N-type semiconductor) forms hetero-junctions, can accelerate electron transmission, so as to
There is substantial amounts of electron transmission to Bi2O2CO3Conduction band, for paranitroanilinum to be reduced into p-phenylenediamine.On the other hand, β-Bi2O33
Hole in valence band is transferred to AgI valence band, so as to greatly reduce the compound of hole and electronics.
Preferably, Bi (NO in the mixed solution of step (1)3)3·5H2O concentration is 0.025~0.2mol/L；HNO3
Concentration be 0.5~1.5mol/L；The concentration of citric acid is 0.0125~0.1mol/L.
Preferably, citric acid concentration is Bi (NO in mixed solution3)3·5H2O concentration 1/2.
It is further preferred that in mixed solution：Bi(NO3)3·5H2O concentration is 0.05~0.1mol/L； HNO3Concentration
For 1mol/L；Citric acid concentration is 0.025~0.05mol/L.
Most preferably, in mixed solution：Bi(NO3)3·5H2O concentration is 0.05mol/L；HNO3Concentration is 1mol/L；
Citric acid concentration is 0.025mol/L.
The pH that mixed solution is adjusted after addition citric acid is 5.5~6.5, preferably 6, it is preferred to use NaOH solution is adjusted,
Its concentration is 6~10mol/L, preferably, 8~10mol/L.
Preferably, in step (1) hydro-thermal reaction 20~25h of time, the temperature of hydro-thermal reaction is 160~200 DEG C.
It is further preferred that the hydro-thermal reaction time is 24h, the temperature of hydro-thermal reaction is 180 DEG C.
Washing process described in step (1) is to be cleaned successively with absolute ethyl alcohol, distilled water.
Preferably, washes of absolute alcohol number is 1~3 time, and distilled water wash number is 2~3 times.Further preferably, nothing
Water-ethanol wash number is 2 times, and distilled water wash number is 3 times.Drying temperature is preferably 80 DEG C.
Preferably, AgNO in step (2)3Mol ratio with KI is (2:1)~(1:2)；Bi2O2CO3With AgNO3Mass ratio
With AgI/Bi2O2CO3Middle AgI load capacity is counted for 2.5~10mol%.
Bi in the present invention2O2CO3、AgNO3Proportioning with KI is with AgI/Bi2O2CO3Middle AgI load capacity be 2.5~
10mol% is counted.
AgI load capacity can influence response of the catalyst to visible ray, influence the separation of photo-generate electron-hole, Jin Erying
Ring the performance of catalyst, the AgI/Bi being prepared in step (2)2O2CO3In photochemical catalyst, AgI load capacity for 2.5%~
10mol% is (with AgI/Bi2O2CO3Molar amount), preferably, AgI load capacity is 2.5%~5mol%；
Further, AgNO3Mol ratio with KI is 2:1~1:2.AgNO3AgI generation is had influence on KI mol ratio
Amount, and then influence the performance of catalyst, still more preferably, AgNO3Mol ratio with KI is 1:1.
Most preferably, Bi2O2CO3、AgNO3Mol ratio with KI is 100:5:5, it is prepared under the conditions of mixture ratios
In catalyst AgI load capacity in 5mol% (with AgI/Bi2O2CO3Molar amount) left and right.The concentration of KI solution be 2.45~
39.2mM；AgNO3Water solution A gNO3Concentration be 4.9~19.6mM.
With AgI/Bi2O2CO3Middle AgI load capacity is that 2.5~10mol% meters refer to AgI/Bi2O2CO3Middle AgI mole
Measure as AgI/Bi2O2CO3The 2.5~10% of mole.
Step (2) drying temperature is 100 DEG C.
Calcining heat influences β-Bi2O3And Bi2O2CO3Ratio, also influences the activity of AgI catalyst, and then has influence on AgI/
β-Bi2O3-Bi2O2CO3The performance of catalyst.Within the specific limits, calcining heat is high, and the performance of catalyst can also be lifted, temperature
Too high, catalyst denaturation, activity on the contrary can step-down.
Therefore, calcining at constant temperature temperature is 250~400 DEG C, 1.5~2.5h of calcination time in step (3), preferably, permanent
Warm calcining heat is 250~350 DEG C, and further preferably, calcining at constant temperature temperature is 300~350 DEG C；Most preferably, calcining heat is
300℃。
When calcining heat is 300 DEG C, the speed of catalyst degradation paranitroanilinum is most fast.The speed of degraded paranitroanilinum
Rate is successively：300℃>350℃>250℃>400 DEG C, and it is above AgI/Bi2O2CO3。
The inventive method is under the above-mentioned preferably cooperation of AgI load capacity and preferred calcination temperature, the photocatalysis that is prepared
Agent has spherical surface flower-like structure, clear-cut；There is very strong sound in full spectrum under UV-Vis DRS scanning
Should, especially in visible-range, the absorption to visible ray has huge raising, has very strong visible light activity；On an equal basis
Under the conditions of, relative to Bi2O2CO3The effect of degraded paranitroanilinum improves 10 times.
AgI/ β-Bi of the present invention2O3-Bi2O2CO3The preparation method of photochemical catalyst, most preferred technique scheme are as follows：
(1) by Bi (NO3)3·5H2O, it is added to 1mol/L HNO3In, stir to whole dissolvings, add citric acid；Bi
(NO3)3·5H2O concentration is 0.05mol/L, citric acid and Bi (NO3)3·5H2O mol ratios 1:2.
(2) with (180 DEG C of temperature) after 10mol/L NaOH tune pH to 6, hydro-thermal reaction 24h, centrifugation, absolute ethyl alcohol is used successively
Cleaning 2 times, distilled water clean 3 times, 80 DEG C drying, grinding, be made Bi2O2CO3；
(3) by AgNO3Distilled water is dissolved in, adds Bi2O2CO310min is stirred, KI solution reactions are added dropwise, centrifuge,
100 DEG C of drying, grinding, are made AgI/Bi2O2CO3；Wherein, AgNO3Mol ratio with KI is 1:1, AgI load capacity is
5mol%；
(4) by AgI/Bi2O2CO3300 DEG C of calcining 2h of constant temperature, are made AgI/ β-Bi in Muffle furnace2O3-Bi2O2CO3。
The present invention also provides a kind of AgI/ β-Bi being prepared such as methods described2O3-Bi2O2CO3Photochemical catalyst.
The present invention also provides one kind and utilizes the AgI/ β-Bi2O3-Bi2O2CO3Photocatalyst treatment nitrobenzene-containing amine waste water
Method, comprise the following steps：
Waste water containing paranitroanilinum and the photochemical catalyst, lasting stirring, it is seen that light irradiation is carried out are added into reactor
Reaction.
Paranitroanilinum concentration influences reaction rate in waste water containing paranitroanilinum, and too high then reaction speed is slow, too low, then
Catalyst wasting phenomenon can be produced.Therefore, consider, it is preferable that the waste strength containing paranitroanilinum be 2.5~
15mg/L, preferably 5~10mg/L.
Preferably, in waste water containing paranitroanilinum, the addition of photochemical catalyst is 0.5~2g/L；Preferably 1~1.5g/
L。
Radiation of visible light uses xenon lamp, power 300W, operating voltage 14V, operating current 21A, filters off wavelength and is less than 420nm
Part.
It is an object of the invention to provide a kind of AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst and preparation method thereof, core are
With Bi2O2CO3Based on, β-Bi can be generated by calcining2O3-Bi2O2CO3Straightforward procedure, and compound photosensitive materials A gI,
It is compound using semiconductor light-catalyst, hetero-junctions is formed, prepares high performance catalyst, accelerates electron transmission, visible ray is improved and rings
Should.So that more paranitroanilinum are reduced into p-phenylenediamine.AgI/β-Bi2O3-Bi2O2CO3Photochemical catalyst is to containing to nitro
The processing of aniline waste water, treatment effect is more preferable under the combination of above-mentioned each optimum condition, there is very big lifting.
Beneficial effects of the present invention are as follows：
(1) prepare that this photochemical catalyst cost is low, and method is simple；
(2) photocatalyst activity is high；
(3) it is good to the processing of paranitroanilinum waste water, effect；
Brief description of the drawings
Figure 1A~Fig. 1 D be the embodiment of the present invention 1 prepare four kinds of photochemical catalysts SEM figure (wherein Figure 1A is Bi2O2CO3；
Figure 1B is β-Bi2O3-Bi2O2CO3；Fig. 1 C are AgI/Bi2O2CO3；Fig. 1 D are AgI/ β-Bi2O3-Bi2O2CO3)。
Fig. 2 is the UV-vis-DRS comparison diagrams of four kinds of photochemical catalysts in the embodiment of the present invention 2.
Fig. 3 is in the embodiment of the present invention 3 under four kinds of photochemical catalyst identical conditions, and degrade paranitroanilinum effect contrast figure.
Fig. 4 is the catalyst that in the embodiment of the present invention 4 prepared by different calcining heats, paranitroanilinum Contrast on effect of degrading
Figure.
Fig. 5 is the catalyst that in the embodiment of the present invention 5 prepared by different AgI load capacity, paranitroanilinum Contrast on effect of degrading
Figure.
Fig. 6 is different AgNO in the embodiment of the present invention 63The catalyst prepared with KI mol ratio, paranitroanilinum of degrading
Effect contrast figure.
Fig. 7 is the schematic diagram of the present invention.
Embodiment
In conjunction with Figure of description and specific embodiment, the present invention is further described.
Embodiment 1
(1) Bi2O2CO3The preparation of photochemical catalyst：
(1) by 1.456g Bi (NO3)3·5H2O, it is added to 1mol/L HNO3In (60mL), stir to whole dissolvings；
(2) dissolving of 0.288g citric acids is added；
(3) pH value of solution is adjusted to 6 with 10mol/L NaOH；
(4) 180 DEG C of hydro-thermal reaction 24h；
(5) centrifuge, clean 3 times with washes of absolute alcohol 2 times, distilled water successively, 80 DEG C of drying, grinding is obtained
Bi2O2CO3。
(2) β-Bi2O3-Bi2O2CO3The preparation of photochemical catalyst, step are as follows：
Bi prepared by (one)2O2CO3What is prepared is placed in Muffle furnace, 300 DEG C, 120min calcinings, obtains β-Bi2O3-
Bi2O2CO3。
(3) AgI/Bi2O2CO3The preparation of photochemical catalyst, step are as follows：
(1) by 0.0167g AgNO3Distilled water is dissolved in, adds 1g Bi2O2CO3Stir 10min；
(2) 0.0163g KI are dissolved in 5mL water, KI solution reactions is added dropwise in (1)；
(3) centrifugation, 100 DEG C of drying, grinding, are made AgI/Bi2O2CO3。
(4) AgI/ β-Bi2O3-Bi2O2CO3The preparation of photochemical catalyst, step are as follows：
AgI/Bi prepared by (three)2O2CO3300 DEG C of constant temperature in Muffle furnace, 2h is calcined, AgI/ β-Bi are made2O3-
Bi2O2CO3。
Fig. 1 is the SEM figures of four kinds of photochemical catalysts.Such as Figure 1A, Bi2O2CO3It is spherical in shape flower-shaped, regular shape；After section is burnt, such as
Figure 1B, β-Bi2O3-Bi2O2CO3Shape does not change；Bi2O2CO3After loaded Ag I, such as Fig. 1 C, spherical surface flower-like structure becomes
It is thick；Such as Fig. 1 D, AgI/ β-Bi2O3-Bi2O2CO3Spherical surface flower-like structure is thickening, and profile is apparent.
Flower-like structure is advantageous to increase specific surface area, is reactant so as to increase the contact area of catalyst and reactant
Combined with more active catalyst sites.In addition, flower-like structure is thickening, surface crystal is reacted, crystallinity improves so that
Catalyst performance increase.
Embodiment 2
Photochemical catalyst Bi prepared by embodiment 12O2CO3、β-Bi2O3-Bi2O2CO3、 AgI/Bi2O2CO3、AgI/β-
Bi2O3-Bi2O2CO3UV-Vis DRS scanning is carried out, obtains UV-vis-DRS comparison diagrams 2.
Such as Fig. 2, Bi2O2CO3Absorbed in visible-range very weak, almost concentrate on ultraviolet region entirely.After calcining, β-
Bi2O3-Bi2O2CO3Strengthen visible light-responded.AgI/Bi2O2CO3To visible absorption also some raisings, especially in wavelength
420nm or so.AgI/β-Bi2O3-Bi2O2CO3There is very strong response in full spectrum, especially can in visible-range, its pair
Seeing the absorption of light has huge raising, and this explanation, catalyst has very strong visible light activity.
Embodiment 3
Add that volume is 50mL, concentration 10mg/L is contain paranitroanilinum (4-NA) waste water, addition into reactor
50mg AgI/ β-Bi2O3-Bi2O2CO3Visible light catalyst, lasting stirring, 30min is stirred to adsorption equilibrium in dark place, is opened
Visible light source, interval 15min samplings, reaction duration 5 hours.
It is photochemical catalyst Bi prepared by embodiment 1 to change photochemical catalyst2O2CO3、β-Bi2O3-Bi2O2CO3、AgI/
Bi2O2CO3, carry out paranitroanilinum Contrast on effect of degrading, as a result such as Fig. 3 and table 1.
Such as Fig. 3, under equal conditions, β-Bi2O3-Bi2O2CO3Paranitroanilinum effect of degrading and Bi2O2CO3Difference is not
Greatly.The modified AgI/Bi prepared2O2CO3、AgI/β-Bi2O3-Bi2O2CO3Relative to Bi2O2CO3, degraded paranitroanilinum effect it is equal
Have and largely lifted.After 5 hours, Bi2O2CO3Middle paranitroanilinum conversion ratio reaches 8.41%, AgI/ β-Bi2O3-
Bi2O2CO3Middle paranitroanilinum conversion ratio reaches 85.45%, about Bi2O2CO310 times.Such as table 1, degradation of phenol speed:
AgI/β-Bi2O3-Bi2O2CO3>AgI/Bi2O2CO3>β-Bi2O3-Bi2O2CO3>Bi2O2CO3。
The different catalysts of table 1 degraded paranitroanilinum speed and effect
Embodiment 4
Calcining heat influences β-Bi2O3And Bi2O2CO3Ratio, also influences the activity of AgI catalyst, and then has influence on AgI/
β-Bi2O3-Bi2O2CO3The performance of catalyst.Within the specific limits, calcining heat is high, and the performance of catalyst can also be lifted, temperature
Too high, catalyst denaturation, activity on the contrary can step-down.
Change AgI/Bi prepared by embodiment 1 (four)2O2CO3The calcining at constant temperature temperature in Muffle furnace, respectively 250 DEG C,
350 DEG C, 400 DEG C, a series of catalyst are prepared.According to the processing method of the paranitroanilinum waste water of embodiment 3, compare catalysis
Agent performance, as a result such as Fig. 4.
Such as Fig. 4, when calcining heat is 300 DEG C, the speed of catalyst degradation paranitroanilinum is most fast.Degraded p-nitrophenyl
The speed of amine is successively：300℃>350℃>250℃>400 DEG C, and it is above AgI/Bi2O2CO3.This explanation, calcining heat with
300 DEG C are advisable.
Embodiment 5
AgI load capacity can influence response of the catalyst to visible ray, influence the separation of photo-generate electron-hole, Jin Erying
Ring the performance of catalyst.
Change embodiment 1AgI/ β-Bi2O3-Bi2O2CO3AgI ratios are 2.5%, 10% during preparation, i.e. change AgNO3、
KI amounts, other operations are constant, prepare the AgI/ β-Bi of the different AgI of series load capacity2O3-Bi2O2CO3, it is right according to embodiment 3
The processing method of nitroaniline waste water, compare catalyst performance, as a result such as Fig. 5.
Such as Fig. 5, the AgI/ β-Bi of different AgI load capacity preparation2O3-Bi2O2CO3, the treatment effeciency of paranitroanilinum
There is notable difference.Wherein, when AgI load capacity is 5%, C AgI/ β-Bi2O3-Bi2O2CO3Processing effect to paranitroanilinum
Fruit is optimal.This explanation, AgI optimum load amount is 5%.
Embodiment 6
AgNO3AgI growing amount is had influence on KI mol ratio, and then influences the performance of catalyst.Fixed embodiment
1AgI/β-Bi2O3-Bi2O2CO3AgNO during preparation3Amount, it is 0.0081g, 0.0245g, 0.0326g to change KI amounts, and other are grasped
Make constant, the different starting AgNO of preparation series3With the AgI/ β-Bi of KI mol ratios2O3-Bi2O2CO3, according to embodiment 3 to nitro
The processing method of aniline waste water, compare catalyst performance, as a result such as Fig. 6.
AgI/ β-the Bi prepared such as Fig. 6, difference starting AgNO3 with KI mol ratios2O3-Bi2O2CO3, the place of paranitroanilinum
Reason efficiency has notable difference.Wherein, AgNO is worked as3It is 1 with KI mol ratios：When 1, AgI/ β-Bi2O3-Bi2O2CO3Paranitroanilinum
Treatment effect it is optimal.This explanation, AgNO3 and KI mol ratio optimal proportion are 1：1.
Claims (9)
- A kind of 1. AgI/ β-Bi2O3-Bi2O2CO3The preparation method of photochemical catalyst, it is characterised in that comprise the following steps：(1) by Bi (NO3)3·5H2O is dissolved in HNO3In, citric acid is then added, obtains mixed solution, then adjusts the pH of mixed solution To the laggard water-filling thermal response of faintly acid, reaction centrifuges after terminating and takes precipitation, after scrubbed, drying and milled processed Bi2O2CO3；(2) by Bi2O2CO3It is scattered in AgNO3The aqueous solution in, be then added dropwise KI solution, reaction terminate after through centrifuging, drying Do, grind to obtain AgI/Bi2O2CO3；(3) by AgI/Bi2O2CO3Calcining at constant temperature obtains AgI/ β-Bi2O3-Bi2O2CO3Photochemical catalyst.
- 2. preparation method according to claim 1, it is characterised in that Bi (NO in the mixed solution of step (1)3)3·5H2O's Concentration is 0.025~0.2mol/L；HNO3Concentration be 0.5~1.5mol/L；The concentration of citric acid is 0.0125~0.1mol/ L。
- 3. preparation method according to claim 1, it is characterised in that the hydro-thermal reaction time is 20~25h in step (1), water Thermal response temperature is 160~200 DEG C.
- 4. preparation method according to claim 1, it is characterised in that AgNO in step (2)3Mol ratio with KI is 2:1~1: 2；Bi2O2CO3With AgNO3Mass ratio with AgI/Bi2O2CO3Middle AgI load capacity is counted for 2.5~10mol%.
- 5. preparation method according to claim 1, it is characterised in that AgI/Bi2O2CO3The temperature of calcining at constant temperature be 250~ 400℃。
- A kind of 6. AgI/ β-Bi being prepared such as Claims 1 to 5 any claim methods described2O3-Bi2O2CO3Light is urged Agent.
- 7. one kind utilizes AgI/ β-Bi as claimed in claim 62O3-Bi2O2CO3The side of photocatalyst treatment nitrobenzene-containing amine waste water Method, it is characterised in that comprise the following steps：Waste water containing paranitroanilinum and the AgI/ β-Bi are added into reactor2O3-Bi2O2CO3Photochemical catalyst, lasting stirring, Radiation of visible light is reacted.
- 8. method according to claim 7, it is characterised in that the concentration of paranitroanilinum is in waste water containing paranitroanilinum 2.5~15mg/L.
- 9. method according to claim 7, it is characterised in that the dosage of photochemical catalyst is 0.5~2g/L.
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