CN106732687B - A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application - Google Patents
A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application Download PDFInfo
- Publication number
- CN106732687B CN106732687B CN201611190202.2A CN201611190202A CN106732687B CN 106732687 B CN106732687 B CN 106732687B CN 201611190202 A CN201611190202 A CN 201611190202A CN 106732687 B CN106732687 B CN 106732687B
- Authority
- CN
- China
- Prior art keywords
- bioi
- organic molecule
- small organic
- ratio
- substance
- 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.)
- Expired - Fee Related
Links
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 239000000126 substance Substances 0.000 claims abstract description 70
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 162
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 239000000243 solution Substances 0.000 claims description 69
- 239000012153 distilled water Substances 0.000 claims description 60
- 235000009518 sodium iodide Nutrition 0.000 claims description 54
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 49
- 239000012279 sodium borohydride Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000005070 sampling Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000002835 absorbance Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000002798 spectrophotometry method Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- -1 wherein M be Co Substances 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 238000005259 measurement Methods 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 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 21
- 229940012189 methyl orange Drugs 0.000 abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052709 silver Inorganic materials 0.000 abstract description 5
- 229910020674 Co—B Inorganic materials 0.000 description 27
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 150000001336 alkenes Chemical class 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 8
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 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 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule, it is grouped as by two kinds of groups of BiOI and M-B, BiOI is dispersed on the surface of M-B amorphous alloy catalyst, and wherein M is any one element in Co, Zn, Cu, Ni, Fe and Ag；The ratio of the amount of the substance of BiOI and M-B is 0.3-0.7.The present invention provides a kind of catalyst of photocatalytic degradation small organic molecule (such as methyl orange and phenol), mainly it is made of BiOI and M-B amorphous alloy, it is low that the catalyst compensates for pure BiOI catalyst the disposal efficiency, and the disadvantages of easily decomposing, the agent of BiOI and M-B cooperative photocatalysis not only can efficiently fast degradation small organic molecule (such as methyl orange, phenol), and the catalyst is reused 10 times, photocatalytic degradation small organic molecule rate is almost unchanged, with good stability and prospects for commercial application.
Description
Technical field
The invention belongs to photocatalysis technology fields, and in particular to a kind of BiOI-M-B association of photocatalytic degradation small organic molecule
With photochemical catalyst and its preparation method and application.
Background technique
With the development of society, waste water control has become one of modern society's great environmental problem urgently to be solved.Now such as
The present, China's major part rivers and lakes because industrial wastewater uncontrolled discharge and the dirt by more serious pollution, to environment
Dye and the health of resident produce large effect.In industrial wastewater, as the industries such as dyestuff, pesticide, leather are discharged
High concentrated organic wastewater account for suitable specific gravity, especially dye product there are the properties such as anti-light solution, heat resistanceheat resistant and antibiont, make at its
It is bigger to manage difficulty.Therefore, the key subjects that practical efficient water treatment technology has become facing mankind are developed.For than
Organic matter more difficult to degrade, traditional processing method generally have physisorphtion, coagulant sedimentation and mixed condensed gas flotation process, electrolysis
Method and biological degradation method etc..And as environmental pollution is increasingly severe, and the continuous improvement to wastewater treatment difficulty, accordingly
There are some new water treating methods, such as membrane extraction method, sonication and photocatalytic degradation method etc..Wherein photocatalysis is dropped
Solution be using clean energy resource, it is and without secondary pollution, therefore cause the extensive concern of society, it is considered to be the most organic wastewater of future
One of processing method.
BiOI has the ability of good photocatalyst for degrading organic pollutant.However individually BiOI is as photochemical catalyst
It is decomposed with easy, the disadvantages of easy photetching.Wherein M can be any one element in Zn, Cu, Ni, Fe and Ag to M-B() nanometer is non-
Crystal alloy catalyst has merged the excellent performance of nanometer and amorphous alloy, has a wide range of applications in catalytic field.
Summary of the invention
The technical problem to be solved by the present invention is to independent BiOI as photochemical catalyst with easily decomposition, easy photetching, to solve
The above problem, the present invention provide a kind of BiOI-M-B cooperative photocatalysis agent and preparation method thereof of photocatalytic degradation small organic molecule
And application.
The object of the present invention is achieved in the following manner:
A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule, by two kinds of group groupings of BiOI and M-B
At BiOI is dispersed on the surface of M-B amorphous alloy catalyst, and wherein M is appointing in Co, Zn, Cu, Ni, Fe and Ag
It anticipates a kind of element；The ratio of the amount of the substance of BiOI and M-B is 0.3-0.7.
The preparation method of the BiOI-M-B cooperative photocatalysis agent of above-mentioned photocatalytic degradation small organic molecule, specific steps are such as
Under:
(1) preparation of amorphous alloy M-B: the soluble-salt of M element is reacted with sodium borohydride generates M-B amorphous alloy
Catalyst；
(2) preparation of BiOI-M-B cooperative photocatalysis agent: bismuth nitrate, NaI, amorphous alloy catalyst M-B and polyethylene
Pyrrolidones generates BiOI-M-B cooperative photocatalysis agent in acid condition.
The step (1) specifically: the soluble-salt for taking M element is dissolved with distilled water, the soluble salt solutions that will be prepared
It is placed on spare in 25-35 DEG C of water bath with thermostatic control；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into
It in dropping funel, is added dropwise in above-mentioned soluble salt solutions, whole process is stirred continuously, and is filtered after being added dropwise to complete, and will be obtained
Solid be put into baking oven, dry at 60-80 DEG C, drying time 2-4h is to get M-B amorphous alloy catalyst.
The step (2) specifically: take NaI, dissolved with distilled water stand-by；Take five nitric hydrate bismuths in three-necked flask,
Add the HNO of 3M3With the amorphous alloy catalyst M-B of step (1) preparation, distilled water is added and is dissolved and is stirred, then
Load weighted polyvinylpyrrolidone is added, adjusts the solution in three-necked flask to pH=2-3 with the NaOH of 1M；By three-necked flask
It is placed in oil bath pan, oil bath temperature is 50-70 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise three mouthfuls
In flask, after being added dropwise to complete, oil bath temperature is set as 110-130 DEG C, flow back 1-5h, and filtering and washing puts obtained solid
Enter in baking oven, dry at 70-90 DEG C, drying time 2-4h is to get BiOI-M-B cooperative photocatalysis agent.
In the step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.1-0.3.
In the step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.2.
In the step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.23-1.26, five hydrations
Bismuth nitrate and HNO3Substance amount ratio be 0.19-0.45, the object of five nitric hydrate bismuths and amorphous alloy catalyst M-B
The ratio of the amount of matter is 0.3-0.7, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.35-0.82.
In the step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.54.
Application of the above-mentioned BiOI-M-B cooperative photocatalysis agent in aqueous-phase photo-catalysis degradation small organic molecule.
According to application of the above-mentioned BiOI-M-B cooperative photocatalysis agent in aqueous-phase photo-catalysis degradation small organic molecule, specifically
Steps are as follows: small organic molecule solution being added in photo catalysis reactor, the agent of BiOI-M-B cooperative photocatalysis is added, opens xenon
Lamp power supply preheats under dark, sampling when catalyst and small organic molecule reach adsorption equilibrium, then opens condensed water and opens again
Lamp samples after 60min；After sampling, sample is centrifugated, takes supernatant to carry out visible spectrophotometry analysis, passes through
The absorbance A of supernatant measures to monitor the photocatalytic degradation effect of small organic molecule.
The BiOI-Ru-B catalyst fine particle generated in aqueous solution has biggish surface energy, easily aggregation and grows up.It is poly-
The effect of vinylpyrrolidone reduces the BiOI-Ru-B catalyst fine particle surface energy generated, its is made to keep lesser partial size,
Polyvinylpyrrolidone is simultaneously not involved in chemical reaction.
Compared with the existing technology, the present invention provides a kind of photocatalytic degradation small organic molecule (such as methyl orange and phenol)
Catalyst is mainly made of BiOI and M-B amorphous alloy, and it is low which compensates for pure BiOI catalyst the disposal efficiency,
And the disadvantages of easily decomposing, the agent of BiOI and M-B cooperative photocatalysis not only can efficiently fast degradation small organic molecule (such as methyl orange,
Phenol etc.), and the catalyst is reused 10 times, and photocatalytic degradation small organic molecule rate is almost unchanged, has good
Stability and prospects for commercial application.
Photochemical catalyst is after carrying out photocatalytic degradation reaction in the present invention, after catalyst solid and aqueous solution separation, light
Catalyst is used directly for hydrogenation reaction again.
Specific embodiment
Embodiment 1:
A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule, by two kinds of group groupings of BiOI and M-B
At BiOI is dispersed on the surface of M-B amorphous alloy catalyst, and wherein M is appointing in Co, Zn, Cu, Ni, Fe and Ag
It anticipates a kind of element；The ratio of the amount of the substance of BiOI and M-B is 0.3-0.7.
The preparation method of the BiOI-M-B cooperative photocatalysis agent of above-mentioned photocatalytic degradation small organic molecule, specific steps are such as
Under:
(1) preparation of amorphous alloy M-B: the soluble-salt of M element is reacted with sodium borohydride generates M-B amorphous alloy
Catalyst；
(2) preparation of BiOI-M-B cooperative photocatalysis agent: bismuth nitrate, NaI, amorphous alloy catalyst M-B and polyethylene
Pyrrolidones generates BiOI-M-B cooperative photocatalysis agent in acid condition.
Step (1) specifically: the soluble-salt for taking M element is dissolved with distilled water, and the soluble salt solutions prepared are placed on
It is spare in 25-35 DEG C of water bath with thermostatic control；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping liquid
It in funnel, is added dropwise in above-mentioned soluble salt solutions, whole process is stirred continuously, and is filtered after being added dropwise to complete, and is consolidated what is obtained
Body is put into baking oven, and dry at 60-80 DEG C, drying time 2-4h is to get M-B amorphous alloy catalyst.
Step (2) specifically: take NaI, dissolved with distilled water stand-by；Take five nitric hydrate bismuths in three-necked flask, then plus
Enter the HNO of 3M3With the amorphous alloy catalyst M-B of step (1) preparation, distilled water is added and is dissolved and is stirred, adds
Load weighted polyvinylpyrrolidone adjusts the solution in three-necked flask to pH=2-3 with the NaOH of 1M；Three-necked flask is placed in
In oil bath pan, oil bath temperature is 50-70 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, three-necked flask is added dropwise
In, after being added dropwise to complete, oil bath temperature is set as 110-130 DEG C, flow back 1-5h, and obtained solid is put into baking by filtering and washing
In case, dry at 70-90 DEG C, drying time 2-4h is to get BiOI-M-B cooperative photocatalysis agent.
In step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.1-0.3.
In step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.2.
In step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.23-1.26, five nitric hydrates
Bismuth and HNO3The ratio of amount of substance be 0.19-0.45, the substance of five nitric hydrate bismuths and amorphous alloy catalyst M-B
The ratio of amount is 0.3-0.7, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.35-0.82.
In step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.54.
Application of the above-mentioned BiOI-M-B cooperative photocatalysis agent in aqueous-phase photo-catalysis degradation small organic molecule.
According to application of the above-mentioned BiOI-M-B cooperative photocatalysis agent in aqueous-phase photo-catalysis degradation small organic molecule, specifically
Steps are as follows: small organic molecule solution being added in photo catalysis reactor, the agent of BiOI-M-B cooperative photocatalysis is added, opens xenon
Lamp power supply preheats under dark, sampling when catalyst and small organic molecule reach adsorption equilibrium, then opens condensed water and opens again
Lamp samples after 60min；After sampling, sample is centrifugated, takes supernatant to carry out visible spectrophotometry analysis, passes through
The absorbance A of supernatant measures to monitor the photocatalytic degradation effect of small organic molecule.
Embodiment 2:
(1) Co (NO is taken3)2·6H2O is dissolved with distilled water, and the cobalt nitrate solution prepared is placed on to 25 DEG C of water bath with thermostatic control
In it is spare；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, is added dropwise
It states in cobalt nitrate solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, at 60 DEG C
Lower drying, drying time 2h is to get Co-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Co-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath temperature
Degree is 50 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will be oily after being added dropwise to complete
Bath temperature is set as 110 DEG C, and flow back 1h, and obtained solid is put into baking oven by filtering and washing, dry at 70 DEG C, when dry
Between 2h to get BiOI-Co-B cooperative photocatalysis agent.
In step (1), Co (NO3)2·6H2The quality of O is 5.0g, Co (NO3)2·6H2The amount of the substance of O and sodium borohydride
Ratio be 0.1.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.23, five nitric hydrate bismuths and HNO3The ratio of amount of substance be 0.19, five nitric hydrate bismuths and amorphous alloy
The ratio of the amount of the substance of catalyst M-B is 0.3, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.35。
Embodiment 3:
(1) Co (NO is taken3)2·6H2O is dissolved with distilled water, and the cobalt nitrate solution prepared is placed on to 26 DEG C of water bath with thermostatic control
In it is spare；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, is added dropwise
It states in cobalt nitrate solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, at 62 DEG C
Lower drying, drying time 2.2h is to get Co-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Co-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.1 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 52 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 112 DEG C, and flow back 1.3h, and obtained solid is put into baking oven by filtering and washing, dry at 72 DEG C, does
Dry time 2.2h is to get BiOI-Co-B cooperative photocatalysis agent.
In step (1), Co (NO3)2·6H2The quality of O is 5.0g, Co (NO3)2·6H2The amount of the substance of O and sodium borohydride
Ratio be 0.12.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.3, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.2, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Co-B is 0.33, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.4。
Embodiment 4:
(1) ZnCl is taken2, dissolved, the liquor zinci chloridi prepared be placed on spare in 27 DEG C of water bath with thermostatic control with distilled water；It takes
Sodium borohydride is dissolved with distilled water, and the sodium borohydride solution prepared is poured into dropping funel, and it is molten that above-mentioned zinc chloride is added dropwise
In liquid, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, dry at 64 DEG C, dry
Time 2.4h is to get Zn-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Zn-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.2 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 54 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 114 DEG C, and flow back 1.6h, and obtained solid is put into baking oven by filtering and washing, dry at 74 DEG C, does
Dry time 2.4h is to get BiOI-Zn-B cooperative photocatalysis agent.
In step (1), ZnCl2Quality be 2.34g, ZnCl2Ratio with the amount of the substance of sodium borohydride is 0.14.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.4, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.24, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Zn-B is 0.36, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.42。
Embodiment 5:
(1) ZnCl is taken2, dissolved, the liquor zinci chloridi prepared be placed on spare in 28 DEG C of water bath with thermostatic control with distilled water；It takes
Sodium borohydride is dissolved with distilled water, and the sodium borohydride solution prepared is poured into dropping funel, and it is molten that above-mentioned zinc chloride is added dropwise
In liquid, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, dry at 66 DEG C, dry
Time 2.6h is to get Zn-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Zn-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.3 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 56 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 116 DEG C, and flow back 2h, and obtained solid is put into baking oven by filtering and washing, dry at 76 DEG C, dry
Time 2.6h is to get BiOI-Zn-B cooperative photocatalysis agent.
In step (1), ZnCl2Quality be 2.34g, ZnCl2Ratio with the amount of the substance of sodium borohydride is 0.16.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.54, five nitric hydrate bismuths and HNO3The ratio of amount of substance be 0.28, five nitric hydrate bismuths and amorphous alloy
The ratio of the amount of the substance of catalyst Z n-B is 0.4, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.45。
Embodiment 6:
(1) CuCl is taken2·2H2O is dissolved with distilled water, the copper chloride solution prepared is placed on standby in 29 DEG C of water bath with thermostatic control
With；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, above-mentioned chlorine is added dropwise
Change in copper solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, is done at 68 DEG C
Dry, drying time 2.8h is to get Cu-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Cu-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.4 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 58 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 118 DEG C, and flow back 2.3h, and obtained solid is put into baking oven by filtering and washing, dry at 78 DEG C, does
Dry time 2.8h is to get BiOI-Cu-B cooperative photocatalysis agent.
In step (1), CuCl2·2H2The quality of O is 2.34g, CuCl2·2H2The ratio of the amount of the substance of O and sodium borohydride
Value is 0.18.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.6, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.3, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Cu-B is 0.43, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.5.
Embodiment 7:
(1) CuCl is taken2·2H2O is dissolved with distilled water, the copper chloride solution prepared is placed on standby in 30 DEG C of water bath with thermostatic control
With；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, above-mentioned chlorine is added dropwise
Change in copper solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, is done at 70 DEG C
Dry, drying time 3h is to get Cu-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Cu-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.5 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 60 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 120 DEG C, and flow back 2.6h, and obtained solid is put into baking oven by filtering and washing, dry at 80 DEG C, does
Dry time 3h is to get BiOI-Cu-B cooperative photocatalysis agent.
In step (1), CuCl2·2H2The quality of O is 2.34g, CuCl2·2H2The ratio of the amount of the substance of O and sodium borohydride
Value is 0.2.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.7, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.33, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Cu-B is 0.46, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.7.
Embodiment 8:
(1) Ni (NO is taken3)2·6H2O is dissolved with distilled water, and the nickel nitrate solution prepared is placed on to 31 DEG C of water bath with thermostatic control
In it is spare；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, is added dropwise
It states in nickel nitrate solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, at 72 DEG C
Lower drying, drying time 3.2h is to get Ni-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Ni-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.6 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 62 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 122 DEG C, and flow back 3h, and obtained solid is put into baking oven by filtering and washing, dry at 82 DEG C, dry
Time 3.2h is to get BiOI-Ni-B cooperative photocatalysis agent.
In step (1), Ni (NO3)2·6H2The quality of O is 5.0g, Ni (NO3)2·6H2The amount of the substance of O and sodium borohydride
Ratio be 0.22.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.8, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.35, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Ni-B is 0.5, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.55.
Embodiment 9:
(1) Ni (NO is taken3)2·6H2O is dissolved with distilled water, and the nickel nitrate solution prepared is placed on to 32 DEG C of water bath with thermostatic control
In it is spare；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, is added dropwise
It states in nickel nitrate solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, at 74 DEG C
Lower drying, drying time 3.4h is to get Ni-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Ni-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.7 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 64 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 124 DEG C, and flow back 3.5h, and obtained solid is put into baking oven by filtering and washing, dry at 84 DEG C, does
Dry time 3.4h is to get BiOI-Ni-B cooperative photocatalysis agent.
In step (1), Ni (NO3)2·6H2The quality of O is 5.0g, Ni (NO3)2·6H2The amount of the substance of O and sodium borohydride
Ratio be 0.24.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 0.9, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.38, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Ni-B is 0.55, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.6.
Embodiment 10:
(1) FeSO is taken4·7H2O is dissolved with distilled water, the ferrum sulfuricum oxydatum solutum prepared is placed on standby in 33 DEG C of water bath with thermostatic control
With；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, above-mentioned sulphur is added dropwise
In sour ferrous solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, is done at 76 DEG C
Dry, drying time 3.6h is to get Fe-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Fe-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.8 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 66 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 126 DEG C, and flow back 4h, and obtained solid is put into baking oven by filtering and washing, dry at 86 DEG C, dry
Time 3.6h is to get BiOI-Fe-B cooperative photocatalysis agent.
In step (1), FeSO4·7H2The quality of O is 4.78g, FeSO4·7H2The ratio of the amount of the substance of O and sodium borohydride
Value is 0.26.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 1.0, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.4, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Fe-B is 0.6, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.65.
Embodiment 11:
(1) FeSO is taken4·7H2O is dissolved with distilled water, the ferrum sulfuricum oxydatum solutum prepared is placed on standby in 34 DEG C of water bath with thermostatic control
With；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride solution prepared is poured into dropping funel, above-mentioned sulphur is added dropwise
In sour ferrous solution, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, is done at 78 DEG C
Dry, drying time 3.8h is to get Fe-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Fe-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=2.9 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath
Temperature is 68 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will after being added dropwise to complete
Oil bath temperature is set as 128 DEG C, and flow back 4.5h, and obtained solid is put into baking oven by filtering and washing, dry at 88 DEG C, does
Dry time 3.8h is to get BiOI-Fe-B cooperative photocatalysis agent.
In step (1), FeSO4·7H2The quality of O is 4.78g, FeSO4·7H2The ratio of the amount of the substance of O and sodium borohydride
Value is 0.28.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 1.1, five nitric hydrate bismuths and HNO3Substance amount ratio be 0.42, five nitric hydrate bismuths are urged with amorphous alloy
The ratio of the amount of the substance of agent Fe-B is 0.65, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.75。
Embodiment 12:
(1) AgNO is taken3, dissolved, the silver nitrate solution prepared be placed on spare in 35 DEG C of water bath with thermostatic control with distilled water；It takes
Sodium borohydride is dissolved with distilled water, and the sodium borohydride solution prepared is poured into dropping funel, and it is molten that above-mentioned silver nitrate is added dropwise
In liquid, whole process is stirred continuously, and is filtered after being added dropwise to complete, and obtained solid is put into baking oven, dry at 80 DEG C, dry
Time 4h is to get Ag-B amorphous alloy catalyst.
(2) NaI is taken, is dissolved with distilled water stand-by；It takes five nitric hydrate bismuths in three-necked flask, adds the HNO of 3M3With
The amorphous alloy catalyst Ag-B of step (1) preparation is added distilled water and is dissolved and stirred, adds load weighted poly- second
Alkene pyrrolidone adjusts the solution in three-necked flask to pH=3 with the NaOH of 1M；Three-necked flask is placed in oil bath pan, oil bath temperature
Degree is 70 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise in three-necked flask, will be oily after being added dropwise to complete
Bath temperature is set as 130 DEG C, and flow back 5h, and obtained solid is put into baking oven by filtering and washing, dry at 90 DEG C, when dry
Between 4h to get BiOI-Ag-B cooperative photocatalysis agent.
In step (1), AgNO3Quality be 4.78g, AgNO3Ratio with the amount of the substance of sodium borohydride is 0.3.
In step (2), the quality of five nitric hydrate bismuths is 0.93g, the amount of the substance of five nitric hydrate bismuths and sodium iodide
Ratio is 1.26, five nitric hydrate bismuths and HNO3The ratio of amount of substance be 0.45, five nitric hydrate bismuths and amorphous alloy
The ratio of the amount of the substance of catalyst Ag-B is 0.7, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is
0.82。
Embodiment 13:
It takes 5.0 g cabaltous nitrate hexahydrates to pour into the dry beaker of 300 mL, is dissolved with 100 mL distilled water.By what is prepared
Cabaltous nitrate hexahydrate solution is placed in 30 DEG C of water bath with thermostatic control.3.23 g sodium borohydrides are taken again, are dissolved with 100 mL distilled water,
It is then poured into clean dropping funel, then sodium borohydride solution is added dropwise in above-mentioned cabaltous nitrate hexahydrate solution, it is whole
A process is stirred continuously, and is filtered after reaction, and solid is put into baking oven 70 DEG C of dryings to get the catalysis of Co-B amorphous alloy
Agent.
It weighs 0.66 g solid NaI to pour into clean beaker, be dissolved with 65 mL distilled water, for use.Take 0.93 g, five water
It closes bismuth nitrate to pour into 500 clean mL three-neck flasks, adds 2.5 mL 3M HNO3With the above-mentioned preparation Co-B of 1.00 g
Amorphous alloy catalyst is put into rotor, pours into the dissolution of 150 mL distilled water and is stirred continuously, then weighs about 2.0 g PVP
(polyvinylpyrrolidone) is adjusted between pH=2~3 with 1 M NaOH.Above-mentioned mixed solution is placed in three-necked bottle, by three necks
Bottle is placed in oil bath pan, at 60 DEG C of oil bath temperature, the above-mentioned NaI solution prepared is placed in dropping funel, three-necked bottle is placed in
On, it is added drop-wise in the mixed solution in above-mentioned three-necked bottle.After being added dropwise to complete, oil bath temperature is set as 120 DEG C, in the temperature
Oil bath 4 h of reflux, then filtering and washing, is put into 80 DEG C of dryings, i.e. BiOI-Co-B(0.5 in baking oven) cooperative photocatalysis agent.
Photochemical catalyst with magnetic agitation photo catalysis reactor in photocatalytic degradation small organic molecule (such as methyl orange and
Phenol) steps are as follows: 200 mL are taken out from 10.056 mg/L methyl orange solutions and are poured into Photoreactor, and 0.20 g is added and urges
Agent opens xenon lamp power supply, 40 min is preheated under dark, sampling when catalyst and methyl orange reach adsorption equilibrium, then
It opens condensed water to turn on light again, be sampled after 60 min.After sampling, by sample with 1000 r/min of revolving speed centrifuge separation 10
min.It takes supernatant to carry out visible spectrophotometry analysis, is measured by the absorbance A of reaction solution and urged to monitor the light of methyl orange
Change degradation effect, the results are shown in Table 1.
Embodiment 14:
By in embodiment 13 0.66 g solid sodium iodide and 1.16 g, five nitric hydrate bismuth be changed to 0.40 g solid NaI and
0.70 g, five nitric hydrate bismuth, other conditions are the same as embodiment 13.Obtained solid is BiOI-Co-B(0.3) catalyst, bismuth element
Ratio with the quality of Co-B is 0.3.Evaluation results are shown in Table 1.
Embodiment 15:
By in embodiment 13 0.66 g solid sodium iodide and 1.16 g, five nitric hydrate bismuth be changed to 0.93 g solid NaI and
1.60 g, five nitric hydrate bismuth, other conditions are the same as embodiment 13.Obtained solid is BiOI-Co-B(0.7) catalyst, bismuth element
Ratio with the quality of Co-B is 0.7.Evaluation results are shown in Table 1.
Embodiment 16:
10.056 mg/L methyl orange solutions in embodiment 1 are changed to 10.054 mg/L phenol solutions, other conditions are the same as real
Apply example 13.Evaluation results are shown in Table 1.
Embodiment 17:
5.0 g cabaltous nitrate hexahydrates in embodiment 13 are changed to 2.34 g ZnCl of the amount of equal substances2Prepare Zn-B amorphous
1.0 g Co-B amorphous alloys in embodiment 13 are changed to 1.0 g Zn-B amorphous alloys, other conditions by alloy catalyst
With embodiment 13.Evaluation results are shown in Table 1.
Embodiment 18:
5.0 g cabaltous nitrate hexahydrates in embodiment 13 are changed to 2.93 g CuCl of the amount of equal substances2·2H2O prepares Cu-
1.0 g Co-B amorphous alloys in embodiment 13 are changed to 1.0 g Cu-B amorphous alloys by B amorphous alloy catalyst, other
Condition is the same as embodiment 13.Evaluation results are shown in Table 1.
Embodiment 19:
5.0 g cabaltous nitrate hexahydrates in embodiment 13 are changed to 5.00 g Ni (NO of the amount of equal substances3)2·6H2O preparation
1.0 g Co-B amorphous alloys in embodiment 13 are changed to 1.0 g Ni-B amorphous alloys by Ni-B amorphous alloy catalyst,
Other conditions are the same as embodiment 13.Evaluation results are shown in Table 1.
Embodiment 20:
5.0 g cabaltous nitrate hexahydrates in embodiment 13 are changed to 4.78 g FeSO of the amount of equal substances4·7H2O prepares Ni-
1.0 g Co-B amorphous alloys in embodiment 13 are changed to 1.0 g Fe-B amorphous alloys by B amorphous alloy catalyst, other
Condition is the same as embodiment 13.Evaluation results are shown in Table 1.
Embodiment 21:
5.0 g cabaltous nitrate hexahydrates in embodiment 13 are changed to 4.78 g AgNO of the amount of equal substances3Prepare Ni-B amorphous
1.0 g Co-B amorphous alloys in embodiment 13 are changed to 1.0 g Ag-B amorphous alloys, other conditions by alloy catalyst
With embodiment 13.Evaluation results are shown in Table 1.
Embodiment 22:
Except outer preparation BiOI, other same embodiments of condition are not added in 1.00g Co-B amorphous alloy catalyst in embodiment 13
13.Evaluation results are shown in Table 1.
Embodiment 23:
With after BiOI-Co-B(0.5) photo-catalytic degradation of methyl-orange in embodiment 13, isolating solid catalyst can be direct
For next light-catalyzed reaction.In this way, catalyst circulation uses 5 times, evaluation result is shown in Table 2.
As it can be seen from table 1 BiOI-Co-B(0.5 prepared by embodiment 13) photochemical catalyst, 60 min can degrade 83%
Methyl orange.Embodiment 14 prepare BiOI-Co-B(0.4) photochemical catalyst, 60 min can degrade 62% methyl orange.Implement
Example 15 prepare BiOI-Co-B(0.7) photochemical catalyst, 60 min can degrade 75% methyl orange.Prepared by embodiment 17
BiOI-Zn-B(0.5) photochemical catalyst, 60 min can degrade 57% methyl orange.BiOI-Cu-B(0.5 prepared by embodiment 18)
Photochemical catalyst, 60 min can degrade 79% methyl orange.BiOI-Ni-B(0.5 prepared by embodiment 19) photochemical catalyst, 60
Min can degrade 75% methyl orange.BiOI-Fe-B(0.5 prepared by embodiment 20) photochemical catalyst, 60 min can degrade 62%
Methyl orange.Embodiment 21 prepare BiOI-Ag-B(0.5) photochemical catalyst, 60 min can degrade 91% methyl orange.Implement
Example 22 prepare pure BiOI photochemical catalyst, 60 min can only degrade 30% methyl orange.This illustrates the BiOI- that the present invention invents
M-B(M can be any one element in Zn, Cu, Ni, Fe and Ag) overcome pure BiOI catalyst photocatalysis efficiency is low to ask
Topic, BiOI-M-B photochemical catalyst can be with high efficiency photocatalysis degradation methyl oranges.Methyl orange has been changed to phenol, BiOI- by embodiment 16
Co-B(0.5) 60 min of photochemical catalyst can degrade 79% phenol.This illustrates that the BiOI-Ru-B that invents of the present invention not only can be with
Degradation methyl orange, but also can be with degradation of phenol.
Embodiment 23 gives BiOI-Co-B(0.5) photochemical catalyst reuse 5 degradation methyl oranges as a result, can be with
Find out that the degradation rate of 5 60 min methyl oranges is stable on 79%, this illustrates BiOI-Co-B(0.5) photochemical catalyst have it is good
Repeat performance and stability, the shortcomings that overcoming pure BiOI easy photetching.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without depart from that overall concept of the invention, several changes and improvements can also be made, these also should be considered as of the invention
Protection scope.
Claims (10)
1. a kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule, it is characterised in that: by BiOI and M-B two
Kind of group is grouped as, and BiOI is dispersed on the surface of M-B amorphous alloy catalyst, wherein M be Co, Zn, Cu, Ni, Fe and
Any one element in Ag；The ratio of the amount of the substance of BiOI and M-B is 0.3-0.7.
2. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 1
Method, it is characterised in that: specific step is as follows:
(1) preparation of amorphous alloy M-B: the soluble-salt of M element is reacted with sodium borohydride generates M-B amorphous alloy catalyst
Agent；
(2) preparation of BiOI-M-B cooperative photocatalysis agent: bismuth nitrate, NaI, amorphous alloy catalyst M-B and polyvinyl pyrrole
Alkanone generates BiOI-M-B cooperative photocatalysis agent in acid condition.
3. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 2
Method, it is characterised in that: the step (1) specifically: the soluble-salt for taking M element is dissolved with distilled water, the solubility that will be prepared
Salting liquid is placed on spare in 25-35 DEG C of water bath with thermostatic control；Sodium borohydride is taken, is dissolved with distilled water, the sodium borohydride prepared is molten
Liquid pours into dropping funel, is added dropwise in above-mentioned soluble salt solutions, and whole process is stirred continuously, and filters after being added dropwise to complete,
Obtained solid is put into baking oven, dry at 60-80 DEG C, drying time 2-4h is to get M-B amorphous alloy catalyst.
4. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 2
Method, it is characterised in that: the step (2) specifically: take NaI, dissolved with distilled water stand-by；Five nitric hydrate bismuths are taken to burn in three mouthfuls
In bottle, the HNO of 3M is added3With the amorphous alloy catalyst M-B of step (1) preparation, distilled water is added and is dissolved and is stirred
It mixes, adds load weighted polyvinylpyrrolidone, adjust the solution in three-necked flask to pH=2-3 with the NaOH of 1M；By three mouthfuls
Flask is placed in oil bath pan, and oil bath temperature is 50-70 DEG C, and the above-mentioned NaI solution prepared is placed in dropping funel, is added dropwise
In three-necked flask, after being added dropwise to complete, oil bath temperature is set as 110-130 DEG C, flow back 1-5h, and filtering and washing is consolidated what is obtained
Body is put into baking oven, and dry at 70-90 DEG C, drying time 2-4h is to get BiOI-M-B cooperative photocatalysis agent.
5. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 3
Method, it is characterised in that: in the step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.1-
0.3。
6. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 5
Method, it is characterised in that: in the step (1), the ratio of the amount of the substance of the soluble-salt and sodium borohydride of M element is 0.2.
7. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 4
Method, it is characterised in that: in the step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.23-1.26,
Five nitric hydrate bismuths and HNO3Substance amount ratio be 0.19-0.45, five nitric hydrate bismuths and amorphous alloy catalyst
The ratio of the amount of the substance of M-B is 0.3-0.7, and the ratio of the quality of five nitric hydrate bismuths and polyvinylpyrrolidone is 0.35-
0.82。
8. the preparation side of the BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule according to claim 7
Method, it is characterised in that: in the step (2), the ratio of the amount of the substance of five nitric hydrate bismuths and sodium iodide is 0.54.
9. BiOI-M-B cooperative photocatalysis agent answering in aqueous-phase photo-catalysis degradation small organic molecule as described in claim 1
With.
10. BiOI-M-B cooperative photocatalysis agent according to claim 9 is in aqueous-phase photo-catalysis degradation small organic molecule
Using, it is characterised in that: specific step is as follows: small organic molecule solution being added in photo catalysis reactor, BiOI-M- is added
B cooperative photocatalysis agent opens xenon lamp power supply, preheats under dark, take when catalyst reaches adsorption equilibrium with small organic molecule
Then sample opens condensed water and turns on light again, samples after 60min；After sampling, sample is centrifugated, takes supernatant progress can
See spectrophotometric analysis, the photocatalytic degradation effect of small organic molecule is monitored by the absorbance A measurement of supernatant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611190202.2A CN106732687B (en) | 2016-12-21 | 2016-12-21 | A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611190202.2A CN106732687B (en) | 2016-12-21 | 2016-12-21 | A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732687A CN106732687A (en) | 2017-05-31 |
| CN106732687B true CN106732687B (en) | 2018-12-04 |
Family
ID=58893434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611190202.2A Expired - Fee Related CN106732687B (en) | 2016-12-21 | 2016-12-21 | A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732687B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198497B (en) * | 2021-04-29 | 2023-03-17 | 清创人和生态工程技术有限公司 | Preparation method and application of nickel-phosphorus amorphous alloy catalyst |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500401A (en) * | 2011-11-11 | 2012-06-20 | 上海大学 | Ag/BioI visible light catalyst and preparation method thereof |
| US10717664B2 (en) * | 2013-08-05 | 2020-07-21 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Photocatalysts based on bismuth oxyhalide, process for their preparation and uses thereof |
| CN104226338B (en) * | 2014-07-04 | 2015-11-11 | 河北联合大学 | A kind of cuprous sulfide quantum dot modifies three-dimensional flower-shaped structure BiOBr composite photocatalyst material and preparation method thereof |
| CN104646040B (en) * | 2015-02-15 | 2016-04-20 | 济南大学 | A kind of BiOI/Zn 2geO 4the preparation method of hetero-junctions visible light catalyst and application |
| CN105056978B (en) * | 2015-09-18 | 2017-07-21 | 浙江工商大学 | A kind of bismuth system modified light catalyst and its preparation method and application |
| CN105344364A (en) * | 2015-11-30 | 2016-02-24 | 环境保护部华南环境科学研究所 | Ferric oxide/bismuth oxybromide composite material and preparation method and application thereof |
| CN105709782B (en) * | 2016-03-09 | 2018-08-07 | 安徽工业大学 | A kind of preparation and application of Ag/AgBr/BiOCl- (001) nanocomposite |
-
2016
- 2016-12-21 CN CN201611190202.2A patent/CN106732687B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732687A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582657B (en) | A kind of TiO2- M-B cooperative photocatalysis agent and its preparation method and application | |
| Zhong et al. | Flexible electrospun carbon nanofiber/tin (IV) sulfide core/sheath membranes for photocatalytically treating chromium (VI)-containing wastewater | |
| CN106495377B (en) | A kind of processing method that nickel waste water is complexed | |
| CN106076261B (en) | A kind of adsorbent for heavy metal and preparation method and application | |
| Fu et al. | Degradation of Ni–EDTA complex by Fenton reaction and ultrasonic treatment for the removal of Ni 2+ ions | |
| Kaur et al. | Bi2WO6/NH2-MIL-88B (Fe) heterostructure: An efficient sunlight driven photocatalyst for the degradation of antibiotic tetracycline in aqueous medium | |
| Mook et al. | Optimisation of Reactive Black 5 dye removal by electrocoagulation process using response surface methodology | |
| CN108525688A (en) | A kind of Fe-based amorphous alloy is used for the application of degradation of dye waste water Methylene Blue | |
| Liao et al. | Facile fabrication of Ti supported CuO film composed of bamboo-leaf-like nanosheets and their high catalytic performance in the oxidative degradation of methylene blue with hydrogen peroxide | |
| CN107262153A (en) | A kind of preparation method of Pd/MIL 100 (Fe) photochemical catalyst | |
| CN105749936A (en) | Metal composite catalyst for selective dechloridation and preparation method thereof | |
| Andrade Jr et al. | Photoelectrocatalytic reduction of nitrobenzene on Bi-doped CuGaS2 films | |
| CN106732687B (en) | A kind of BiOI-M-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application | |
| Saran et al. | Pilot scale thin film plate reactors for the photocatalytic treatment of sugar refinery wastewater | |
| Wu et al. | Wool-coiled bimetallic oxysulfide MoSrOS catalyst synthesis for catalytic reduction of toxic organic pollutants and heavy metal ions | |
| Lou et al. | In-situ oxidation synthesis of Cu2O/Ag/AgCl microcubes with enhanced visible-light photocatalytic activity | |
| Liang et al. | Performance of selenate removal by biochar embedded nano zero-valent iron and the biological toxicity to Escherichia coli | |
| Masunga et al. | Magnetically separable samarium doped copper ferrite-graphitic carbon nitride nanocomposite for photodegradation of dyes and pharmaceuticals under visible light irradiation | |
| Gul et al. | Review elucidating graphene derivatives (GO/rGO) supported metal sulfides based hybrid nanocomposites for efficient photocatalytic dye degradation | |
| Zhao et al. | Preparation of CuO/γAl2O3 catalyst for degradation of azo dyes (reactive brilliant red X–3B): an optimization study | |
| Pan et al. | Functional Ag-doped coralloid titanosilicate zeolite (CTS-Ag) for efficiently catalytic and photodegradative removal of free cyanides and copper/zinc-cyanide complexes in real wastewater | |
| Xing et al. | Highly efficient activation of peroxymonosulfate by novel CuO-Chrysotile catalytic membrane for degradation of p-nitrophenol | |
| Montazer et al. | Synthesis of cuttlebone/carbon quantum dots/nickel oxide nanocomposite for visible light photodegradation of malachite green used for environmental remediation | |
| Miao et al. | Photocatalytic degradation of the azo dye acid red 14 in nanosized TiO2 suspension under simulated solar light | |
| CN106732689B (en) | A kind of BiOI-Ru-B cooperative photocatalysis agent of photocatalytic degradation small organic molecule and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181204 Termination date: 20191221 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |