CN109046396A - A kind of Z-type photochemical catalyst and its preparation method and application - Google Patents
A kind of Z-type photochemical catalyst and its preparation method and application Download PDFInfo
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- CN109046396A CN109046396A CN201810752091.2A CN201810752091A CN109046396A CN 109046396 A CN109046396 A CN 109046396A CN 201810752091 A CN201810752091 A CN 201810752091A CN 109046396 A CN109046396 A CN 109046396A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims abstract description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021612 Silver iodide Inorganic materials 0.000 claims abstract description 20
- 239000004332 silver Substances 0.000 claims abstract description 20
- 238000005286 illumination Methods 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 229940045105 silver iodide Drugs 0.000 claims abstract description 19
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 150000002367 halogens Chemical group 0.000 claims abstract description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 235000013675 iodine Nutrition 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 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 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- 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
- B01J27/08—Halides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
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- 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 Z-type photochemical catalysts and its preparation method and application.The Z-type photochemical catalyst is BiOYnI1‑n/ Ag/AgI-x, wherein Y is halogen；X is the molar ratio of silver element and iodine, and value range is 0~1；N is 0~1, and n ≠ 1.The present invention in bismuth oxyiodide by mixing silver and silver iodide, Z-type photochemical catalyst has been prepared, improve bismuth oxyiodide due to conduction level it is higher caused by catalytic action is weaker and catalytic efficiency reduces defect, the catalytic activity and catalytic efficiency of the Z-type photochemical catalyst be obviously improved.Moreover, the preparation method of the Z-type photochemical catalyst is simple, and can be by the dosage and illumination condition of control soluble silver salt, the contents of control silver and silver iodide, and then adjust the photocatalysis performance of photochemical catalyst.
Description
Technical field
The present invention relates to photocatalysis field technical fields, more particularly, to a kind of Z-type photochemical catalyst and preparation method thereof
And application.
Background technique
Photocatalysis is a kind of low energy consumption, economical, safety, the environmental protection technology of greenization, because low energy consumption for it, reaction condition temperature
With the advantages that reaction product is without secondary pollution, be applied to the fields such as sewage treatment, air cleaning and water decomposition hydrogen manufacturing at present.
BiOX solid solution (201710823696.1) is a kind of novel photochemical catalyst, because its unique layer structure makes it have
Good electron-transport efficiency and good catalytic performance, and the conduction band of BiOX solid solution and valence band location can be according to realities
Border use demand changes the additional proportion of different halogens, to be adjusted.But due to the conduction band of BiOX solid solution
Energy level is higher, keeps the oxidability of BiOX solid solution weaker, limits it in the further development of photocatalysis field.
In research in recent years, has a large amount of papers and show that constructing Z-type photocatalytic system is that one kind effectively improves light and urges
The synthetic strategy of agent photocatalysis performance.In Z-type photocatalytic system, it is located at light similar in the energy level in different semiconductors
Raw electronics will be combined with each other with hole by electronic media, so that the higher light induced electron of oxidability and reducing power are more
Strong photohole is saved, and is substantially increased photochemical catalyst and is obtained catalytic efficiency.Therefore, BiOX Z-type photocatalysis is constructed
System is to improve a kind of feasible method of BiOX photocatalysis performance.
Summary of the invention
The purpose of the present invention is to provide a kind of Z-type photochemical catalysts.The present invention be mixed in bismuth oxyiodide elemental silver and
Silver iodide, improve bismuth oxyiodide due to conduction level it is higher caused by catalytic action is weaker and what catalytic efficiency reduced lacks
It falls into, the catalytic activity and catalytic efficiency of the Z-type photochemical catalyst are obviously improved.
Another object of the present invention is to provide the preparation methods of the Z-type photochemical catalyst.
A further object of the present invention is to provide the applications of the Z-type photochemical catalyst.
Above-mentioned purpose of the invention is achieved by following scheme:
A kind of Z-type photochemical catalyst, the Z-type photochemical catalyst are BiOYnI1-n/ Ag/AgI-x, wherein Y is halogen；X is silver element
With the molar ratio of iodine, value range is 0~1；N is 0~1, and n ≠ 1.
In BiOYnI1-nIn/Ag/AgI-x type photochemical catalyst, silver iodide and bismuth oxyiodide are respectively as reducing agent and oxidation
Agent, silver-colored simple substance is as electronic media.Silver iodide and bismuth oxyiodide generate photo-generate electron-hole pairs, so under the conditions of light activated
Photo-generate electron-hole pairs separate afterwards, and light induced electron transits on respective conduction level, and photohole then stays in respectively
Valence-band level on.Under the action of electronic media silver simple substance, silver iodide photohole similar in energy level and bismuth oxyiodide photoproduction
Electronics is mutually compound, so that remaining the stronger photohole of oxidability in Z-type photocatalytic system and reducing power is stronger
Light induced electron, effectively improve the catalytic effect of photochemical catalyst.Meanwhile the amount of electronic media silver simple substance is to Z-type photocatalysis
The catalytic effect of agent has large effect, if silver-colored simple substance content is too low, can not be effectively facilitated point of photo-generate electron-hole pairs
From, conversely, if silver-colored simple substance too high levels, can provide excessive complex loci, so the content of silver-colored simple substance it is excessive or it is very few all
It will affect photocatalysis effect.Therefore, the content for reasonably adjusting silver-colored simple substance has the catalytic effect of photochemical catalyst important meaning
Justice.
Preferably, the Y is bromine or chlorine；The n is 0.3,0.5 or 0.9；The x is 0.05,0.1,0.15 and 0.2.
It is highly preferred that the x is 0.15.
The present invention also protects the preparation method of the Z-type photochemical catalyst simultaneously, includes the following steps:
S1. bismuth oxyiodide and soluble silver salt solution are mixed, reaction generates silver iodide, obtains suspension；
S2. suspension is stirred under illumination condition and reduction reaction occurs, the Z-type photochemical catalyst can be obtained；
Wherein, the bismuth oxyiodide is BiOClnI1-n、BiOBrnI1-nOr BiOI, wherein n is 0.1~1, and n ≠ 1.
The purpose of step S1 be in order in bismuth oxyiodide Surface Creation silver iodide, by control the dosage of soluble silver salt with
And the reaction time controls the production quantities of silver iodide；The purpose of step S2 is under illumination condition, so that silver iodide restore
Reaction generates elemental silver, by control illumination condition and reaction time, controls the production quantity of elemental silver.
Preferably, the molar ratio of silver element and iodine is 0.01~0.5 in the suspension；The illumination condition
Are as follows: intensity of illumination 50mW/cm2~200mW/cm2, light application time is 2~20min, and the vertical range of light source and suspension is 10
~30cm.
It is highly preferred that the molar ratio of silver element and iodine is 0.15 in suspension；The illumination condition are as follows: illumination is strong
Degree is 120mW/cm2~140mW/cm2, light application time 10min, the vertical range of light source and suspension is 20cm；During Illumination
In, can stirred suspension, mixing speed be 400~600r/min.
Preferably, the preparation process of the bismuth oxyiodide includes the following steps: iodide or iodide and other first
The mixture of halide is configured as halogen solutions；Then bismuth source is added to mix, then carries out photocatalytic reaction, can be prepared into
To bismuth oxyiodide.
Preferably, the total moles ratio of the bismuth source and halogen element is 1:0.5~1.5；It is highly preferred that bismuth source and halogen element
Total moles ratio is 1:1.
Preferably, the bismuth source is without hydration bismuth nitrate or bismuth chloride；The iodide are sodium iodide or potassium iodide；It is described
Other halide are the soluble halides such as sodium chloride, potassium chloride, zinc chloride, sodium bromide or potassium bromide.
Preferably, in the preparation process of the bismuth oxyiodide, for the ease of be uniformly mixed can be stirred, ultrasound etc.
Reason, ultrasound condition are 100~150W of power, and stirring rate is 400~600r/min.
Preferably, the step S1 is carried out at room temperature, and suspension can be stirred, until whole iodines generates
Silver iodide；The soluble silver salt is silver nitrate.
The Z-type photochemical catalyst is photocatalytically degradating organic dye (such as methyl orange, rhodamine B etc.), and organic pollutant is (such as
Phenol, aniline etc.), the application in terms of antibiotic (such as tetracycline, Ciprofloxacin etc.) is also within the scope of the present invention.
Compared with prior art, the invention has the following advantages:
The present invention has been prepared Z-type photochemical catalyst, has improved bismuth oxyiodide by mixing silver and silver iodide in bismuth oxyiodide
Due to conduction level it is higher caused by catalytic action is weaker and catalytic efficiency reduces defect, the Z-type photochemical catalyst urges
Change activity and catalytic efficiency is obviously improved.Moreover, the preparation method of the Z-type photochemical catalyst is simple, and can pass through
The dosage and illumination condition of soluble silver salt, the content of control silver and silver iodide are controlled, and then the light for adjusting photochemical catalyst is urged
Change performance.
Detailed description of the invention
Fig. 1 is BiOBr0.3I0.7/ Ag/Ag-x mechanism of degradation schematic diagram.
Fig. 2 is BiOBr0.3I0.7The photocatalysis performance figure of different photochemical catalysts in/Ag/Ag-x series.
Fig. 3 is BiOBr0.3I0.7The transmission electron microscope figure of/Ag/Ag-0.15 photochemical catalyst.
Specific embodiment
The present invention is made combined with specific embodiments below and further being elaborated, the embodiment is served only for explaining this
Invention, is not intended to limit the scope of the present invention.Test method as used in the following examples is normal unless otherwise specified
Rule method；Used material, reagent etc., unless otherwise specified, for the reagent and material commercially obtained.
Embodiment 1
A kind of Z-type photochemical catalyst, is prepared by following procedure:
(1) 0.5g BiOBr is taken0.3I0.7Photochemical catalyst is added into the 50mL silver nitrate solution of various concentration, and wherein silver nitrate is molten
Silver element and BiOBr in liquid0.3I0.7The molar ratio of middle iodine is respectively 0.05,0.1,0.15,0.2；Gained suspension is existed
It stirs 1 hour at room temperature, makes AgI in-situ precipitate in BiOBr0.3I0.7On；
(2) gained suspension being placed under 300W xenon lamp, output electric current is 15mA, and the vertical range with solution plane is 30cm,
Illumination 10min is stirred under the rate of 500r/min.After the completion of illumination, products therefrom is centrifugated, is cleaned 3 times with deionized water
It is dry at 60 DEG C afterwards, obtain a series of BiOX Z-type photochemical catalyst BiOBr0.3I0.7/ Ag/AgI-x(BAA-x), wherein x
For the molar ratio of silver element and iodine.
The present embodiment is to remove BiOBr0.3I0.7For be illustrated, can be BiOCl in actual fabrication processnI1-n、
BiOBrnI1-n(x=0~1) or BiOI, the BiOX of other different proportions are prepared by raw material.The reference above process,
It is prepared for BiOBr0.5I0.5/Ag/AgI-x、BiOBr0.9I0.1/Ag/AgI-x。
Performance test: with BiOBr0.3I0.7/ Ag/AgI-x, wherein x is 0.05,0.1,0.15 and 0.2, for representative, test
Its performance.
The above-mentioned photochemical catalyst prepared is taken to carry out photocatalysis effect experiment, specific experiment process are as follows: weigh 100mg respectively
Photochemical catalyst is added in the methyl orange solution that 150mL concentration is 10mg/L, and it is flat to reach absorption by stirring 30min at dark
Weighing apparatus then provides radiation of visible light using 300W xenon lamp and carries out light-catalyzed reaction, takes about 7mL solution, centrifugal filtration every 5min
Catalyst, using the absorbance of methyl orange in measurement of ultraviolet-visible spectrophotometer filtrate, using the time as abscissa, when measurement, is filtered
The concentration of the concentration of methyl orange and original concentration ratio is that ordinate is mapped in liquid, catalytic effect experimental result such as Fig. 2 institute
Show.
The result shows that even if the different Z-type photochemical catalyst BAA-x of x value, photocatalysis performance will be better than zirconyl oxyhalides
Bismuth, as we know from the figure BiOBr0.3I0.7, BAA-0.05, BAA-0.1 and BAA0.2 degradation rate be respectively 0.04528,
0.04673,0.06261,0.07637；When x value is 0.15, the photocatalysis performance of BAA-0.15 photochemical catalyst is best, light
Degradation rate can achieve 89% in 30min, degradation rate 0.07994min-1。
The Z-type photochemical catalyst of preparation is observed under transmission electron microscope, transmission electron microscope figure such as Fig. 3
Shown, silver iodide and the silver-colored equal growth in situ of simple substance are on bismuth oxyiodide as we know from the figure, it was demonstrated that utilize conjunction provided by the present invention
Z-type photochemical catalyst can be effectively synthesized at method.
The BiOBr0.3I0.7The mechanism that/Ag/Ag-x plays a role is as shown in Figure 1.Wherein, silver iodide and iodine in catalyst
Bismuth oxide is respectively as reducing agent and oxidant, and silver-colored simple substance is as electronic media.Silver iodide and bismuth oxyiodide are in light activated item
Under part, photo-generate electron-hole pairs are generated, then photo-generate electron-hole pairs separate, and light induced electron transits to respective conduction band energy
In grade, and photohole then stays in respective valence-band level.Under the action of electronic media silver simple substance, iodate similar in energy level
Silver-colored photohole and bismuth oxyiodide light induced electron are mutually compound, so that it is stronger to remain oxidability in Z-type photocatalytic system
Photohole and the stronger light induced electron of reducing power, effectively improve the catalytic effect of photochemical catalyst.
Embodiment 2
Referring to the preparation method in embodiment 1, the difference is that the bismuth oxyiodide used is BiOCl0.3I0.7, it is prepared
BiOCl0.3I0.7/ Ag/AgI-x, wherein the value range of x is 0~1.
The Z-type photochemical catalyst being specifically prepared has BiOCl0.3I0.7/Ag/AgI-0.15、BiOCl0.3I0.7/Ag/AgI-
0.1 and BiOCl0.3I0.7/Ag/AgI-0.2。
Embodiment 3
Referring to the preparation method in embodiment 1, the difference is that the bismuth oxyiodide used is BiOBr0.5I0.5, it is prepared
BiOBr0.5I0.5/ Ag/AgI-x, wherein the value range of x is 0~1.
The Z-type photochemical catalyst being specifically prepared has BiOBr0.5I0.5/Ag/AgI-0.15、BiOBr0.5I0.5/Ag/AgI-
0.1 and BiOBr0.5I0.5/Ag/AgI-0.2。
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of shield range can also be made on the basis of above description and thinking for those of ordinary skill in the art
Other various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (10)
1. a kind of Z-type photochemical catalyst, which is characterized in that the Z-type photochemical catalyst is BiOYnI1-n/ Ag/AgI-x, wherein Y is halogen
Element；X is the molar ratio of silver element and iodine, and value range is 0~1；N is 0~1, and n ≠ 1.
2. Z-type photochemical catalyst according to claim 1, which is characterized in that the Y is bromine or chlorine；The n be 0.3,0.5 or
0.9；The value range of the x is 0.05,0.1,0.15 or 0.2.
3. the preparation method of Z-type photochemical catalyst as claimed in claim 1 or 2, which comprises the steps of:
S1. bismuth oxyiodide and soluble silver salt solution are mixed, reaction generates silver iodide, obtains suspension；
S2. suspension is issued into raw reduction reaction in illumination condition, the Z-type photochemical catalyst can be obtained；
Wherein, the bismuth oxyiodide is BiOClnI1-n、BiOBrnI1-nOr BiOI, wherein n is 0~1, and n ≠ 1.
4. the preparation method of Z-type photochemical catalyst according to claim 3, which is characterized in that in the suspension silver element with
The molar ratio of iodine is 0.01~0.5；The illumination condition are as follows: intensity of illumination 50mW/cm2~200mW/cm2, illumination
Time is 2~20min, and the vertical range of light source and suspension is 10~30cm.
5. the preparation method of Z-type photochemical catalyst according to claim 4, which is characterized in that in the suspension silver element with
The molar ratio of iodine is 0.15；The illumination condition are as follows: intensity of illumination 120mW/cm2~140mW/cm2, light application time
For 10min, the vertical range of light source and suspension is 20cm；In During Illumination, can stirred suspension, mixing speed be 400~
600r/min。
6. the preparation method of Z-type photochemical catalyst according to claim 3, which is characterized in that the preparation of the bismuth oxyiodide
Journey includes the following steps: that the mixture of iodide or iodide and other halide is first configured as halogen solutions；Then
Bismuth source is added to mix, bismuth oxyiodide can be prepared.
7. the preparation method of Z-type photochemical catalyst according to claim 6, which is characterized in that the bismuth source and halogen element it is total
Molar ratio is 1:0.5~1.5.
8. the preparation method of Z-type photochemical catalyst according to claim 7, which is characterized in that the bismuth source and halogen element it is total
Molar ratio is 1:1.
9. the preparation method of Z-type photochemical catalyst according to claim 3, which is characterized in that the step S1 is in room temperature condition
Lower progress, suspension can be stirred, until whole silver elements generates silver iodide；The soluble silver salt is silver nitrate.
10. Z-type photochemical catalyst as claimed in claim 1 or 2 is in terms of photocatalytically degradating organic dye, organic pollutant or antibiotic
Application.
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