CN105797754A - Silver chloride-titanium dioxide nanotube composite material and preparation method and application thereof - Google Patents
Silver chloride-titanium dioxide nanotube composite material and preparation method and application thereof Download PDFInfo
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- CN105797754A CN105797754A CN201610256649.9A CN201610256649A CN105797754A CN 105797754 A CN105797754 A CN 105797754A CN 201610256649 A CN201610256649 A CN 201610256649A CN 105797754 A CN105797754 A CN 105797754A
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- silver chloride
- nanotube composite
- titania nanotube
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000002071 nanotube Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OMZLKELSTLHYSQ-UHFFFAOYSA-M chlorosilver oxygen(2-) titanium(4+) Chemical compound [Ag]Cl.[O-2].[O-2].[Ti+4] OMZLKELSTLHYSQ-UHFFFAOYSA-M 0.000 title abstract 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 23
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 29
- 239000004332 silver Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 26
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- 239000005844 Thymol Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960000790 thymol Drugs 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LECSHJWIACEDPZ-UHFFFAOYSA-N ethane-1,2-diamine naphthalene hydrochloride Chemical compound C(CN)N.C1=CC=CC2=CC=CC=C12.Cl LECSHJWIACEDPZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy 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
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
Abstract
The invention provides a silver chloride-titanium dioxide nanotube composite material and a preparation method and application thereof, and belongs to the field of composite materials. A chemical formula of the silver chloride-titanium dioxide nanotube composite material is AgCl/TNTs. The invention further provides a preparation method of the silver chloride-titanium dioxide nanotube composite material. The method comprises the steps of firstly mixing and stirring titanium dioxide P25 with NaOH solution to obtain mixed solution; then putting the mixed solution into a reaction kettle, increasing temperature from room temperature to 130 to 150 DEG C according to speed of 2 DEG C/min, and maintaining the temperature for 24h to obtain mixture; finally adding AgNO3 into the mixture for drying, and calcining the solid obtained after drying for 2h at 400 DEG C to obtain the silver chloride-titanium dioxide nanotube composite material. The invention further provides application of the silver chloride-titanium dioxide nanotube composite material as photocatalyst. The photocatalyst can reduce nitrate into nitrogen gas, the conversion rate of nitrate is 94.5 percent and the selectivity of nitrogen gas is 92.9 percent.
Description
Technical field
The invention belongs to field of compound material, be specifically related to a kind of silver chloride-titania nanotube composite
And its preparation method and application.
Background technology
Flourish along with agricultural, substantial amounts of nitrogen enters in water body the pollution causing nitrate, how to subtract
Light and preventing and treating water body nitrate pollution has become as an extremely urgent problem.Traditional processing method is deposited
Processing time length and be easily generated the problem of secondary pollution, so research one efficiently and thoroughly nitrate goes
Except means have become as the most common problem paid close attention to.In recent years, photocatalysis technology quickly grows, especially
Reach its maturity especially in terms of processing organic pollutants, be expected in the near future be applied to the place of actual sewage
Reason.Same, it is current most potential one side that photocatalysis technology is applied to the removal of nitrate in water
Method.
It is that exploitation has efficient degradation efficiency and high nitrogen that photocatalysis technology processes the core of nitrate in water
Selective photocatalyst.Titanium dioxide is cheap and easy to get with it, nontoxic, and chemical property is relatively stable
Advantage is paid close attention to by various countries scientific worker.But, it is inefficient on catalysis reduction nitrate, and
Nitrogen selective is the highest, need further to improve.Titania nanotube is with titanium dioxide as raw material
Obtained by hydro-thermal method and post processing, there is bigger specific surface area and more surface activity site.Chlorine
Changing silver and also serve as a kind of photocatalyst, more report uses it for the degraded of organic pollution, after illumination
Form Ag/AgCl plasma resonance system so that its photocatalysis performance has bigger lifting.Existing system
Standby Ag AgCl/TNTs ternary photocatalyst, use it for methylene blue degraded (Wen Yanyuan ， Ding Ming.
The Anatase TiO that Ag@AgCl modifies2The preparation of nanotube and photocatalysis performance thereof. catalysis journal, 2011,
32 (1): 36-45.), the method is complex and loaded down with trivial details, relatively time-consuming arduously.Relevant prepare silver chloride-dioxy
Change titanium nano tube catalyst and be applied to the research that photo catalytic reduction nitrate is nitrogen there is not been reported.
Summary of the invention
The invention aims to provide a kind of silver chloride-titania nanotube composite and preparation thereof
Methods and applications, this preparation method is simple, and the silver chloride obtained-titania nanotube composite can conduct
Photocatalyst reduction nitrate is nitrogen.
Present invention firstly provides a kind of silver chloride-titania nanotube composite, the chemistry of this composite
Formula is: AgCl/TNTs.
The present invention also provides for the preparation method of a kind of silver chloride-titania nanotube composite, including:
Step one: by titanium dioxide P25 and NaOH solution mix and blend, obtain mixed solution；
Step 2: mixed solution step one obtained is put in reactor, with the speed of 2 DEG C/min from room
Temperature is warming up to 130-150 DEG C, and keeps 24h, obtains mixture；
Step 3: by AgNO3Join in the mixture that step 2 obtains, at 80-100 DEG C, be dried 12-24
H, calcines dried solid 2h at 400 DEG C, obtains silver chloride-titania nanotube composite.
Preferably, the mixing time of described step one is 30-60min.
Preferably, the quality (g) of described step one titanium dioxide P25: NaOH solution (ml) is
(0.6-1.0): (30-50).
Preferably, the concentration of described step one NaOH solution is 10mol L-1。
Preferably, after described step 2 obtains mixture, also include mixture is carried out pickling processes: will
Mixture distilled water cyclic washing to pH value is 6.8-7.2, then uses 0.1mol L-1HCl solution be washed till
PH value is 1.0, through ultrasonic 30-60min, then stands 3-5h.
Preferably, described titanium dioxide P25 and AgNO3Mass ratio be ((0.6-1.0): (0.01-0.1).
The present invention also provides for the application as photocatalyst of the above-mentioned silver chloride-titania nanotube composite.
Preferably, described silver chloride-titania nanotube composite is as photocatalyst also orthonitric acid
Salt is nitrogen.
Beneficial effects of the present invention
Present invention firstly provides a kind of silver chloride-titania nanotube composite, the chemistry of this composite
Formula is: AgCl/TNTs.This material has nanotube pattern and bigger specific surface area, multiple in acid cleaning process
Close AgCl and can significantly improve material light catalysis reduction nitrate ability and stable circulation performance, and do not destroy
The pattern of nanotube, having high efficiency photocatalysis reduction nitrate nitrogen is the ability of nitrogen.
The present invention also provides for the preparation method of a kind of silver chloride-titania nanotube composite, and existing skill
Art compares, and the method for the present invention is the simplest, and raw material is easy to get, and pattern is homogeneous, the load of AgCl and TNTs
Synthesis carry out simultaneously, save time and cost.
The present invention also provides for the application as photocatalyst of the above-mentioned silver chloride-titania nanotube composite,
It is nitrogen that this photocatalyst can reduce nitrate, test result indicate that: use above photocatalysis system, instead
After should carrying out 30 minutes, the conversion ratio of nitrate is 94.5%, and nitrogen selective is 92.9%, and produces relatively
Few nitrite and ammonia nitrogen.Additionally, AgCl/TNTs is after recycling four times, catalytic effect keeps height
Effect is stable.
Accompanying drawing explanation
Fig. 1 is AgCl/TNTs material each parameter under photocatalysis experimental system of the embodiment of the present invention 1 preparation
Concentration is over time.
Fig. 2 is that the AgCl/TNTs material of the embodiment of the present invention 1 preparation enters under photocatalysis experimental system continuously
Four circulating effect figures of row.
Detailed description of the invention
Present invention firstly provides a kind of silver chloride-titania nanotube composite, the chemistry of this composite
Formula is: AgCl/TNTs.
The present invention also provides for the preparation method of a kind of silver chloride-titania nanotube composite, including:
Step one: by titanium dioxide P25 and NaOH solution mix and blend, described mixing time is preferably
30-60min, obtains mixed solution；The quality (g) of described titanium dioxide P25: NaOH solution (ml)
It is preferably (0.6-1.0): (30-50)；The concentration of NaOH solution is preferably 10mol L-1；
Step 2: mixed solution step one obtained is put in reactor, described reactor is preferably poly-
The reactor of tetrafluoroethene liner, then with the speed of 2 DEG C/min from room temperature to 130-150 DEG C, and protect
Hold 24h, obtain mixture；Mixture is carried out pickling processes, is preferably: the mixture after cooling is taken
Go out, be 6.8-7.2 with distilled water cyclic washing to pH value, then use 0.1mol L-1HCl solution be washed till
PH value is 1.0, through ultrasonic 30-60min, and stands 3-5h；
Step 3: by AgNO3Join in the mixture that step 2 obtains, preferably by mixture again with pure
Being washed to pH value is 6.8-7.2, is dried 12-24h, dried solid is placed in Muffle at 80-100 DEG C
In stove, at 400 DEG C, calcine 2h, obtain silver chloride-titania nanotube composite.Described dioxy
Change titanium P25 and AgNO3Mass ratio be preferably ((0.6-1.0): (0.01-0.1).
The present invention also provides for the application as photocatalyst of the above-mentioned silver chloride-titania nanotube composite.
According to the present invention, described silver chloride-titania nanotube composite reduces nitre as photocatalyst
Hydrochlorate is nitrogen, and detailed process is:
0.20gAgCl/TNTs photocatalyst is put into nitrate (initial concentration C0=100mgN/ L) molten
In liquid (200ml), in dark place stirring 30min to reach adsorption equilibrium, it is subsequently added into 0.1M formic acid molten
Liquid in system as hole trapping agents, be then turn on circulating water cooling device, then open light source, treat light source
Irradiating reaction system after Wen Ding, reaction temperature is room temperature, is kept stirring in course of reaction, takes out every 5min
A small amount of sample, takes supernatant after centrifugal and obtains water sample and make follow-up mensuration, and the illumination reaction time is 30
min.In water sample, testing index has the concentration of nitrate, nitrite and ammonia nitrogen, is respectively adopted thymol and divides
Light photometry, hydrochloride naphthodiamide spectrophotography and indigo spectrophotometry, all use ultraviolet-visible to divide
Light photometer is measured analyzing the conversion ratio of nitrate and nitrogen selective.
Below in conjunction with specific embodiment, the present invention done further detailed description, the raw material related in embodiment
It is commercially available.
Embodiment 1
By the 10mol L of 0.6g P25 Yu 30ml-1NaOH solution mix and blend 60min, afterwards will be mixed
Close liquid to be transferred in teflon-lined reactor, put into temperature programming case, with the speed of 2 DEG C/min
Rate is from room temperature to 150 DEG C, and keeps 24h, is taken out by the mixture after cooling, repeatedly washes with distilled water
Wash and be about 7.0 to pH value, then use 0.1mol L-1HCl solution be washed till pH value and be about 1.0, Jing Guochao
After sound 30min, and standing 3h, in mixture, add the AgNO of 0.007g, 0.0373g and 0.079g3,
Mixture is washed till pH value with pure water again and is about 7.0, in the baking oven of 80 DEG C, be then dried 12h, will be dry
Solid after dry is placed in Muffle furnace, calcines 2h at 400 DEG C, and i.e. obtaining AgCl content is 1%, 5% and
The silver chloride of 10%-titania nanotube composite.
Embodiment 2
By the 10mol L of 0.8g P25 Yu 40ml-1NaOH solution mix and blend 45min, afterwards will be mixed
Close liquid to be transferred in teflon-lined reactor, put into temperature programming case, with the speed of 2 DEG C/min
Rate is from room temperature to 140 DEG C, and keeps 48h, is taken out by the mixture after cooling, repeatedly washes with distilled water
Wash and be about 6.8 to pH value, then use 0.1mol L-1HCl solution be washed till pH value and be about 1.0, Jing Guochao
After sound 30min, and standing 3h, in mixture, add the AgNO of 0.01g3, by mixture again
It is washed till pH value with pure water and is about 7.0, in the baking oven of 100 DEG C, be then dried 12h, by dried solid
It is placed in Muffle furnace, at 400 DEG C, calcines 2h, i.e. obtain silver chloride-titania nanotube composite.
The AgCl/TNTs Surface Physical Chemistry character that embodiment 2 obtains is: average pore size: 21.6nm；BET ratio
Surface area: 248m2·g-1；Total pore volume (when relative pressure is 0.97): 1.01cm3·g-1；
Hole type: mesoporous.
Embodiment 3
By the 10mol L of 1.0g P25 Yu 50ml-1During NaOH solution mix and blend 30min, afterwards will
Mixed liquor is transferred in teflon-lined reactor, puts into temperature programming case, with 2 DEG C/min's
Speed is from room temperature to 130 DEG C, and keeps 24h, is taken out, with distilled water repeatedly by the mixture after cooling
Washing is about 7.2 to pH value, then uses 0.1mol L-1HCl solution be washed till pH value and be about 1.0, pass through
After ultrasonic 60min, and standing 5h, in mixture, add the AgNO of 0.1g3, by mixture again
It is washed till pH value with pure water and is about 7.2, in the baking oven of 80 DEG C, be then dried 24h, dried solid is put
In Muffle furnace, at 400 DEG C, calcine 2h, i.e. obtain silver chloride-titania nanotube composite.
Embodiment 4
AgCl/TNTs 0.20g embodiment 1 obtained puts into the sodium nitrate of configuration (just as photocatalyst
Beginning concentration C0=100mgN/ L) in solution (200ml), in dark place stirring 30min to reach adsorption equilibrium,
Be subsequently added into 0.1M formic acid solution in system as hole trapping agents, be then turn on circulating water cooling device,
Opening light source again uses high voltage mercury lamp to be light source, and dominant wavelength is 365nm, after light stability, irradiate reactant
System, reaction temperature is room temperature, is kept stirring in course of reaction, takes out a small amount of sample, Jing Guoli every 5min
Taking supernatant after the heart to obtain water sample and make follow-up mensuration, the illumination reaction time is 30min.Water sample measures and refers to
Indicate the concentration of nitrate, nitrite and ammonia nitrogen, be respectively adopted thymol spectrophotometry method, hydrochloric acid naphthalene
Ethylenediamine spectrophotography and indigo spectrophotometry, all use ultraviolet-visible spectrophotometer to be measured
To analyze conversion ratio and the nitrogen selective of nitrate.
The performance nitrate transformation rate of the photo catalytic reduction nitrate of AgCl/TNTs and nitrogen selective are evaluated:
Wherein, C (NO3 -) nitrate transformation rate, %；
S(N2) nitrogen selective, %；
[NO3-N]0Initial nitrate nitrogen concentration, mgN L-1
[NO3-N]tT nitrate nitrogen concentration, mgN·L-1
[NO2-N]tT nitrite nitrogen concentration, mgN·L-1
[NH4-N]tT ammonia nitrogen concentration, mgN L-1
Fig. 1 is AgCl/TNTs material each parameter concentration under photocatalysis system of the embodiment of the present invention 1 preparation
Over time.Fig. 1 illustrates: along with the increase of light application time, the concentration of nitrate is on a declining curve,
Nitrite and ammonia nitrogen concentration are the most in rising trend.After illumination 30 minutes, nitrate transformation rate is according to public affairs
Formula is calculated as 94.5%, and nitrogen conversion ratio is calculated as 92.9% according to formula, illustrates that this material can convert efficiently
Nitrate is nitrogen.
Fig. 2 is that the AgCl/TNTs material of the embodiment of the present invention 1 preparation is carried out continuously under photocatalysis system
Four circulating effect figures.Fig. 2 illustrates: four times continuous experiment effect is relatively stable, and nitrate transformation rate is respectively
It is 94.5%, 99.7%, 98.5% and 97.5%.Illustrate that this material circulation serviceability is relatively stable, have certain
Use value.
Claims (9)
1. silver chloride-titania nanotube composite, it is characterised in that the change of this composite
Formula is: AgCl/TNTs.
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 1
Method, it is characterised in that including:
Step one: by titanium dioxide P25 and NaOH solution mix and blend, obtain mixed solution；
Step 2: mixed solution step one obtained is put in reactor, with the speed of 2 DEG C/min from room
Temperature is warming up to 130-150 DEG C, and keeps 24h, obtains mixture；
Step 3: by AgNO3Join in the mixture that step 2 obtains, at 80-100 DEG C, be dried 12-24
H, calcines dried solid 2h at 400 DEG C, obtains silver chloride-titania nanotube composite.
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 2
Method, it is characterised in that the mixing time of described step one is 30-60min.
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 2
Method, it is characterised in that the quality (g) of described step one titanium dioxide P25: NaOH solution (ml) is
(0.6-1.0): (30-50).
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 2
Method, it is characterised in that the concentration of described step one NaOH solution is 10mol L-1。
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 2
Method, it is characterised in that after described step 2 obtains mixture, also includes carrying out mixture pickling processes:
It is 6.8-7.2 by mixture distilled water cyclic washing to pH value, then uses 0.1mol L-1HCl solution wash
It is 1.0 to pH value, through ultrasonic 30-60min, then stands 3-5h.
The preparation side of a kind of silver chloride-titania nanotube composite the most according to claim 2
Method, it is characterised in that described titanium dioxide P25 and AgNO3Mass ratio be ((0.6-1.0):
(0.01-0.1)。
8. the silver chloride described in claim 1-titania nanotube composite answering as photocatalyst
With.
Silver chloride the most according to claim 8-titania nanotube composite is as photocatalyst
Application, it is characterised in that described silver chloride-titania nanotube composite is as photocatalyst also
Orthonitric acid salt is nitrogen.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732690A (en) * | 2016-11-15 | 2017-05-31 | 武汉理工大学 | Ag@AgCl/TiO2The preparation method of graphene oxide composite material |
| CN107349944A (en) * | 2017-08-31 | 2017-11-17 | 桂林融通科技有限公司 | A kind of preparation method of silver bromide titanium dioxide nano-tube composite catalyst |
| CN107774286A (en) * | 2017-09-29 | 2018-03-09 | 郑州爱可安环保技术有限公司 | A kind of method of low temperature preparation composite photo-catalyst |
| CN108187703A (en) * | 2017-12-11 | 2018-06-22 | 昆明理工大学 | A kind of preparation method of silver/silver chlorate/titanium dioxide composite photocatalyst |
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| CN109718859A (en) * | 2019-01-08 | 2019-05-07 | 东北师范大学 | A kind of Ag/TiO2/ MIL-125 (Ti) composite material and preparation method and Morphological control |
| CN111921550A (en) * | 2020-07-17 | 2020-11-13 | 杭州师范大学 | MXene/titanium dioxide nanotube composite material photocatalyst and preparation method thereof |
| CN113198515A (en) * | 2021-05-19 | 2021-08-03 | 上海城投原水有限公司 | Ternary photocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385981A (en) * | 2008-10-30 | 2009-03-18 | 南京大学 | Catalyst for photocatalysis and degradation of benzene and nitrates |
| CN101537350A (en) * | 2009-04-27 | 2009-09-23 | 武汉理工大学 | Ag/AgCl/TiO* nanotube array plasma visible-light photocatalyst and preparation method thereof |
| CN104941615A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Preparation method of Ag/AgCl/TiO2 nanotube |
-
2016
- 2016-04-22 CN CN201610256649.9A patent/CN105797754A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385981A (en) * | 2008-10-30 | 2009-03-18 | 南京大学 | Catalyst for photocatalysis and degradation of benzene and nitrates |
| CN101537350A (en) * | 2009-04-27 | 2009-09-23 | 武汉理工大学 | Ag/AgCl/TiO* nanotube array plasma visible-light photocatalyst and preparation method thereof |
| CN104941615A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Preparation method of Ag/AgCl/TiO2 nanotube |
Non-Patent Citations (4)
| Title |
|---|
| YUXIN TANG ET AL.: "Visible-light plasmonic photocatalyst anchored on titanate nanotubes: a novelnanohybrid with synergistic effects of adsorption and degradation", 《RCS ADVANCES》 * |
| 姚仲鹏著: "《空气净化原理、设计与应用》", 30 September 2014, 中国科学技术出版社 * |
| 杨保祥等著: "《钛基材料制造》", 31 January 2015, 冶金工业出版社 * |
| 柳丽芬等: "Ag/TiO2光催化还原硝酸氮", 《无机化学学报》 * |
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