CN105727901A - Preparation method of titanium dioxide photocatalytic adsorbing material - Google Patents
Preparation method of titanium dioxide photocatalytic adsorbing material Download PDFInfo
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- CN105727901A CN105727901A CN201610279013.6A CN201610279013A CN105727901A CN 105727901 A CN105727901 A CN 105727901A CN 201610279013 A CN201610279013 A CN 201610279013A CN 105727901 A CN105727901 A CN 105727901A
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- 239000000463 material Substances 0.000 title claims abstract description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 title abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title abstract description 5
- 229920001661 Chitosan Polymers 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 230000003197 catalytic effect Effects 0.000 claims description 47
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 abstract description 17
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 abstract description 17
- 229960000623 carbamazepine Drugs 0.000 abstract description 17
- 229960001680 ibuprofen Drugs 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 238000007146 photocatalysis Methods 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000648 terne Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- 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 discloses a preparation method of a titanium dioxide photocatalytic adsorbing material. The titanium dioxide photocatalytic adsorbing material obtained by the preparation method can be used for not only effectively improving the photocatalytic performance of TiO2 and simultaneously solving the problem that the photocatalytic material is difficultly separated and recovered. According to the preparation method disclosed by the invention, a photo-reduction method is firstly adopted for preparing an Ag elementary substance, the Ag elementary substance is loaded on the surface of TiO2 to form an Ag-loaded TiO2 photocatalyst, and then the purpose of inhibiting electron and hole recombination is achieved, so that the photocatalytic efficiency of the catalyst is improved; then the chitosan made of high-molecular materials is adopted as an immobilized base material to immobilize Ag-loaded TiO2; the obtained novel titanium dioxide photocatalytic adsorbing material not only has a good adsorbing effect, but also is easily recovered and separated, can be applied to treatment of emerging pollutants PPCPs; and known from an experimental result, the effect of removing carbamazepine and ibuprofen in PPCPs is good.
Description
Technical field
The preparation method that the present invention relates to a kind of optically catalytic TiO 2 adsorbing material, belongs to photocatalysis composite adsorbing material technical field.
Background technology
Medicine and personal care articles (pharmaceuticalsandpersonalcareproducts, PPCPs) it is be suggested first in Daughton and Ternes in 1999 the one section of literature review about medicine and personal-care supplies jointly delivered, discussing " PPCPs " in literary composition to the pollution of environment and ecological risk, " PPCPs " is just widely accepted as the proper noun of medicine and personal-care supplies subsequently.Early 1990s, the annual production of Germany's personal-care supplies has just reached 550,000 tons, and improving constantly along with expanding economy and quality of life, and yield and the consumption of PPCPs increase increasingly, and kind is increasingly various, and structure is also increasingly sophisticated.Owing to China is populous, herding and culture fishery flourishing, the production of PPCPs and use total amount always to occupy the world " leading " status.At present, PPCPs has become as one of international study hotspot problem as the pollutant that a class environment is emerging, but in China but without causing enough attention.
Both at home and abroad the degradation process method of PPCPs mainly there are the methods such as biodegradation, adsorption treatment, membrane filtration technique and advanced oxidation at present.Existing owing to PPCPs is of a great variety for biodegradation method, chemical property diversity is relatively big, and the degradation pathway in water body differs, it is difficult to the problem that common one program removes whole PPCPs；It is big that absorption simultaneously there is also adsorbent reactivation energy consumption, and material can only be made from a phase transfer to another phase, and the absorbability after regeneration has decline in various degree, and this brings the problem can not ignore to the use of absorption method；Membrane technology is good to its treatment effect, but membrane process investment and operating cost are high, easily block, it is necessary to high-caliber pretreatment and regular Chemical cleaning, there is also concentrate and processes problem.Photocatalysis oxidation technique is under sunlight or ultraviolet source existent condition, produces hole and the electronics pair with stronger redox ability at energy excitation lower semiconductor.In water body, hole and electronics to producing the oxidation base with relatively Strong oxdiative ability, to major part Organic substance in water can effectively mineralising removal, twice transformation will not be caused.Conventional treatment-photocatalysis technology group technology more can play its advantage, moreover it is possible to the organic intermediate products of trace in decomposition water, be processed conventionally one is supplemented and strengthening；It addition, the available solar energy endlessly of photocatalysis technology, can reducing operating cost on the one hand, on the other hand environment-protecting clean, low-carbon (LC) runs.Remove the new method of offer and thinking for solving hardly degraded organic substance, have a good application prospect.
TiO2Photocatalysis technology, as the green environmental protection technique of a kind of cleaning, low energy consumption, has tempting application prospect in pollution control, synthesis new material etc..But TiO2Photocatalysis technology exists that photo-quantum efficiency is relatively low, catalytic efficiency has much room for improvement, catalyst be difficult to immobilized, be not easy to the problems such as recovery.
Summary of the invention
Goal of the invention: the preparation method that the technical problem to be solved is to provide a kind of optically catalytic TiO 2 adsorbing material, by the immobilized Ag-TiO of chitosan that this preparation method obtains2Complex microsphere is with absorption and photocatalysis performance.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
The preparation method of a kind of optically catalytic TiO 2 adsorbing material, described optically catalytic TiO 2 adsorbing material is first Ag to be deposited on TiO2Surface, then the TiO of Ag will be loaded with2It is immobilized on chitosan to prepare.
The preparation method of above-mentioned optically catalytic TiO 2 adsorbing material, specifically includes following steps:
Step 1, by the desired amount of TiO2Add and ultrasonic in 250～350mL water be mixed to get aaerosol solution A；
Step 2, adds a certain amount of silver nitrate and citric acid in aaerosol solution A, adopts irradiation under ultraviolet ray a period of time to obtain aaerosol solution B after mixing；
Step 3, adds 3mL hydrochloric acid and 8～10g chitosan in aaerosol solution B, and stirring obtains milky solution C；
Step 4, is added dropwise in sodium hydroxide solution by milky solution C, is cleaned by head product use water until the pH value of solution after cleaning is in neutrality, clean post-drying and can obtain end-product after reaction a period of time.
Wherein, in step 1, described ultrasonic intensity is 70～90W.
Wherein, in step 2, the intensity of described ultraviolet light is 12W～18W, and wavelength is 254nm.
Wherein, in step 2, the addition mass ratio of described silver nitrate and citric acid is 1: 1～2.
Wherein, in step 4, the concentration of described sodium hydroxide solution is 0.2mol/L～0.4mol/L.
Wherein, in step 4, described baking temperature is 80 DEG C～105 DEG C.
Wherein, in step 4, in described end-product, TiO on chitosan2Supported quantity is chitosan mass 50%～150%；The load capacity of silver simple substance is TiO2The 0.1%～0.6% of quality.
The optically catalytic TiO 2 adsorbing material that the preparation method of above-mentioned optically catalytic TiO 2 adsorbing material prepares application in degraded PPCPs.
Ag electron-withdrawing power is strong, allows light excite the electronics of generation from TiO2Transfer on Ag, and light excites the hole of generation rest on TiO2On, thus reach to suppress the purpose of electronics and hole-recombination, thus improving the photocatalysis efficiency of catalyst.Ag-TiO2It is immobilized on chitosan, prepares into microsphere form, the absorbability of chitosan can not only be utilized to increase TiO2Surface area load, and convenient recycling, it is to avoid the problem that powder body adsorbent difficulty reclaims.Preparation method of the present invention first by Ag load at TiO2On, then the TiO of Ag will be loaded with2With chitosan compound, thus obtaining the catalysis material of a kind of immobilized Ag doping titanium dioxide of chitosan having absorption and photocatalysis performance concurrently, it utilizes Ag-TiO2High light degradation property, improve the target degradation product photodegradation rate in photocatalyst surface, it utilizes the immobilized Ag-TiO of chitosan2Complex microsphere, strengthens the settleability of catalysis material.
Compared with prior art, the invention have the advantages that:
The optically catalytic TiO 2 adsorbing material that preparation method of the present invention obtains is effectively increased TiO2Photocatalytic oxidation properties, also solve the problem that catalysis material is not readily separated recovery simultaneously；Preparation method of the present invention first adopts photoreduction met hod to prepare Ag simple substance, and makes it be deposited on TiO2Surface forms the TiO being loaded with Ag2Photocatalyst, reaches to suppress the purpose of electronics and hole-recombination, thus improving the photocatalysis efficiency of catalyst；Adopt macromolecular material chitosan as the immobilized TiO being loaded with Ag of immobilized base material again2；The optically catalytic TiO 2 adsorbing material obtained not only has good adsorption effect, and be easily recycled and separate, can being applied to process emerging pollutant PPCPs, result is it can be seen that it is good to the carbamazepine in PPCPs and ibuprofen removal effect by experiment.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope phenogram that the optically catalytic TiO 2 adsorbing material that embodiment 1 prepares amplifies 70 times；
Fig. 2 is the scanning electron microscope phenogram that the optically catalytic TiO 2 adsorbing material that embodiment 1 prepares amplifies 50000 times；
Fig. 3 is the transmission electron microscope phenogram of the optically catalytic TiO 2 adsorbing material that embodiment 1 prepares；
Fig. 4 is the optically catalytic TiO 2 adsorbing material recycling design sketch that embodiment 1 prepares；
Fig. 5 is the graph of relation of the optically catalytic TiO 2 adsorbing material for preparing of embodiment 1 degradation effect to carbamazepine and ibuprofen and time；
Fig. 6 is the graph of relation of the optically catalytic TiO 2 adsorbing material for preparing of embodiment 1 degradation effect to carbamazepine and ibuprofen and dosage.
Detailed description of the invention
Below in conjunction with drawings and Examples, technical scheme is described in detail.
Embodiment 1
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 8gTiO2Add and 300mL distilled water adopts the ultrasonic 60min of 70W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.04g) silver nitrate of quality 0.5% and 0.005g citric acid, adopt ultraviolet light (12W, wavelength is 254nm) to process 120min after stirring 60min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 8g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 20ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 4cm, syringe needle internal diameter is 0.7mm) milky solution C is instilled sodium hydroxide (0.3mol/L, solution level is 15cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and can obtain end-product.
Embodiment 2
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 4gTiO2Add and 250mL distilled water adopts the ultrasonic 90min of 70W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.012g) silver nitrate of quality 0.3% and 0.003g citric acid, adopt ultraviolet light (16W, wavelength is 254nm) to process 150min after stirring 45min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 8g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 40ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 3cm, syringe needle internal diameter is 0.5mm) milky solution C is instilled sodium hydroxide (0.3mol/L, solution level is 15cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and can obtain end-product.
Embodiment 3
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 4.5gTiO2Add and 250mL distilled water adopts the ultrasonic 120min of 70W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.027g) silver nitrate of quality 0.6% and 0.006g citric acid, adopt ultraviolet light (18W, wavelength is 254nm) to process 120min after stirring 30min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 9g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 50ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 3cm, syringe needle internal diameter is 0.7mm) milky solution C is instilled sodium hydroxide (0.3mol/L, solution level is 10cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and can obtain end-product.
Embodiment 4
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 10gTiO2Add and 350mL distilled water adopts the ultrasonic 90min of 90W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.03g) silver nitrate of quality 0.3% and 0.006g citric acid, adopt ultraviolet light (18W, wavelength is 254nm) to process 120min after stirring 30min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 10g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 40ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 6cm, syringe needle internal diameter is 0.7mm) milky solution C is instilled sodium hydroxide (0.2mol/L, solution level is 10cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and can obtain end-product.
Embodiment 5
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 12gTiO2Add and 350mL distilled water adopts the ultrasonic 120min of 90W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.072g) silver nitrate of quality 0.6% and 0.01g citric acid, adopt ultraviolet light (16W, wavelength is 254nm) to process 120min after stirring 45min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 8g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 50ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 6cm, syringe needle internal diameter is 0.7mm) milky solution C is instilled sodium hydroxide (0.4mol/L, solution level is 15cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and can obtain end-product.
Embodiment 6
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 9gTiO2Add and 300mL distilled water adopts the ultrasonic 90min of 80W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.054g) silver nitrate of quality 0.6% and 0.006g citric acid, adopt ultraviolet light (12W, wavelength is 254nm) to process 90min after stirring 60min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 9g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 20ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 4cm, syringe needle internal diameter is 0.7mm) milky solution C is instilled sodium hydroxide (0.4mol/L, solution level is 20cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 105 DEG C after cleaning and can obtain end-product.
Embodiment 7
The preparation method of optically catalytic TiO 2 adsorbing material of the present invention, specifically includes following steps:
Step 1, by 5gTiO2Add and 250mL distilled water adopts the ultrasonic 60min of 80W obtain aaerosol solution A；
Step 2, adds TiO in aaerosol solution A2(0.005g) silver nitrate of quality 0.1% and 0.002g citric acid, adopt ultraviolet light (12W, wavelength is 254nm) to process 90min after stirring 60min and obtain mix suspending solution B；
Step 3, adds 3mL hydrochloric acid and 10g chitosan in aaerosol solution B, and stirring makes its mix homogeneously obtain milky solution C；
Step 4, (sample rate is 20ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 4cm, syringe needle internal diameter is 1mm) milky solution C is instilled sodium hydroxide (0.4mol/L, solution level is 20cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 90 DEG C after cleaning and can obtain end-product.
Embodiment 8
The preparation method of the immobilized optically catalytic TiO 2 adsorbing material of chitosan, specifically includes following steps:
Step 1, by 8gTiO2Add and 300mL distilled water adopts the ultrasonic 60min of 70W obtain aaerosol solution A；
Step 2, adds 3mL hydrochloric acid and 8g chitosan in aaerosol solution A, and stirring makes its mix homogeneously obtain milky solution D；
Step 3, (sample rate is 20ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 4cm, syringe needle internal diameter is 0.7mm) milky solution D is instilled sodium hydroxide (0.3mol/L, solution level is 15cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and obtain the immobilized optically catalytic TiO 2 adsorbing material of chitosan.
Embodiment 9
The preparation method of chitosan adsorbing material, specifically includes following steps:
Step 1, adds 300mL distilled water by 3mL hydrochloric acid and 8g chitosan, and stirring makes its mix homogeneously obtain milky solution E；
Step 2, (sample rate is 20ml/h to adopt automatic injector, syringe needle distance sodium hydroxide solution liquid level is 4cm, syringe needle internal diameter is 0.7mm) milky solution E is instilled sodium hydroxide (0.3mol/L, solution level is 15cm) in solution, head product adopts distilled water clean until the pH value of solution after cleaning is in neutrality after standing a night, dry at 80 DEG C after cleaning and obtain chitosan adsorbing material.
Fig. 1～Fig. 3 is the scanning electron microscope phenogram of optically catalytic TiO 2 adsorbing material of the present invention, by scheming it is known that the optically catalytic TiO 2 adsorbing material of the present invention is ball-type.It is loaded with the TiO of Ag2With chitosan compound, rub assorted together into ball-type, ball-type is conducive to better catalytic degradation, absorption and sedimentation.
Adsorption experiment: room is tested process and selected the pollutant of ibuprofen and carbamazepine representatively PPCPs, the initial concentration of ibuprofen and carbamazepine is 5mg/L, mixing speed is 150rpm, ultraviolet light intensity is 12W, 365nm, the photocatalysis adsorbing material dosage that embodiment 1～9 prepares is 6g/L, and the response time is 60min.High performance liquid chromatography is adopted to calculate the clearance of pollutant before and after reaction.
The photocatalysis adsorbing material that embodiment 1～9 prepares is as shown in table 1 to the removal effect of carbamazepine and ibuprofen:
Table 1
| Embodiment | Carbamazepine | Ibuprofen |
| 1 | 74.53% | 90.34% |
| 2 | 62.51% | 85.44% |
| 3 | 64.66% | 83.69% |
| 4 | 79.33% | 93.76% |
| 5 | 78.94% | 93..23% |
| 6 | 76.02% | 91.87% 5--> |
| 7 | 66.43% | 85.91% |
| 8 | 59.92% | 82.63% |
| 9 | 9.12% | 13.59% |
。
By table 1 it can be seen that the immobilized optically catalytic TiO 2 adsorbing material of chitosan for preparing of embodiment 8, its photocatalytic oxidation degradation effect does not have the photocatalysis adsorbing material of the present invention good, and therefore it will lower than the photocatalysis adsorbing material of the present invention to the clearance of pollutant；Pollutant can only be carried out Adsorption by the chitosan light adsorbing material that embodiment 9 prepares, it is impossible to it is carried out photocatalytic oxidation degradation removal.
Fig. 4 is the photocatalysis performance figure of absorption degradation repeatedly rear optically catalytic TiO 2 adsorbing material of the present invention, as shown in Figure 4, target degradation product is still had the clearance of more than 70% by optically catalytic TiO 2 adsorbing material of the present invention after the 5th degraded absorption, illustrates that the regenerability of the optically catalytic TiO 2 adsorbing material of the present invention is good.
The optically catalytic TiO 2 adsorbing material that for embodiment 1 prepare at different conditions degraded situation to carbamazepine and ibuprofen is presented herein below.
(1) impact of adsorption time:
At room temperature, initial concentration is carbamazepine and the ibuprofen solution of 5mg/L, 150rpm, and ultraviolet light intensity is 12W, and dosage is 6g/L.As shown in Figure 5, the clearance of carbamazepine and ibuprofen is increased by optically catalytic TiO 2 adsorbing material of the present invention with the increase of adsorption time, in initial 30min, the degradation rate of ibuprofen and carbamazepine is quickly increased by catalysis material, the degradation efficiency of ibuprofen increases to 78%, and the degradation rate of carbamazepine increases to 58%.Between 30min to 120min, the degradation rate of target degradation product slows down gradually, and ibuprofen merely add 19%, and carbamazepine adds 26%.After 120min, the degradation rate of ibuprofen no longer changes, and then the degradation rate of carbamazepine progressively increases to 99%.
(2) impact of catalyst amounts:
At room temperature, initial concentration is carbamazepine and the ibuprofen solution of 5mg/L, 150rpm, and ultraviolet light intensity is 12W, and the response time is 60min.As shown in Figure 6, along with the increase of optically catalytic TiO 2 adsorbing material dosage of the present invention, the clearance of carbamazepine and ibuprofen is also constantly increased by it, and when its dosage is more than 6g/L, being further added by dosage can not effectively increase clearance.
Obviously, above-described embodiment is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here without also giving exhaustive to all of embodiment, these changes extended out or variation are also among protection scope of the present invention.
Claims (9)
1. the preparation method of an optically catalytic TiO 2 adsorbing material, it is characterised in that: described optically catalytic TiO 2 adsorbing material is first Ag to be deposited on TiO2Surface, then the TiO of Ag will be loaded with2It is immobilized on chitosan to prepare.
2. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 1, it is characterised in that specifically include following steps:
Step 1, by the desired amount of TiO2Add and ultrasonic in 250～350mL water be mixed to get aaerosol solution A；
Step 2, adds a certain amount of silver nitrate and citric acid in aaerosol solution A, adopts irradiation under ultraviolet ray a period of time to obtain aaerosol solution B after mixing；
Step 3, adds 3mL hydrochloric acid and 8～10g chitosan in aaerosol solution B, and stirring obtains milky solution C；
Step 4, is added dropwise in sodium hydroxide solution by milky solution C, is cleaned by head product use water until the pH value of solution after cleaning is in neutrality, clean post-drying and can obtain end-product after reaction a period of time.
3. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 1, described ultrasonic intensity is 70～90W.
4. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 2, the intensity of described ultraviolet light is 12W～18W, and wavelength is 254nm.
5. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 2, the addition mass ratio of described silver nitrate and citric acid is 1: 1～2.
6. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 4, the concentration of described sodium hydroxide solution is 0.2mol/L～0.4mol/L.
7. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 4, described baking temperature is 80 DEG C～105 DEG C.
8. the preparation method of optically catalytic TiO 2 adsorbing material according to claim 2, it is characterised in that: in step 4, in described end-product, TiO on chitosan2Supported quantity is chitosan mass 50%～150%；The load capacity of silver simple substance is TiO2The 0.1%～0.6% of quality.
9. the optically catalytic TiO 2 adsorbing material that the preparation method of the optically catalytic TiO 2 adsorbing material described in claim 1 prepares application in degraded PPCPs.
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