CN105689004A - Modified TiO2/SiO2 composite catalyst and preparation method thereof - Google Patents
Modified TiO2/SiO2 composite catalyst and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 96
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 90
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 90
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 90
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 67
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims 2
- 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 abstract description 38
- 229940043267 rhodamine b Drugs 0.000 abstract description 36
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001868 water Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 238000002474 experimental method Methods 0.000 description 13
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- 230000001105 regulatory effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003403 water pollutant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 102000007562 Serum Albumin Human genes 0.000 description 2
- 108010071390 Serum Albumin Proteins 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
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- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a modified TiO2/SiO2 composite catalyst and further discloses a preparation method for the modified composite catalyst. According to the modified TiO2/SiO2 composite catalyst disclosed by the invention, the enriching capability of the catalyst to dye molecules in water can be greatly improved, so that the photocatalytic degradation capability to dye wastewater (in particular wastewater containing rhodamine B) is improved; thus, the modified catalyst disclosed by the invention has a very good treatment effect on high-concentration dye wastewater, and the enriching effect of the composite catalyst to pollutants in the water cannot be greatly affected even if the ratio of SiO2 added in the composite catalyst is not high; in addition, the preparation method disclosed by the invention has the advantages that the raw materials are readily available, the cost is low, the reaction conditions are mild, and the method is pollution-free to environments.
Description
Technical field
The present invention relates to a kind of modified TiO2/SiO2Composite catalyst, the preparation method further relating to above-mentioned modified composite catalyst。
Background technology
The annual production of China's dyestuff is maintained at 18～220,000 t, accounts for the 40% of world's dyestuff total output。Dye industry belongs to high energy consumption, high pollutive industries。According to estimates, China often produces 1t dyestuff, about waste discharge 744m3。And in whole production and use procedure, a large amount of dyestuffs (more than 10%) enter in natural water, waste water from dyestuff amount is just in continuous rise。Rhodamine B has the features such as cheap, color and luster is bright and new, chemical property, and often by some illegal retailers coloring agent as food, to strengthen the color of food, but health can be produced very big harm by this。Relevant research shows, RhB not only can store in serum albumin and transport, and the conformation of serum albumin and molecular entergy level can be produced significantly impact, and being caused mutation by some external uncertain material, the derivant ultimately generating rhodamine can promote apoptosis。Processing method such as biochemical process, coagulation sedimentation, electrolysis etc. conventional at present, is all difficult to meet discharge standard requirement。
With TiO2Conductor photocatalysis method for representing can produce the hydroxyl radical free radical (HO) with strong oxidizing property, it is possible to the organic molecule make many Stability Analysis of Structures, being difficult to be decomposed by the microorganisms is converted into carbon dioxide, water and inorganic ions etc.。By TiO2Be carried on Silica Surface and can effectively solve its recovery problem in the application, and silica gel in catalytic process with TiO2Playing cooperative effect, meanwhile, silica gel has the advantages such as abundant species, cheap and easy to get, surface nature can be modified according to actual needs。
The process of light-catalyzed reaction occurs mainly in catalyst surface, and therefore photocatalyst will directly affect the efficiency of whole light-catalyzed reaction for the accumulation ability of pollutant in water body。For TiO2/SiO2Composite catalyst, first pollutant are adsorbed on SiO2Surface, then owing to diffusion migrates to TiO2Surface carries out light-catalyzed reaction。Although SiO2There is big specific surface area, it is possible to strengthen the accumulation ability to pollutant to a certain extent, but for TiO2/SiO2Composite catalyst, too much SiO2Addition can reduce TiO2Percentage composition, the photocatalytic activity of catalyst will be affected, so SiO in composite catalyst2Addition not easily too much, which limits its concentration effect to water pollutant, especially the dye wastewater treatment poor effect to high concentration, therefore by modified SiO2TiO is improved on surface2/SiO2The accumulation ability of pollutant is the effective way improving catalyst activity by composite catalyst。
Summary of the invention
The technical problem to be solved is to provide a kind of modified TiO that rhodamine B in waste water from dyestuff has high adsorption-photocatalytic degradation ability2/SiO2Composite catalyst。
The present invention also to solve the technical problem that and be to provide the above-mentioned modified TiO that rhodamine B in waste water from dyestuff has high adsorption-photocatalytic degradation ability2/SiO2The preparation method of composite catalyst。
For solving above-mentioned technical problem, the technical solution adopted in the present invention is:
A kind of modified TiO2/SiO2Composite catalyst, its chemical structural formula is:
Above-mentioned modified TiO2/SiO2The preparation method of composite catalyst, specifically includes following steps:
Step 1, prepares TiO by sol-gel process2/SiO2Composite catalyst: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol are mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by a certain amount of concentration3, a certain amount of volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, form uniform colloidal sol, and uniform colloidal sol is first placed in the baking oven of 65 DEG C and 100 DEG C and toasts 48h, obtain xerogel, it is neutral with distilled water cyclic washing to cleaning mixture again, then adopts absolute ethanol washing twice, and dry at 100 DEG C, calcine 4 hours under uniform temperature in Muffle furnace after material after drying is ground, obtain TiO2/SiO2Composite catalyst；
Step 2, by the TiO of step 12/SiO2Composite catalyst joins γ-mercaptopropyl trimethoxysilane (MPTS) and N, in the mixed solution of dinethylformamide (DMF), condensing reflux continuously stirred 12 hours at a certain temperature, filter to obtain coarse granule, then extract in apparatus,Soxhlet's 24 hours for extractant with toluene, remove the unreacted γ-mercaptopropyl trimethoxysilane of Silica Surface, extract is used absolute ethanol washing several times, and dry, modified composite catalyst TiO can be obtained2/SiO2-MPTS。
Wherein, in step 1, described HNO3Addition be 6～12mL, the addition of described HF is 2～5mL。
Wherein, in step 1, described calcining heat is 300～700 DEG C。
Wherein, in step 2, for every 1gTiO2/SiO2Composite catalyst, the addition volume of described γ-mercaptopropyl trimethoxysilane is 0.5～2ml, and the addition volume of described DMF is 10～15ml。
Wherein, in step 2, described TiO2/SiO2The mixed liquor of composite catalyst and γ-mercaptopropyl trimethoxysilane and DMF reacts at 60～90 DEG C。
The present invention modifiies TiO2/SiO2The preparation principle of composite catalyst: first pass through sol-gel process and prepare TiO2/SiO2Composite catalyst, then the TiO that will prepare2/SiO2There is graft reaction in composite catalyst, namely obtain the modified TiO of the present invention in the DMF (DMF) mixed solution with γ-mercaptopropyl trimethoxysilane (MPTS)2/SiO2Composite catalyst (TiO2/SiO2-MPTS) ,-SH group in molecule is by the rhodamine B molecule in electrostatic attraction, chemical bond enrichment water body, thus substantially increasing TiO2/SiO2-MPTS is to the absorbability of rhodamine B in water body。
Beneficial effect: compared to prior art, the modified TiO of the present invention2/SiO2Composite catalyst can be greatly improved the catalyst accumulation ability to water pollutant, thus improve the photocatalytic degradation capability to dyes molecule (especially rhodamine B molecule), therefore the waste water from dyestuff of high concentration is also had good treatment effect by the modified catalyst of the present invention, though in composite catalyst SiO2Additional proportion not high, without too much affecting the composite catalyst concentration effect to water pollutant；It addition, the preparation method of the present invention prepares TiO by sol-gel process2/SiO2Composite catalyst, then again through to TiO2/SiO2Composite catalyst surface carries out chemical modification, at SiO2The surface grafting functional group of functionalization, modified composite catalyst is greatly improved to the absorbability of rhodamine B in water body, thus promoting the activity of modified composite catalyst photocatalytic degradation, the preparation method raw material of the present invention is easy to get, cost is low, reaction condition is gentle and environmentally safe。
Accompanying drawing explanation
Fig. 1 is the modified TiO of the present invention2/SiO2The process chart of method for preparing composite catalyst；
Fig. 2 is the modified TiO of the present invention2/SiO2The XRD spectrum figure of composite catalyst；
Fig. 3 is the modified TiO of the present invention2/SiO2Composite catalyst before modified after infrared spectrum comparison diagram；
Fig. 4 is the modified TiO of the present invention2/SiO2The Raman spectrogram of composite catalyst；
Fig. 5 is the modified TiO of the present invention2/SiO2Composite catalyst adsorption dynamics adsorption kinetics figure to rhodamine B afterwards before modified；
Fig. 6 is the modified TiO of the present invention2/SiO2Rhodamine B is adsorbed the Changing Pattern figure with pH value by composite catalyst before modified afterwards；
Fig. 7 is the modified TiO of the present invention2/SiO2Composite catalyst comparison diagram to the adsorption-photocatalytic degradation performance of rhodamine B afterwards before modified。
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme is further described。
Embodiment 1
The present invention modifiies TiO2/SiO2Composite catalyst, its chemical structural formula is:
This modified TiO2/SiO2The preparation method of composite catalyst comprises the steps:
Step 1, prepares TiO by sol-gel process2/SiO2Composite catalyst: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol are mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by 6mL concentration3, 2mL volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, form uniform colloidal sol, and uniform colloidal sol is first placed in the baking oven of 65 DEG C and 100 DEG C and toasts 48h, obtain xerogel, it is neutral with distilled water cyclic washing to cleaning mixture again, then adopts absolute ethanol washing twice, and dry at 100 DEG C, calcine 4 hours at 300 DEG C in Muffle furnace after material after drying is ground, obtain TiO2/SiO2Composite catalyst；
Step 2, takes the TiO of 2g step 12/SiO2Composite catalyst joins 2mL γ-mercaptopropyl trimethoxysilane (MPTS) and 20mLN, in the mixed solution that dinethylformamide (DMF) forms, condensing reflux continuously stirred 12 hours at 60 DEG C, filter to obtain coarse granule, then extract in apparatus,Soxhlet's 24 hours for extractant with toluene, remove the unreacted γ-mercaptopropyl trimethoxysilane of Silica Surface, extract is used absolute ethanol washing several times, and dry, modified composite catalyst TiO can be obtained2/SiO2-MPTS。
Embodiment 2
The present invention modifiies TiO2/SiO2Composite catalyst, its chemical structural formula is:
This modified TiO2/SiO2The preparation method of composite catalyst comprises the steps:
Step 1, prepares TiO by sol-gel process2/SiO2Composite catalyst: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol are mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by 8mL concentration3, 3mL volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, form uniform colloidal sol, and uniform colloidal sol is first placed in the baking oven of 65 DEG C and 100 DEG C and toasts 48h, obtain xerogel, it is neutral with distilled water cyclic washing to cleaning mixture again, then adopts absolute ethanol washing twice, and dry at 100 DEG C, calcine 4 hours at 500 DEG C in Muffle furnace after material after drying is ground, obtain TiO2/SiO2Composite catalyst；
Step 2, takes the TiO of 2g step 12/SiO2Composite catalyst joins 3mL γ-mercaptopropyl trimethoxysilane (MPTS) and 25mLN, in the mixed solution that dinethylformamide (DMF) forms, condensing reflux continuously stirred 12 hours at 70 DEG C, filter to obtain coarse granule, then extract in apparatus,Soxhlet's 24 hours for extractant with toluene, remove the unreacted γ-mercaptopropyl trimethoxysilane of Silica Surface, extract is used absolute ethanol washing several times, and dry, modified composite catalyst TiO can be obtained2/SiO2-MPTS。
Embodiment 3
The present invention modifiies TiO2/SiO2Composite catalyst, its chemical structural formula is:
This modified TiO2/SiO2The preparation method of composite catalyst comprises the steps:
Step 1, prepares TiO by sol-gel process2/SiO2Composite catalyst: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol are mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by 10mL concentration3, 4mL volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, form uniform colloidal sol, and uniform colloidal sol is first placed in the baking oven of 65 DEG C and 100 DEG C and toasts 48h, obtain xerogel, it is neutral with distilled water cyclic washing to cleaning mixture again, then adopts absolute ethanol washing twice, and dry at 100 DEG C, calcine 4 hours at 600 DEG C in Muffle furnace after material after drying is ground, obtain TiO2/SiO2Composite catalyst；
Step 2, takes the TiO of 2g step 12/SiO2Composite catalyst joins 3.5mL γ-mercaptopropyl trimethoxysilane (MPTS) and 30mLN, in the mixed solution that dinethylformamide (DMF) forms, condensing reflux continuously stirred 12 hours at 80 DEG C, filter to obtain coarse granule, then extract in apparatus,Soxhlet's 24 hours with toluene for extractant, remove the unreacted γ-mercaptopropyl trimethoxysilane of Silica Surface, extract is used absolute ethanol washing several times, and dry, modified composite catalyst TiO can be obtained2/SiO2-MPTS。
Embodiment 4
The present invention modifiies TiO2/SiO2Composite catalyst, its chemical structural formula is:
This modified TiO2/SiO2The preparation method of composite catalyst comprises the steps:
Step 1, prepares TiO by sol-gel process2/SiO2Composite catalyst: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol are mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by 12mL concentration3, 5mL volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, form uniform colloidal sol, and uniform colloidal sol is first placed in the baking oven of 65 DEG C and 100 DEG C and toasts 48h, obtain xerogel, it is neutral with distilled water cyclic washing to cleaning mixture again, then adopts absolute ethanol washing twice, and dry at 100 DEG C, calcine 4 hours at 700 DEG C in Muffle furnace after material after drying is ground, obtain TiO2/SiO2Composite catalyst；
Step 2, takes the TiO of 2g step 12/SiO2Composite catalyst joins 4mL γ-mercaptopropyl trimethoxysilane (MPTS) and 30mLN, in the mixed solution that dinethylformamide (DMF) forms, condensing reflux continuously stirred 12 hours at 90 DEG C, filter to obtain coarse granule, then extract in apparatus,Soxhlet's 24 hours for extractant with toluene, remove the unreacted γ-mercaptopropyl trimethoxysilane of Silica Surface, extract is used absolute ethanol washing several times, and dry, modified composite catalyst TiO can be obtained2/SiO2-MPTS。
Measure the TiO of embodiment 1～4 preparation respectively2/SiO2-MPTS is to the adsorption-photocatalytic degradation removal ability of rhodamine B in solution:
Taking 450mL rhodamine B initial concentration is the solution of 100mg/L, and regulating pH value of solution is 5, adds the TiO of 0.45g embodiment 1 preparation2/SiO2-MPTS catalyst, constant temperature oscillation 1h, upon adsorption reach balance after, open ultraviolet source irradiation 3h, carry out photocatalytic degradation experiment, treat that experiment terminates, take out solution, and with high speed centrifuge centrifugal after, measure the concentration of rhodamine B in supernatant, according to following formulaObtain clearance, in (1) formula: R is clearance (%), C0For the initial concentration (mg/L) of rhodamine B, C in solutioneThe concentration (mg/L) of rhodamine B in solution after reacting for adsorption-photocatalytic degradation, result is as shown in table 1；
Taking 450mL rhodamine B initial concentration is the solution of 100mg/L, and regulating pH value of solution is 5, adds the TiO of 0.45g embodiment 2 preparation2/SiO2-MPTS catalyst, constant temperature oscillation 1h, upon adsorption reach balance after, open ultraviolet source irradiation 3h, carry out photocatalytic degradation experiment, treat that experiment terminates, take out solution, and with high speed centrifuge centrifugal after, measuring the concentration of rhodamine B in supernatant, obtain clearance, result is as shown in table 1；
Taking 450mL rhodamine B initial concentration is the solution of 100mg/L, and regulating pH value of solution is 5, adds the TiO of 0.45g embodiment 3 preparation2/SiO2-MPTS catalyst, constant temperature oscillation 1h, upon adsorption reach balance after, open ultraviolet source irradiation 3h, carry out photocatalytic degradation experiment, treat that experiment terminates, take out solution, and with high speed centrifuge centrifugal after, measuring the concentration of rhodamine B in supernatant, obtain clearance, result is as shown in table 1；
Taking 450mL rhodamine B initial concentration is the solution of 100mg/L, and regulating pH value of solution is 5, adds the TiO of 0.45g embodiment 4 preparation2/SiO2-MPTS catalyst, constant temperature oscillation 1h, upon adsorption reach balance after, open ultraviolet source irradiation 3h, carry out photocatalytic degradation experiment, treat that experiment terminates, take out solution, and with high speed centrifuge centrifugal after, measuring the concentration of rhodamine B in supernatant, obtain clearance, result is as shown in table 1；
Table 1 is the modified TiO that embodiment 1～4 prepares2/SiO2The composite catalyst clearance to rhodamine B:
The TiO that embodiment 3 is prepared2/SiO2-MPTS carries out XRD spectrum phenetic analysis:
Fig. 2 is the TiO of embodiment 32/SiO2The XRD phenogram of-MPTS, as can be seen from the figure TiO2/SiO2TiO in-MPTS2Main exist with Anatase, and the angle of diffraction 2 θ is the diffraction maximum of 25.37 °, 37.03 °, 48.12 °, 53.97 °, 62.74,68.79 ° and 75.4 ° (101), (103), (200), (105), (204), (116) and (215) crystal faces being belonging respectively to sharp titanium phase。
The TiO that embodiment 3 is prepared2/SiO2-MPTS and TiO before modified2/SiO2Carry out infrared spectrum characterization analysis:
Fig. 3 is the TiO of embodiment 32/SiO2-MPTS and TiO before modified2/SiO2Infrared spectrogram, relative analysis find, modified, TiO2/SiO2-MPTS is at 2970cm-1And 2925cm-1Place occurs in that the stretching vibration peak of-CH, it was shown that modifying agent MPTS is bonded to TiO2/SiO2On。
The TiO that embodiment 3 is prepared2/SiO2-MPTS carries out Raman Characterization analysis:
Fig. 4 is the TiO of embodiment 32/SiO2The Raman spectrogram of-MPTS, be can be seen that at 2580cm by collection of illustrative plates-1There is the characteristic absorption peak of-SH in modifying agent MPTS in place, and itself and FTIR prove modifying agent MPTS and SiO jointly2There occurs binding effect ,-SH is connected on SiO2Surface, changes the surface nature of material, thus strengthening Catalyst Adsorption performance。
Utilize the TiO that embodiment 3 prepares2/SiO2-MPTS and TiO before modified2/SiO2Rhodamine B is carried out adsorption experiment:
(1) adsorption dynamics adsorption kinetics
Take the solution that two parts of 200mL rhodamine B initial concentrations are 40mg/L to be respectively placed in tool plug conical flask, a copy of it solution adds the TiO of 0.2g embodiment 32/SiO2-MPTS, adds 0.2g TiO before modified in another part of solution2/SiO2Catalyst, in constant temperature oscillator (constant temperature 25 DEG C vibration), after separated in time takes out solution and is centrifuged with high speed centrifuge, measures the concentration of rhodamine B in supernatant, according to following formulaObtain adsorbance Qt, and draw the relation curve of adsorbance-time, result as it is shown in figure 5, wherein, in above formula: QtFor adsorbance (mg/g), C0For adsorbing the concentration (mg/L) of rhodamine B in front solution, CeFor the concentration (mg/L) in solution after absorption, V is liquor capacity (L), W is catalyst quality (g)。From fig. 5, it can be seen that modified TiO2/SiO2The maximal absorptive capacity of rhodamine B can be reached 36.8mg/g by-MPTS, greatly exceed TiO before modified2/SiO2Adsorbance 6.25mg/g。
(2) impact of pH value
Take the solution that a series of 50mL rhodamine B initial concentration is 40mg/L to fill in conical flask in tool, be separately added into the TiO of 0.05g embodiment 32/SiO2-MPTS and 0.05g TiO before modified2/SiO2Catalyst, under condition of different pH, constant temperature oscillation 3h, upon adsorption reach balance after, take out solution, and with high speed centrifuge centrifugal after, measure the concentration of rhodamine B in supernatant, obtain adsorbance, and draw out the relation curve of adsorbance and pH value, see Fig. 6, it will be appreciated from fig. 6 that TiO2/SiO2Absorption and TiO to rhodamine B2/SiO2-MPTS presents different rules: TiO2/SiO2The maximum adsorption pH=5 of RhB is maximum, and after pH value is more than 5, eliminating rate of absorption begins to decline；And TiO2/SiO2Being adsorbed in taken pH value range of rhodamine B is increased by-MPTS along with the increase of solution ph, is held essentially constant after pH value is more than 5。Utilize TiO prepared by embodiment 32/SiO2-MPTS and TiO before modified2/SiO2The adsorption-photocatalytic degradation carrying out rhodamine B removes experiment:
Taking the solution that two parts of 450mL rhodamine B initial concentrations are 100mg/L to be respectively placed in tool plug conical flask, regulating pH value of solution is 5, adds the TiO of 0.45g embodiment 3 in a copy of it solution2/SiO2-MPTS, adds 0.45g TiO before modified in another part of solution2/SiO2Catalyst, constant temperature oscillation 1h, upon adsorption reach balance after, open ultraviolet source irradiation 3h, carry out photocatalytic degradation experiment。Starting to experiment to terminate from experiment, separated in time takes out solution, and with high speed centrifuge centrifugal after, measure the concentration of rhodamine B in supernatant, according to formulaObtaining clearance, result is as shown in Figure 7。
From figure 7 it can be seen that TiO2/SiO2-MPTS and TiO before modified2/SiO2To the clearance of rhodamine B respectively 97.7% and 30.7%, modified TiO is described2/SiO2The adsorption-photocatalytic degradation removal ability of rhodamine B is significantly improved by-MPTS, and this is due to TiO2/SiO2-SH group in-MPTS molecule is by the rhodamine B molecule in electrostatic attraction, chemical bond enrichment water body such that it is able to be greatly improved TTiO2/SiO2-MPTS is to the absorbability of rhodamine B in water body。
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 cannot all of embodiment be given exhaustive。And the apparent change that these spirit belonging to the present invention are extended out or variation are still among protection scope of the present invention。
Claims (7)
1. a modified TiO2/SiO2Composite catalyst, it is characterised in that: its chemical structural formula is:
2. modified TiO described in a claim 12/SiO2The preparation method of composite catalyst, it is characterised in that: comprise the steps:
Step 1, utilizes sol-gel process to prepare TiO2/SiO2Composite catalyst；
Step 2, by the TiO of step 12/SiO2Composite catalyst joins γ-mercaptopropyl trimethoxysilane and N, in the mixed solution of dinethylformamide, condensing reflux continuously stirred a few hours at a certain temperature, filter to obtain coarse granule, then extract in apparatus,Soxhlet's for extractant with toluene, finally namely extract is obtained modified composite catalyst TiO through washing, drying and processing2/SiO2-MPTS。
3. modifiy TiO according to claim 22/SiO2The preparation method of composite catalyst, it is characterised in that: in step 1, described TiO2/SiO2The preparation method of composite catalyst specifically includes following steps: 10mL tetrabutyl titanate, 5mL silester and 45mL dehydrated alcohol is mixed, is configured to A mixed liquor；It is the HNO of 1mol/L by a certain amount of concentration3, a certain amount of volumetric concentration be 3% HF and 12mL dehydrated alcohol mixing, be configured to B mixed liquor；While stirring B mixed liquor is added dropwise in A mixed liquor, forms uniform colloidal sol, after drying, obtain xerogel, xerogel can be obtained TiO through washing, drying and calcination processing2/SiO2Composite catalyst。
4. modifiy TiO according to claim 32/SiO2The preparation method of composite catalyst, it is characterised in that: described HNO3Addition be 6～12mL, the addition of described HF is 2～5mL。
5. modifiy TiO according to claim 32/SiO2The preparation method of composite catalyst, it is characterised in that: described calcining heat is 300～700 DEG C。
6. modifiy TiO according to claim 22/SiO2The preparation method of composite catalyst, it is characterised in that: in step 2, for every 1gTiO2/SiO2Composite catalyst, the addition volume of described γ-mercaptopropyl trimethoxysilane is 0.5～2ml, and the addition volume of described DMF is 10～15ml。
7. modifiy TiO according to claim 22/SiO2The preparation method of composite catalyst, it is characterised in that: in step 2, described TiO2/SiO2The mixed liquor of composite catalyst and γ-mercaptopropyl trimethoxysilane and DMF reacts at 60～90 DEG C。
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