CN106824151A - A kind of lignin-base mesoporous titanium dioxide photocatalytic material, preparation method and application - Google Patents
A kind of lignin-base mesoporous titanium dioxide photocatalytic material, preparation method and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 45
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- 239000002585 base Substances 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000013049 sediment Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 12
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 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 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241001062009 Indigofera Species 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 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—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Abstract
The invention discloses a kind of lignin-base mesoporous titanium dioxide photocatalytic material, preparation method and application, the catalysis material has high-specific surface area, good visible light-responded performance, can there is application well in photocatalytically degradating organic dye；Preparation method has the advantages that simple and easy to apply, cheap and reproducible simultaneously；Lignin-base mesoporous titanium dioxide photocatalytic material of the invention, is mesoporous TiO 2 particle obtained in lignin as template, wherein described titanium dioxide contains two kinds of crystalline phases of Anatase and Rutile Type.
Description
Technical field
The present invention relates to a kind of catalysis material, preparation method and application, it is situated between more specifically to a kind of lignin-base
Porous titanium dioxide catalysis material, preparation method and application.
Background technology
It is increasingly serious the problems such as energy shortage and environmental pollution with continuing to develop for today's society, directly constrain people
The sustainable development of class society.How these problems are solved using a kind of efficient means as the task of top priority.It is well known that
Solar energy is a kind of inexhaustible energy, if it is possible to make full use of solar energy, energy shortage and environmental pollution
The problems such as will greatly be alleviated.
Modern industry discharge many pollutant conventional treatment methods be difficult to effectively solution, wherein organic dyestuff (including
Methylene blue, rhodamine B, methyl orange etc.) some common Recalcitrant chemicals have a large amount of discharges in the industry such as dye is knitted,
Cause serious environmental pollution.Research shows, the active material produced under conditions of illumination using semiconductor light-catalyst
These organic dye pollutants can effectively be decomposed.Therefore, in order to solve the environmental problem that this pollutant brings, recent decades
Carry out scientists from all over the world to being had made extensive and intensive studies using solar energy photodissociation organic dye pollutant, and achieve a large amount of
Progress.The conductor photocatalysis material of current most study is titanium dioxide (TiO2), but due to its semiconductor band-gap energy compared with
Greatly (3.2eV), so its photocatalytic activity can only be limited in photon energy UV light region higher.But the 70% of sunshine
Energy above all concentrates on visible region, therefore photochemical catalyst of the research with visible light-responded performance is significant.
Mesoporous TiO 2 has specific surface area and continuous skeleton higher, is a kind of photocatalysis material being highly profitable
Material.And be used for light-catalysed titanium dioxide and generally exist with Anatase or Rutile Type, research finds that the light of Anatase is urged
Change activity generally higher than Rutile Type, so research of the major part on optically catalytic TiO 2 concentrates on anatase crystalline substance
Phase.Two kinds of different crystalline phases of nearest research display catalysis material of the same race have different energy levels, and two-phase interface has can
Quick separating photo-generate electron-hole pair can be played a part of.For example, Degussa companies of Germany commercialization P-25 catalysis materials are
It is made up of 80% Anatase and 20% Rutile Type, its photocatalytic activity has exceeded pure anatase phase titanium dioxide.At present
Commercial titanium dioxide based photocatalyst such as P25 catalyst has the small (50-70m of specific surface area2/ g), to the absorption speed of natural light
Rate is low, it is seen that the technical problem such as light photocatalytic activity is weak.
Lignin is that a kind of multiring structure is complicated, solid netted macromolecule organic (seeing below formula), there is alcohol hydroxyl on molecule
The functional groups such as base (a), phenolic hydroxyl group (b), carboxyl, are conducive to macromolecular structure to modify.In nature, the reserves of lignin are only secondary
It is in cellulose and annual with tens billion of tons of speed regeneration.Pulp and paper industry will isolate about 1.4 from plant every year
Hundred million tons of celluloses, while obtain 50,000,000 tons or so of lignin byproduct, but so far, lignin more than 95% or
Rivers are directly discharged into " black liquor ", cause secondary pollution serious, or burned after concentration, be seldom utilized effectively.With people
The understanding of the problems such as class environmental pollution and crisis of resource deepens continuously, and what this kind of natural polymer of lignin had can be again
The property such as raw, degradable is increasingly subject to pay attention to.Comprehensive development and utilization is carried out to it extremely urgent, if based on lignin,
The characteristic of its net high-polymer organic matter is played, then fully can then be solved well with reference to mesoporous titanium dioxide photocatalytic activity
Above-mentioned problem, while for recycling for lignin opens new path.
The content of the invention
It is an object of the invention to solve problems of the prior art, there is provided a kind of lignin-base mesoporous TiO 2
Catalysis material, the catalysis material has high-specific surface area, good visible light-responded performance.
It is a further object to provide the preparation method of above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material,
The preparation method has the advantages that simple and easy to apply, cheap and reproducible；The present invention also provides the catalysis material simultaneously
The O that answers in photocatalytically degradating organic dye is used.
The present invention is achieved by the following technical solutions：
Lignin-base mesoporous titanium dioxide photocatalytic material of the invention, is mesoporous two obtained in lignin as template
Titan oxide particles, wherein described titanium dioxide contains two kinds of crystalline phases of Anatase and Rutile Type.
The above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material of the present invention, its further technical scheme is described
Mesoporous TiO 2 grain diameter is 5-20nm, and specific surface area is 120-180m2/g。
The above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material of the present invention, its further technical scheme is Jie
Porous titanium dioxide catalysis material is, with lignin as template, with titanium tetrachloride as titanium source, to be prepared with direct hydrolysis method.
The preparation method of the above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material of the present invention, it is comprised the following steps：
(1) 1-10g alkali lignin crude product particles are taken to be dissolved in the 5-20wt%NaOH solution of 10-200mL, is stirred at room temperature
3-12h, filtering removes insoluble matter, obtains lignin liquor；
(2) under the conditions of being sufficiently stirred for, it is the hydrochloric acid of 0.1-1.0mol/L that concentration is added dropwise in the lignin liquor for obtaining
Solution, controls pH=1-5, stirs 1-4h；Filtering, the precipitation solid washing that will be obtained, then 80-100 DEG C of drying under vacuum condition,
Obtain purifying lignin solid；
(3) will obtain purifying the lignin aqueous solution that lignin solid is made into concentration 1-10g/L, 20-40 is incubated in water-bath
Under the conditions of DEG C, by titanium tetrachloride aqueous solution, then it is slowly dropped in the lignin liquor of 10-1000mL, concentration is then added dropwise is
The hydrochloric acid solution of 0.1-1.0mol/L, controls pH=1-5, and quick stirring obtains mixture；To be stirred at 20-40 DEG C of this mixture
10-100min, 10-100min is stirred at being subsequently heated to 60-100 DEG C；Ammoniacal liquor is added, pH=7-8 is adjusted；It is stirred for 10-
After 100min, centrifugation obtains amorphous sediment thing；
(4) the amorphous sediment thing filtering that will be obtained, aging 6-24h, obtains jello, then be washed with deionized water at room temperature
Wash 3-4 times, remove Cl-, then with absolute ethanol washing 1-2 times, the solid product obtained after filtering 80-100 under vacuum
DEG C drying, through ball milling after, calcine 1-5h at 400-600 DEG C, the solid particle for obtaining as lignin-base meso-porous titanium dioxide
Titanium catalysis material.
The above-mentioned preparation method of the present invention, its further technical scheme is that the washing described in step (2) is to use deionization
Washing 3-4 time, under vacuum condition 80-100 DEG C of drying time for 8 hours and more than.
The above-mentioned preparation method of the present invention, its further technical scheme can also be the titanium tetrachloride described in step (3)
The aqueous solution is that 0.1-10g titanium tetrachlorides are added in 10-1000mL water to be made into.
The above-mentioned preparation method of the present invention, its further technical scheme can also be the solid product described in step (4)
Under vacuum 80-100 DEG C of drying time be 8 hours and more than.
The above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material of the present invention can well should in light-catalyzed reaction
With.
The above-mentioned lignin-base mesoporous titanium dioxide photocatalytic material of the present invention can be in photocatalytically degradating organic dye
Application；Further technical scheme is that described organic dyestuff is methylene blue, rhodamine B or methyl orange.
The present invention has the advantages that compared with prior art：
Lignin-base mesoporous titanium dioxide photocatalytic material of the invention has high-specific surface area, good visible light-responded
Performance, specific surface area is up to 120-180m2/g.Preparation method has simple and easy to apply, cheap and reproducible etc. excellent simultaneously
Point；The other lignin-base mesoporous titanium dioxide photocatalytic material can photocatalytically degradating organic dye well, such as urged in light
Its degradation amount is up to more than 70% when changing degradation of methylene blue.
Brief description of the drawings
Fig. 1 is mesoporous TiO 2 (comparative example 1), the XRD spectra of lignin-base mesoporous TiO 2 (embodiment 1)；
Fig. 2 (a) is mesoporous TiO 2 (comparative example 1), the N of lignin-base mesoporous TiO 2 (embodiment 1)2Absorption-
Desorption figure；
Fig. 2 (b) is mesoporous TiO 2 (comparative example 1), the N of lignin-base mesoporous TiO 2 (embodiment 1)2Aperture point
Butut；
The visible light photocatalysis of Fig. 3 mesoporous TiO 2s (comparative example 1), lignin-base mesoporous TiO 2 (embodiment 1)
The curve map of degradation of methylene blue, is referenced as the degradation curve figure of commercial Degussa P25 photochemical catalysts.
Specific embodiment
Embodiment 1
The preparation of lignin-base mesoporous titanium dioxide photocatalytic material
(1) 1g alkali lignin crude product particles are taken to be dissolved in the 10wt%NaOH solution of 20mL, 4h are stirred at room temperature, filtered,
Insoluble matter is removed, lignin liquor is obtained；
(2) concentration is added dropwise under the conditions of being sufficiently stirred for, in the lignin liquor obtained toward (1) for the hydrochloric acid of 0.1mol/L is molten
Liquid, controls pH=4, stirs 1h.Filtering, the precipitation solid that will be obtained is washed with deionized water 3-4 times, the lower 85 DEG C of dryings of vacuum condition
At one night, lignin solid must be purified；
(3) the lignin solid for obtaining (2) is made into the lignin liquor of concentration 5g/L, and 25 DEG C of conditions are incubated in water-bath
Under, 1g titanium tetrachlorides are added to wiring solution-forming in 100mL water, then be slowly dropped in the lignin liquor of 100mL, then drop
Plus concentration is the hydrochloric acid solution of 0.1mol/L, strong agitation controls pH=5.30min will be stirred at 25 DEG C of this mixture, then
30min is stirred at being heated to 80 DEG C.Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 30min, centrifugation is obtained without fixed
Shape sediment；
(4) sediment for obtaining (3) is filtered, at room temperature aging 10h, and the jello for obtaining is washed with deionized number
It is secondary, to remove Cl-, then with absolute ethanol washing twice, filtering.The solid product for obtaining 85 DEG C of dryings one under vacuum
Night, ball milling calcines 2h at 500 DEG C, obtains final product lignin-base photocatalysis solid particle.
The XRD diffracting spectrums of lignin-base photochemical catalyst are as shown in figure 1, the prepared lignin-base meso-porous titanium dioxide of explanation
Titanium has two kinds of crystalline phases of anatase and rutile, and the proportion (A%) of wherein anatase phase can be calculated by following formula：
A (%)=100/ (1+1.265Ir/Ia), Ir and Ia are respectively the diffraction maximum of 2 θ=27.4 ° of Rutile Type in formula
With the diffraction maximum of 2 θ=25.3 ° of Anatase.The skeleton of above-mentioned twin crystal mesoporous TiO 2 is calculated by the result in Fig. 1
In contain 94% Anatase, 6% Rutile Type.The isothermal nitrogen adsorption desorption curve of lignin-base mesoporous TiO 2 is as schemed
Shown in 2 (a), its BET specific surface area is 165.8m2/ g, average pore size is 5.2nm.
It is sub- using the lignin-base twin crystal mesopore titania photocatalyst visible light photocatalytic degradation prepared by the present embodiment 1
Methyl blue, obtains the degradation curve figure shown in Fig. 3, and can be seen as reference with the degradation curve figure of commodity Degussa P25
Go out within the time period of 200min, methylene blue degradation amount is 73%, during with commercial Degussa P25 as photochemical catalyst only
Degrade about 10%.Contrast and experiment can be seen that lignin-base mesoporous titanium dioxide photocatalytic material manufactured in the present embodiment
Material has superior visible light catalytic performance.
Embodiment 2
Lignin solid being prepared with embodiment 1, and being made into the lignin liquor of concentration 1g/L, 25 DEG C are incubated in water-bath
Under the conditions of, 0.5g titanium tetrachlorides are added to wiring solution-forming in 100mL water, then be slowly dropped in the lignin liquor of 100mL,
It is the hydrochloric acid solution of 0.1mol/L that concentration is then added dropwise, and strong agitation controls pH=5.To be stirred at 25 DEG C of this mixture
30min, 30min is stirred at being subsequently heated to 80 DEG C.Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 30min, centrifugation point
From obtaining amorphous sediment thing；Sediment is filtered, at room temperature aging 6h, the jello for obtaining is washed with deionized three times, with
Cl- is removed, then, filtering. with absolute ethanol washing twice.The solid product for obtaining 80 DEG C of dried overnight, balls under vacuum
Mill, 2h is calcined at 500 DEG C, obtains final product lignin-base photocatalysis solid particle.
It is sub- using the lignin-base twin crystal mesopore titania photocatalyst visible light photocatalytic degradation prepared by the present embodiment 2
Methyl blue, the time period methylene indigo plant degradation amount of 200min is 65%, during with commercial Degussa P25 as photochemical catalyst
Methylene blue degradation rate about 10%.
Embodiment 3
Lignin solid being prepared with embodiment 1, and being made into the lignin liquor of concentration 8g/L, 25 DEG C are incubated in water-bath
Under the conditions of, 2g titanium tetrachlorides are added to wiring solution-forming in 100mL water, then be slowly dropped in the lignin liquor of 100mL, with
It is the hydrochloric acid solution of 0.1mol/L that concentration is added dropwise afterwards, and strong agitation controls pH=5.30min will be stirred at 25 DEG C of this mixture,
1h is stirred at being subsequently heated to 80 DEG C.Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 1h, centrifugation obtains amorphous
Sediment；Sediment is filtered, at room temperature aging 12h, the jello for obtaining is washed with deionized three times, to remove Cl-, then
With absolute ethanol washing twice, filter.The solid product for obtaining 90 DEG C of dried overnight, ball millings under vacuum, then at 550 DEG C
Lower calcining 2h, obtains final product lignin-base photocatalysis solid particle.
It is sub- using the lignin-base twin crystal mesopore titania photocatalyst visible light photocatalytic degradation prepared by the present embodiment 2
Methyl blue, the time period methylene indigo plant degradation amount of 200min is 70%, during with commercial Degussa P25 as photochemical catalyst
Methylene blue degradation rate about 10%.
Embodiment 4
Lignin solid being prepared with embodiment 1, and being made into the lignin liquor of concentration 1g/L, 25 DEG C are incubated in water-bath
Under the conditions of, 1g titanium tetrachlorides are added to wiring solution-forming in 100mL water, then be slowly dropped in the lignin liquor of 100mL, with
It is the hydrochloric acid solution of 0.1mol/L that concentration is added dropwise afterwards, and strong agitation controls pH=5.15min will be stirred at 25 DEG C of this mixture,
90min is stirred at being subsequently heated to 60 DEG C.Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 30min, centrifugation is obtained
Amorphous sediment thing；Sediment is filtered, at room temperature aging 10h, the jello for obtaining is washed with deionized three times, to remove
Cl-, then, filtering. with absolute ethanol washing twice.The solid product for obtaining 85 DEG C of dried overnight, ball millings under vacuum, then
In 2h is calcined at 500 DEG C, lignin-base photocatalysis solid particle is obtained final product.
It is sub- using the lignin-base twin crystal mesopore titania photocatalyst visible light photocatalytic degradation prepared by the present embodiment 2
Methyl blue, the time period methylene indigo plant degradation amount of 200min is 62%, during with commercial Degussa P25 as photochemical catalyst
Methylene blue degradation rate about 10%.
Embodiment 5
Lignin solid being prepared with embodiment 1, and being made into the lignin liquor of concentration 10g/L, 25 are incubated in water-bath
Under the conditions of DEG C, 1g titanium tetrachlorides are added to wiring solution-forming in 100mL water, then are slowly dropped in the lignin liquor of 100mL,
It is the hydrochloric acid solution of 0.1mol/L that concentration is then added dropwise, and strong agitation controls pH=5.To be stirred at 25 DEG C of this mixture
30min, 1h is stirred at being subsequently heated to 90 DEG C.Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 1h, centrifugation is obtained
Amorphous sediment thing；Sediment is filtered, at room temperature aging 12h, the jello for obtaining is washed with deionized three times, to remove
Cl-, then, filtering. with absolute ethanol washing twice.The solid product for obtaining 90 DEG C of dried overnight, ball millings under vacuum, then
In 2h is calcined at 550 DEG C, lignin-base photocatalysis solid particle is obtained final product.
It is sub- using the lignin-base twin crystal mesopore titania photocatalyst visible light photocatalytic degradation prepared by the present embodiment 2
Methyl blue, the time period methylene indigo plant degradation amount of 200min is 66%, during with commercial Degussa P25 as photochemical catalyst
Methylene blue degradation rate about 10%.
Comparative example 1
The preparation of common mesoporous TiO 2
(1) take 1g titanium tetrachlorides to be dissolved in 100mL water, strong agitation 1h, it is the hydrochloric acid of 0.1mol/L that concentration is then added dropwise
Solution, strong agitation controls pH=5.30min will be stirred at 25 DEG C of this mixture, 30min is stirred at being subsequently heated to 80 DEG C.
Ammoniacal liquor is added, the pH=7 of solution is adjusted.After being stirred for 30min, centrifugation obtains amorphous sediment thing；
(2) sediment for obtaining (1) is filtered, at room temperature aging 10h, and the jello for obtaining is washed with deionized three
It is secondary, to remove Cl-, then with absolute ethanol washing twice, filtering.The solid product for obtaining 80 DEG C of dryings one under vacuum
Night, ball milling calcines 2h at 500 DEG C, obtains final product mesoporous titanium dioxide photocatalytic solid particle.
The XRD diffracting spectrums of the mesopore titania photocatalyst are as shown in figure 1, the prepared mesoporous dioxy of twin crystal of explanation
Changing titanium has two kinds of crystalline phases of anatase and rutile, wherein containing 15% Anatase, 85% Rutile Type.Mesoporous TiO 2
Isothermal nitrogen adsorption desorption curve as shown in Fig. 2 (a), its BET specific surface area be 43.8m2/ g, average pore size is
15.6nm.Using the twin crystal mesopore titania photocatalyst visible light photocatalytic degradation methylene blue prepared by this comparative example 1, obtain
Degradation curve figure shown in Fig. 3, and with the degradation curve figure of commodity Degussa P25 as reference, it can be seen that
In the time period of 200min, methylene blue degradation amount is about 55%, and during with commerciality Degussa P25 as photochemical catalyst
Only degrade about 10%.Two experimental results of contrast can be seen that the twin crystal mesoporous titanium dioxide photocatalytic of the preparation of this comparative example 1
Agent has preferably visible light catalytic performance.
Claims (10)
1. a kind of lignin-base mesoporous titanium dioxide photocatalytic material, it is characterised in that be situated between obtained in lignin as template
Porous titanium dioxide particle, wherein described titanium dioxide contains two kinds of crystalline phases of Anatase and Rutile Type.
2. lignin-base mesoporous titanium dioxide photocatalytic material according to claim 1, it is characterised in that described is mesoporous
Titanium dioxide granule particle diameter is 5-20nm, and specific surface area is 120-180m2/g。
3. lignin-base mesoporous titanium dioxide photocatalytic material according to claim 2, it is characterised in that the mesoporous dioxy
It is, with lignin as template, with titanium tetrachloride as titanium source, to be prepared with direct hydrolysis method to change titanium catalysis material.
4. the preparation method of a kind of lignin-base mesoporous titanium dioxide photocatalytic material as described in claim 1-3 is any, its
It is characterised by comprising the following steps：
(1) 1-10g alkali lignin crude product particles are taken to be dissolved in the 5-20wt%NaOH solution of 10-200mL, 3- is stirred at room temperature
12h, filtering removes insoluble matter, obtains lignin liquor；
(2) under the conditions of being sufficiently stirred for, it is the hydrochloric acid solution of 0.1-1.0mol/L that concentration is added dropwise in the lignin liquor for obtaining,
Control pH=1-5, stirs 0.5-4h；Filtering, the precipitation solid washing that will be obtained, then 80-100 DEG C of drying under vacuum condition, obtain
To purifying lignin solid；
(3) will obtain purifying the lignin aqueous solution that lignin solid is made into concentration 1-10g/L, 20-40 DEG C of bar is incubated in water-bath
Under part, by titanium tetrachloride aqueous solution, then it is slowly dropped in the lignin liquor of 10-1000mL, it is 0.1- that concentration is then added dropwise
The hydrochloric acid solution of 1.0mol/L, controls pH=1-5, and quick stirring obtains mixture；10- will be stirred at 20-40 DEG C of this mixture
100min, 10-100min is stirred at being subsequently heated to 60-100 DEG C；Ammoniacal liquor is added, pH=7-8 is adjusted；It is stirred for 10-100min
Afterwards, centrifugation, obtains amorphous sediment thing；
(4) the amorphous sediment thing filtering that will be obtained, aging 6-24h, obtains jello, then 3- is washed with deionized at room temperature
4 times, remove Cl-, then with absolute ethanol washing 1-2 times, the solid product obtained after filtering is done for 80-100 DEG C under vacuum
It is dry, through ball milling after, calcine 1-5h at 400-600 DEG C, the solid particle for obtaining as lignin-base mesoporous TiO 2 light
Catalysis material.
5. preparation method according to claim 4, it is characterised in that the washing described in step (2) is that 3- is washed with deionized water
4 times, under vacuum condition 80-100 DEG C of drying time be 8 hours and more than.
6. preparation method according to claim 4, it is characterised in that the titanium tetrachloride aqueous solution described in step (3) be by
0.1-10g titanium tetrachlorides are made into being added to 10-1000mL water.
7. preparation method according to claim 4, it is characterised in that the solid product described in step (4) is under vacuum
80-100 DEG C of drying time be 8 hours and more than.
8. a kind of lignin-base mesoporous titanium dioxide photocatalytic material as described in claim 1-3 is any is in light-catalyzed reaction
Application.
9. application according to claim 8, it is characterised in that be the application in photocatalytically degradating organic dye.
10. application according to claim 9, it is characterised in that described organic dyestuff is methylene blue, rhodamine B or first
Base orange.
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