CN101444724A - Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst - Google Patents
Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst Download PDFInfo
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- CN101444724A CN101444724A CNA2008101543781A CN200810154378A CN101444724A CN 101444724 A CN101444724 A CN 101444724A CN A2008101543781 A CNA2008101543781 A CN A2008101543781A CN 200810154378 A CN200810154378 A CN 200810154378A CN 101444724 A CN101444724 A CN 101444724A
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Abstract
In order to degrade the pollutants in water and atmosphere by the photocatalysis technology, the invention discloses a method for preparing a high activity non-metallic ion co-doped titanium dioxide photochemical catalyst. In the photochemical catalyst, titanium ester or titanate is used as a precursor, non-metallic compound comprising boron, carbon, nitrogen, fluorin, silicon, phosphor, sulfur, chlorine, bromine, iodine, and the like, are used as doping agents, the high activity non-metallic ion co-doped titanium dioxide photochemical catalyst is prepared by adopting the sol gel method. Compared with a titanium dioxide photochemical catalyst single-doped with pure titanium dioxide and the non-metallic irons, the visible light catalytic activity of the titanium dioxide photochemical catalyst on the degradation of parachlorophenol is greatly improved, and the ultraviolet light catalytic activity can also exceed the catalytic activity of the pure titanium dioxide catalyst. The method also has the advantages that the preparation technique is simple, the equipment requirement is low; the particle diameter of the product is small, the specific surface is relatively high, the dispersivity is good, thus having a wide application prospect in the environmental cleaning scientific field.
Description
[technical field]
The invention belongs to the photocatalysis technology field, be mainly used in the depollution of environment, provide a kind of preparation to have the method for the highly active titanium dioxide optical catalyst of two kinds of nonmetalloid codopes for utilizing the pollutant in photocatalysis technology degradation water and the atmosphere.
[background technology]
World today's energy crisis and ecological deterioration force people to seek the more new method of cleaning, reproducible new forms of energy and improvement environment.Titanium dioxide has characteristics such as good stability, photoelectric transformation efficiency and photocatalytic activity height, not only can and remove transition metal ions as photochemical catalyst non-selectivity ground degradable organic pollutant, and be the light-guide material of surface sensitizing solar cell, have widely application prospect in the research field of environmental improvement and clean energy resource.
But, pure TiO
2The energy gap of (Detitanium-ore-type) is 3.2eV (387.5nm), can only absorb ultraviolet light part in the sunshine (only account for sunshine 4%), and spectral response range is narrow, and is low to the effective rate of utilization of solar energy.In recent years, people are for improving TiO
2Visible light-responded and photocatalytic activity has been made many effort, and wherein one of topmost approach is exactly TiO
2Metal or nonmetallic ion-doped.Calendar year 2001, people such as Asahi " science " magazine (Science, 2001, reported the TiO of nitrogen ion doping on 293:269-217)
2Visible light catalyst has higher ultraviolet-visible photocatalytic activity, and this result of study proves that nonmetallic ion-doped (as N, C, S, B and F etc.) can increase TiO
2The absorption of catalyst visible light improves TiO effectively
2The ultraviolet-visible photocatalysis efficiency of catalyst, thus showing great attention to of people caused at home and abroad.The existing report of relevant patent, as: visible light-responded photochemical catalyst and its production and application (application number: 03158740.2) had; Process for preparing highly efficient titania photocatalyst (application number: 200410081226.5); A kind of preparation method of nitrogen-doped anatase-type nanometer titanium dioxide (application number: 200510011665.3); A kind of method (application number: 200610134927.X) for preparing the Doped Mesoporous nano titanium oxide photocatalyst; Kation S and anion N codope one-dimensional nano structure TiO
2Photochemical catalyst and preparation method thereof (application number: 200710071317.4); A kind of load type nitrogen intermingle with one-dimensional structure TiO
2And preparation method thereof (application number: 200810059650.8).
Metal or nonmetallic ion-doped TiO
2Catalyst forms doped energy-band in energy gap, expanded TiO to a certain extent
2The photoresponse scope, cause the visible light catalytic ability to strengthen, but the ultraviolet-visible photocatalysis efficiency is still not high, does not reach requirement of actual application, and preparation method's program complexity, not easy to operate, cost or equipment require high.
The present invention is intended to solve key difficult problems such as the low and visible light catalytic efficient of the solar energy utilization ratio of titanium dioxide optical catalyst is low, develops " high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) photochemical catalyst ", and set up preparation " high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) photochemical catalyst " and new method, and the preparation method is simple, easy to operate, cost and equipment require low.The present invention will lay the foundation for high efficiency, high-performance and the practical application in the environmental improvement field that realizes titanium deoxide catalyst.
[summary of the invention]
The present invention is a presoma with titanate esters or titanate, is adulterant with the nonmetallic compound, uses the Prepared by Sol Gel Method high activity non-metallic ion co-doped titanium dioxide photochemical catalyst.The invention has the advantages that: (1) technology is simple, low for equipment requirements, easy to operate; (2) product cut size is less, and specific area is bigger, good dispersion; (3) the high activity non-metallic ion co-doped titanium dioxide (TiO for preparing
2-x-yA
xM
y) photochemical catalyst has characteristics such as two-phase codope, microcosmic surface multi-factor structure, and with pure TiO
2Singly mix nonmetallic ion TiO
2Compare, visible light-responded acquisition greatly strengthens, and has improved ultraviolet-visible light catalysis activity effectively (than pure TiO
2Visible light catalysis activity improved 7.6 times, than the TiO that singly mixes the N ion
2Visible light catalyst is high 1.9 times; And the ultraviolet catalytic activity has also surpassed pure TiO
2Catalyst).
Innovative point of the present invention: (1) is non-metallic ion co-doped by two kinds, makes TiO
2Produce the two-phase doped energy-band in the catalyst based energy gap respectively, with pure TiO
2Singly mix the TiO of nonmetallic ion
2Compare, the generation of two-phase doped energy-band has caused the remarkable enhancing of catalyst visible absorption, thereby has improved TiO
2Visible light catalysis activity.(2) because the synergy of two kinds of nonmetalloids and the existence of two-phase doped energy-band have strengthened the photo-generated carrier separation, suppress that it is compound, improved the probability that photo-generated carrier is participated in light-catalyzed reaction, the contaminant molecule of effectively having degraded.So this catalyst has very high ultraviolet-visible photocatalytic activity.
[description of drawings]
The X ray diffracting spectrum of Fig. 1 embodiment 3,6 is (with pure TiO
2, singly mix the TiO of N
2Singly mix the TiO of B
2Relatively);
The visible light photocatalytic degradation parachlorophenol curve of Fig. 2 embodiment 3,6 is (with no photochemical catalyst TiO
2, pure TiO
2, singly mix the TiO of N
2Singly mix the TiO of B
2Relatively);
The ultraviolet catalytic degraded parachlorophenol curve of Fig. 3 embodiment 3,6 is (with no photochemical catalyst TiO
2, pure TiO
2, singly mix the TiO of N
2Singly mix the TiO of B
2Relatively);
Below in conjunction with specific embodiments and the drawings the present invention is described further, and specifies photocatalysis effect of the present invention.
[specific embodiment]
Concrete preparation method of the present invention is as follows:
1. high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) preparation of photochemical catalyst
1. at normal temperatures, a certain amount of compound that contains nonmetalloid A is added diluent, fully stir and it was dissolved fully in 15 minutes; 2. add acidulant; 3. titanate esters or titanate are added diluent, evenly stirred 15 minutes; 4. add a certain amount of compound that contains nonmetalloid M, at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain nano-TiO
2Gel or sediment; 5. with this gel or sediment through 70 ℃ of-120 ℃ of oven dry, grind into powder, 400 ℃-500 ℃ calcinings are 2.0-4.0 hour in air atmosphere, promptly make high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) photochemical catalyst.
2, for carrying out the activity contrast, in implementation process, prepared pure titinium dioxide (TiO respectively
2-pure), the titanium dioxide (TiO of single nitrating
2-N) and the titanium dioxide (TiO of single boron-doping
2-B) three comparative sample:
(1) TiO
2-pure Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just do not add any nonmetallic compound, and, after system adds acidic catalyst, drip quantitative high purity water (18.2M Ω cm again the 2. in the step
-1).
(2) TiO
2-N Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just the 1. the step do not add nonmetallic compound, and 3. add a certain amount of nitrogen-containing compound in the step the.
(3) TiO
2-B Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just the 1. the step add a certain amount of boron-containing compound, and 3. do not add nonmetallic compound in the step the.
3, in the above preparation process, the addition of various reactants is:
The mol ratio of nonmetallic compound and titanate esters or titanate is 1: 20-10: 1;
The volume ratio of diluent and titanate esters or titanate is 2: 1-10: 1;
The volume ratio of acidulant and titanate esters is 1: 30-1: 4.
Described titanate esters or titanate can be any or several mixing in butyl titanate, titanium propanolate, isopropyl titanate, tetraethyl titanate, tetraethyl titanate, isopropyl titanate, titanium sulfate, titanium trichloride, titanium tetrachloride, Titanium Nitrate or the metatitanic acid; Preferred butyl titanate.
Described diluent can be the monobasic or the dihydroxylic alcohols of carbon number no more than 4, as any or several mixing in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, four butanols; Also can be any or several mixing of organic solvents such as propyl ester, ethyl acetate, butyl acetate; Preferred absolute ethyl alcohol.
Described acidulant can be any or several mixing in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glacial acetic acid, the perchloric acid; Preferred hydrochloric acid (analyzing pure).
Described nonmetalloid can be boron, carbon, nitrogen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, iodine etc.
Described nonmetallic compound can be one or more mixing in the nonmetallic compound that dissolves in above-mentioned diluent that contains arbitrary element among element B, C, N, F, Si, P, S, Cl, Br, the I.
Described boron-containing compound can be any or several mixing in boric acid, triethyl borate, trimethylborate, fluoboric acid, the boron trifluoride-acetate complex compound.
Described carbon compound can be any or several mixing in glucose, urea, the TBAH.
Described nitrogen-containing compound can be any or several mixing in ammoniacal liquor, methylamine, aniline, urea, thiocarbamide, ethylenediamine, ammonium chloride, ammonium fluoride, ammonium carbonate, carbonic hydroammonium, diisopropylamine, triethanolamine or the hexamethylenetetramine.
Described fluorochemical can be any or several mixing in sodium fluoride, ammonium fluoride, fluoboric acid, the boron trifluoride-acetate complex compound.
Described silicon-containing compound can be any or several mixing in ethyl orthosilicate or the sodium metasilicate.
Described phosphorus-containing compound can be any or several mixing in sodium phosphate, the phosphoric acid.
Described sulfur-containing compound can be any or several mixing in thiocarbamide, carbon disulfide, vulcanized sodium, the sulfuric acid.
Described chlorine-containing compound can be any or several mixing in carbon tetrachloride, hydrochloric acid, chloric acid, perchloric acid, lithium chloride or the potassium chloride.
Described bromine-containing compound can be any or several mixing in bromine simple substance, hydrobromic acid, bromic acid, hyperbromic acid, lithium bromide or the KBr.
The described iodine compound that contains can be any or several mixing in elemental iodine, hydroiodic acid, acid iodide, periodic acid, lithium iodide or the KI.
The evaluation method of photocatalytic activity: as outer irradiation source, radiation wavelength is λ with the Philips HPA 400/30S lamp of 400W〉320nm, use the optical filter of 400nm to filter ultraviolet light in the visible light experiment; Catalyst amount is 10mg; Reactor is apart from light source 13cm; 40ml concentration is 50 * 10
-6The parachlorophenol solution of mol/L is as the target degradation product; Logical O in the parachlorophenol solution
2Amount is 6ml/min; Solution concentration and temperature balance in the magnetic agitation maintenance system, the air-cooled maintenance reaction temperature of fan is in [(25 ± 2) ℃]; Get the centrifugation of 1.5ml reactant liquor at regular intervals, get supernatant liquor, replace the pyrrole quinoline as developer, with ultraviolet-visible spectrophotometer (UV-16PC with 4-amino ammonia, Tianjin, island company) measures the parachlorophenol solution concentration, demarcate the photocatalytic activity of catalyst.
For a better understanding of the present invention, the present invention is described in further detail, but the scope of protection of present invention is not limited to the represented scope of embodiment below in conjunction with embodiment.
Embodiment 1
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, measure 2ml ethyl orthosilicate (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Adding 3ml concentration is 25% ammoniacal liquor (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtains sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid silicon and nitrogen co-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 1.39g bromine simple substance (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 3.05g thiocarbamide (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level pair of nonmetalloid bromine and sulphur codope at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 240mg boric acid (6.11 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Adding 3ml concentration is 25% ammoniacal liquor (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtains sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid boron and nitrogen co-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 3.29g sodium phosphate dodecahydrate (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 1.68g sodium fluoride (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid phosphorus and fluorin-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, measure 2ml ethyl orthosilicate (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 6.16g carbon tetrachloride (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, obtained sediment in still aging 1-5 days; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid silicon and chlorine co-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
Embodiment 6
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 380mg boric acid (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Adding 3ml concentration is 25% ammoniacal liquor (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtains sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid boron and nitrogen co-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
Embodiment 7
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 2.20g elemental iodine (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 3.05g thiocarbamide (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level pair of nonmetalloid iodine and sulphur codope at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 3.29g sodium phosphate dodecahydrate (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Adding 3ml concentration is 25% ammoniacal liquor (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtains sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pair of nonmetalloid phosphorus and nitrogen co-doped TiO at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 1.56g glucose (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 5.16g bromic acid (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level pair of nonmetalloid carbon and bromine codope at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
At normal temperatures, measure the 40ml absolute ethyl alcohol and place on the magnetic stirring apparatus, take by weighing 380mg boric acid (8.65 * 10
-3Mol) add absolute ethyl alcohol, fully stir and it was dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure); Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), evenly stir 15 minutes; Add 7.04g acid iodide (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level pair of nonmetalloid boron and iodine codope at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
Comparative Examples 1
At normal temperatures, measuring the 40ml absolute ethyl alcohol places on the magnetic stirring apparatus; Add 1ml hydrochloric acid (analyzing pure) and 1ml ultra-pure water and fully stirring successively; Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain gel; This gel is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain nano level pure TiO2 photochemical catalyst at 450 ℃ of air atmospheres of Muffle furnace.
Comparative Examples 2
At normal temperatures, measuring the 40ml absolute ethyl alcohol places on the magnetic stirring apparatus; Add 1ml hydrochloric acid (analyzing pure) and fully stirring; Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), full and uniform vigorous stirring is 15 minutes; Adding 3ml concentration is 25% ammoniacal liquor (0.04mol), at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtains sediment; This sediment is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level single nitrating element at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
Comparative Examples 3
At normal temperatures, measure the 40ml absolute ethyl alcohol, take by weighing 240mg boric acid (6.11 * 10
-3Mol) add absolute ethyl alcohol, place fully to stir on the magnetic stirring apparatus it to be dissolved fully in 15 minutes; Add 1ml hydrochloric acid (analyzing pure) and 1ml ultra-pure water and fully stirring successively; Slowly splash into 12ml concentration and be 98% butyl titanate (3.46 * 10
-2Mol), full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain gel; This gel is placed in the baking oven 100 ℃ of bakings 10 hours with evaporating solvent, use the agate mortar grind into powder, put into crucible and calcined 2.5 hours, promptly obtain the TiO of nano level single boron-doping element at 450 ℃ of air atmospheres of Muffle furnace
2Photochemical catalyst.
1-3, specific embodiment 3 and 6, Comparative Examples 1-3 explanation in conjunction with the accompanying drawings:
TiO at nonmetalloid B that makes by embodiment 3 and N codope
2In the photochemical catalyst, TiO
2Be the anatase phase, average grain diameter is 9.9nm.TiO wherein
2Be respectively 100: 17.65 and 86: 100 with the mol ratio of B element and N element.The specific area of this catalyst reaches 97.84m
2/ g, and pure TiO
2Specific area be 63.76m
2/ g singly mixes the TiO of N
2Specific area be 77.84m
2/ g singly mixes the TiO of B
2Specific area be 82.25m
2/ g.This shows the TiO of two nonmetalloid B and N codope
2Photochemical catalyst is than other three kinds of TiO
2Photochemical catalyst, its specific area is bigger.This has just increased the contact area of catalyst and reaction molecular, can adsorb more contaminant molecule, thereby more helps improving TiO
2The activity of photochemical catalyst.With above-mentioned photocatalytic activity evaluation method, under radiation of visible light, the degradation rate of parachlorophenol is 78.18% after 8 hours; Under ultraviolet excitation, the degradation rate of parachlorophenol is 90% after 1 hour.And on year-on-year basis under the condition, pure TiO
2Degradation rate be respectively 9.09% and 73.68%; Singly mix the TiO of N
2Degradation rate be respectively 26.92% and 95.16%; Singly mix the TiO of B
2Degradation rate be respectively 31.03% and 84.38%.This shows the TiO of two nonmetalloid B and N codope
2Photochemical catalyst and pure TiO
2, singly mix the TiO of B ion
2Singly mix the TiO of N ion
2Compare, its visible light-responded acquisition greatly strengthens, and has improved TiO effectively
2Ultraviolet-the visible light catalysis activity of photochemical catalyst is (than pure TiO
2Visible light catalysis activity improved 7.6 times, than the TiO that singly mixes the N ion
2Visible light catalyst is high 1.9 times, than the TiO that singly mixes the B ion
2Visible light catalyst is high 1.5 times; And its ultraviolet catalytic activity has also surpassed pure TiO
2Catalyst).
TiO at nonmetalloid B that makes by embodiment 6 and N codope
2In the photochemical catalyst, TiO
2Be anatase phase, TiO
2Be respectively 100: 25 and 86: 100 with the mol ratio of B element and N element.The specific area of this catalyst reaches 98.83m
2/ g.With above-mentioned photocatalytic activity evaluation method, under radiation of visible light, the degradation rate of parachlorophenol is 69.64% after 8 hours; Under ultraviolet excitation, degradation rate is 80.33% after 1 hour.
At the pure TiO that makes by Comparative Examples 1
2In the photochemical catalyst, TiO
2Be the anatase phase, its specific area is 63.76m
2/ g.With above-mentioned photocatalytic activity evaluation method, under radiation of visible light, the degradation rate of parachlorophenol is 9.09% after 8 hours; Under ultraviolet excitation, degradation rate is 73.68% after 1 hour.
At the TiO that singly mixes the N element that makes by Comparative Examples 2
2In the photochemical catalyst, TiO
2Be anatase phase, TiO
2With the mol ratio of N element be 86: 100, its specific area is 77.84m
2/ g.With above-mentioned photocatalytic activity evaluation method, under radiation of visible light, the degradation rate of parachlorophenol is 26.92% after 8 hours; Under ultraviolet excitation, degradation rate is 95.16% after 1 hour.
At the TiO that singly mixes the B element that makes by Comparative Examples 3
2In the photochemical catalyst, TiO
2Be anatase phase, TiO
2With the mol ratio of B element be 100: 17.65, its specific area is 82.25m
2/ g.With above-mentioned photocatalytic activity evaluation method, under radiation of visible light, the degradation rate of parachlorophenol is 31.03% after 8 hours; Under ultraviolet excitation, degradation rate is 83.05% after 1 hour.
Claims (7)
1, a kind of preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst.This catalyst is a presoma with titanate esters or titanate, is adulterant with the nonmetallic compound, uses the Prepared by Sol Gel Method high activity non-metallic ion co-doped titanium dioxide photochemical catalyst.
2, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 is as follows:
A). high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) preparation of photochemical catalyst
1. at normal temperatures, a certain amount of compound that contains nonmetalloid A is added diluent, fully stir and it was dissolved fully in 15 minutes; 2. add acidulant; 3. titanate esters or titanate are added diluent, evenly stirred 15 minutes; 4. add a certain amount of compound that contains nonmetalloid M, at room temperature full and uniform vigorous stirring 6-12 hour, still aging 1-5 days, obtain nano-TiO
2Gel or sediment; 5. with this gel or sediment through 70 ℃ of-120 ℃ of oven dry, grind into powder, 400 ℃-500 ℃ calcinings are 2.0-4.0 hour in air atmosphere, promptly make high activity non-metallic ion co-doped titanium dioxide (TiO
2-x-yA
xM
y) photochemical catalyst.
B). for carrying out the activity contrast, in implementation process, prepared pure titinium dioxide (TiO respectively
2-pure), the titanium dioxide (TiO of single nitrating
2-N) and the titanium dioxide (TiO of single boron-doping
2-B) three comparative sample:
(1) TiO
2-pure Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just do not add any nonmetallic compound, and, after system adds acidulant, drip quantitative high purity water (18.2M Ω cm again the 2. in the step
-1).
(2) TiO
2-N Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just the 1. the step do not add nonmetallic compound, and 3. add a certain amount of nitrogen-containing compound in the step the.
(3) TiO
2-B Preparation of catalysts
Preparation process and TiO
2-x-yA
xM
ySimilar, just the 1. the step add a certain amount of boron-containing compound, and 3. do not add nonmetallic compound in the step the.
C). in the preparation process, the addition of various reactants is:
The mol ratio of nonmetallic compound and titanate esters or titanate is 1: 20-10: 1;
The volume ratio of diluent and titanate esters or titanate is 2: 1-10: 1;
The volume ratio of acidulant and titanate esters is 1: 30-1: 4.
3, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 and 2 is characterized in that described titanate esters or titanate are selected from following a kind of or several mixing and add: any or several mixing in butyl titanate, titanium propanolate, isopropyl titanate, tetraethyl titanate, tetraethyl titanate, isopropyl titanate, titanium sulfate, titanium trichloride, titanium tetrachloride, Titanium Nitrate or the metatitanic acid; Preferred butyl titanate.
4, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 and 2 is characterized in that described nonmetalloid can be boron, carbon, nitrogen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, iodine etc.
5, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 and 2 is characterized in that described nonmetallic compound can be for containing any or several element such as B, C, N, F, Si, P, S, Cl, Br, I.
Described boron-containing compound can be any or several mixing in boric acid, triethyl borate, trimethylborate, fluoboric acid, the boron trifluoride-acetate complex compound.
Described carbon compound can be any or several mixing in glucose, urea, the TBAH.
Described nitrogen-containing compound can be any or several mixing in ammoniacal liquor, methylamine, aniline, urea, thiocarbamide, ethylenediamine, ammonium chloride, ammonium fluoride, ammonium carbonate, carbonic hydroammonium, diisopropylamine, triethanolamine or the hexamethylenetetramine.
Described fluorochemical can be any or several mixing in sodium fluoride, ammonium fluoride, fluoboric acid, the boron trifluoride-acetate complex compound.
Described silicon-containing compound can be any or several mixing in ethyl orthosilicate or the sodium metasilicate.
Described phosphorus-containing compound can be any or several mixing in sodium phosphate, the phosphoric acid.
Described sulfur-containing compound can be any or several mixing in thiocarbamide, carbon disulfide, vulcanized sodium, the sulfuric acid.
Described chlorine-containing compound can be any or several mixing in carbon tetrachloride, hydrochloric acid, chloric acid, perchloric acid, lithium chloride or the potassium chloride.
Described bromine-containing compound can be any or several mixing in bromine simple substance, hydrobromic acid, bromic acid, hyperbromic acid, lithium bromide or the KBr.
The described iodine compound that contains can be any or several mixing in elemental iodine, hydroiodic acid, acid iodide, periodic acid, lithium iodide or the KI.
6, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 and 2, it is characterized in that described diluent can be the monobasic or the dihydroxylic alcohols of carbon number no more than 4, as any or several mixing in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, four butanols; Also can be any or several mixing of organic solvents such as propyl ester, ethyl acetate, butyl acetate.
7, the preparation method of high activity non-metallic ion co-doped titanium dioxide photochemical catalyst according to claim 1 and 2 is characterized in that described acidulant can be any or several mixing in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, glacial acetic acid, the perchloric acid.
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