CN102500363A - Noble metal orientation load titanium dioxide photocatalyst and preparation method thereof - Google Patents
Noble metal orientation load titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a noble metal orientation load titanium dioxide photocatalyst and a preparation method thereof. A titanium dioxide carrier has a rutile phase structure and a uniform spherical appearance, wherein the microsphere diameter is about 10 to 16 mu m; the surface is cracked; the titanium dioxide carrier is formed by self-assembling nanowires with the length of 5 to 8 mu m and diameter of 3 to 6 mu m; and the exposed surface of each nanowire is a crystal face (110). The noble metal is one or more of platinum, gold, ruthenium, rhodium, silver and palladium; the load quantity of the noble metal is 0 to 3 percent of the mass of the titanium dioxide carrier; the noble metal exists in the form of a zero-valence simple substance; the grain size of the noble metal is 2 to 10 nm; and the noble metal is orientationally deposited on the crystal face (110) of the titanium dioxide nanowires. The noble metal load titanium dioxide material serving as an effective photocatalyst is applied to light degradation of organic pollutants in a waste water solution.
Description
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Technical field
The present invention relates to a kind of noble metal oriented load titanium dioxide optical catalyst and preparation method thereof in the conductor photocatalysis field.
Background technology
Under the background of and ecological deterioration in short supply at the global energy, people have to accelerate the paces of new energy development and environmental protection, so the development and utilization of solar energy has been received the concern energetically of countries in the world.Wherein, photocatalysis technology has and directly utilizes advantages such as solar energy, catalysis material are with low cost, environmental friendliness, non-secondary pollution, becomes the primary study object in the energy and the environmental protection field.Along with developing rapidly of photocatalysis technology, photocatalysis is forming an independently research field, and has given play to important function at the aspects such as the synthetic and depollution of environment of solar energy conversion and novel substance.The core of photocatalysis technology is a photochemical catalyst.In numerous semiconductor light-catalysts, titanium dioxide with its photocatalytic activity is high, oxidability is strong, chemical stability good, nontoxic, cost is low and extremely people's favor is present most popular photochemical catalyst.But the band structure of titanium dioxide self has determined it in photocatalysis technology is used, also to exist some defectives: (rutile is 3.0 eV to the greater band gap of (1) titanium dioxide; Anatase is 3.2 eV); Spectral response range is narrower, and light absorption wavelength mainly concentrates on ultra-violet (UV) band (< 387.5 nm), and the ultraviolet light part that is radiated ground only accounts for about 5 % of sunshine; So from utilizing the angle of solar energy, titanium dioxide utilizes the efficient of solar energy very low.(2) recombination rate of photo-generated carrier is higher, causes quantum efficiency lower, and the quantum efficiency of conventional titanium dioxide semiconductor photochemical catalyst has only about 4 %.(3) there is deactivation phenomenom in some volatile organic contaminant processes of optically catalytic TiO 2 oxidation, makes its commercial Application receive great restriction.Therefore, how to improve the quantum efficiency of titanium dioxide optical catalyst and expand the focus that its spectral response range to visible light is a current research.Existing document shows, deposits an amount of noble metal at titanium dioxide surface and not only can effectively catch trap for the right separation in light induced electron-hole provides, and suitable precious metal concentration can also strengthen degree of expansion and the absorption intensity of titanium dioxide at visible-range.But still there are very big problem in the structure and the carrying method of noble metal carried titanium dioxide material at present, have seriously restricted the improvement and the practical application thereof of photochemical catalyst performance.
Summary of the invention
The method that the purpose of this invention is to provide a kind of noble metal oriented load titanium dioxide optical catalyst makes the titanium dioxide optical catalyst of noble metal load have excellent ultraviolet and visible light catalytic performance.
Noble metal oriented load titanium dioxide optical catalyst of the present invention is to be formed on titania support by the noble metal orientated deposition.Titania support is the rutile phase structure; Have uniform spherical pattern, the surface is the cracking shape, and its microsphere diameter is about 10～16 μ m; Be to be that 5～8 μ m, diameter are that the nano wire self assembly of 3～6nm forms by length, the exposed crystal face of every nano wire is (110) face.Noble metal is one or more in platinum, gold, ruthenium, rhodium, silver, the palladium; The noble metal load capacity is 0～3% of a titania support quality; Noble metal exists with the zeroth order simple substance form, and granular size is 2～10nm, and orientated deposition is on (110) of titanium dioxide nano thread crystal face.
Titania support of the present invention prepares by following step:
(1) keeps under the uniform temperature condition titanium-containing compound dropwise being joined in the deionized water under vigorous stirring, be made into the solution that titanium ion concentration is 2.1～3.6M;
(2) solution that step (1) is obtained continues to stir 0.5～8 hour, slowly heat up then and under specified temp insulated and stirred obtain colloidal solution;
(3) colloidal solution of step (2) gained is packed in the polytetrafluoroethyllining lining, compactedness 40%～90% is put into stainless steel hydro-thermal still with liner, puts into the programme-control baking oven afterwards and heat-treats at a certain temperature, obtains white depositions;
(4) white depositions that step (3) is obtained spends deionised water for several times, and dried under the uniform temperature in baking oven obtains the microballoon that is formed by the self assembly of red schorl phase titanium dioxide nano line at last.
Temperature conditions in the above-mentioned steps (1) is 0～20 ℃; Titanium-containing compound is one or more in titanyl sulfate, butyl titanate, titanium tetrachloride, the titanium trichloride.
Temperature conditions in the above-mentioned steps (2) is 25 ~ 50 ℃, and mixing time is 4～8 hours.
Heat treatment temperature in the above-mentioned steps (3) is 120～200 ℃, and heat treatment time is 2～10 hours.
Dried temperature in the above-mentioned steps (4) is 40～80 ℃, and the dried time is 5～20 hours.
Described noble metal oriented load titanium dioxide optical catalyst can be realized according to following step:
(1) taking by weighing the titania support powder that 0.5～2g prepares, is that 0～3% ratio of titania support quality takes by weighing precious metal salt in the noble metal load capacity simultaneously, joins then and forms suspension in the aqueous solution;
(2), the titania support powder is evenly disperseed in the precious metal cation precursor water solution with the vigorous stirring 2～6 hours under the magnetic stirring apparatus effect of the suspension in the step (1);
(3) suspension that step (2) is obtained places under the specific light source, when keeping vigorous stirring, carries out photo-irradiation treatment;
(4) sample in the step (3) is centrifugal, washing for several times, dried under certain temperature in baking oven.
Precious metal salt can be one or more in chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum chloride, platinic sodium chloride, chlorauride, potassium chloroaurate, ammonium chloraurate, sodium chloraurate, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodium acid potassium, acetic acid rhodium, silver nitrate, ruthenic chloride, iodate ruthenium, ruthenium hydrochloride potassium, ruthenium hydrochloride sodium, palladium bichloride, palladium, the potassium chloropalladate in the above-mentioned steps (1).
The light source that illumination is used in the above-mentioned steps (3) is 300W xenon lamp or the dominant wavelength sterilizing viltalight lamp as 254nm, and the photo-irradiation treatment time is 3.5～6 hours.
Baking temperature in the above-mentioned steps (4) is 40～80 ℃, and be 5～20 hours drying time.
The noble metal oriented load photocatalysis material of titanium dioxide that adopts the present invention to prepare; Uniform component; Special self-assembled structures helps the transmission of electronics, and the specific area that nano wire is huge helps the absorption and the deposition of metal ion, and the redox property of the exposed crystal face of nano wire has determined the load situation of metal simultaneously; Interaction between titanium dioxide and the noble metal can effectively improve the separative efficiency in light induced electron-hole, thereby improves photo-quantum efficiency.In addition, the load of noble metal has also increased catalyst to absorption of visible light, makes material have visible light catalysis activity.This preparation process does not need the auxiliary of organic formwork agent, in the certain reaction temperature and time, just can obtain the titanium dioxide microballoon sphere (10～16 μ m) of micron number magnitude and the titanium dioxide microballoon sphere of noble metal load.Technical process is simple, and preparation parameter is easy to control, and good reproducibility can synthesize in scale, and the compound formation temperature is low in the building-up process, and the product particle diameter is evenly distributed.
The titanium dioxide microballoon sphere material of red schorl phase titanium dioxide microballoon provided by the invention and noble metal oriented load can be used as catalysis material.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the photocatalysis material of titanium dioxide of noble metal platinum load among the embodiment 2.
Fig. 2 is the stereoscan photograph of the photocatalysis material of titanium dioxide of the noble metal platinum load that has micro-sphere structure among the embodiment 2.
Fig. 3 is the local transmission electron microscope photo of the photocatalysis material of titanium dioxide of the noble metal platinum load that has micro-sphere structure among the embodiment 2.
Fig. 4 is the activity curve of the photocatalysis material of titanium dioxide of noble metal platinum load among the embodiment 2 photocatalytic degradation methyl orange (initial concentration is 10ppm) under ultraviolet (λ=254nm) and visible light (λ>400nm) is shone.
The specific embodiment
Below further illustrate characteristics of the present invention through embodiment, but be not limited to embodiment.
Experimental technique among the following embodiment if no special instructions, is conventional method.
Embodiment 1: the preparation of titania support material
Keeping temperature is 0
oUnder the condition of C, the titanium tetrachloride of 9.5mL is dropwise joined in the deionized water of 30.5mL under the magnetic agitation effect, be made into the solution that titanium ion concentration is 2.1M, the solution that obtains is continued to stir 8 hours, slowly be warmed up to 25 then
oC and insulated and stirred obtained colloidal solution in 8 hours, the colloidal solution that obtains were packed in the polytetrafluoroethyllining lining into compactedness 40%; Liner is put into stainless steel hydro-thermal still; Put into 120 ℃ of heat treatments of programme-control baking oven 10 hours, obtain white depositions, this white depositions is spent deionised water for several times; 40 ℃ of dried are 20 hours in baking oven, obtain titanium dioxide microballoon sphere at last.Through the X-ray diffracting spectrum analysis, show that its thing is the titanium dioxide of rutile phase mutually.Through ESEM and transmission electron microscope observing microscopic appearance, the result shows that this powder has the cracking spherical structure, and by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous, the average particulate diameter of bead is about 15 μ m.
Embodiment 2: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that the 0.025mmol chloroplatinic acid is made into 60mL, after fully stirring, add the titania support material of 0.5g embodiment 1 preparation, vigorous stirring is 2 hours then.Keep mixing speed constant, the suspension that obtains is placed under the xenon lamp, open xenon lamp according to 6 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 80 ℃ of dryings promptly got the titania powder that noble metal platinum is modified in 5 hours.Fig. 1 is the X-ray diffracting spectrum of the self assembly titanium dioxide microballoon sphere powder of the metal platinum modification of embodiment preparation for this reason; From collection of illustrative plates, can find out; Its thing is the titanium dioxide of rutile phase mutually; The characteristic peak that does not have tangible metal platinum possibly be because the load capacity of metal is very few on the one hand, possibly be because due to the dispersion of Pt nanoparticle very evenly on the other hand.Fig. 2 is the whole pattern photo of powder under JEOL JSM-6700 type field emission scanning electron microscope for this reason, and as can be seen from the figure this powder has the cracking spherical structure, and the microballoon average particulate diameter is about 14 μ m.Fig. 3 is the photo of the local pattern of powder under JEM-2010 type transmission electron microscope for this reason; Can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 5 μ m, diameter are 6nm, and metal platinum particles is of a size of 5nm, and its orientated deposition is on (110) of nano wire face.It is 4.6cm that the titania powder that this noble metal platinum of 40mg is modified places internal diameter with 80mL methyl orange solution (concentration is 10ppm), grow and be the circular reactor of 17cm; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the irradiation of wavelength of 254nm at radiation wavelength respectively greater than the halogen tungsten lamp of 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.As can beappreciated from fig. 4; This material is as photochemical catalyst; The degradation rate of methyl orange is 100% in 40 minutes under the effect of ultraviolet light, and under the effect of visible light, the degradation rate in 7 hours is 68%; No matter under ultraviolet light or visible light effect, all show excellent catalytic performance, be a kind of catalysis material that can the active response sunshine.
Embodiment 3: the preparation of titania support
Keeping temperature is 20
oUnder the condition of C, the titanium tetrachloride of 36.2mL is dropwise joined in the deionized water of 53.8mL under the magnetic stirring apparatus effect, be made into the solution that titanium ion concentration is 3.6M, the solution that obtains is continued to stir 0.5 hour, slowly be warmed up to 50 then
oC and insulated and stirred obtained colloidal solution in 8 hours, the colloidal solution that obtains were packed in the polytetrafluoroethyllining lining into compactedness 90%; Liner is put into stainless steel hydro-thermal still; Put into 200 ℃ of heat treatments of programme-control baking oven 2 hours, obtain white depositions, this white depositions is spent deionised water for several times; 80 ℃ of dried are 5 hours in baking oven, obtain titanium dioxide microballoon sphere at last.Through the X-ray diffracting spectrum analysis, show that its thing is the titanium dioxide of rutile phase mutually.Through ESEM and transmission electron microscope observing microscopic appearance, the result shows that this powder has the cracking spherical structure, and by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous, the average particulate diameter of bead is about 10 μ m.
Embodiment 4: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that the 0.146mmol radium chloride is made into 80mL, after fully stirring, add the titania support of 0.5g embodiment 3 preparations, vigorous stirring is 4 hours then.Keep mixing speed constant, the suspension that obtains is placed under the ultraviolet, opened uv illumination 3.5 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 40 ℃ of dryings promptly got the titania powder that Noble Metal Rhodium is modified in 20 hours.X-ray diffracting spectrum shows that its thing is the titanium dioxide of rutile phase mutually, does not have the characteristic peak of tangible metal rhodium, this possibly be since the load capacity of metal very few due to.Can find out that from the observed whole pattern of JEOL JSM-6700 type field emission scanning electron microscope this powder has the cracking spherical structure, the microballoon average particulate diameter is about 10 μ m.From JEM-2010 type transmission electron microscope observing to local pattern can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 8 μ m, diameter are 3nm; And the metal rhodium particle size is 2nm, and its orientated deposition is on (110) of nano wire face.It is 4.6cm that the titania powder that this Noble Metal Rhodium of 40mg is modified places internal diameter with 80mL methyl orange solution (concentration is 10ppm), grow and be the circular reactor of 17cm; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the irradiation of wavelength of 254nm at radiation wavelength respectively greater than the halogen tungsten lamp of 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.The result shows that this material is as photochemical catalyst; The degradation rate of methyl orange is 100% in 95 minutes under action of ultraviolet light; Degradation rate under the visible light effect in 7 hours is 55%, shows excellent catalytic performance, is a kind of catalysis material that can the active response sunshine.
Embodiment 5: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that 0.02562mmol chloroplatinic acid and 0.0463mmol silver chlorate are made into 100mL, after fully stirring, add the titania support of 2g embodiment 3 preparations, vigorous stirring is 6 hours then.Keep mixing speed constant, the suspension that obtains is placed under the xenon lamp, open xenon lamp according to 4.5 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 60 ℃ of dryings promptly got the titania powder of metal platinum modified by silver in 10 hours.X-ray diffracting spectrum shows that its thing is the titanium dioxide of rutile phase mutually, does not have the characteristic peak of tangible metal, this possibly be since the load capacity of metal very few due to.Can find out that from the observed whole pattern of JEOL JSM-6700 type field emission scanning electron microscope this powder has the cracking spherical structure, the microballoon average particulate diameter is about 10 μ m.From JEM-2010 type transmission electron microscope observing to local pattern can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 6 μ m, diameter are 5nm; And metal platinum particles is of a size of 5nm, and its orientated deposition is on (110) of nano wire face.It is that 4.6cm, length are the circular reactor of 17cm that titania powder that this noble metal platinum-Yin of 40mg is co-modified and 80mL methyl orange solution (concentration is 10ppm) place internal diameter; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the visible light radiation of wavelength of 254nm at radiation wavelength respectively greater than 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.This material is as photochemical catalyst; The degradation rate of the methyl orange under action of ultraviolet light in 45 minutes is 100%, and under the visible light effect, the degradation rate in 7 hours is 75%; Having improved its catalytic performance under ultraviolet light and visible light simultaneously, is a kind of catalysis material that can the active response sunshine.
Embodiment 6: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that the 0.0254mmol gold chloride is made into 70mL, after fully stirring, add 0.5g embodiment 1 preparation titania support, vigorous stirring is 6 hours then.Keep mixing speed constant, the suspension that obtains is placed under the xenon lamp, opened uv illumination 4.5 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 60 ℃ of dryings promptly got the titania powder of golden modification in 12 hours.Can find out that from X-ray diffracting spectrum its thing is the titanium dioxide of rutile phase mutually, the characteristic peak of gold not significantly, this possibly be since the load capacity of metal very few due to.Can find out that from the observed whole pattern of JEOL JSM-6700 type field emission scanning electron microscope this powder has the cracking spherical structure, the microballoon average particulate diameter is about 15 μ m.From JEM-2010 type transmission electron microscope observing to local pattern can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 7 μ m, diameter are 4nm; And the metallic gold particle size is 5nm, and its orientated deposition is on (110) of nano wire face.It is 4.6cm that the titania powder that this Precious Metals-Gold of 40mg is modified places internal diameter with 80mL methyl orange solution (concentration is 10ppm), grow and be the circular reactor of 17cm; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the irradiation of wavelength of 254nm at radiation wavelength respectively greater than the halogen tungsten lamp of 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.The result shows this material as photochemical catalyst, and the degradation rate of the methyl orange under ultraviolet light in 50 minutes is 100%, and degradation rate is 80% in 7 hours under visible light, is a kind of catalysis material that can the active response sunshine.
Embodiment 7: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that 0.0254mmol gold chloride and 0.047mmol palladium bichloride are made into 100mL, after fully stirring, add 1g embodiment 1 preparation titania support, vigorous stirring is 6 hours then.Keep mixing speed constant, the suspension that obtains is placed under the uviol lamp, opened uv illumination 5 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 70 ℃ of dryings promptly got the titania powder that the metallic gold palladium is modified in 7 hours.Can find out that from X-ray diffracting spectrum its thing is the titanium dioxide of rutile phase mutually.Can find out that from the observed whole pattern of JEOL JSM-6700 type field emission scanning electron microscope this powder has the cracking spherical structure, the microballoon average particulate diameter is about 15 μ m.From JEM-2010 type transmission electron microscope observing to local pattern can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 6 μ m, diameter are 4nm; And the metallic gold particle size is 6nm, and its orientated deposition is on (110) of nano wire face.It is that 4.6cm, length are the circular reactor of 17cm that titania powder that this Precious Metals-Gold-palladium of 40mg is co-modified and 80mL methyl orange solution (concentration is 10ppm) place internal diameter; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the irradiation of wavelength of 254nm at radiation wavelength respectively greater than the halogen tungsten lamp of 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.The result show this material as photochemical catalyst under ultraviolet light in 60 minutes degradation rate be 100%, the degradation rate under visible light in 7 hours is 70%, has shown excellent photocatalysis performance.
Embodiment 8: the preparation of noble metal oriented load titanium dioxide optical catalyst
Get the aqueous solution that the 0.0495mmol ruthenic chloride is made into 90mL, after fully stirring, add 1g embodiment 1 preparation titania support, vigorous stirring is 3 hours then.Keep mixing speed constant, the suspension that obtains is placed under the xenon lamp, open xenon lamp according to 5 hours.After illumination finishes, suspension is left standstill, abandon supernatant liquor, collecting precipitation spends the centrifugal several of deionised water, obtains end product, and product is put in the baking oven, and 50 ℃ of dryings promptly got the titania powder that metal Ru is modified in 15 hours.Can find out that from X-ray diffracting spectrum its thing is the titanium dioxide of rutile phase mutually, does not have the characteristic peak of tangible metal Ru, this possibly be since the load capacity of metal very few due to.Can find out that from the observed whole pattern of JEOL JSM-6700 type field emission scanning electron microscope this powder has the cracking spherical structure, the microballoon average particulate diameter is about 15 μ m.From JEM-2010 type transmission electron microscope observing to local pattern can find out; Titanium dioxide microballoon sphere is by roughly being parallel to each other and length forms than the assembling of the nano wire of homogeneous; The nanometer line length is that 5 μ m, diameter are 3nm; And the metal Ru particle size is 2nm, and its orientated deposition is on (110) of nano wire face.It is 4.6cm that the titania powder that this noble ruthenium of 40mg is modified places internal diameter with 80mL methyl orange solution (concentration is 10ppm), grow and be the circular reactor of 17cm; Dark reaction through 8 hours reaches adsorption equilibrium; Be under the ultraviolet light and the irradiation of wavelength of 254nm at radiation wavelength respectively greater than the halogen tungsten lamp of 400nm; By certain time interval sampling 3mL; Liquid becomes colorless in the question response device, and the suspension that takes out is centrifugal in 8000 rev/mins in centrifuge, is its ultra-violet absorption spectrum of UV, visible light spectrophotometric determination of Perkin-Elmer UV lambda 35 through model.As can be seen from the figure, this material as photochemical catalyst under uviol lamp in 100 minutes the degradation rate of methyl orange be 100%, degradation rate is 50% in 7 hours under visible light, shows excellent photocatalysis performance.
Claims (12)
1. a noble metal oriented load titanium dioxide optical catalyst is to be formed on titania support by the noble metal orientated deposition; Titania support is the rutile phase structure; Have uniform spherical pattern, the surface is the cracking shape, and its microsphere diameter is about 10～16 μ m; Be to be that 5～8 μ m, diameter are that the nano wire self assembly of 3～6nm forms by length, the exposed surface of every nano wire is 110 crystal faces; Noble metal is one or more in platinum, gold, ruthenium, rhodium, silver, the palladium, and load capacity is 0～3% of a titania support quality, and noble metal exists with the zeroth order simple substance form, and granular size is 2～10nm, and orientated deposition is on 110 crystal faces of titanium dioxide nano thread.
2. the preparation method of the described titania support of claim 1 may further comprise the steps:
(1) keeps under the uniform temperature condition titanium-containing compound dropwise being joined in the deionized water under vigorous stirring, be made into the solution that titanium ion concentration is 2.1～3.6M;
(2) solution that step (1) is obtained continues to stir 0.5～8 hour, slowly heat up then and under specified temp insulated and stirred obtain colloidal solution;
(3) colloidal solution of step (2) gained is packed in the polytetrafluoroethyllining lining, compactedness 40%～90% is put into stainless steel hydro-thermal still with liner, puts into the programme-control baking oven afterwards and heat-treats at a certain temperature, obtains white depositions;
(4) white depositions that step (3) is obtained spends deionised water for several times, and dried under the uniform temperature in baking oven obtains the microballoon that is formed by the self assembly of red schorl phase titanium dioxide nano line at last.
3. preparation method according to claim 2 is characterized in that: the temperature conditions in the step (1) is 0～20 ℃; Titanium-containing compound is one or more in titanyl sulfate, butyl titanate, titanium tetrachloride, the titanium trichloride.
4. preparation method according to claim 2 is characterized in that: the temperature conditions in the step (2) is 25 ~ 50 ℃, and mixing time is 4～8 hours.
5. preparation method according to claim 2 is characterized in that: the heat treatment temperature in the step (3) is 120～200 ℃, and heat treatment time is 2～10 hours.
6. preparation method according to claim 2 is characterized in that: the dried temperature in the step (4) is 40～80 ℃, and the dried time is 5～20 hours.
7. the preparation method of the described noble metal oriented load of claim 1 titanium dioxide optical catalyst may further comprise the steps:
(1) taking by weighing the titania support powder that 0.5～2g prepares, is that 0～3% ratio of titania support quality takes by weighing precious metal salt in the noble metal load capacity simultaneously, joins then and forms suspension in the aqueous solution;
(2), the titania support powder is evenly disperseed in the precious metal cation precursor water solution with the vigorous stirring 2～6 hours under the magnetic stirring apparatus effect of the suspension in the step (1);
(3) suspension that step (2) is obtained places under the specific light source, when keeping vigorous stirring, carries out photo-irradiation treatment;
(4) sample in the step (3) is centrifugal, washing for several times, dried under certain temperature in baking oven.
8. preparation method according to claim 7 is characterized in that: precious metal salt can be one or more in chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum chloride, platinic sodium chloride, chlorauride, potassium chloroaurate, ammonium chloraurate, sodium chloraurate, radium chloride, iodate rhodium, rhodium nitrate, chlorine rhodium acid potassium, acetic acid rhodium, silver nitrate, ruthenic chloride, iodate ruthenium, ruthenium hydrochloride potassium, ruthenium hydrochloride sodium, palladium bichloride, palladium, the potassium chloropalladate in the step (1).
9. preparation method according to claim 7 is characterized in that: the titania support powder is 0.5 ~ 2g.
10. preparation method according to claim 7 is characterized in that: the noble metal load capacity is 0～3% of a titania support quality.
11. preparation method according to claim 7 is characterized in that: the light source that illumination is used in the step (3) is 300W xenon lamp or the dominant wavelength sterilizing viltalight lamp as 254nm, and the photo-irradiation treatment time is 3.5～6 hours.
12. preparation method according to claim 7 is characterized in that: the baking temperature in the step (4) is 40～80 ℃, and be 5～20 hours drying time.
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| CN114377672A (en) * | 2022-01-12 | 2022-04-22 | 周口师范学院 | In-situ preparation method of precious metal and black mesoporous titanium dioxide nanocomposite |
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