CN107930620A - The preparation method of the air purification photocatalyst of titanium dioxide surface load super-small noble metal - Google Patents
The preparation method of the air purification photocatalyst of titanium dioxide surface load super-small noble metal Download PDFInfo
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- CN107930620A CN107930620A CN201711230830.3A CN201711230830A CN107930620A CN 107930620 A CN107930620 A CN 107930620A CN 201711230830 A CN201711230830 A CN 201711230830A CN 107930620 A CN107930620 A CN 107930620A
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- noble metal
- air purification
- preparation
- titanium dioxide
- photocatalyst
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000004887 air purification Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007921 spray Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000010944 silver (metal) Substances 0.000 claims description 9
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- NZIGZHDIUCTKQH-UHFFFAOYSA-N Cl[Ru+2].[NH4+] Chemical compound Cl[Ru+2].[NH4+] NZIGZHDIUCTKQH-UHFFFAOYSA-N 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000008247 solid mixture Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910018885 Pt—Au Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SZIUTZDYFMEYKQ-UHFFFAOYSA-N [NH4+].[Cl-].[Ru] Chemical compound [NH4+].[Cl-].[Ru] SZIUTZDYFMEYKQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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Abstract
The invention discloses a kind of preparation method of the air purification photocatalyst of titanium dioxide surface load super-small noble metal, by commercial TiO2(P25, similarly hereinafter) mixed with noble metal precursor liquor, water and ethanol are added into the solid mixture, become a certain concentration suspension, abundant ultrasonic disperse, and dried in spray dryer high temperature quick break, metal precursor crystal growth is avoided, finally obtains powdered solid predecessor.Gained solid precursors are calcined in a reducing atmosphere, up to TiO2M photocatalyst materials.This method preparation process is easy to operate, technique is simple, it is pollution-free, cost is low, for the support type photocatalyst obtained using P25 as substrate, your nano-particle diameter is equably carried on P25 surfaces between 0.3 1nm, have broad application prospects with high effective catalytic active area and excellent air purification ability, thus in air purification field.
Description
Technical field
The present invention relates to a kind of TiO2The air of area load super-small noble metal M (M=Pt, Au, Ag, Pd, Ru, Ir)
Purify the preparation method of photocatalyst, it is more particularly to a kind of P25 apparent heights are dispersed, the minimum particle diameter of load (between
0.3nm-1nm) the preparation method of your nano particle.
Background technology
Room air pollution is to endanger one of 5 overall situation factors of human health, and research shows that there are 500 in room air
A variety of volatile organic matters, such as formaldehyde, benzene carcinogenicity pollutant.Photocatalysis oxidation technique is because its is environmental-friendly, degradation capability
Air purifying process that is strong and becoming most competitiveness.Wherein, TiO2(P25, similarly hereinafter) material is with its cheap, chemical stabilization
The advantages that property is good, catalytic activity is high becomes most popular photocatalyst material.In addition, noble metal nano particles, such as Pt, Au,
Ag, Pd, Ru, Ir etc., have higher surface energy and superficial catalytic activation, there is uniqueness to urge volatile organic matter in air
Change acts on, and its performance is stablized, and is star's catalysis material in catalytic field.
Research confirms to be supported on noble metal nano particles on cheap semiconductor photocatalyst material, can not only improve your gold
The utilization ratio of metal nano-particle, reduces the manufacturing cost of material, moreover it is possible to effectively improves semiconductor-noble metal support type photocatalyst
The photocatalysis performance of material.The catalytic performance of such material depends primarily upon noble metal and the combination of semiconductor photocatalyst material is steady
Qualitative, noble metal is in physical quantitys such as the distributing homogeneity of semiconductor surface, size, composition, structures.Such material is ground at present
The pattern for being directed generally to modified semi-conducting material, structure, crystalline phase etc. are studied carefully, so as to fulfill effectively dividing for its inside photo-generated carrier
From, and then improve its catalytic activity.
But so far, had no in preparation to support type semiconductor-noble metal catalysis material synthesis report on
P25 apparent heights disperse, uniform load size between 0.3 nanometer of -1 nano-noble metal nano particle report.It is right at present at the same time
The preparation of metal nanocrystal is typically all to be carried out using photo-reduction sedimentation or infusion process, these methods are difficult to receive noble metal
The distribution of rice grain, size carry out Effective Regulation, are unfavorable for mass producing, therefore greatly limit it and answered in large-scale production
With.
The content of the invention
To solve drawbacks described above existing in the prior art, it is an object of the invention to provide one kind effectively to suppress expensive
Metal makes it with superfine small size uniform, firm is supported on titanium dioxide (P25, similarly hereinafter) table in the reunion of semiconductor surface
Face, and technique is simple, and pollution-free, cost is low, can realize method prepared by batch.The supported titanium obtained2- M (M=
Pt, Au, Ag, Pd, Ru, Ir) photocatalyst is using P25 as substrate, noble metal nano particles (diameter is between 0.3-1nm) are equably born
P25 surfaces are loaded in, there is high effective catalytic active area and excellent air purification ability, thus are had in air purification field
Have broad application prospects.
The present invention is realized by following technical proposals.
The preparation method of the air purification photocatalyst of titanium dioxide surface load super-small noble metal provided by the invention,
Comprise the following steps：
1) first will be according to TiO2Mass ratio with noble metal is 1：10-1:1000, by TiO2Powder and noble metal precursor body
Solution mixes, then into the mixed liquor according to solid content (TiO2With noble metal gross mass) and water and ethanol 10：600：400
Mass ratio adds water and ethanol, and it is 10% to make formed suspension ratio containing solid quality, then carries out abundant ultrasound to it
After scattered, it is passed through quick break in spray dryer and dries, metal precursor crystal growth is avoided, before collecting powdered solid content
Drive thing；
2) the solid predecessor is placed in Muffle furnace, 400 DEG C is warming up to 5 DEG C/min, in the hydrogen argon gas of hydrogen 5%
Calcined in gaseous mixture, the product after calcining is TiO2- M photocatalyst materials.
Further, contained noble metal is one kind in Pt, Au, Ag, Pd, Ru or Ir in the noble metal precursor liquid.
Further, the noble metal precursor liquid is the salting liquid of soluble correspondence noble metal, corresponding your gold of solubility
It is respectively chloroplatinic acid, gold chloride, silver nitrate, chlorine palladium acid, ruthenium hydrochloride ammonium or chloro-iridic acid to belong to salt.
Further, the concentration of salt solution of the noble metal is 50-100mM.
Further, in the step 1), the suspension that is formed contains 10% solid content, after abundant ultrasonic disperse, is passed through spray
In mist drier, the flow velocity for keeping suspension is 10-1000ml/h.
Further, in the step 1), drier drying temperature setting range is 100-180 DEG C.
Further, in the step 2), reducing atmosphere is the hydrogen argon gas gaseous mixture of hydrogen 5%.
Further, in the step 2), solid predecessor is warming up to 400 DEG C in Muffle furnace with 5 DEG C/min, calcination time
2h。
Whole preparation process of the present invention is easy to operate, and technique is simple, available for supported titanium2- M (M=Pt, Au, Ag,
Pd, Ru, Ir) photocatalyst material batch prepare.This method is pollution-free, and cost is low, the supported titanium obtained2- M (M=Pt,
Au, Ag, Pd, Ru, Ir) photocatalyst is using P25 as substrate, your nano particle (diameter is between 0.3nm-1nm) is equably carried on
P25 surfaces, have high effective catalytic active area and excellent air purification ability, thus have extensively in air purification field
Wealthy application prospect.
Sprayed by spray dryer high temperature, dry suspension quick break, can effectively suppress noble metal precursor body
The forming core of salt is grown up, and is made precious metal ion uniform adsorption and is highly dispersed in P25 particle surfaces, further forges in a reducing atmosphere
Burn, promote the precious metal ion original position forming core of these high degree of dispersion and form size to receive between 0.3 nanometer -1 nanometer of noble metal
Rice corpuscles is carried on P25 surfaces.
Brief description of the drawings
The transmission electron microscope picture that it is commercial P25 that Fig. 1, which is,；
Fig. 2 is TiO prepared by embodiment 12The transmission electron microscope picture of-Au photocatalysts；
Fig. 3 is TiO prepared by embodiment 22The transmission electron microscope picture of-Ir photocatalysts；
Fig. 4 is TiO prepared by embodiment 32The transmission electron microscope picture of-Pd photocatalysts；
Fig. 5 is TiO prepared by embodiment 42The transmission electron microscope picture of-Pt photocatalysts；
Fig. 6 is TiO prepared by embodiment 52The transmission electron microscope picture of-Ru photocatalysts；
Fig. 7 is TiO prepared by embodiment 62The transmission electron microscope picture of-Pt-Au photocatalysts.
Embodiment
The invention will be described in further detail with reference to the accompanying drawings and examples, but is not intended as doing any limit to invention
The foundation of system.
The preparation method of the air purification photocatalyst of the titanium dioxide surface load super-small noble metal of the present invention, including
Following step：
1) first will be according to TiO2Mass ratio with noble metal is 1：10-1:1000, by TiO2Powder and noble metal precursor body
Solution mixes, and the Concentration of precursor solution of noble metal be 50-100mM, in noble metal precursor liquid contained noble metal be Pt, Au, Ag, Pd,
One kind in Ru or Ir；Noble metal precursor liquid corresponds to the salting liquid of noble metal, corresponding soluble precious-metal salinity for solubility
Wei not chloroplatinic acid, gold chloride, silver nitrate, chlorine palladium acid, ruthenium hydrochloride ammonium or chloro-iridic acid；According to solid content (TiO2With mixing for noble metal
Compound) and water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, fully super
After sound disperses, it is passed through in spray dryer, the flow velocity for keeping suspension is 10-1000ml/h, and drier drying temperature sets model
Enclose for 100-180 DEG C, avoid metal precursor crystal growth, collection obtains powdered solid predecessor.
2) powdered solid predecessor is placed in Muffle furnace, 400 DEG C is warming up to 5 DEG C/min, in the hydrogen of hydrogen 5%
2h is calcined in argon gas gaseous mixture,.Calcining promotes the precious metal ion original position forming core of these high degree of dispersion and to form super-small expensive
Metal nanoparticle is carried on oxide surface, you can obtains the new TiO that high uniformity disperses, particle diameter is minimum2- M (M=Pt,
Au, Ag, Pd, Ru, Ir) photocatalyst material, the product after calcining is TiO2- M photocatalyst materials.
Specific embodiment is given below to further illustrate the present invention.
Embodiment 1：
First, the TiO of 200g is weighed2Insert in beaker, then add HAuCl thereto4Solution, the noble metal added
Contained noble metal (Au) and TiO in precursor liquid2Mass ratio be 1：100.According to solid content (TiO2With the mixture of noble metal) with
Water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, abundant ultrasonic disperse
Afterwards, it is passed through in spray dryer, the flow velocity for keeping suspension is 100ml/h, and drier drying temperature setting range is 120 DEG C,
Quick break drying is carried out, collects powdered solid content predecessor.Then, gained solid predecessor is inserted in Muffle furnace, with 5
DEG C/min be warming up to 400 DEG C calcining 2h, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%, the product after calcining is TiO2-
Au photocatalyst materials.
Fig. 1 is business TiO2(P25) transmission electron microscope picture, it can be seen that the particle diameter of its single nanoparticle is about left in 25nm
The right side, the smooth non-loaded particle in surface.Fig. 2 is the transmission electron microscope picture using the P25 after present invention load 1%Au, it can be seen that Au
Nano particle (average grain diameter about 0.9nm) is equably carried on P25 surfaces.
Embodiment 2：
First, the TiO of 200g is weighed2Insert in beaker, then add H thereto2IrCl6Solution, the noble metal added
Contained noble metal (Ir) and TiO in precursor liquid2Mass ratio be 1：500.According to solid content (TiO2With the mixture of noble metal) with
Water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, abundant ultrasonic disperse
Afterwards, it is passed through in spray dryer, the flow velocity for keeping suspension is 200ml/h, and drier drying temperature setting range is 140 DEG C,
Quick break drying is carried out, collects powdered solid content predecessor.Then, gained solid predecessor is inserted in Muffle furnace, with 5
DEG C/min be warming up to 400 DEG C calcining 2h, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%, the product after calcining is TiO2-
Ir photocatalyst materials.
Fig. 3 is the transmission electron microscope picture using the P25 after load factor 0.2%Ir of the present invention, it can be seen that Ir nano particles
(average grain diameter about 0.5nm) is equably carried on P25 surfaces.
Embodiment 3：
First, the TiO of 200g is weighed2Insert in ball grinder, chlorine palladium acid solution, your gold added then added thereto
Belong to contained noble metal (Pd) and TiO in precursor liquid2Mass ratio be 1：10.According to solid content (TiO2With the mixture of noble metal)
With water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, fully ultrasound point
After dissipating, it is passed through in spray dryer, the flow velocity for keeping suspension is 500ml/h, and drier drying temperature setting range is 150
DEG C, quick break drying is carried out, collects powdered solid content predecessor.Then, gained solid predecessor is inserted in Muffle furnace,
400 DEG C of calcining 2h are warming up to 5 DEG C/min, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%, the product after calcining is
TiO2- Pd photocatalyst materials.
Fig. 4 is the transmission electron microscope picture using the P25 after present invention load 5%Pd, it can be seen that Pd nano particles (average grain
Footpath about 1nm) equably it is carried on P25 surfaces.
Embodiment 4：
First, the TiO of 200g is weighed2Insert in ball grinder, then add H thereto2PtCl6Solution, your gold added
Belong to contained noble metal (Pt) and TiO in precursor liquid2Mass ratio be 1：200.According to solid content (TiO2With the mixture of noble metal)
With water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, fully ultrasound point
After dissipating, it is passed through in spray dryer, the flow velocity for keeping suspension is 800ml/h, and drier drying temperature setting range is 180
DEG C, quick break drying is carried out, collects powdered solid content predecessor.Then, gained solid predecessor is inserted in Muffle furnace,
400 DEG C of calcining 2h are warming up to 5 DEG C/min, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%, the product after calcining is
TiO2- Pt photocatalyst materials.
Fig. 5 is the transmission electron microscope picture using the P25 after present invention load 0.5%Pt, it can be seen that Pt nano particles are (average
Particle diameter about 0.3nm) equably it is carried on P25 surfaces.
Embodiment 5：
First, the TiO of 200g is weighed2Insert in ball grinder, then add ruthenium hydrochloride ammonia solution thereto, what is added is expensive
Contained noble metal (Ru) and TiO in metal front liquid2Mass ratio be 1：1000, according to solid content (TiO2With the mixing of noble metal
Thing) and water and ethanol 10：600：400 mass ratio adds water and ethanol, forms the suspension containing 10% solid content, fully ultrasound
After scattered, it is passed through in spray dryer, the flow velocity for keeping suspension is 400ml/h, and drier drying temperature setting range is 140
DEG C, quick break drying is carried out, collects powdered solid content predecessor.Then, gained solid predecessor is inserted in Muffle furnace,
400 DEG C of calcining 2h are warming up to 5 DEG C/min, 2h is calcined in the hydrogen argon gas gaseous mixture of hydrogen 5%.Then, by gained solid-state
Predecessor is inserted in Muffle furnace, 400 DEG C of calcining 2h is warming up to 5 DEG C/min, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%
Product after calcining is TiO2- Ru photocatalyst materials.
Fig. 6 is the transmission electron microscope picture using the P25 after present invention load 0.1%Ru, it can be seen that Ru nano particles are (average
Particle diameter 0.9nm) equably it is carried on P25 surfaces.
Embodiment 6：
First, the TiO of 200g is weighed2Insert in ball grinder, then add H thereto2PtCl6Solution and HAuCl4Solution,
Contained noble metal (Pt, Au) and TiO in the noble metal precursor liquid added2Mass ratio be 1：100.According to solid content (TiO2With
The mixture of noble metal) and water and ethanol 10：600：400 mass ratio adds water and ethanol, is formed outstanding containing 10% solid content
Turbid, after abundant ultrasonic disperse, is passed through in spray dryer, and the flow velocity for keeping suspension is 1000ml/h, drier drying temperature
It is 170 DEG C to spend setting range, carries out quick break drying, collects powdered solid content predecessor.Then, by gained solid forerunner
Thing is inserted in Muffle furnace, is warming up to 400 DEG C of calcining 2h with 5 DEG C/min, in the hydrogen-argon-mixed middle calcining 2h of hydrogen 5%, is forged
Product after burning is TiO2- Pt-Au photocatalyst materials.
Fig. 7 is the transmission electron microscope picture using the P25 after present invention load 0.5%Pt and 0.5%Au, it can be seen that Pt-Au
Nano particle (average grain diameter 0.6nm) is equably carried on P25 surfaces.
The invention is not limited in above-described embodiment, on the basis of technical solution disclosed by the invention, the skill of this area
Art personnel are according to disclosed technology contents, it is not necessary to which performing creative labour can make one to some of which technical characteristic
A little to replace and deform, these are replaced and deformation is within the scope of the present invention.
Claims (9)
1. the preparation method of the air purification photocatalyst of titanium dioxide surface load super-small noble metal, it is characterised in that bag
Include following step：
1) first will be according to TiO2Mass ratio with noble metal is 1：10-1:1000, by TiO2Powder is mixed with noble metal precursor liquid
Close, then into the mixed liquor according to solid content TiO2With noble metal gross mass and water and ethanol 10：600：400 mass ratio adds
Enter water and ethanol, form suspension；Subsequent abundant ultrasonic disperse, and high temperature quick break is dried, collection obtains powdered solid
Predecessor；
2) the solid predecessor is placed in Muffle furnace, is heated up with certain speed, calcined in gaseous mixture reducing atmosphere, calcined
Product afterwards is TiO2- M photocatalyst materials.
2. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that contained noble metal is one kind in Pt, Au, Ag, Pd, Ru or Ir in the noble metal precursor liquid.
3. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 2
Method, it is characterised in that the noble metal precursor liquid is the salting liquid of soluble correspondence noble metal, corresponding your gold of solubility
It is respectively chloroplatinic acid, gold chloride, silver nitrate, chlorine palladium acid, ruthenium hydrochloride ammonium or chloro-iridic acid to belong to salt.
4. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 3
Method, it is characterised in that the concentration of salt solution of the noble metal is 50-100mM.
5. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that in the step 1), the suspension formed contains solid content for 10%.
6. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that in the step 1), the flow velocity for being passed through suspension in spray dryer is 10-1000ml/h.
7. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that in the step 1), dryer temperature setting range is 100 DEG C -180 DEG C.
8. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that in the step 2), reducing atmosphere is the hydrogen argon gas gaseous mixture of hydrogen 5%.
9. the preparation of the air purification photocatalyst of titanium dioxide surface load super-small noble metal according to claim 1
Method, it is characterised in that in the step 2), solid precursors are warming up to 400 DEG C in Muffle furnace with 5 DEG C/min, during calcining
Between 2h.
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