CN105797722A - Method for preparing precious metal particle modified ZnO composite photocatalytic material - Google Patents
Method for preparing precious metal particle modified ZnO composite photocatalytic material Download PDFInfo
- Publication number
- CN105797722A CN105797722A CN201610196263.3A CN201610196263A CN105797722A CN 105797722 A CN105797722 A CN 105797722A CN 201610196263 A CN201610196263 A CN 201610196263A CN 105797722 A CN105797722 A CN 105797722A
- Authority
- CN
- China
- Prior art keywords
- zno
- noble metal
- reactor
- precious metal
- vacuum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 title claims abstract description 12
- 239000010970 precious metal Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 13
- 230000001699 photocatalysis Effects 0.000 title abstract description 10
- 239000000843 powder Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910000510 noble metal Inorganic materials 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000005119 centrifugation Methods 0.000 claims description 17
- 239000011941 photocatalyst Substances 0.000 claims description 16
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000005286 illumination Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000015598 salt intake Nutrition 0.000 claims description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000004917 polyol method Methods 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing a precious metal particle modified ZnO composite photocatalytic material.According to the method, ZnO is prepared through a polyol method, then the surface of ZnO is processed through low-temperature plasmas to change the polarity of ZnO, and finally, precious metal ions attached to the surface of ZnO are reduced into precise metal particles in a photo-reduction mode.The method is simple in process, and the obtained material has strong photocatalytic activity to common dye pollutants.
Description
Technical field
The invention belongs to field of new, be specifically related to the preparation method that a kind of noble metal modifies ZnO composite photocatalyst material.
Background technology
Nano-ZnO is a kind of II-VI important race's conductor oxidate, has and TiO2Approximate energy gap (3.37eV), has in some Organic substance of degrading and compares TiO2Higher catalysis activity.In actual application, nano-ZnO also exists the problem such as band gap length, photo-generate electron-hole recombination probability is high, easy photoetch.
Noble metal decorated semi-conducting material is considered as a kind of effective ways promoting light induced electron to separate with hole.When semiconductor surface and noble metal contacts, carrier can redistribute, and electronics transfers to, from the quasiconductor that fermi level is higher, the metal that fermi level is relatively low, until their fermi level is identical, thus forming Schottky energy barrier.Schottky energy barrier is the effective trap catching light induced electron, and the electronics of generation as the receiving body of light induced electron, can be made to flow to noble metal, and hole is then stayed on the semiconductor, it is achieved that efficiently separating of they, improves the photocatalytic activity of semi-conducting material.It addition, the noble metal decorated band structure that also can change quasiconductor, it is more beneficial for absorbing energy photons, improves the utilization rate of sunlight.
Xu Lihong etc. adopt sol-gel process to prepare ZnO nano crystalline substance, recycle p-Mercaptoaniline surface reduction Ag+Method be prepared for ZnO/Ag composite (preparation of ZnO/Ag nano-complex and optical property, Physical Experiment, 2011,31 (10): 12-14), the method to adopt the p-Mercaptoaniline of irritant stink to reduce.The vertical strong method waiting employing high-temperature roasting predecessor basic zinc carbonate of well is prepared for ZnO nanoparticle, method again through photo-reduction depositing noble metal is prepared for the (preparation of Pd/ZnO and Ag/ZnO composite nanoparticle of Pd/ZnO and Ag/ZnO composite nanoparticle, characterize and photocatalytic activity, catalysis journal, 2002, 23 (4): 336-340), the method adopts photo-reduction mode to carry out depositing noble metal, avoid the use of organic reducing agent, but owing to the adhesion between nano-ZnO and precious metal ion is poor, make the noble metal amount being deposited on ZnO nanoparticle surface few, and in combination with loosely.
Summary of the invention
The technical problem to be solved is to provide the preparation method that a kind of noble metal modifies ZnO composite photocatalyst material, and the method not only technique is simple, and common dyes pollutant are had very strong photocatalytic activity by resulting materials.
The technical scheme realizing above-mentioned purpose is: prepares ZnO initially with polyol process, then adopts low temperature plasma ZnO to carry out surface treatment to change its polarity；Finally by the mode of photo-reduction, the precious metal ion being adsorbed on ZnO surface is made to be reduced to noble metal granule.
The preparation method that a kind of noble metal provided by the invention modifies ZnO composite photocatalyst material; carry out as steps described below: 5-10mmol zinc acetate dihydrate is joined in 25mL solvent by (1); it is to slowly warm up to 80 DEG C; stirring 10-15min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection; it is to slowly warm up to 180-220 DEG C; insulation 60-120min, insulation naturally cools to room temperature after terminating; centrifugation; thick product uses dehydrated alcohol, deionized water wash 3 times respectively, and 40-50 DEG C of vacuum drying obtains ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 20-50Pa；Stablizing glow discharge after 3-5min, discharge power 100-150W, discharge time, 10-20min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.0%-1.5%, is subsequently adding a certain amount of precious metal salt, after it is completely dissolved, sonic oscillation 5-10min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 20-30min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 6-10h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 40-50 DEG C of vacuum drying, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
As preferably, the solvent described in step (1) is the one in glycerol, oleic acid, dodecanediol.
As preferably, the precious metal salt described in step (2) is Palladous chloride. or silver nitrate, and precious metal salt consumption is the 0.085%-4% of ZnO powder quality.
As shown from the above technical solution: the present invention prepares ZnO initially with polyol process, then adopts low temperature plasma that ZnO powder is carried out surface treatment, the mode deposited by photo-reduction prepares noble metal modification ZnO composite photocatalyst material.Low Temperature Plasma Treating adds the quantity of ZnO surface polar groups, not only increase the binding strength of noble metal granule and ZnO particle, and making the noble metal loading amount on ZnO powder surface increase, common contaminant is had the photocatalytic activity of excellence by resulting materials.
The invention has the beneficial effects as follows: adopting Low Temperature Plasma Treating to improve the quantity of ZnO surface polar groups and then the binding strength of raising noble metal granule and ZnO particle, increase the noble metal loading amount on ZnO powder surface, the method is easy and simple to handle, environmental protection.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiments present invention solely for the purpose of illustration, but not the scope being intended to limit the present invention in any manner.
Embodiment 1
(1) 5mmol zinc acetate dihydrate is joined in 25mL glycerol, be to slowly warm up to 80 DEG C, stir 10min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 180 DEG C, is incubated 120min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 40 DEG C of vacuum dryings, obtain ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 20Pa；Stablizing glow discharge after 3min, discharge power 100W, discharge time, 20min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.0%, is subsequently adding 0.00085g Palladous chloride., after it is completely dissolved, sonic oscillation 5min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 20min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 6h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 40 DEG C of vacuum dryings, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
Comparative example 1
(1) 5mmol zinc acetate dihydrate is joined in 25mL glycerol, be to slowly warm up to 80 DEG C, stir 10min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 180 DEG C, is incubated 120min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 40 DEG C of vacuum dryings, obtain ZnO powder；
(2) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.0%, is subsequently adding 0.00085g Palladous chloride., after it is completely dissolved, sonic oscillation 5min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 20min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 6h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 40 DEG C of vacuum dryings, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
Comparative example 2
5mmol zinc acetate dihydrate is joined in 25mL glycerol, is to slowly warm up to 80 DEG C, stir 10min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 180 DEG C, is incubated 120min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 40 DEG C of vacuum dryings, obtain ZnO powder.
Embodiment 2
(1) 10mmol zinc acetate dihydrate is joined in 25mL oleic acid, be to slowly warm up to 80 DEG C, stir 15min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 220 DEG C, is incubated 60min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 50 DEG C of vacuum dryings, obtain ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 50Pa；Stablizing glow discharge after 5min, discharge power 150W, discharge time, 10min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.5%, is subsequently adding 0.04g silver nitrate, after it is completely dissolved, sonic oscillation 10min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 30min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 10h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 50 DEG C of vacuum dryings, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
Embodiment 3
(1) 8mmol zinc acetate dihydrate is joined in 25mL dodecanediol, be to slowly warm up to 80 DEG C, stir 12min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 200 DEG C, is incubated 90min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 45 DEG C of vacuum dryings, obtain ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 40Pa；Stablizing glow discharge after 4min, discharge power 120W, discharge time, 15min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.25%, is subsequently adding 0.01g Palladous chloride., after it is completely dissolved, sonic oscillation 8min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 25min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 8h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 45 DEG C of vacuum dryings, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
Embodiment 4
(1) 6mmol zinc acetate dihydrate is joined in 25mL oleic acid, be to slowly warm up to 80 DEG C, stir 13min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 210 DEG C, is incubated 75min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 42 DEG C of vacuum dryings, obtain ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 40Pa；Stablizing glow discharge after 3.5min, discharge power 130W, discharge time, 18min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.3%, is subsequently adding 0.02g silver nitrate, after it is completely dissolved, sonic oscillation 6min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 28min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 9h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 42 DEG C of vacuum dryings, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
Embodiment 5
Photocatalysis performance is evaluated: weighs the composite photo-catalyst of preparation in 50mg embodiment 1～4 and comparative example 1～2 respectively and joins in dyestuff (methylene blue, the Weak Acid Red B) solution that 80mL concentration is 50mg/L, after solution is placed in dark place stirring 2h, take 5mL and react suspension, the supernatant is taken at a high speed after (10000r/min) centrifugation, under λ max, the absorbance of solution is measured with 722s visible spectrophotometer, thus the dye strength remained in solution after extrapolating illumination, then it is calculated as follows the catalysis material absorption property to dyestuff:
In formula: C0Before-dark absorption, dye strength in dye wastewater；CtAfter-dark absorption 2h, dye strength in dye wastewater.
By above-mentioned residue dye liquor UV light (power 15W, wavelength 365nm) irradiate, light source distance liquid level distance is 10cm, after illumination 2h, take 5mL and react suspension, take the supernatant after (10000r/min) centrifugation at a high speed, under λ max, measure the absorbance of solution with 722s visible spectrophotometer, thus the dye strength remained in solution after extrapolating illumination.It is calculated as follows degradation rate:
In formula: η is degradation rate；C1Before light degradation, dye strength in dye wastewater；C is after illumination 2h, dye strength in dye wastewater.
Table 1 sample Photocatalytic Degradation Property to dyestuff
Can be seen that from upper table experimental data, embodiment 1, comparative example 1 gained catalysis material photocatalysis performance are substantially better than comparative example 2, and this is owing to noble metal loading adds the separation efficiency in light induced electron and hole；Owing to Low Temperature Plasma Treating improves the binding strength of noble metal granule and ZnO particle, increase the noble metal loading amount on ZnO powder surface so that the photocatalytic activity of embodiment 1 resulting materials is higher than comparative example 1.It addition, because methylene blue is under irradiation under ultraviolet ray, it is easy to light degradation, its degradation rate is generally high than Weak Acid Red B.
Claims (3)
1. the preparation method that a noble metal modifies ZnO composite photocatalyst material, it is characterised in that: step is as follows:
(1) 5-10mmol zinc acetate dihydrate is joined in 25mL solvent, be to slowly warm up to 80 DEG C, stir 10-15min; after zinc acetate dihydrate is completely dissolved; under nitrogen protection, it is to slowly warm up to 180-220 DEG C, is incubated 60-120min; after insulation terminates; naturally cooling to room temperature, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively; 40-50 DEG C of vacuum drying, obtains ZnO powder；
(2) being placed in by above-mentioned ZnO powder in Low Temperature Plasma Treating instrument cavity, open vacuum pump, when vacuum is 5Pa in reaction cavity, pass into air, adjusting gas flow to vacuum in reaction cavity is 20-50Pa；Stablizing glow discharge after 3-5min, discharge power 100-150W, discharge time, 10-20min, after electric discharge terminates, took out ZnO powder, standby；
(3) 1gZnO powder is dispersed in the acetic acid aqueous solution of 20mL1.0%-1.5%, is subsequently adding a certain amount of precious metal salt, after it is completely dissolved, sonic oscillation 5-10min；Then above-mentioned solution is transferred in quartz photochemical reactor processed, after being sealed by reactor, with High Purity Nitrogen air-blowing 20-30min, remove the oxygen in reactor as far as possible；Then by reactor 400W high voltage mercury lamp (λ max=365nm, radiant intensity 0.61W/cm2) illumination 6-10h, after reaction terminates, centrifugation, thick product uses dehydrated alcohol, deionized water wash 3 times respectively, 40-50 DEG C of vacuum drying, obtains noble metal decorated particle and modifies nano-ZnO composite photocatalyst material.
2. the preparation method that a kind of noble metal according to claim 1 modifies ZnO composite photocatalyst material, it is characterised in that: the solvent described in step (1) is the one in glycerol, oleic acid, dodecanediol.
3. the preparation method that a kind of noble metal according to claim 1 modifies ZnO composite photocatalyst material, it is characterized in that: the precious metal salt described in step (2) is Palladous chloride. or silver nitrate, precious metal salt consumption is the 0.085%-4% of ZnO powder quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610196263.3A CN105797722A (en) | 2016-03-31 | 2016-03-31 | Method for preparing precious metal particle modified ZnO composite photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610196263.3A CN105797722A (en) | 2016-03-31 | 2016-03-31 | Method for preparing precious metal particle modified ZnO composite photocatalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105797722A true CN105797722A (en) | 2016-07-27 |
Family
ID=56459362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610196263.3A Pending CN105797722A (en) | 2016-03-31 | 2016-03-31 | Method for preparing precious metal particle modified ZnO composite photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105797722A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124478A1 (en) * | 2018-12-20 | 2020-06-25 | Beijing Guanghe New Energy Technology Co., Ltd. | Catalyst compositions and methods for producing long-chain hydrocarbon molecules |
| CN117299232A (en) * | 2023-09-26 | 2023-12-29 | 华北电力大学 | Method for synthesizing hydroxyaldehyde by catalyzing dihydric alcohol and preparing hydrogen by coupling |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050249660A1 (en) * | 2004-02-20 | 2005-11-10 | Industrial Technology Research Institute | Nanostructured zinc oxide photocatalyst for visible light and manufacturing method of the same |
| CN104475097A (en) * | 2014-11-11 | 2015-04-01 | 华中科技大学 | Palladium-zinc oxide nanocomposite, and preparation method and applications thereof |
-
2016
- 2016-03-31 CN CN201610196263.3A patent/CN105797722A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050249660A1 (en) * | 2004-02-20 | 2005-11-10 | Industrial Technology Research Institute | Nanostructured zinc oxide photocatalyst for visible light and manufacturing method of the same |
| CN104475097A (en) * | 2014-11-11 | 2015-04-01 | 华中科技大学 | Palladium-zinc oxide nanocomposite, and preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| SANG-HUN NAM等: "Enhancement of photocatalytic activity of synthesized ZnO nanoparticles with oxygen plasma treatment", 《CATALYSIS TODAY》 * |
| 徐建等: "表面羟基对Pd/ZnO 复合材料光催化性能的影响", 《华东理工大学学报（自然科学报）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124478A1 (en) * | 2018-12-20 | 2020-06-25 | Beijing Guanghe New Energy Technology Co., Ltd. | Catalyst compositions and methods for producing long-chain hydrocarbon molecules |
| CN113260453A (en) * | 2018-12-20 | 2021-08-13 | 北京光合新能科技有限公司 | Catalyst composition and process for producing long chain hydrocarbon molecules |
| CN117299232A (en) * | 2023-09-26 | 2023-12-29 | 华北电力大学 | Method for synthesizing hydroxyaldehyde by catalyzing dihydric alcohol and preparing hydrogen by coupling |
| CN117299232B (en) * | 2023-09-26 | 2024-04-19 | 华北电力大学 | Method for synthesizing hydroxyaldehyde by catalyzing dihydric alcohol and preparing hydrogen by coupling |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Au and Pt selectively deposited on {0 0 1}-faceted TiO2 toward SPR enhanced photocatalytic Cr (VI) reduction: The influence of excitation wavelength | |
| CN101653728B (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| Bahareh et al. | High photocatalytic activity of light-driven Fe2TiO5 nanoheterostructure toward degradation of antibiotic metronidazole | |
| CN103934012B (en) | SnS 2/ g-C 3n 4composite nano plate photochemical catalyst and preparation method | |
| CN101745377B (en) | Method for preparing visible light photocatalyst Bi2O3/TiO | |
| CN102553560A (en) | Preparation method of titanium dioxide/graphene composite photocatalyst | |
| CN104383952B (en) | A kind of Ag/g-C3N4/TiO2/ AC Catalysts and its preparation method and application | |
| CN101537354A (en) | Preparation method of visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof | |
| Wang et al. | Hydrothermal deposition of Cu2O-Ag nanoparticles co-sensitized TiO2 nanotube arrays and their enhanced photoelectrochemical performance | |
| CN110252326B (en) | Copper tungstate @ zinc oxide composite photocatalyst and preparation method and application thereof | |
| Feng et al. | Fabrication of layered (CdS-Mn/MoS2/CdTe)-promoted TiO2 nanotube arrays with superior photocatalytic properties | |
| CN102600823A (en) | Preparation method of graphene/titania composite material | |
| CN103506142A (en) | Molybdenum disulfide/silver phosphate composite visible light photocatalytic material and preparation method thereof | |
| CN100427204C (en) | Method for preparing Ag sensitized zinc oxide photocatalyst with visible light activity | |
| CN102605385A (en) | Method for preparing methanol from carbon dioxide by photoelectric catalytic reduction | |
| CN108704662A (en) | A kind of metalloporphyrin/graphite phase carbon nitride composite photo-catalyst | |
| Shang et al. | The promoted photoelectrocatalytic degradation of rhodamine B over TiO2 thin film under the half-wave pulsed direct current | |
| Zhang et al. | High value-added fluorescence upconversion agents-assisted nano-semiconductors for efficient wide spectral response photocatalysis: Exerting energy transfer effect and applications | |
| CN105797722A (en) | Method for preparing precious metal particle modified ZnO composite photocatalytic material | |
| CN102534725A (en) | Method for preparing Ag2S-doped TiO2 nanotube electrode | |
| CN105771953A (en) | Preparation method of zinc titanate and titanium dioxide composite nano material | |
| Wei et al. | Dual molecules engineered carbon nitride for achieving outstanding photocatalytic H2O2 production | |
| Ping et al. | Flexible TiO2 nanograss array film decorated with oxygen vacancies introduced by facile chemical reduction and their photocatalytic activity | |
| CN108355470A (en) | A kind of Ag-TiO2/Ti(NO2)/ITO optoelectronic poles, electrical enhanced photocatalysis reaction unit and its application | |
| CN108144599A (en) | A kind for the treatment of process of bismuthino composite photocatalyst for degrading dyeing waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160727 |
|
| WD01 | Invention patent application deemed withdrawn after publication |