CN108067229A - A kind of Pd/BiVO4 composite nanos photochemical catalyst and its preparation method and application - Google Patents
A kind of Pd/BiVO4 composite nanos photochemical catalyst and its preparation method and application Download PDFInfo
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- CN108067229A CN108067229A CN201611011642.7A CN201611011642A CN108067229A CN 108067229 A CN108067229 A CN 108067229A CN 201611011642 A CN201611011642 A CN 201611011642A CN 108067229 A CN108067229 A CN 108067229A
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- 229910002915 BiVO4 Inorganic materials 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 241000549556 Nanos Species 0.000 title claims 2
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 72
- 239000000725 suspension Substances 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 22
- 235000014653 Carica parviflora Nutrition 0.000 claims description 20
- 241000243321 Cnidaria Species 0.000 claims description 18
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 238000007146 photocatalysis Methods 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 101150003085 Pdcl gene Proteins 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 8
- 239000002923 metal particle Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 238000003912 environmental pollution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 105
- 230000000694 effects Effects 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 229910052763 palladium Inorganic materials 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000003223 protective agent Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000002800 charge carrier Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000132059 Carica parviflora Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007704 wet chemistry method 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
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of Pd/BiVO4Composite nano photochemical catalyst and its preparation method and application, BiVO4For coralloid nano structure, Pd uniform loads are in BiVO4Surface, the grain size of Pd is 10~30nm, and load capacity is 0.2~2.0wt%；The load of Pd significantly reduces the combined efficiency of photo-generate electron-hole pair; further improve light-catalyzed reaction activity; the preparation method of photochemical catalyst is succinctly easy to operate; the load of noble metal nano particles is without additional protective agent; also eliminate prolonged hydro-thermal recombination process; simultaneously a step thermal reduction is used to reduce the waste in water-heat process to noble metal raw material, realize the high-efficient carrier of Metal Palladium, reduce the cost of catalyst preparation；Obtained photochemical catalyst can be used in Visible Light Induced Photocatalytic waste water reaction, have good degrading activity and excellent repeatable utilization ratio；Be conducive to the sustainable development of economic environment.
Description
Technical field
The present invention relates to catalyst preparation technical field, more particularly, to a kind of Pd/BiVO4Composite nano light is urged
Agent and its preparation method and application.
Background technology
In recent years, due to the strong oxidizing property that photocatalytic semiconductor material is shown, universality is reacted and can to sunlight
The advantage of each side is directly utilized etc., application of the photocatalysis technology in terms of environmental treatment and energy development is made to have obtained extensively
Concern and substantial amounts of research.However, photocatalysis technology is still faced with some limitations, major embodiment in industrial applications at present
：1st, to the effective rate of utilization of sunlight（Mainly for visible ray）It is low；2nd, the lasting stability of catalyst material is poor；3rd, it is catalyzed
The recycling of agent and repeatable utilization rate are poor, easy in inactivation.
Pucherite（BiVO4）Because its suitable narrow bandgap（~2.4eV）It is made to have good absorption to visible ray.Separately
On the one hand, other narrow-band semiconductors are compared to（Such as CdS）, BiVO4Extremely rare chemical stability is shown, so as to effectively
Improve catalysis material sunlight irradiation under service efficiency and the service life, still, BiVO4As photochemical catalyst there is also
The limitation of itself, especially prominent is a little that its light excites the photo-generate electron-hole generated to easily compound, reduction charge carriers
The separative efficiency of son, this is also the defects of all narrow-band semiconductors is common.Therefore, composite photocatalyst is prepared to urge to improve light
It is to solve single crystalline phase BiVO to change reactivity4The low effective way of reaction efficiency.Lot of documents report, noble metal nano particles
Load can significantly improve the activity of light-catalyzed reaction, this is mainly due to noble metal nano particles to photo-generate electron-hole pair
Efficiently separate, so as to extend the service life of photo-generated charge carriers.In addition, the surface plasma resonance effect that noble metal possesses
It should（SPR）It also contributes to expand effective uptake region of the composite material to light, further enhances the activity of light-catalyzed reaction.
The Chinese patent of Publication No. CN104084215 A discloses a kind of BiVO of three-dimensional ordered macroporous structure4Load
The preparation method of ferroso-ferric oxide and noble metal is big using poly (methyl methacrylate) micro-sphere as templated synthesis three-dimensional order
The BiVO of pore structure4, reuse the equi-volume impregnating using isopropanol as solvent and realize Fe3O4Payload, finally again with poly-
Vinyl alcohol obtains the uniform load of noble metal as protective agent using low temperature bubbling reduction method；Publication No. CN104001496 A
Chinese patent disclose a kind of compound BiVO4The preparation method of nanosheet photocatalyst passes through wet chemistry method combination water
BiVO has been prepared in hot method4The trielement composite material of/graphene/palladium.Particularly, the BiVO that will be prepared separately4, stone
The compound ultrasonic disperse of black alkene and palladium is uniformly mixed, then will be combined togather by the method for hydro-thermal.
The method of these above-mentioned carried noble metals is complicated for operation, and additional addition protective agent is needed during carried noble metal, is used
The method of hydro-thermal, the time is long, high using noble metal amount, causes the waste of precious metal material, thus add catalyst into
This, and photocatalysis performance does not protrude.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing in the prior art, provide a kind of Pd/BiVO4
Composite nano photochemical catalyst.
Second object of the present invention is to provide above-mentioned Pd/BiVO4The preparation method of composite nano photochemical catalyst.
Third object of the present invention is to provide above-mentioned Pd/BiVO4The application of composite nano photochemical catalyst.
The purpose of the present invention is what is be achieved by the following technical programs：
A kind of Pd/BiVO4Composite nano photochemical catalyst, the BiVO4For coralloid nano structure, wherein each coral branch
A length of 300~600 nm of branch, a diameter of 80~300 nm, the Pd are nano-metal particle, and uniform load is in BiVO4Table
Face, the grain size of the Pd is 10~30nm, and the load capacity of the Pd is 0.2~2.0wt%.
Preferably, wherein the branch of each coral branch a length of 400~500 nm, a diameter of 150~200 nm, the grain of the Pd
Footpath is 15~25nm, and the load capacity of the Pd is 0.5~1.0wt%.
The photochemical catalyst using with visible light-responded photochemical catalyst BiVO4 as carrier, its area load activity into
Divide nanometer metal palladium particle, photo-generate electron-hole can not only be promoted to be provided largely to efficiently separating, while for degradation reaction
Active reaction sites so that the Pd/BiVO of preparation4Composite nano photochemical catalyst has good photocatalytic activity.
The present invention also provides the Pd/BiVO4The preparation method of composite nano photochemical catalyst, which is characterized in that including
Following steps：
S1. five nitric hydrate bismuths are added in nitric acid and dissolve to obtain presoma acid solution A, ammonium metavanadate is added to molten in ammonium hydroxide
Solve presoma lye B；
S2. polyethylene glycol and blocked polyethers F-127 difference is soluble in water, obtained aqueous solution is added separately to presoma
In acid solution A and precursor solution B, solution A and solution B are respectively obtained；
S3. be vigorously stirred it is lower solution A is mixed into obtain yellow suspension with solution B, adjust the pH of yellow suspension to be neutral or
Close to neutrality, it is for use to be further continued for stirring；
S4. yellow suspension S3 obtained is transferred in reaction kettle, at 70~120 DEG C, when reaction 18~30 is small, filters, is clear
Yellow powder is obtained after washing；
S5. by PdCl2Ultrasonic disperse obtains PdCl in deionized water2Suspension, by PdCl2The yellow powder that suspension is obtained with S4
Last BiVO4Persistently it is sufficiently stirred to obtain brown purees；
S6. by brown purees using after temperature-programmed calcination to get Pd/BiVO4Composite nano photochemical catalyst, wherein institute
The calcination temperature of temperature programming is stated as 400~500 DEG C, roasting time is 1~3h, and heating rate is 1~3 DEG C/min.
Preferably, the pH that yellow suspension is adjusted in S3 is 6~8.
Preferably, the concentration of five nitric hydrate bismuths described in S1 is 0.1~0.5 mol/L, and the concentration of nitric acid is 2~6 mol/
The molar ratio of L, five nitric hydrate bismuths and nitric acid is 0.1~0.5：4；The concentration of ammonium metavanadate be 0.1~0.5 mol/L, ammonium hydroxide
Concentration for 1~3 mol/L, the molar ratio of ammonium metavanadate and ammonium hydroxide is 0.1~0.5：2.
Preferably, the stirring and dissolving time of S1 presomas acid solution A and presoma lye B are 10~60 minutes.
Preferably, the concentration of Aqueous Solutions of Polyethylene Glycol described in S2 be 1~10 g/L, the Aqueous Solutions of Polyethylene Glycol of the addition
Volume ratio with presoma acid solution A is 1：3~6；The concentration of the F-127 polyether aqueous solutions is 5~20 g/L, is added to forerunner
The volume ratio of F-127 polyether aqueous solutions and presoma lye B in body lye B is 1：3~6.
Preferably, the mixing time that is further continued for of solution A described in S2 and solution B is 30~90min.
Preferably, the time that stirring is further continued for described in S3 is 50~70min.
Preferably, the volume of yellow suspension described in S4 accounts for the 40~60% of reaction kettle total measurement (volume).
Preferably, PdCl described in S52PdCl in suspension2Volume be 1~2 mL.
Preferably, PdCl described in S52With yellow powder BiVO4Mass ratio be 0.004~0.04：1.
The present invention also provides above-mentioned Pd/BiVO4Composite nano photochemical catalyst is in photocatalysis treatment environmental pollution waste water
Application.
Specifically utilize the Pd/BiVO4Phenol in composite nano photocatalyst for degrading waste water.
Compared with prior art, the invention has the advantages that：
The present invention provides a kind of Pd/BiVO4Composite nano photochemical catalyst, the BiVO4It is described for coralloid nano structure
Pd is nano-metal particle, and uniform load is in BiVO4Surface, the grain size of the Pd is 10~30nm, the load of the Pd
It measures as 0.2~2.0wt%；For industrial catalyst P25, which can be greatly improved to visible ray（400 nm
~700 nm）Absorption, the load of Pd significantly reduces the combined efficiency of photo-generate electron-hole pair, further improves light and urge
Change reactivity, the preparation method of the photochemical catalyst is succinctly easy to operate, and the load of noble metal nano particles is without additional guarantor
Agent is protected, prolonged hydro-thermal recombination process is also eliminated, while is reduced using a step thermal reduction in water-heat process to your gold
Belong to the waste of raw material, realize the high-efficient carrier of Metal Palladium, reduce the cost of catalyst preparation；Obtained photochemical catalyst
Available in Visible Light Induced Photocatalytic waste water reaction, there is good degrading activity and excellent repeatable utilization ratio；Be conducive to through
The sustainable development of Ji environment.
Description of the drawings
Fig. 1 is Pd/BiVO prepared by embodiment 14The SEM pictures of composite nano photochemical catalyst.
Fig. 2 is Pd/BiVO prepared by embodiment 14The photocatalytic activity data of composite nano photochemical catalyst.
Fig. 3 is the Pd/BiVO prepared by embodiment 24The activity data of the retest of composite nano photochemical catalyst.
Specific embodiment
Below in conjunction with the content that Figure of description and specific embodiment further illustrate the present invention, but should not be construed as pair
The limitation of the present invention.In the case of without departing substantially from spirit of the invention and essence, the modification made to the method for the present invention, step, condition
Or replace, it all belongs to the scope of the present invention.Unless otherwise noted, experimental method used in embodiment is people in the art
Conventional method and technology known to member, reagent or material are to be obtained by commercial sources.
The load capacity of Pd described in following embodiment refers to Pd and BiVO4Mass ratio half percentage.
Embodiment 1
Pd/BiVO4The preparation method of composite nano photochemical catalyst includes the following steps：
（1）Under the conditions of 70 DEG C, the five nitric hydrate bismuths of 0.03 mol are added in the nitric acid of 4 mol/L of 100 mL, are filled
Stirring is divided to be completely dissolved solid, presoma acid solution A is obtained, the ammonium vanadate of 0.03 mol is added to 2 mol/L of 100 mL
Ammonium hydroxide in, being sufficiently stirred is completely dissolved solid, obtains presoma acid solution B；
（2）The F-127 polyethers of the polyethylene glycol of 0.23g and 0.58g are dissolved in respectively in 25mL deionized waters, then are added separately to
In presoma acid solution A and precursor solution B, solution A and solution B are obtained, then continues to stir 30min respectively；
（3）In the case where being vigorously stirred, solution A is mixed with solution B, after obtaining the suspension of yellow, adjusting pH value of solution is
Neutrality, it is persistently for use after stirring 1h；
（4）Gained yellow suspension is moved in hydrothermal reaction kettle, the volume of yellow suspension accounts for hydrothermal reaction kettle total measurement (volume)
Half, autoclave body are the stainless steel hydrothermal reaction kettle with polytetrafluoroethylene (PTFE) Inner linings, react under conditions of 80 DEG C and take out afterwards for 24 hours,
Centrifugal filtration, drying obtain yellow powder by gained yellow powder with deionized water eccentric cleaning several times, are BiVO4；
（5）By about 0.004 g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 1.0 mL2Suspension weighs 1.0 g
BiVO4Powder and obtained PdCl2Suspension is sufficiently stirred, after obtaining the purees of brown；
（6）By brown purees be placed in Muffle furnace with the heating rate of 2.5 DEG C/min rise to 450 DEG C keep 2h after to get to
Pd/BiVO4Composite nano photochemical catalyst.
The Pd/BiVO that the present embodiment is prepared4Composite nano photocatalyst structure is as shown in Figure 1, BiVO4With coral
Coral shape nanostructured, Pd is nano-metal particle and is uniformly firmly supported on BiVO4Surface, wherein the grain size of Pd for 10~
30nm, BiVO4Coralliform structure in each coral branch branch a length of 300~500 nm, a diameter of the 100 of each coral branch
The load capacity of~300 nm, Pd are 0.2wt%.
Using the Pd/BiVO4Composite nano photochemical catalyst carries out photocatalysis liquid phase degradation of phenol and is as follows：
（1）The Pd/BiVO that the present embodiment is prepared4It is containing for 5 ppm that composite nano photochemical catalyst, which is added to concentration,
In the sewage of phenol（Pd/BiVO4Concentration of the composite nano photochemical catalyst in phenol solution is 1g/L）, ultrasonic agitation 30~
60s makes catalyst uniformly disperse in the solution；
（2）Using xenon lamp as lamp source, will be blocked using optical filter less than the photoresist of 420 nm, only by radiation of visible light make reaction into
Row, samples at regular intervals；
（3）Samples taken is centrifuged at once, takes supernatant liquor, using in measurement of ultraviolet-visible spectrophotometer solution
The concentration of phenol.
As a result as shown in Figure 2, in visible ray（Xenon source with optical filter）Irradiation under, the sewage containing phenol
Volume for 45mL, be compared to blank assay（no photocatalysis）And as reference（P25, titanium dioxide）'s
Contrast experiment, Pd/BiVO4Effective degradation is shown to pollutant.
Embodiment 2
Pd/BiVO4The preparation method of composite nano photochemical catalyst includes the following steps：
（1）Under the conditions of 70 DEG C, the five nitric hydrate bismuths of 0.03 mol are added in the nitric acid of 4 mol/L of 100 mL, are filled
Stirring is divided to be completely dissolved solid, presoma acid solution A is obtained, the ammonium vanadate of 0.03 mol is added to 2 mol/L of 100 mL
Ammonium hydroxide in, being sufficiently stirred is completely dissolved solid, obtains presoma acid solution B；
（2）The F-127 polyethers of the polyethylene glycol of 0.23g and 0.58g are dissolved in respectively in 25mL deionized waters, then are added separately to
In presoma acid solution A and precursor solution B, solution A and solution B are obtained, then continues to stir 30min respectively；
（3）In the case where being vigorously stirred, solution A is mixed with solution B, after obtaining the suspension of yellow, adjusting pH value of solution is
Neutrality, it is persistently for use after stirring 1h；
（4）Gained yellow suspension is moved in hydrothermal reaction kettle, the volume of yellow suspension accounts for hydrothermal reaction kettle total measurement (volume)
Half, autoclave body are the stainless steel hydrothermal reaction kettle with polytetrafluoroethylene (PTFE) Inner linings, react under conditions of 80 DEG C and take out afterwards for 24 hours,
Centrifugal filtration, drying obtain yellow powder by gained yellow powder with deionized water eccentric cleaning several times, are BiVO4；
（5）By 0.02 g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 1.0 mL2Suspension weighs 1.0 g BiVO4
Powder and PdCl2Suspension is sufficiently stirred, after obtaining the purees of brown；
（6）By brown purees be placed in Muffle furnace with the heating rate of 2.5 DEG C/min rise to 450 DEG C keep 2h after to get to
Pd/BiVO4Composite nano photochemical catalyst.
The Pd/BiVO that the present embodiment is prepared4Composite nano photochemical catalyst, BiVO4With coralloid nano structure,
Pd is nano-metal particle and is uniformly firmly supported on BiVO4Surface, wherein the grain size of Pd be 10~30nm, BiVO4Coral
A length of 300~500 nm of branch of each coral branch in coral shape structure, a diameter of 100~300 nm of each coral branch, Pd's
Load capacity is 1.0wt%.
It is by high speed centrifugation rotation that remaining reaction is molten after experiment condition according to Fig. 2 completes active testing with step
After liquid is separated with photochemical catalyst and carries out cleaning for several times to catalyst with deionized water, drying repeats above-mentioned active testing,
The results are shown in Figure 3, from figure 3, it can be seen that catalyst shows excellent repeatable usability.
Embodiment 3
Pd/BiVO4The preparation method of composite nano photochemical catalyst includes the following steps：
（1）Under the conditions of 20 DEG C, in the nitric acid for the 2mol/L that the five nitric hydrate bismuths of 0.01 mol are added to 75 mL, fully
Stirring is completely dissolved solid, obtains presoma acid solution A, the ammonium vanadate of 0.01 mol is added to the ammonia of 1 mol/L of 75 mL
In water, being sufficiently stirred is completely dissolved solid, obtains presoma acid solution B；
（2）The F-127 polyethers of the polyethylene glycol of 0.23g and 0.58g are dissolved in respectively in 25mL deionized waters, then are added separately to
In presoma acid solution A and precursor solution B, solution A and solution B are obtained, then continues to stir 60min respectively；
（3）In the case where being vigorously stirred, solution A is mixed with solution B, after obtaining the suspension of yellow, adjusting pH value of solution is
8, it is persistently for use after stirring 70min；
（4）Gained yellow suspension is moved in hydrothermal reaction kettle, the volume of yellow suspension accounts for hydrothermal reaction kettle total measurement (volume)
Half, autoclave body are the stainless steel hydrothermal reaction kettle with polytetrafluoroethylene (PTFE) Inner linings, are taken out after reacting 30h under conditions of 70 DEG C,
Centrifugal filtration, drying obtain yellow powder by gained yellow powder with deionized water eccentric cleaning several times, are BiVO4；
（5）By about 0.03 g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 1.0 mL2Suspension weighs 1.0 g
BiVO4Powder and PdCl2Suspension is sufficiently stirred, after obtaining the purees of brown；
（6）Brown purees is placed in Muffle furnace and rises to 400 DEG C with the heating rate of 1 DEG C/min and keeps after 1h to get to Pd/
BiVO4Composite nano photochemical catalyst.
The Pd/BiVO that the present embodiment is prepared4Composite nano photochemical catalyst, BiVO4With coralloid nano structure,
Pd is nano-metal particle and is uniformly firmly supported on BiVO4Surface, wherein the grain size of Pd be 10~30nm, BiVO4Coral
A length of 300~500 nm of branch of each coral branch in coral shape structure, a diameter of 100~300 nm of each coral branch, Pd's
Load capacity is 1.5wt%.
Embodiment 4
Pd/BiVO4The preparation method of composite nano photochemical catalyst includes the following steps：
（1）Under the conditions of 70 DEG C, the five nitric hydrate bismuths of 0.03 mol are added in the nitric acid of 4 mol/L of 100 mL, are filled
Stirring is divided to be completely dissolved solid, presoma acid solution A is obtained, the ammonium vanadate of 0.03 mol is added to 2 mol/L of 100 mL
Ammonium hydroxide in, being sufficiently stirred is completely dissolved solid, obtains presoma acid solution B；
（2）The F-127 polyethers of the polyethylene glycol of 0.5g and 1.0g are dissolved in respectively in 25mL deionized waters, then before being added separately to
It drives in body acid solution A and precursor solution B, obtains solution A and solution B, then continue to stir 60min respectively；
（3）In the case where being vigorously stirred, solution A is mixed with solution B, after obtaining the suspension of yellow, adjusting pH value of solution is
Neutrality, it is persistently for use after stirring 1h；
（4）Gained yellow suspension is moved in hydrothermal reaction kettle, the volume of yellow suspension accounts for hydrothermal reaction kettle total measurement (volume)
Half, autoclave body are the stainless steel hydrothermal reaction kettle with polytetrafluoroethylene (PTFE) Inner linings, react under conditions of 80 DEG C and take out afterwards for 24 hours,
Centrifugal filtration, drying obtain yellow powder by gained yellow powder with deionized water eccentric cleaning several times, are BiVO4；
（5）By about 0.004 g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 1.0 mL2Suspension weighs 1.0 g
BiVO4Powder and obtained PdCl2Suspension is sufficiently stirred, after obtaining the purees of brown；
（6）By brown purees be placed in Muffle furnace with the heating rate of 2.5 DEG C/min rise to 450 DEG C keep 2h after to get to
Pd/BiVO4Composite nano photochemical catalyst.
The Pd/BiVO that the present embodiment is prepared4Composite nano photocatalyst structure is as shown in Figure 1, BiVO4With coral
Coral shape nanostructured, Pd is nano-metal particle and is uniformly firmly supported on BiVO4Surface, wherein the grain size of Pd for 10~
30nm, BiVO4Coralliform structure in each coral branch branch a length of 400~600 nm, a diameter of the 80 of each coral branch
The load capacity of~200 nm, Pd are 0.2wt%.
Embodiment 5
Pd/BiVO4The preparation method of composite nano photochemical catalyst includes the following steps：
（1）Under the conditions of 50 DEG C, in the nitric acid for the 6mol/L that the five nitric hydrate bismuths of 0.04 mol are added to 150 mL, fully
Stirring is completely dissolved solid, obtains presoma acid solution A, the ammonium vanadate of 0.04 mol is added to 3 mol/L's of 150 mL
In ammonium hydroxide, being sufficiently stirred is completely dissolved solid, obtains presoma acid solution B；
（2）The F-127 polyethers of the polyethylene glycol of 0.5g and 1.0g are dissolved in respectively in 25mL deionized waters, then before being added separately to
It drives in body acid solution A and precursor solution B, obtains solution A and solution B, then continue to stir 90min respectively；
（3）In the case where being vigorously stirred, solution A is mixed with solution B, after obtaining the suspension of yellow, adjusting pH value of solution is
6, it is persistently for use after stirring 50min；
（4）Gained yellow suspension is moved in hydrothermal reaction kettle, the volume of yellow suspension accounts for hydrothermal reaction kettle total measurement (volume)
Half, autoclave body are the stainless steel hydrothermal reaction kettle with polytetrafluoroethylene (PTFE) Inner linings, are taken out after reacting 18h under conditions of 120 DEG C,
Centrifugal filtration, drying obtain yellow powder by gained yellow powder with deionized water eccentric cleaning several times, are BiVO4；
（5）By about 0.04 g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 2.0 mL2Suspension weighs 1.0 g
BiVO4Powder and PdCl2Suspension is sufficiently stirred, after obtaining the paste of brown；
（6）After brown paste drawout, it is placed in Muffle furnace after rising to 500 DEG C of holding 1h with the heating rate of 3 DEG C/min,
Obtain Pd/BiVO4Composite nano photochemical catalyst.
The Pd/BiVO that the present embodiment is prepared4Composite nano photochemical catalyst, BiVO4With coralloid nano structure,
Pd is nano-metal particle and is uniformly firmly supported on BiVO4Surface, wherein the grain size of Pd be 10~30nm, BiVO4's
A length of 400~600 nm of branch of each coral branch in coralliform structure, a diameter of 80~200 nm of each coral branch, Pd's
Load capacity is 2.0wt%.
Comparative example 1
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, step
Suddenly（6）It is carried out by following operation：Brown purees, which is placed in Muffle furnace, to be risen to 450 DEG C and keeps after 2 h to get to Pd/BiVO4It is multiple
Mould assembly nano-photocatalyst.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：It is directly heat-treated to obtain without temperature programming
Composite photocatalyst, light-catalyzed reaction activity under visible light illumination decrease, and reason is：Heat-treat temperature
It is rapidly promoted so that Pd easily reunites blocking, can not be dispersed in BiVO with the short grained size uniform of nanometer4Surface, even
Depart from, payload can not be formed, so as to cause the reduction in the reactivity site of Pd load capacity and photochemical catalyst, separately
One side Pd and BiVO4Between the reduction of contact probability also result in the combined efficiency increases of photo-generated charge carriers so that it is anti-
It should activity decline.
Comparative example 2
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, step
Suddenly（5）It is carried out by following operation：By about 0.1g PdCl2Ultrasonic disperse obtains PdCl in the deionized water of 1.0 mL2Suspension claims
Take 1.0 g BiVO4Powder and obtained PdCl2Suspension is sufficiently stirred, and obtains the purees of brown.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：BiVO4Surface by Pd particles wrap up cover so that
BiVO4The absorption and use efficiency of light is declined.And in this composite photocatalyst, BiVO4It assumes responsibility for main light absorption and swashs
Hair generates the effect of photo-generate electron-hole, and the obtained light induced electron with high activity is again by shape between noble metal and semiconductor
Into Schottky barrier be transferred to Pd surfaces, and then act on object complete photocatalytic degradation reaction.However, Pd is to BiVO4
Package so that the quantity of photo-generated charge carriers is reduced, so that greater number of reactivity substance can not be formed, cause light
The decline of catalytic reaction activity.
Comparative example 3
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, save
Slightly step（2）Operation, i.e., do not add any polymer adjustment BiVO4Microstructure.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：Being not added with the sample of polymer can not obtain having high ratio
The BiVO of the coralliform structure of surface area4, it was demonstrated that the guiding role that polymer grows material microstructure.Meanwhile at this
Under method, metal Pd does not form nano particle, and uniform load is in BiVO4Surface, BiVO4Apparent form sink to Metal Palladium
Product mode has decisive influence.
Comparative example 4
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, step
Suddenly（2）Operation in, polyethylene glycol and F-127 polyethers are dissolved in respectively in 25mL deionized waters, then are added separately to precursor B
In acid solution and A precursor solutions, then continue to stir 30min respectively.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：Two kinds of polymer is exchanged, can not obtain that there is high ratio
The BiVO of the coralliform structure of surface area4.Meanwhile under this methodology, metal Pd does not form nano particle, and uniform load exists
BiVO4Surface, BiVO4Apparent form have decisive influence to the depositional mode of Metal Palladium.
Comparative example 5
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, step
Suddenly（2）Operation in, F-127 polyethers is replaced with into citric acid.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：Change structure directing agent, can not obtain with Gao Bibiao
The BiVO of the coralliform structure of area4.Meanwhile under this methodology, metal Pd does not form nano particle, and uniform load is in BiVO4
Surface, BiVO4Apparent form have decisive influence to the depositional mode of Metal Palladium.
Comparative example 6
Experimental method with embodiment 1, it is unique unlike, Pd/BiVO4In the preparation method of composite nano photochemical catalyst, step
Suddenly（2）Operation in, only add in one kind in polyethylene glycol and F-127 polyethers, then continue to stir 30min respectively.
The Pd/BiVO being prepared using this comparative example4Composite nano photochemical catalyst carries out photocatalysis described in embodiment 1
Liquid phase degradation of phenol（Biodegrading process is the same as embodiment 1）, the result shows that：Polyethylene glycol and one kind in F-127 polyethers are only added in,
It can not obtain the BiVO of the coralliform structure with high-specific surface area4.Meanwhile under this methodology, metal Pd does not form nanometer
Particle, uniform load is in BiVO4Surface, BiVO4Apparent form have decisive influence to the depositional mode of Metal Palladium.
Claims (11)
1. a kind of Pd/BiVO4Composite nano photochemical catalyst, which is characterized in that the BiVO4For coralloid nano structure, wherein
Branch a length of 300~600 nm, a diameter of 80~300 nm, the Pd of each coral branch are nano-metal particle, and uniformly negative
It is loaded in BiVO4Surface, the grain size of the Pd is 10~30nm, and the load capacity of the Pd is 0.2~2.0wt%.
2. according to the method described in claim 1, it is characterized in that：A length of 400~500 nm of branch of wherein each coral branch, directly
Footpath is 150~200 nm, and the grain size of the Pd is 15~25nm, and the load capacity of the Pd is 0.5~1.0wt%.
3. Pd/BiVO described in claim 14The preparation method of composite nano photochemical catalyst, which is characterized in that including following step
Suddenly：
S1. five nitric hydrate bismuths are added in nitric acid and dissolve to obtain presoma acid solution A, ammonium metavanadate is added to molten in ammonium hydroxide
Solve presoma lye B；
S2. polyethylene glycol and blocked polyethers F-127 difference is soluble in water, obtained aqueous solution is added separately to presoma
In acid solution A and precursor solution B, solution A and solution B are respectively obtained；
S3. be vigorously stirred it is lower solution A is mixed into obtain yellow suspension with solution B, adjust the pH of yellow suspension to be neutral or
Close to neutrality, it is for use to be further continued for stirring；
S4. yellow suspension S3 obtained is transferred in reaction kettle, at 70~120 DEG C, when reaction 18~30 is small, filters, is clear
Yellow powder is obtained after washing；
S5. by PdCl2Ultrasonic disperse obtains PdCl in deionized water2Suspension, by PdCl2The yellow powder that suspension is obtained with S4
Last BiVO4Persistently it is sufficiently stirred to obtain brown purees；
S6. by brown purees using after temperature-programmed calcination to get Pd/BiVO4Composite nano photochemical catalyst, wherein described
The calcination temperature of temperature programming is 400~500 DEG C, and roasting time is 1~3h, and heating rate is 1~3 DEG C/min.
4. Pd/BiVO according to claim 34The preparation method of composite nano photochemical catalyst, which is characterized in that described in S1
The concentration of five nitric hydrate bismuths is 0.1~0.5 mol/L, and the concentration of nitric acid is 2~6 mol/L, five nitric hydrate bismuths and nitric acid
Molar ratio be 0.1~0.5：4；The concentration of ammonium metavanadate is 0.1~0.5 mol/L, and the concentration of ammonium hydroxide is 1~3 mol/L, partially
The molar ratio of ammonium vanadate and ammonium hydroxide is 0.1~0.5：2.
5. Pd/BiVO according to claim 34The preparation method of composite nano photochemical catalyst, which is characterized in that S1 forerunner
The stirring and dissolving time of body acid solution A and presoma lye B are 10~60 minutes.
6. Pd/BiVO according to claim 34The preparation method of composite nano photochemical catalyst, which is characterized in that described in S2
The concentration of Aqueous Solutions of Polyethylene Glycol is 1~10 g/L, the Aqueous Solutions of Polyethylene Glycol of the addition and the volume ratio of presoma acid solution A
For 1：3~6；The concentration of the F-127 polyether aqueous solutions be 5~20 g/L, the F-127 polyethers being added in presoma lye B
The volume ratio of aqueous solution and presoma lye B are 1：3~6, the solution A and solution B be further continued for mixing time for 30~
90min。
7. Pd/BiVO according to claim 34The preparation method of composite nano photochemical catalyst, which is characterized in that adjusted in S3
Section yellow suspension pH be further continued for described in 6~8, S3 stir time be 50~70min.
8. the preparation method of Pd/BiVO4 composite nanos photochemical catalyst according to claim 3, which is characterized in that described in S4
The volume of yellow suspension accounts for the 40~60% of reaction kettle total measurement (volume).
9. Pd/BiVO according to claim 34The preparation method of composite nano photochemical catalyst, which is characterized in that described in S5
PdCl2PdCl in suspension2Volume be 1~2 mL, the PdCl2With yellow powder BiVO4Mass ratio for 0.004~
0.04：1.
10. Pd/BiVO described in claim 14Composite nano photochemical catalyst answering in photocatalysis treatment environmental pollution waste water
With.
11. application according to claim 10, which is characterized in that be to utilize the Pd/BiVO4Composite nano photocatalysis
Phenol in agent degrading waste water.
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