CN105536770B - A kind of pucherite based photocatalyst and preparation method and application - Google Patents
A kind of pucherite based photocatalyst and preparation method and application Download PDFInfo
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- CN105536770B CN105536770B CN201610053901.6A CN201610053901A CN105536770B CN 105536770 B CN105536770 B CN 105536770B CN 201610053901 A CN201610053901 A CN 201610053901A CN 105536770 B CN105536770 B CN 105536770B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000013078 crystal Substances 0.000 claims abstract description 48
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 229910003206 NH4VO3 Inorganic materials 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000013049 sediment Substances 0.000 claims abstract description 9
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 150000001804 chlorine Chemical class 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910016978 MnOx Inorganic materials 0.000 claims description 6
- 229910019923 CrOx Inorganic materials 0.000 claims description 5
- 229910002451 CoOx Inorganic materials 0.000 claims description 4
- 229910015189 FeOx Inorganic materials 0.000 claims description 4
- 229910015711 MoOx Inorganic materials 0.000 claims description 4
- 229910005855 NiOx Inorganic materials 0.000 claims description 4
- 229910020669 PbOx Inorganic materials 0.000 claims description 4
- 229910019897 RuOx Inorganic materials 0.000 claims description 4
- 239000003426 co-catalyst Substances 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910018957 MClx Inorganic materials 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 241000165940 Houjia Species 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000010935 stainless steel Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002256 photodeposition Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GMMPQONJUVJOEP-UHFFFAOYSA-N [C].[C].C(C)=O Chemical compound [C].[C].C(C)=O GMMPQONJUVJOEP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- -1 antifreeze Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FDXIKKBHVBSBFN-UHFFFAOYSA-N [C].[C].C=O Chemical compound [C].[C].C=O FDXIKKBHVBSBFN-UHFFFAOYSA-N 0.000 description 1
- UPUZLJDFULGKCC-UHFFFAOYSA-N acetaldehyde;hydrate Chemical compound O.CC=O UPUZLJDFULGKCC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A kind of pucherite based photocatalyst and preparation method and application, is related to photochemical catalyst.The chemical formula of pucherite based photocatalyst is BiVO4, its crystalline phase is monoclinic phase, and its crystallite dimension is 1~5 μm, and its pattern is prismatic table shape, and its particular crystal plane exposed is { 010 } and { 110 } crystal face.Preparation method：First by presoma NH4VO3With Bi (NO3)3It is dissolved in aqueous solution of nitric acid, and the pH value of solution is adjusted with ammoniacal liquor, then adds the concentration that soluble chlorine salt dissolving is used to adjust Chlorine in Solution ion, after ageing, sediment is transferred in the stainless steel autoclave of polytetrafluoro liner and carries out hydro-thermal process；Then orange-yellow powder filter is separated, and be washed with deionized, dry roasting, produce pucherite based photocatalyst.Pucherite based photocatalyst can be in the application in photocatalytic conversion formaldehyde or acetaldehyde dihydric alcohol.Simply easily system, stable in catalytic performance, reactivity are high for low in raw material price, catalyst.
Description
Technical field
The present invention relates to photochemical catalyst, is specifically related to a kind of pucherite based photocatalyst and preparation method and application.
Background technology
Photocatalysis is a kind of technology with fine development prospect, is had in terms of photocatalysis degradation organic contaminant
Active application, while also have good application potential in terms of photocatalytic water.In addition, also have among photocatalysis organic synthesis
Good application prospect.1912, Ciamician proposed the theory of photocatalysis organic synthesis first, and subsequent photocatalysis is organic
Synthetic method has obtained quick development.Using sunshine the side of high valuable chemicals is produced from abundant and cheap raw material
Method is considered as one of most attractive mode for realizing sustainable chemistry synthesis.It is related among photocatalysis organic synthesis a variety of
Redox reaction, wherein carbon carbon coupling reaction have the carbon carbon coupling of highly important Research Significance, particularly small molecule anti-
Consequence should be occupied wherein.The formation of carbon-carbon bond is the core content during organic synthesis.Traditional carbon carbon is even
There is the shortcomings of severe reaction conditions, Atom economy difference and unfriendly environment in connection reaction, and photocatalysis carbon carbon coupling reaction is led to
Paradoxical reaction mild condition, response path is short, and Atom economy is high, has wide application and development prospect.
Dihydric alcohol is a kind of important basic chemical industry raw material, has ten as crosslinking agent and chain extender etc. in polyester industrial
Point important application, it is widely used as hygroscopic agent, antifreeze, lubricant and molten in food, medicine and cosmetics industry in addition
Agent etc..The larger dihydric alcohol of current needs amount mainly has ethylene glycol, propane diols, butanediol and hexylene glycol etc..Ethylene glycol is in polyester
Being had a wide range of applications with antifreezing agent etc., the global demand amount of ethylene glycol in 2010 has just reached 20,000,000 tons, and with every
The speed in year 5~10% is increasing.The key industry production line of ethylene glycol has ethylene epoxidizing hydrolysis route and oxalic acid at present
Ester through hydrogenation route.Propane diols is the important source material of unsaturated polyester (UP), epoxy resin, polyurethane resin, and the dosage of this respect accounts for
45% or so of propane diols aggregate consumption, its industrial process are mainly expoxy propane hydrolysis route.The life of most dihydric alcohols
Production is all with oil or coal-based feedstocks, is prepared by multi-step process, and generally existing synthetic route is long, manufacture method compared is multiple
Miscellaneous, energy consumption it is higher and to environment it is unfriendly the problems such as.Therefore, seek new green synthesis method be used for produce dihydric alcohol for
The development of related industry is particularly significant.
Low-carbon aldehyde mainly has formaldehyde, acetaldehyde etc., and formaldehyde industrially mainly passes through catalysis oxidation system by methanol or methane
It is standby, and acetaldehyde is mainly prepared by ethanol or ethene by catalysis oxidation, therefore there is the advantages of cheap and easy to get.With formaldehyde or acetaldehyde
For raw material, the method being coupled by photocatalysis carbon carbon prepares the synthesis of the dihydric alcohols such as ethylene glycol, propane diols and butanediol come a step
Route has the advantages of green, economically feasible.The Key of Implementation of photocatalysis carbon carbon coupling synthetic route is efficiently partly
The design synthesis of conductor catalysis material.
The pattern and its exposure crystal face of semi-conducting material have a significant impact for its photocatalysis performance.Prismatic table shape pucherite is sudden and violent
The particular crystal plane of dew is { 010 } and { 110 } crystal face, and the control to its pattern and exposure crystal face ratio is still more difficult at present.
There is document report to control the pattern of pucherite and crystal face by adding surfactant or crystal face directed agents, but method is more
Complexity, can not realize the modulation of exposed crystal face ratio wide scope, and control effect is unsatisfactory.It is a kind of simple it is therefore desirable to develop
Effective method controls the pattern of pucherite and crystal face, and then promotes the separation in its light induced electron and hole, and promotes surface
Course of reaction, so as to reach high photocatalytic activity.
The content of the invention
It is an object of the invention to provide a kind of adjustable pucherite based photocatalyst of exposed crystal face ratio and its preparation side
Method.
Another object of the present invention is to provide the pucherite based photocatalyst in photocatalytic conversion formaldehyde or acetaldehyde system
Application in dihydric alcohol.The dihydric alcohol includes ethylene glycol, propane diols, butanediol.
The chemical formula of the pucherite based photocatalyst is BiVO4, its crystalline phase is monoclinic phase, and its crystallite dimension is 1~5 μ
M, its pattern are prismatic table shape, and its particular crystal plane exposed is { 010 } and { 110 } crystal face.
The preparation method of the pucherite based photocatalyst, is comprised the following steps that：
First by presoma NH4VO3With Bi (NO3)3It is dissolved in aqueous solution of nitric acid, and the pH value of solution is adjusted with ammoniacal liquor, so
The concentration that soluble chlorine salt dissolving is used to adjust Chlorine in Solution ion is added afterwards, and after ageing, sediment is transferred to polytetrafluoro liner
Stainless steel autoclave in carry out hydro-thermal process；Then orange-yellow powder filter is separated, and be washed with deionized, after drying
Roasting, produces pucherite based photocatalyst.
The NH4VO3With Bi (NO3)3Mole can be 20~80mmol, the volume of aqueous solution of nitric acid can be 100~
400mL, the concentration of nitric acid can be 1~4M, and the pH value of solution can be 1~3 after ammoniacal liquor regulation.
The soluble chlorine salt dissolving can use MClx, wherein, M may be selected from Ia, IIa, IIIa, IVa, Ib, IIb, IIIb,
IVb, Vb, VIb, VIIb, the metallic element in VIII, and 1≤x≤4, the concentration of chlorion can be 0.01~5.0mol dm-3。
The time of the ageing can be 2h.
The temperature of the hydro-thermal process can be 160~220 DEG C, and the time of hydro-thermal process can be 10~30h.Pass through above-mentioned water
The control of heat condition, particularly Cl-The regulation of concentration, it is possible to achieve { 010 } tune of the exposure ratio of crystal face from 10%~90%
Control.
The roasting can be calcined 2h in 500 DEG C.
The pucherite based photocatalyst can carried metal co-catalyst or metal oxide promoters.
The exposed adjustable pucherite of crystal face ratio can be by the method for light deposition, in { 010 } and { 110 } crystal face table
Distinguish carried metal or metal oxide promoters in face.The metal and metal oxide may be selected from Pt, Pd, Rh, Au, Ag,
IrOx、RuOx、Cu2O、VOx、CrOx、MoOx、WOx、FeOx、NiOx、CoOx、PbOx、MnOxAt least one of Deng, 1 in oxide
≤x≤3.The load capacity of co-catalyst can be 0.1%~10% by mass percentage.
The pucherite based photocatalyst can be in the application in photocatalytic conversion formaldehyde or acetaldehyde dihydric alcohol.The binary
Alcohol includes ethylene glycol, propane diols, butanediol.
The method of pucherite based photocatalyst catalyzed conversion formaldehyde or acetaldehyde dihydric alcohol is as follows：
Pucherite based photocatalyst is added in the aqueous solution of formaldehyde or acetaldehyde, under agitation the oxygen in removing system
Gas, xenon lamp is opened, is separated pucherite based photocatalyst with solution after reaction, then dihydric alcohol is separated with other products.
The pucherite based photocatalyst may be selected from the prismatic table shape pucherite that { 010 } crystal face exposure ratio is 10%~90%
In one kind.The pucherite based photocatalyst may be selected from { 010 } and { 110 } crystal plane surface and be loaded with 0.1%~10% respectively
One kind in the pucherite of metal and metal oxide, the metal and metal oxide may be selected from Pt, Pd, Rh, Au, Ag,
IrOx、RuOx、Cu2O、VOx、CrOx、MoOx、WOx、FeOx、NiOx、CoOx、PbOx、MnOxAt least one of Deng, 1 in oxide
≤x≤3。
The proportioning of the photochemical catalyst and aldehyde-aqueous solution can be (10~100) mg:(5~100) mL, wherein, photochemical catalyst
Calculated by mass, aldehyde-aqueous solution is in terms of volume.Oxygen in the system of removing under agitation, can be with taking out under agitation
Vacuum or the oxygen being passed through in the method removing system of inert gas.The power of the xenon lamp can be 50~500W.The light is urged
Changing reaction can be reacted under ultraviolet light or visible light conditions.The time of reaction can be 1~100h.The catalyst and solution
Catalyst can be separated with solution by the method for centrifuging or filtering.It is described can be by distilling, depressurizing by ethylene glycol and accessory substance
Distillation or post separation separate dihydric alcohol with other products.
The adjustable pucherite sill of exposed crystal face ratio can realize that visible ray and ultraviolet light light are urged as catalyst
Change the method for formaldehyde carbon carbon coupling preparing ethylene glycol.
The adjustable pucherite sill of exposed crystal face ratio can realize that visible ray and ultraviolet light light are urged as catalyst
Change the method that formaldehyde and acetaldehyde carbon carbon are coupled propane diols processed.
The adjustable pucherite sill of exposed crystal face ratio can realize that visible ray and ultraviolet light light are urged as catalyst
Change the method that acetaldehyde carbon carbon is coupled butanediol processed.
The beneficial effects of the invention are as follows：Compared with the preparation method of traditional regulation and control pucherite crystal face, the invention provides
A kind of new regulates and controls pucherite pattern and exposes the simple of crystal face ratio by adjusting hydrothermal condition particularly chlorine ion concentration
Preparation method.Compared with traditional method for preparing low-carbon dihydric alcohol, the present invention provides one kind and passes through formaldehyde and the step light of acetaldehyde one
It is catalyzed the new method of carbon carbon coupling preparing ethylene glycol, propane diols or butanediol.It is of the invention that there is raw material compared with existing synthesis technique
Cheap, simply easily system, stable in catalytic performance, reactivity are high for catalyst, and reaction condition is gentle, technical process it is simple and
Advantages of environment protection.
Brief description of the drawings
Fig. 1 is the shape appearance figure of pucherite based photocatalyst.
Fig. 2 be by cl concn regulate and control made from different { 010 } and { 110 } crystal faces exposure ratios prismatic table shape pucherite
Scanning electron microscope (SEM) photograph.
Fig. 3 is the scanning electron microscope (SEM) photograph for the prismatic table shape pucherite that { 010 } crystal face exposure ratio is 50%.
Fig. 4 is that { 110 } crystal face-selective loads MnOxVanadic acid bismuth-based catalysts scanning electron microscope (SEM) photograph.
Fig. 5 is formaldehyde reaction for preparing glycol product liquid chromatogram.
Embodiment
The present invention is described further with instantiation below in conjunction with the accompanying drawings.
Embodiment 1
First by presoma NH4VO3(50mmol) and Bi (NO3)3·5H2O (50mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 2.0.Then a certain amount of KCl is added to use
In regulation Chlorine in Solution ion concentration be 0.03mol dm-3.After being aged 2h, it is the poly- of 100mL that sediment is transferred into capacity
Hydro-thermal process is carried out in tetrafluoro inner liner stainless steel autoclave, hydrothermal condition is 210 DEG C, 20h.By orange-yellow powder filter after cooling
Separation, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.I.e.
Obtain the BiVO that { 010 } crystal face exposure ratio is 20%4- { 010 } 20% catalyst.Take BiVO made from 10mg4- { 010 } 20%,
It is added in the solution for the Formaldehyde-water that 5mL formaldehyde weight/mass percentage composition is 20%.Vacuumize or be passed through under agitation indifferent gas
Body, after the oxygen in removing system, 200W xenon lamp is opened, light-catalyzed reaction 24h is carried out under the conditions of ultraviolet-visible light.Instead
After answering liquid to filter, efficient liquid phase chromatographic analysis shows that the conversion ratio of formaldehyde is 25%, and the selectivity of ethylene glycol is 40%, ethylene glycol
Yield be 10%.
Embodiment 2
First by presoma NH4VO3(50mmol) and Bi (NO3)3·5H2O (50mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 1.8.Then a certain amount of NaCl is added to use
In regulation Chlorine in Solution ion concentration be 3.0mol dm-3.After being aged 2h, sediment is transferred to capacity as poly- the four of 100mL
Hydro-thermal process is carried out in fluorine inner liner stainless steel autoclave, hydrothermal condition is 190 DEG C, 30h.By orange-yellow powder filter point after cooling
From, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.Produce
{ 010 } BiVO that crystal face exposure ratio is 80%4- { 010 } 80% catalyst.Further using Photodeposition in BiVO4's
{ 110 } crystal face deposition MnOx, produce MnOx-BiVO4- { 010 } 80% catalyst.Take MnO made from 10mgx-BiVO4-{010}
80%, it is in 15% solution of formaldehyde-acetaldehyde-water to be added to 5mL formaldehyde and acetaldehyde weight/mass percentage composition.Take out under agitation
Vacuum is passed through inert gas, after the oxygen in removing system, opens 300W xenon lamp, is carried out under the conditions of ultraviolet-visible light
Light-catalyzed reaction 12h.After reacting liquid filtering, efficient liquid phase chromatographic analysis shows that the total conversion of formaldehyde and acetaldehyde is 15%, second
The overall selectivity of glycol, propane diols and butanediol is 50%, and the total recovery of ethylene glycol, propane diols and butanediol is 7.5%.
Embodiment 3
First by presoma NH4VO3(60mmol) and Bi (NO3)3·5H2O (60mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 2.0.Then a certain amount of ZnCl is added2
Concentration for adjusting Chlorine in Solution ion is 0.5mol dm-3.After being aged 2h, it is the poly- of 100mL that sediment is transferred into capacity
Hydro-thermal process is carried out in tetrafluoro inner liner stainless steel autoclave, hydrothermal condition is 200 DEG C, 24h.By orange-yellow powder filter after cooling
Separation, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.I.e.
Obtain the BiVO that { 010 } crystal face exposure ratio is 60%4- { 010 } 60% catalyst.Further using Photodeposition in BiVO4's
{ 010 } crystal face deposition Pt, MnO is deposited in { 110 } crystal facex, produce Pd-MnOx-BiVO4- { 010 } 60% catalyst.Take 50mg systems
The Pd-MnO obtainedx-BiVO4- { 010 } 60% catalyst, it is added to acetaldehyde-water that 10mL acetaldehyde weight/mass percentage composition is 50%
In solution.Vacuumize or be passed through under agitation inert gas, after the oxygen in removing system, 500W xenon lamp is opened, visible
Light-catalyzed reaction 100h is carried out under optical condition.After reacting liquid filtering, efficient liquid phase chromatographic analysis shows that the conversion ratio of acetaldehyde is
5.4%, the selectivity of butanediol is 56%, and the yield of butanediol is 3.0%.
Embodiment 4
First by presoma NH4VO3(50mmol) and Bi (NO3)3·5H2O (50mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 2.0.Then a certain amount of MgCl is added2
Concentration for adjusting Chlorine in Solution ion is 0.2mol dm-3.After being aged 2h, it is the poly- of 100mL that sediment is transferred into capacity
Hydro-thermal process is carried out in tetrafluoro inner liner stainless steel autoclave, hydrothermal condition is 200 DEG C, 24h.By orange-yellow powder filter after cooling
Separation, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.I.e.
Obtain the BiVO that { 010 } crystal face exposure ratio is 50%4- { 010 } 50% catalyst.Further using Photodeposition in BiVO4's
{ 010 } crystal face deposition Pt and CrOx, produce Pt-CrOx-BiVO4- { 010 } 50% catalyst.Take Pt-CrO made from 20mgx-
BiVO4- { 010 } 50% catalyst, it is added in the solution for the Formaldehyde-water that 5mL formaldehyde weight/mass percentage composition is 20%.Stirring
Under vacuumize or be passed through inert gas, after the oxygen in removing system, 300W xenon lamp is opened, under the conditions of ultraviolet-visible light
Carry out light-catalyzed reaction 24h.After reacting liquid filtering, efficient liquid phase chromatographic analysis shows that the conversion ratio of formaldehyde is 35%, ethylene glycol
Selectivity be 39%, the yield of ethylene glycol is 14%.
Embodiment 5
First by presoma NH4VO3(50mmol) and Bi (NO3)3·5H2O (50mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 2.0.Then a certain amount of CuCl is added2
Concentration for adjusting Chlorine in Solution ion is 0.2mol dm-3.After being aged 2h, it is the poly- of 100mL that sediment is transferred into capacity
Hydro-thermal process is carried out in tetrafluoro inner liner stainless steel autoclave, hydrothermal condition is 200 DEG C, 24h.By orange-yellow powder filter after cooling
Separation, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.I.e.
Obtain the BiVO that { 010 } crystal face exposure ratio is 50%4- { 010 } 50% catalyst.Further using Photodeposition in BiVO4's
{ 010 } crystal face deposition Pt and WOx, CoO is deposited in { 110 } crystal facex, produce Pt-WOx-CoOx-BiVO4- { 010 } 50% catalyst.
Take Pt-WO made from 20mgx-CoOx-BiVO4- { 010 } 50% catalyst, 5mL formaldehyde weight/mass percentage composition is added to as 20%
Formaldehyde-water solution in.Vacuumize or be passed through under agitation inert gas, after the oxygen in removing system, open 500W's
Xenon lamp, light-catalyzed reaction 48h is carried out under the conditions of ultraviolet-visible light.After reacting liquid filtering, efficient liquid phase chromatographic analysis shows first
The conversion ratio of aldehyde is 46%, and the selectivity of ethylene glycol is 41%, and the yield of ethylene glycol is 19%.
Embodiment 6
First by presoma NH4VO3(50mmol) and Bi (NO3)3·5H2O (50mmol) is dissolved in 200mL concentration of nitric acid
In the 2.0M aqueous solution, and the pH value for adjusting solution with ammoniacal liquor under agitation is 2.0.Then a certain amount of LiCl is added to use
In regulation Chlorine in Solution ion concentration be 0.2mol dm-3.After being aged 2h, sediment is transferred to capacity as poly- the four of 100mL
Hydro-thermal process is carried out in fluorine inner liner stainless steel autoclave, hydrothermal condition is 200 DEG C, 24h.By orange-yellow powder filter point after cooling
From, and be washed with deionized repeatedly, and in 60 DEG C of drying overnight.After drying, the powder is calcined 2h in 500 DEG C.Produce
{ 010 } BiVO that crystal face exposure ratio is 50%4- { 010 } 50% catalyst.Further using Photodeposition in BiVO4's
{ 010 } crystal face deposition Pt and VOx, MnO is deposited in { 110 } crystal facex, produce Pt-VOx-MnOx-BiVO4- { 010 } 50% catalyst.
Take Pt-VO made from 20mgx-MnOx-BiVO4- { 010 } 50% catalyst, 5mL formaldehyde weight/mass percentage composition is added to as 20%
Formaldehyde-water solution in.Vacuumize or be passed through under agitation inert gas, after the oxygen in removing system, open 500W's
Xenon lamp, light-catalyzed reaction 80h is carried out under the conditions of ultraviolet-visible light.After reacting liquid filtering, efficient liquid phase chromatographic analysis shows first
The conversion ratio of aldehyde is 58%, and the selectivity of ethylene glycol is 38%, and the yield of ethylene glycol is 22%.
The particular crystal plane of its exposure of pucherite of the present invention is { 010 } and { 110 } crystal face, by changing hydrothermal condition,
The particularly concentration of chlorion, the exposure ratio of { 010 } and { 110 } crystal face can be regulated and controled.The invention provides one kind with crystal face
The adjustable pucherite of ratio and addition agent modified pucherite are photochemical catalyst, realize that formaldehyde and acetaldehyde photocatalysis carbon carbon are coupled second processed
The photocatalytic process of glycol, propane diols and butanediol.There is the process raw material cheap and easy to get, catalyst performance stabilised, reaction to live
Property it is high, reaction condition is gentle, technical process is simple and advantages of environment protection.
Claims (8)
1. a kind of preparation method of pucherite based photocatalyst, it is characterised in that the chemical formula of the pucherite based photocatalyst is
BiVO4, its crystalline phase is monoclinic phase, and its crystallite dimension is 1~5 μm, and its pattern is prismatic table shape, and its particular crystal plane exposed is
{ 010 } and { 110 } crystal face；
The preparation method comprises the following steps that：
First by presoma NH4VO3With Bi (NO3)3It is dissolved in aqueous solution of nitric acid, and the pH value of solution, Ran Houjia is adjusted with ammoniacal liquor
Enter the concentration that soluble chlorine salt dissolving is used to adjust Chlorine in Solution ion, after ageing, sediment is transferred to polytetrafluoro liner not
Hydro-thermal process is carried out in rust steel autoclave；Then orange-yellow powder filter is separated, and be washed with deionized, roasted after drying
Burn, produce pucherite based photocatalyst；
The soluble chlorine salt dissolving uses MClx, wherein, M is selected from Ia, IIa, IIIa, IVa, Ib, IIb, IIIb, IVb, Vb, VIb,
VIIb, the metallic element in VIII, and 1≤x≤4, the concentration of chlorion is 0.01~5.0mol dm-3；
The time of the ageing is 2h；The temperature of the hydro-thermal process is 160~220 DEG C, time of hydro-thermal process for 10~
30h。
A kind of 2. preparation method of pucherite based photocatalyst as claimed in claim 1, it is characterised in that the NH4VO3And Bi
(NO3)3Mole be respectively 20~80mmol, the volume of aqueous solution of nitric acid is 100~400mL, and the concentration of nitric acid is 1~4M,
The pH value of solution is 1~3 after ammoniacal liquor regulation.
3. a kind of preparation method of pucherite based photocatalyst as claimed in claim 1, it is characterised in that described to be calcined in 500 DEG C
Middle roasting 2h.
A kind of 4. preparation method of pucherite based photocatalyst as claimed in claim 1, it is characterised in that the vanadic acid bismuthino light
Catalyst carried metal co-catalyst or metal oxide promoters；
The metal and metal oxide are selected from Pt, Pd, Rh, Au, Ag, IrOx、RuOx、Cu2O、VOx、CrOx、MoOx、WOx、
FeOx、NiOx、CoOx、PbOx、MnOxAt least one of, 1≤x≤3 in oxide；The load capacity of co-catalyst presses quality percentage
Than for 0.1%~10%.
5. the photochemical catalyst prepared by a kind of preparation method of pucherite based photocatalyst as claimed in claim 1 is in catalyzed conversion
The application of formaldehyde or acetaldehyde dihydric alcohol, it is characterised in that the dihydric alcohol includes ethylene glycol, propane diols, butanediol.
6. application as claimed in claim 5, it is characterised in that pucherite based photocatalyst catalyzed conversion formaldehyde or acetaldehyde binary
The method of alcohol is as follows：
Pucherite based photocatalyst is added in the aqueous solution of formaldehyde or acetaldehyde, the oxygen in removing system, is opened under agitation
Xenon lamp is opened, separates pucherite based photocatalyst with solution after reaction, then dihydric alcohol is separated with other products.
7. application as claimed in claim 5, it is characterised in that the pucherite based photocatalyst is selected from { 010 } crystal face exposure ratio
Example is one kind in 10%~90% prismatic table shape pucherite；The pucherite based photocatalyst is selected from { 010 } and { 110 } crystal face
Surface is loaded with one kind in the pucherite of 0.1%~10% metal and metal oxide, metal and the metal oxidation respectively
Thing is selected from Pt, Pd, Rh, Au, Ag, IrOx、RuOx、Cu2O、VOx、CrOx、MoOx、WOx、FeOx、NiOx、CoOx、PbOx、MnOxIn
At least one, 1≤x≤3 in oxide.
8. application as claimed in claim 6, it is characterised in that the pucherite based photocatalyst and formaldehyde or acetaldehyde it is water-soluble
The proportioning of liquid is (10~100) mg:(5~100) mL, wherein, pucherite based photocatalyst is calculated by mass, formaldehyde or acetaldehyde
The aqueous solution is in terms of volume；Oxygen in the system of removing under agitation, with vacuumizing or be passed through inert gas under agitation
Method removing system in oxygen；The power of the xenon lamp is 50~500W；Light-catalyzed reaction is in ultraviolet light or visible striation
Reacted under part；The time of reaction is 1~100h；The catalyst and solution are by the method that centrifuges or filter by catalyst
Separated with solution；It is described dihydric alcohol is separated with other products by distill, be evaporated under reduced pressure or post separation by dihydric alcohol with it is other
Product separates.
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| CN100434165C (en) * | 2006-06-30 | 2008-11-19 | 中国科学院上海硅酸盐研究所 | Method for preparing visible light catalyst of Nano crystal BiVO4 in high activity through ultrasound chemistry |
| CN101717116B (en) * | 2009-12-18 | 2011-05-04 | 北京工业大学 | Surface active agent assisting alcohol-hydrothermal method for preparing anthoid BiVO4 |
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