CN109107605A - Ammonium decatungstate with high-efficiency photocatalytic oxidation and application thereof - Google Patents
Ammonium decatungstate with high-efficiency photocatalytic oxidation and application thereof Download PDFInfo
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- CN109107605A CN109107605A CN201810741462.7A CN201810741462A CN109107605A CN 109107605 A CN109107605 A CN 109107605A CN 201810741462 A CN201810741462 A CN 201810741462A CN 109107605 A CN109107605 A CN 109107605A
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- quaternary ammonium
- ammonium salt
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 title abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 24
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 23
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- -1 tetramethyl quaternary ammonium salt Chemical class 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract 3
- 150000001768 cations Chemical class 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 21
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000005457 optimization Methods 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Abstract
The invention belongs to the field of chemical industry, and particularly discloses a deca-poly ammonium tungstate catalyst with high-efficiency photocatalytic oxidation and application thereof. The catalyst is ammonium decatungstate taking tetramethyl quaternary ammonium salt, tetraethyl quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt as cations, has good photocatalytic activity, can utilize visible light and molecular oxygen, and can implement green selective oxidation of bio-based micromolecule 5-hydroxymethylfurfural by taking an acidic aqueous solution as a promoter in an acetonitrile medium, thereby effectively carrying out photocatalytic oxidation on 5-hydroxymethylfurfural to convert into corresponding oxygen-containing products 2, 5-furandicarboxaldehyde or 2, 5-furandicarboxylic acid. The reaction system is environment-friendly, green and pollution-free, and has very important significance for cleanly producing the oxidation product of the 5-hydroxymethylfurfural.
Description
Technical field
The invention belongs to chemical field, specifically discloses a kind of ten poly- wolframic acid ammonium salts with high-efficiency photocatalysis oxidization and urge
Agent and its application.
Background technique
Currently, environmental pollution and fossil energy shortage are two serious problems that the whole world faces, find renewable and have
The substitute of the fuels and chemicals of sustainable development has become research hotspot.Chemical industry is by their focus
It concentrates among production technology, using with environmental-friendly biomass resource.Biomass resource have it is cheap, reserves are rich
Richness, it is renewable the advantages that.The renewable substance such as lignin, cellulose, hemicellulose, it is resourceful and cheap.It can using them
Platform chemicals 5 hydroxymethyl furfural (HMF) is prepared with conversion.HMF can lead to as important one of biology base platform chemicals
Reproducible biomass carbohydrates dehydration preparation is crossed, has obtained extensive concern, HMF can be further converted to various Gao Pin
Matter fuel and high added value compound, such as 2,5-furandaldehyde (DFF) or 2,5-furandicarboxylic acid (FDCA), therefore gradually
As research hotspot.
2,5-furandicarboxylic acid (FDCA) and 2,5- diformyl furans (DFF) are all important organic synthesis intermediate,
Various alkyl substitutions or esters furan derivatives can be used to prepare, therefore the catalysis oxidation of HMF receives extensive research.Mesh
Preceding 5 hydroxymethyl furfural catalysis oxidation main method has chemical catalysis, enzymatic and electro-catalysis.Chemical catalysis is mainly using tool
There are the reagent (such as chromate, bichromate, permanganate) of strong oxidizing property, homogeneous metal salt and carried noble metal catalysis
Agent.These oxidising agents have the shortcomings that environmental pollution, there are toxicity, and catalyst is expensive, at high cost.There is document report
Using copper as catalyst, using molecular oxygen or hydrogen peroxide as oxidant, although solving cost problem, selectivity of product
It is relatively low.
With light-catalysed rise, it is most promising to become the problems such as solving current energy crisis and environmental pollution
One of technology.Photocatalysis oxidation technique also has developing history in decades, achieves significant progress in Industrial Wastewater Treatment.
Some effective photochemical catalyst such as TiO2, Fe-TiO2, Cr-SiO2, V2O5-Al2O3, NaY, Fe (III) porphyrin
complexes, Fe(III)Cl3With Cu (II) Cl2And di-Os (VI) complex oneself be employed successfully in ultraviolet or can
The photochemical catalytic oxidation conversion process of light-exposed catalytic molecular oxygen selection hydrocarbon.The conductor oxidate photocatalysis reported at present
It is convenient that agent has the advantages that inexpensive, recycling reuses；But its ultraviolet, particularly visible light catalytic molecular oxygen selective oxidation efficiency is still
It is lower.Although some transient metal complexes show higher photocatalytic oxidation efficiency, but its high synthesis cost limits it
Application.Through studying, the solid or solution (in water or certain organic solvents) of organic ammonium coordinated compound are in ultraviolet light
It will become blue under radiation, certain systems even can also become blue in the sunlight；In addition coordinated compound hydrogenates saturated carbon
Closing object has very tempting photooxidation catalytic activity (O2 For oxidant), therefore as photocatalyst applications in organic
It is the research topic that Chemistry of Polyacids field is more active in recent years in chemical reaction.Since ten poly- wolframic acid ammonium salts are inhaled in visible region
Receive weak, photocatalytic oxidation efficiency is low, and the conversion ratio being used in the research of photocatalysis performance is generally lower.
System is conserved in order to develop the selective catalysis of green and efficient 5 hydroxymethyl furfural, not for the prior art
Foot, the present invention intends to solve will be with the ten of the different carbon chain quaternary ammonium salt of length poly- wolframic acid ammonium salt (the poly- wolframic acid quaternary ammonium salts of tetramethyl ten, four
The poly- wolframic acid quaternary ammonium salt of butyl ten) it is catalyst, develop with the oxygen selective oxidation of excited by visible light coordinated compound photocatalytic molecules
The reaction system of HMF, and some acid solution promoters are selected to improve its photocatalysis efficiency.
Summary of the invention
The object of the present invention is to provide a kind of synthetic methods of ten poly- wolframic acid quaternary ammonium salts for preparing high-quality, obtain length not
Ten poly- wolframic acid ammonium salt (tetramethyl based quaternary ammonium salt, tetrem based quaternary ammonium salt, tetrapropyl quaternary ammonium salt, tetrabutyl seasons of same carbon chain quaternary ammonium salt
Ammonium salt), and be used for using molecular oxygen as oxidant, acetonitrile as reaction medium, under room temperature, normal pressure, condensing condition, it is seen that light illumination
The research system of catalysis oxidation 5 hydroxymethyl furfural.
The method of ten poly- wolframic acid quaternary ammonium salts of preparation of the present invention, comprising the following steps:
(1) it after the tungstate dihydrate acid sodium of 6.0 g being dissolved in 35 mL water, is fitted into three-necked flask, is put into 25 DEG C of water-bath, delay
Slowly the hydrochloric acid of 2 mol/L is added dropwise thereto, adjusts pH value in 2.3；
(2) reaction solution is quickly transferred in 80 DEG C of water-baths, continues to adjust pH in 2.05 with the hydrochloric acid solution prepared；
(3) after polymerizeing 10 min, the quaternary ammonium salt aqueous solution of the different carbon chain prepared is slowly added dropwise to three-necked flask, is gradually had big
It measures white precipitate to generate, adjusts pH in the numerical value of step (2) with hydrochloric acid solution, the reaction was continued 25 min are fully cooled, filter
To white solid.
The invention has the following advantages that
(1) catalyst raw material needed for is easy to get, and synthesis process is simple；
(2) entire reaction system mild condition, green, environmental protection.
Specific embodiment
The following examples are however to be not limited to the specific embodiment listed of the present invention to further explanation of the invention
The embodiment of description.
Embodiment 1: the preparation method method of ten poly- wolframic acid quaternary ammonium salts of high-quality used in the present invention, including following step
It is rapid:
(1) it after the tungstate dihydrate acid sodium of 6.0 g being dissolved in 35 mL water, is fitted into three-necked flask, is put into 25 DEG C of water-bath, delay
Slowly the hydrochloric acid of 2 mol/L is added dropwise thereto, adjusts pH value in 2.3；
(2) reaction solution is quickly transferred in 80 DEG C of water-baths, continues to adjust pH in 2.05 with the hydrochloric acid solution prepared；
(3) after polymerizeing 10 min, by quaternary ammonium salt (the tetramethyl based quaternary ammonium salt, tetrem based quaternary ammonium salt, tetrapropyl of the different carbon chain prepared
Quaternary ammonium salt, tetrabutyl quaternary ammonium salt) aqueous solution is slowly added dropwise to three-necked flask, gradually has a large amount of white precipitates to generate, and it is molten with hydrochloric acid
Liquid adjusts pH in the numerical value of step (2), the reaction was continued 25 min, is fully cooled, suction filtration obtains white solid.
Embodiment 2-5: tetramethyl, tetraethyl, tetrapropyl, the tetrabutyl ten being prepared in method described in embodiment 1
Poly- wolframic acid ammonium salt is catalyst (2 mmol%), and molecular oxygen as oxidant, reaction solution is 5.0 mL, and acetonitrile makees medium, and water is addition
Agent, reaction temperature are 25 DEG C, under normal pressure (1 atm), condensing condition, the catalysis oxidation under the irradiation of 35W tungsten halogen lamp visible light
5 hydroxymethyl furfural (0.02 mol/L), reaction time are 12 h.Reaction product passes through gas chromatographic analysis.Concrete outcome is shown in Table
1。
The poly- wolframic acid quaternary ammonium salt photochemical catalytic oxidation 5 hydroxymethyl furfural of 1 tetraalkyl of table ten.
Embodiment 6-12: the tetramethyl coordinated compound (0.25-3.0 being prepared in method described in embodiment 1
Mmol %) it is catalyst, the chromatography of photocatalysis oxidation reaction and reaction product is carried out according to step described in [0009].
Concrete outcome is shown in Table 2.
Influence of the additional amount of 2 catalyst of table to catalytic molecular oxygen oxidation 5 hydroxymethyl furfural under visible light.
Embodiment 13-17: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1 is
Catalyst, hydrochloric acid (0.05-0.4 mol/L) are additive, carry out photocatalysis oxidation reaction according to step described in [0009]
With the chromatography of reaction product.Concrete outcome is shown in Table 3.
Influence of the additional amount of 3 hydrochloric acid of table to catalytic molecular oxygen oxidation 5 hydroxymethyl furfural under visible light.
Embodiment 18-21: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1 is
Catalyst, water (1.0-7.0 mol/L) are additive, according to the progress photocatalysis oxidation reaction of step described in [0009] and instead
Answer the chromatography of product.Concrete outcome is shown in Table 4.
Influence of the additional amount of 4 water of table to catalytic molecular oxygen oxidation 5 hydroxymethyl furfural under visible light.
Embodiment 22-24: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1 is
Catalyst, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) are additive, and 5 hydroxymethyl furfural (0.02-0.1 mol/L) is
Reaction substrate carries out the chromatography of photocatalysis oxidation reaction and reaction product according to step described in [0009].Specific knot
Fruit is shown in Table 5.
5 concentration of substrate of table to catalyst under visible light catalytic molecular oxygen oxidation the strong methyl furfural of 5- influence.
Embodiment 25-30: the tetramethyl coordinated compound (2mmol %) being prepared in method described in embodiment 1 is
Catalyst, hydrochloric acid (0.2mol/L) and water (5.0mol/L) are additive, and reaction time 6-16h is described according to [0009]
The step of carry out photocatalysis oxidation reaction and reaction product chromatography.Concrete outcome is shown in Table 5.
Influence of 5 reaction time of table to catalytic molecular oxygen oxidation 5 hydroxymethyl furfural under visible light.
Embodiment 31-32: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1
For catalyst, light source, hydrochloric acid (0.2 mol/L) and water are done with the tungsten halogen lamp (corresponding respectively to embodiment 31,32) of 15 W, 65 W
(5.0 mol/L) is additive, and the chromatography of photocatalysis oxidation reaction and reaction product is carried out according to step described in [0009]
Analysis.Concrete outcome is shown in Table 6.
Influence of 6 tungsten halogen lamp of table to catalytic molecular oxygen oxidation 5 hydroxymethyl furfural under visible light.
Embodiment 33-35: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1 is
Catalyst makees oxidant with oxygen (1-2 atm), and hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) are additive, when reaction
Between 12h, according to step described in [0009] carry out photocatalysis oxidation reaction and reaction product chromatography, overall yield of reaction
It is 45.12%.
Embodiment 36: the tetramethyl coordinated compound (2 mmol %) being prepared in method described in embodiment 1 is to urge
Agent, with air oxidant, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) are additive, described according to [0009]
Step carries out the chromatography of photocatalysis oxidation reaction and reaction product, overall yield of reaction 24.12%.
Detailed description of the invention: Fig. 1 is built-in light-source formula Photoreactor；The poly- wolframic acid ammonium salt (a) of Fig. 2 tetrabutyl ten and tetramethyl ten
The uv-spectrogram of poly- wolframic acid ammonium salt (b).
Claims (8)
1. a kind of effective visible light catalytic system for preparing corresponding oxygenated compound by 5 hydroxymethyl furfural selective oxidation, feature
It is: is cationic with the tetramethyl based quaternary ammonium salt of high-quality, tetrem based quaternary ammonium salt, tetrapropyl quaternary ammonium salt, tetrabutyl quaternary ammonium salt
One of ten poly- wolframic acid ammonium salts are that catalyst reacts under room temperature, normal pressure using 5 hydroxymethyl furfural as substrate, and purity oxygen is oxygen
Agent, acetonitrile are reaction medium, and water is additive, and acidic aqueous solution is to promote agent, using built-in light-source formula Photoreactor, natural light
Light source is tungsten halogen lamp.
2. the method according to claim 1, it is characterised in that using 5 hydroxymethyl furfural as substrate, concentration of substrate 0.02-
0.1 mol/L。
3. the method according to claim 1, it is characterised in that using tungsten halogen lamp is light source, and irradiation power is 15-65 W.
4. the method according to claim 1, it is characterised in that with tetramethyl based quaternary ammonium salt, tetrem based quaternary ammonium salt, tetrabutyl season
Ammonium salt is that one of the ten poly- wolframic acid ammonium salts of cation are catalyst, and the catalyst of optimization is the poly- wolframic acid quaternary ammonium of tetramethyl ten
Salt, dosage are the 0.25-3.0 mmol% of reaction substrate.
5. the method according to claim 1, it is characterised in that use molecular oxygen as oxidant, pressure 1-2atm.
6. the method according to claim 1, it is characterised in that using water as additive, dosage is 1.0-7.0 mol/L.
7. the method according to claim 1, it is characterised in that acidic aqueous solution is promotor, using hydrochloric acid (0.05-0.4
It mol/L) is acid accelerator.
8. the method according to claim 1, it is characterised in that the reaction time is 6 ~ 16 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810741462.7A CN109107605B (en) | 2018-07-09 | 2018-07-09 | Ammonium decatungstate with high-efficiency photocatalytic oxidation and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810741462.7A CN109107605B (en) | 2018-07-09 | 2018-07-09 | Ammonium decatungstate with high-efficiency photocatalytic oxidation and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN109107605A true CN109107605A (en) | 2019-01-01 |
| CN109107605B CN109107605B (en) | 2021-05-04 |
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