CN109107605B - 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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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 title abstract description 23
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 24
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 17
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 tetramethyl quaternary ammonium salt Chemical class 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical group 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 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 5
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 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
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 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
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 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
- 238000001308 synthesis method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
- 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
-
- 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
- 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
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- 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
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical industry, and particularly discloses an ammonium decatungstate catalyst with high-efficiency photocatalytic oxidation and application thereof. The catalyst is ammonium decatungstate with 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 in an acetonitrile medium, an acidic aqueous solution is used as a promoter to implement green selective oxidation of bio-based micromolecule 5-hydroxymethylfurfural, so that 5-hydroxymethylfurfural can be effectively subjected to photocatalytic oxidation to be converted into a corresponding oxygen-containing product 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 the field of chemical industry, and particularly discloses an ammonium decatungstate catalyst with high-efficiency photocatalytic oxidation and application thereof.
Background
At present, environmental pollution and fossil energy shortage are two serious problems facing the world, and the search for renewable and sustainable fuel and chemical alternatives has become a research hotspot. The chemical industry has focused their attention on production processes that employ environmentally friendly biomass resources. The biomass resource has the advantages of low price, rich reserves, reproducibility and the like. The renewable substances such as lignin, cellulose, hemicellulose and the like are abundant and cheap in resources. By utilizing the compound, 5-Hydroxymethylfurfural (HMF) as a platform compound can be prepared by conversion. HMF, one of important bio-based platform compounds, can be prepared by dehydrating renewable biomass carbohydrates, has attracted much attention, and can be further converted into various high-quality fuels and high value-added compounds, such as 2, 5-furandicarboxaldehyde (DFF) or 2, 5-furandicarboxylic acid (FDCA), and the like, and thus has gradually become a research hotspot.
2, 5-Furanedicarboxylic acid (FDCA) and 2, 5-Diformylfuran (DFF) are important organic synthesis intermediates, and can be used for preparing various alkyl substituted or ester furan derivatives, so that the catalytic oxidation of HMF is widely researched. At present, the main methods for catalytic oxidation of 5-hydroxymethylfurfural include chemical catalysis, enzyme catalysis and electrocatalysis. The chemical catalysis method mainly adopts reagents with strong oxidizing property (such as chromate, dichromate, permanganate and the like), homogeneous metal salts and supported noble metal catalysts. These oxidizing agents have the disadvantages of environmental pollution and toxicity, and the catalysts are expensive and costly. There are reports in the literature that the use of copper as a catalyst and molecular oxygen or hydrogen peroxide as an oxidant, although solving the cost problem, results in relatively low product selectivity.
With the rise of photocatalysis, the photocatalysis technology becomes one of the most promising technologies for solving the problems of the current energy crisis, environmental pollution and the like. Photocatalytic oxidation technology has been developed for decades and has made significant progress in industrial wastewater treatment. Some effective photocatalysts such as TiO2，Fe-TiO2，Cr-SiO2，V2O5-Al2O3，NaY，Fe (III) porphyrin complexes, Fe(III)Cl3And Cu (II) Cl2And di-Os (VI) complex have been successfully used in UV or visible light catalyzed photocatalytic oxidative conversion of molecular oxygen-selective hydrocarbons. The semiconductor oxide photocatalyst reported at present has the advantages of low price and convenient recovery and reuse; but its ultraviolet, especially visible light, catalytic molecular oxygen selective oxidation efficiency is still low. Some transition metal complexes, while exhibiting high photocatalytic oxidation efficiency, have high synthesis costs that limit their applications. It has been found that organic ammonium decatungstate solids or solutions (in water or certain organic solvents) turn blue under UV radiation, and that certain systems may even turn blue on dayIt also turns blue in light; in addition, the decatungstate has very attractive photo-oxidation catalytic activity (O) on saturated hydrocarbon2 Is an oxidizing agent) and thus its application as a photocatalyst to organic chemical reactions is an active research topic in the field of polyacid chemistry in recent years. Because the absorption of the ammonium decatungstate in a visible light region is weak, the photocatalytic oxidation efficiency is low, and the conversion rate of the ammonium decatungstate used for the research of the photocatalytic performance is generally low.
In order to develop a green and efficient selective catalytic maintenance system for 5-hydroxymethylfurfural, aiming at the defects of the prior art, the invention aims to develop a reaction system for selectively oxidizing HMF by using decatungstate photocatalysis molecular oxygen excited by visible light by using ammonium decatungstate (tetramethyldecatungstate quaternary ammonium salt and tetrabutyldecatungstate quaternary ammonium salt) of carbon chain quaternary ammonium salts with different lengths as a catalyst and select certain acidic solution accelerators to improve the photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a synthesis method for preparing high-quality quaternary ammonium decatungstate, which is a research system for catalytic oxidation of 5-hydroxymethylfurfural by visible light irradiation under normal temperature, normal pressure and condensation conditions by using molecular oxygen as an oxidant and acetonitrile as a reaction medium to obtain the quaternary ammonium decatungstate (tetramethyl quaternary ammonium salt, tetraethyl quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt) of carbon chain quaternary ammonium salts with different lengths.
The method for preparing the quaternary ammonium decatungstate comprises the following steps:
(1) dissolving 6.0 g of sodium tungstate dihydrate in 35 mL of water, putting the solution into a three-neck flask, putting the three-neck flask into a water bath kettle at 25 ℃, slowly dropwise adding 2mol/L hydrochloric acid into the three-neck flask, and adjusting the pH value to 2.3;
(2) quickly transferring the reaction solution into a water bath at 80 ℃, and continuously adjusting the pH value to 2.05 by using a prepared hydrochloric acid solution;
(3) and (3) after polymerization for 10 min, slowly dropwise adding the prepared quaternary ammonium salt aqueous solution with different carbon chains into a three-neck flask, gradually generating a large amount of white precipitates, adjusting the pH value to the value in the step (2) by using a hydrochloric acid solution, continuously reacting for 25 min, fully cooling, and performing suction filtration to obtain a white solid.
The invention has the following advantages:
(1) the required catalyst raw materials are easy to obtain, and the synthesis process is simple;
(2) the whole reaction system has mild conditions, and is green and environment-friendly.
Drawings
FIG. 1 shows a photoreactor with a built-in light source.
FIG. 2 shows UV spectra of tetrabutylammonium decatungstate (a) and tetramethylammonium decatungstate (b).
Detailed Description
The following examples are further illustrative of the present invention and are not to be construed as limiting the invention to the particular examples set forth.
Example 1: the preparation method of the high-quality quaternary ammonium decatungstate comprises the following steps:
(1) dissolving 6.0 g of sodium tungstate dihydrate in 35 mL of water, putting the solution into a three-neck flask, putting the three-neck flask into a water bath kettle at 25 ℃, slowly dropwise adding 2mol/L hydrochloric acid into the three-neck flask, and adjusting the pH value to 2.3;
(2) quickly transferring the reaction solution into a water bath at 80 ℃, and continuously adjusting the pH value to 2.05 by using a prepared hydrochloric acid solution;
(3) after polymerization is carried out for 10 min, slowly dropwise adding the prepared quaternary ammonium salt (tetramethyl quaternary ammonium salt, tetraethyl quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt) water solution with different carbon chains into a three-neck flask, gradually generating a large amount of white precipitates, adjusting the pH value to the value in the step (2) by using a hydrochloric acid solution, continuously reacting for 25 min, fully cooling, and carrying out suction filtration to obtain a white solid.
Examples 2 to 5: the method of example 1 is used to prepare tetramethyl ammonium tungstate, tetraethyl ammonium tungstate, tetrapropyl ammonium tungstate and tetrabutyl ammonium tungstate as catalysts (2 mmol%), molecular oxygen as an oxidant, 5.0 mL of reaction solution, acetonitrile as a medium, water as an additive, the reaction temperature is 25 ℃, 5-hydroxymethylfurfural (0.02 mol/L) is catalytically oxidized under the irradiation of visible light of a 35W tungsten halogen lamp under the conditions of normal pressure (1 atm) and condensation, and the reaction time is 12 hours. The reaction product was analyzed by gas chromatography. Specific results are shown in table 1.
Table 1 quaternary ammonium tetraalkyldecatungstate photocatalytically oxidizes 5-hydroxymethylfurfural.
Examples 6 to 12: the photocatalytic oxidation reaction and the chromatographic analysis of the reaction product were carried out in accordance with the procedure described in [0021] using the tetramethyldecatungstate (0.25 to 3.0 mmol%) prepared in example 1 as a catalyst. The specific results are shown in Table 2.
Table 2 effect of catalyst addition on catalytic oxidation of 5-hydroxymethylfurfural with molecular oxygen under visible light.
Examples 13 to 17: the photocatalytic oxidation reaction and the chromatographic analysis of the reaction product were carried out by the procedure described in [0021] using tetramethyldecatungstate (2 mmol%) obtained by the method described in example 1 as a catalyst and hydrochloric acid (0.05 to 0.4 mol/L) as an additive. The specific results are shown in Table 3.
TABLE 3 Effect of hydrochloric acid addition on catalytic molecular oxygen oxidation of 5-hydroxymethylfurfural under visible light.
Examples 18 to 21: the photocatalytic oxidation reaction and the chromatographic analysis of the reaction product were carried out by the procedure described in [0021] using tetramethyldecatungstate (2 mmol%) obtained by the method described in example 1 as a catalyst and water (1.0 to 7.0 mol/L) as an additive. The specific results are shown in Table 4.
Table 4 effect of water addition on catalytic oxidation of 5-hydroxymethylfurfural with molecular oxygen under visible light.
Examples 22 to 24: using tetramethyldecatungstate (2 mmol%) obtained by the method described in example 1 as a catalyst, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) as additives, and 5-hydroxymethylfurfural (0.02 to 0.1 mol/L) as a reaction substrate, a photocatalytic oxidation reaction and a chromatographic analysis of a reaction product were carried out in accordance with the procedure described in [0021 ]. The specific results are shown in Table 5.
Table 5 effect of substrate concentration on the catalytic oxidation of 5-hydroxymethylfurfural by molecular oxygen with catalyst under visible light.
Examples 25 to 30: the photocatalytic oxidation reaction and the chromatographic analysis of the reaction product were carried out according to the procedure described in [0021] with the catalyst of tetramethyldecatungstate (2 mmol%) prepared in example 1, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) as additives, and the reaction time of 6-16 h. The specific results are shown in Table 6.
Table 6 effect of reaction time on catalytic molecular oxygen oxidation of 5-hydroxymethylfurfural under visible light.
Examples 31 to 32: using the tetramethyldecatungstate (2 mmol%) prepared in example 1 as a catalyst, tungsten halogen lamps (15W and 65W, respectively, corresponding to examples 31 and 32) as a light source, and hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) as additives, a photocatalytic oxidation reaction and a chromatographic analysis of the reaction product were carried out in accordance with the procedure described in [0021 ]. The specific results are shown in Table 7.
The effect of a tungsten halogen lamp in table 7 on the catalytic oxidation of 5-hydroxymethylfurfural by molecular oxygen under visible light.
Examples 33 to 35: using the tetramethyldecatungstate (2 mmol%) prepared in example 1 as a catalyst, oxygen (1-2 atm) as an oxidizing agent, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) as additives, the reaction time was 12 hours, and the photocatalytic oxidation reaction and the chromatographic analysis of the reaction product were performed according to the procedure described in [0021], and the total reaction yield was 45.12%. The specific results are shown in Table 8.
Table 8 effect of oxygen tension on catalytic molecular oxygen oxidation of 5-hydroxymethylfurfural under visible light.
Example 36: using tetramethyldecatungstate (2 mmol%) prepared in example 1 as a catalyst, air as an oxidizing agent, hydrochloric acid (0.2 mol/L) and water (5.0 mol/L) as additives, a photocatalytic oxidation reaction and a chromatographic analysis of a reaction product were performed according to the procedure described in [0021], and the total reaction yield was 24.12%.
Claims (6)
1. An efficient visible-light-catalyzed process for the selective oxidation of 5-hydroxymethylfurfural to the corresponding oxygen-containing compound, characterized by: one of high-quality tetramethyl quaternary ammonium salt, tetraethyl quaternary ammonium salt, tetrapropyl quaternary ammonium salt and tetrabutyl quaternary ammonium salt which are taken as cationic ammonium decatungstate salts is taken as a catalyst, 5-hydroxymethylfurfural is taken as a substrate and reacts at normal temperature and normal pressure, pure oxygen is taken as an oxidant, acetonitrile is taken as a reaction medium, 1.0-7.0 mol/L of water is taken as an additive, 0.05-0.4 mol/L of hydrochloric acid is taken as an acid promoter, a light source built-in photoreactor is adopted, a natural light source is a halogen tungsten lamp, and the irradiation power is 15-65W.
2. The method according to claim 1, wherein 5-hydroxymethylfurfural is used as a substrate, and the substrate concentration is 0.02 to 0.1 mol/L.
3. The method of claim 1, wherein the catalyst is one of ammonium decatungstate salts having a cation of tetramethylquaternary ammonium salt, tetraethylquaternary ammonium salt, tetrabutylquaternary ammonium salt, and the amount of the catalyst is 0.25 to 3.0 mmol% of the reaction substrate.
4. A process according to claim 3, characterized in that the catalyst used is tetramethyldecatungstate quaternary ammonium salt.
5. The method according to claim 1, characterized in that molecular oxygen is used as the oxidizing agent, the pressure of which is 1-2 atm.
6. The process according to claim 1, wherein the reaction time is 6 to 16 hours.
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