CN109621983A - Optical and thermal synergistic catalyst and its application of aromatic aldehyde are obtained for selective oxidation aromatic alcohol - Google Patents
Optical and thermal synergistic catalyst and its application of aromatic aldehyde are obtained for selective oxidation aromatic alcohol Download PDFInfo
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- CN109621983A CN109621983A CN201811567848.7A CN201811567848A CN109621983A CN 109621983 A CN109621983 A CN 109621983A CN 201811567848 A CN201811567848 A CN 201811567848A CN 109621983 A CN109621983 A CN 109621983A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000003287 optical effect Effects 0.000 title claims abstract description 48
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical group O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 54
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 27
- 235000019445 benzyl alcohol Nutrition 0.000 description 17
- 238000005286 illumination Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012675 alcoholic extract Substances 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical compound [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- -1 CdS Chemical class 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses optical and thermal synergistic catalyst and its applications that aromatic aldehyde is obtained for selective oxidation aromatic alcohol, which be combined by photochemical catalyst and thermocatalyst.Catalyst of the invention obtains aromatic aldehyde for selective oxidation aromatic alcohol, and stability is high, activity is high, reaction condition is mild and nontoxic and pollution-free, energy consumption is very low.
Description
Technical field
The present invention relates to a kind of catalyst that aromatic aldehyde is obtained for selective oxidation aromatic alcohol.
Background technique
Aromatic aldehyde is the indispensable intermediate for synthesizing perfume, drug and some other fine chemicals, industrially
With very big application value.Tradition prepares the method (chemical oxidization method or thermocatalytic method) of aromatic aldehyde, and there are serious defects
And deficiency, such as need using a large amount of toxic or there is corrosive oxidant (KMnO4、CrIV、ClO-And Cl2), and can consume
Big energy goes to maintain necessary special reaction environment.These defects and deficiency do not meet Green Chemistry objective.Due to photocatalysis
Reaction has the innate advantages such as highly selective, clean power source and mild reaction condition, so for catalysis oxidation fragrance
It is a kind of extraordinary method that alcohol, which selectively produces aromatic aldehyde,.However, it is desirable to industrially there is feasibility, the catalysis of participation
Agent should enough efficiently, such as can only absorb ultraviolet light broad-band gap photochemical catalyst with regard to unsuitable.So how to design light
Catalyst is a problem to be solved with the efficiency for improving its catalysis oxidation aromatic alcohol.
Summary of the invention
The present invention is intended to provide it is a kind of for selective oxidation aromatic alcohol obtain aromatic aldehyde optical and thermal synergistic catalyst and its
Preparation method and application, it is intended to solve industrially to prepare asking for aromatic aldehyde highly energy-consuming, high pollution and preparation process complexity now
Topic.
Aromatic alcohol is converted to the process that aromatic aldehyde is a dehydrogenation, present invention discover that metal oxide and metal oxidation are compound
Object is the dehydrogenation thermocatalyst of more efficient.And on the other hand, the photohole of photochemical catalyst can aoxidize aromatic alcohol to fragrance
Aldehyde, such as CdS, forbidden bandwidth 2.4eV have stable electrochemistry and spectrochemical property, and CdS was also once urged for selectivity
Change oxidation aromatic alcohol, but its efficiency is unsatisfactory.Therefore, the present invention is attempted thermocatalyst (such as Cr2O3/Al2O3) and light
Catalyst (such as CdS) is made into a kind of composite material, so that this composite catalyst has light heat synergetic action catalysis oxidation fragrance
The ability of alcohol.
The present invention is to realize goal of the invention, is adopted the following technical scheme that
The invention discloses a kind of optical and thermal synergistic catalyst that aromatic aldehyde is obtained for selective oxidation aromatic alcohol, heat
Point is: the optical and thermal synergistic catalyst is combined by photochemical catalyst and thermocatalyst.Preferably, the thermocatalyst
For Cr2O3、 CeO2、ZnO、ZrO2、TiO2Or Cr2O3-Al2O3, the photochemical catalyst is CdS, ZnIn2S4、In2S3、CdIn2S4、
CdLa2S4、 CdxZn1-xS (x=0-1), Zn3In3S6、TiO2Or C3N4.In the optical and thermal synergistic catalyst, the thermocatalytic
The quality of agent accounts for the 1%-99% of the photochemical catalyst quality.
It is furthermore preferred that the optical and thermal synergistic catalyst is that have thermocatalyst Cr in the area load of photochemical catalyst CdS2O3-
Al2O3(it is denoted as (Cr2O3/Al2O3)/CdS, is abbreviated as CAO/CdS), thermocatalyst Cr2O3/Al2O3It is by bulk multi-hole
Al2O3As main body, Cr2O3It is embedded in Al2O3In hole, photochemical catalyst is CdS nanometer rods.The structure of entire catalyst is fluffy
The porous thermocatalyst of pine is supported in CdS nanometer rods, with the increase of thermocatalyst CAO content, outside CdS nanometer rods
Gradually form package structure.In the optical and thermal synergistic catalyst, as the thermocatalyst Cr2O3-Al2O3Quality account for institute
When stating the 50% of photochemical catalyst CdS mass, catalytic performance is best.
The preparation method of above-mentioned optical and thermal synergistic catalyst, is to be add to deionized water photochemical catalyst and thermocatalyst,
5-6h is persistently stirred, is then centrifuged for, dries, is i.e. acquisition optical and thermal synergistic catalyst.
The present invention further discloses the applications of the optical and thermal synergistic catalyst, i.e., for being used as catalyst, selectively urge
Change oxidation aromatic alcohol and obtains aromatic aldehyde.The H of thermocatalyst and aromatic alcohol in optical and thermal synergistic catalystαWith alcoholic extract hydroxyl group phase interaction
With so that C-H is weakened, so that the hole (h of photocatalyst surface+) and superoxide radical (O2 -) oxygen can be more easier
Change aromatic alcohol and generates aromatic aldehyde.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, catalyst stability of the invention is high, activity is high, reaction condition is mild and nontoxic and pollution-free, energy consumption is very low.
2, it is 51.6% that photo-thermal catalyst choice Oxybenzene methyl alcohol prepared by the present invention, which generates the yield of benzaldehyde, is compared
3.1 times and 2.8 times have been respectively increased in single thermocatalytic CAO (16.7%) and photochemical catalyst CdS (18.1%), have had very
High industrial application value.
Detailed description of the invention
Fig. 1 is the XRD spectrum of single photochemical catalyst CdS, thermocatalyst CAO and optical and thermal synergistic catalyst x%CAO/CdS；
Fig. 2 is single photochemical catalyst CdS (Fig. 2 (A)), thermocatalyst CAO (Fig. 2 (B)) and optical and thermal synergistic catalyst
The SEM image of 50%CAO/CdS (Fig. 2 (C)), 90%CAO/CdS (Fig. 2 (D))；
Fig. 3 is single photochemical catalyst CdS (Fig. 2 (A)), thermocatalyst CAO (Fig. 2 (B)) and optical and thermal synergistic catalyst
The TEM map of 50%CAO/CdS (Fig. 2 (C)), 90%CAO/CdS (Fig. 2 (D))；
Fig. 4 is the TEM-Mapping map of optical and thermal synergistic catalyst 50%CAO/CdS, in which: (A) is optical and thermal collaboration
The local T EM map of catalyst 50%CAO/CdS, (B)-(F) are respectively the distribution diagram of element of Al, S, Cr, Cd and O element；
Fig. 5 is the XPS test spectral of optical and thermal synergistic catalyst 50%CAO/CdS；
Fig. 6 is using CdS, CAO and x%CAO/CdS catalyst at radiation of visible light (0.1g catalyst, 353.15K, 4h)
Lower selective oxidation benzyl alcohol prepares the activity figure of benzaldehyde；
Fig. 7 is selected under heating and radiation of visible light (0.05g catalyst, 353.15K, 4h) respectively using CdS, CAO
Property Oxybenzene methyl alcohol prepares the activity of benzaldehyde, with 50%CAO/CdS catalyst radiation of visible light (0.1g catalyst,
353.15K, 4h) under selective oxidation benzyl alcohol prepare the active comparison diagram of benzaldehyde；
Fig. 8 is CdS, CAO and 50%CAO/CdS catalyst DMPO-O after illumination 6min2 -ESR signal map；
Fig. 9 is the ESR signal map of CdS, CAO and 50%CAO/CdS catalyst DMPO-OH after illumination 3min；
Figure 10 is the mechanism figure that photo-thermal catalyst choice Oxybenzene methyl alcohol prepared by the present invention generates benzaldehyde.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
The invention discloses the optical and thermal synergistic catalysts being combined by photochemical catalyst and thermocatalyst, are used for selecting
Selecting property aoxidizes aromatic alcohol and obtains aromatic aldehyde.The present embodiment tests it as catalysis by taking optical and thermal synergistic catalyst CAO/CdS as an example
Agent generates the effect of benzaldehyde to selective oxidation benzyl alcohol, while with single photochemical catalyst CdS nanometer rods, thermocatalyst
CAO is as a comparison.
The present embodiment optical and thermal synergistic catalyst CAO/CdS's the preparation method is as follows:
(1) preparation of photochemical catalyst CdS nanometer rods:
CdS nanometer rods use solvent structure, are added 15mmol's in the polytetrafluoroethyllining lining of 100mL autoclave
Cd(NO3)2·4H2The thiocarbamide of 0 and 45mmol adds 60mL ethylenediamine solution, stirs 30min, after waiting solid to be completely dissolved
Magneton is taken out, polytetrafluoroethyllining lining is placed in steel bushing and is sealed, 160 DEG C of reaction 48h in baking oven are then placed in；After reaction
Bright yellow solid is obtained, is repeatedly washed through dehydrated alcohol and deionized water and then 80 DEG C of vacuum drying 8h, i.e. acquisition light is urged
Agent CdS nanometer rods.
(2) preparation of thermocatalyst CAO:
Cr (the NO of 2.0g template agent F127 and 473.89mg is weighed first3)3·9H2O is placed in 50mL beaker, is added
20mL dehydrated alcohol persistently stirs 4h, obtains solution A；
A 50mL beaker is separately taken, 3.65g aluminium isopropoxide and 10mL dehydrated alcohol is added, it is dense that 3.2mL is added dropwise while stirring
Nitric acid after waiting aluminium isopropoxide to be completely dissolved, 10mL dehydrated alcohol is added into solution again, obtains solution B；
Solution B is slowly transferred in solution A, continues to stir 5h, obtains green solution；This solution is directly placed into air blast
60 DEG C of baking 48h, make its solvent volatilize completely in drying box, and gained sample is put into Muffle furnace and calcines 6h under the conditions of 700 DEG C, institute
Obtaining dark green solid is thermocatalytic Cr2O3-Al2O3(CAO)。
(3) preparation of optical and thermal synergistic catalyst CAO/CdS:
By required mass ratio, photochemical catalyst CdS nanometer rods prepared by step (1) and step (2) and thermocatalyst CAO,
It is put into the beaker equipped with deionized water, persistently stirs 5-6h, be then centrifuged for drying, is i.e. acquisition optical and thermal synergistic catalyst x%
CAO/CdS, wherein x% is thermocatalyst Cr2O3-Al2O3Quality account for the percentage of photochemical catalyst CdS mass.For x pairs of comparison
The influence of catalyst performance, the present embodiment prepare optical and thermal synergistic catalyst 1%CAO/CdS, 5%CAO/CdS, 10%CAO/ altogether
CdS, 20%CAO/CdS, 50%CAO/CdS, 80%CAO/CdS, 90%CAO/CdS, 95%CAO/CdS, 99%CAO/CdS.
Fig. 1 is the XRD spectrum of single photochemical catalyst CdS, thermocatalyst CAO and optical and thermal synergistic catalyst x%CAO/CdS,
As can be seen from the figure as the increase of thermocatalyst content, the characteristic diffraction peak of photochemical catalyst CdS gradually decrease, work as thermocatalytic
Agent content angle 33 ° of position the characteristic diffraction peak of thermocatalyst can occur as seen from the figure when reach 80%.
Fig. 2 is single photochemical catalyst CdS (Fig. 2 (A)), thermocatalyst CAO (Fig. 2 (B)) and optical and thermal synergistic catalyst
The SEM image of 50%CAO/CdS (Fig. 2 (C)), 90%CAO/CdS (Fig. 2 (D)).As can be seen from the figure: photochemical catalyst CdS
For nanometer rods, thermocatalyst CAO is mainly bulk multi-hole structure, and it can be seen that with heat from Fig. 2 (C) and Fig. 2 (D)
The increase of the compound content of catalyst, photochemical catalyst are gradually wrapped.
Fig. 3 is single photochemical catalyst CdS (Fig. 3 (A)), thermocatalyst CAO (Fig. 3 (B)) and optical and thermal synergistic catalyst
The TEM map of 50%CAO/CdS (Fig. 3 (C)), 90%CAO/CdS (Fig. 3 (D)).As can be seen from the figure photochemical catalyst CdS is true
Actually nanometer rods and its length is about 0.2-1 μm, there are porous structures on the surface thermocatalyst CAO, and from Fig. 3 (C) and Fig. 3
(D) it can be seen that the increase with the compound content of thermocatalyst in, photochemical catalyst is gradually wrapped.
Fig. 4 is the TEM-Mapping map of optical and thermal synergistic catalyst 50%CAO/CdS, as can be seen from the figure 50%
The content distribution situation of each element in CAO/CdS catalyst, each element is regular distribution, due to Cr2O3Content is few,
So the Cr constituent content shown in Fig. 4 (D) is less.
Fig. 5 is the XPS test spectral of optical and thermal synergistic catalyst 50%CAO/CdS: optical and thermal synergistic catalyst 50%CAO/
The full spectrogram of CdS (Fig. 5 (A)), Cr 2p High-Resolution Map (Fig. 5 (B)), Cd 3d High-Resolution Map (Fig. 5 (C)), Al 2p High-Resolution Map
(Fig. 5 (D)), S 2p High-Resolution Map (Fig. 5 (E)) and O 1s High-Resolution Map (Fig. 5 (F)).As can be seen from the figure Cd 3d high score
Distinguish that figure splits into two peaks Cd 3d5/2 (404.5eV) and Cd 3d3/2 (411.2eV), this and Cd2+Value it is consistent.Cd3d5/2
6.7eV difference between the combination energy at the peak Cd3d3/2 is also Cd2+The feature of state.Occur in 161.3eV and 159.5eV
The peak S 2p is S2-Normal condition.There are two peaks in the spectrum of Cr 2p, and one is located at 588.0eV, another peak is located at
588.5eV showing Cr2O3In Cr be Cr3+State.Its corresponding Photoelectron peak of the O and Al observed appears in 530.5eV
(O1s) and the position 74.1eV (Al2p), show O and Al with O respectively2-And Al3+Normal condition exist.
It is generated to test optical and thermal synergistic catalyst x%CAO/CdS manufactured in the present embodiment to selective oxidation benzyl alcohol
The effect of benzaldehyde, at the same it is raw to selective oxidation benzyl alcohol with single thermocatalyst CAO and single photochemical catalyst CdS
A comparison is done at the effect of benzaldehyde, experimental method is as follows: being 0.038mol/L benzene first by 0.1g catalyst and 15mL concentration
The benzotrifluoride solution of alcohol is placed in 100mL polytetrafluoroethylcontainer container, is then covered in visual autoclave.In photocatalysis
Before reaction carries out, the oxygen of 10min is first led into reaction kettle, to have the function that exclude air in reaction kettle, then proceedes to lead to
Enter oxygen and reacting kettle inner pressure is maintained at 0.1Mpa.Then consersion unit is placed on magnetic stirring apparatus, in the shape of isolation light
Under state, dark adsorption took stirs 30min, so that catalyst is uniformly dispersed in the solution, and reach desorption adsorption equilibrium.Later
It uses the xenon lamp of 300W as the transmitting light source of visible light, removes wave with optical filter (λ > 420nm, Bo Fei Lay Instrument Ltd.)
The long light for being less than 420nm irradiates 4h to reaction solution, and measuring visual reaction under high pressure temperature in the kettle using thermocouple is 353.15K.
After reaction, catalyst and reaction substrate are separated with centrifuge, obtain the supernatant after required reaction, in solution
The concentration of various substances carries out quantitative analysis with gas chromatograph (GC-2014, Suzhou Shimadzu Shimadzu).Reactant turns
Rate, the yield of product, selectivity can be indicated with formula (1)-(3):
Conversion ratio (%)=[(C-CAlcohol)/C0]×100 (1)；
Yield (%)=CAldehyde/C0×100 (2)；
Selectivity (%)=[CAldehyde/(C0–CAlcohol)]×100 (3)；
In formula, C0For the initial concentration of aromatic alcohol, CAlcoholAnd CAldehydeIt is the concentration and generation of benzyl alcohol after reaction terminates respectively
Corresponding benzaldehyde concentration.
By above-mentioned experimental method, using CdS, CAO and x%CAO/CdS catalyst radiation of visible light (0.1g catalyst,
353.15 K, 4h) under selective oxidation benzyl alcohol prepare the conversion ratio of benzaldehyde, yield, selectivity as shown in table 1, partially urge
The activity figure that agent selective oxidation benzyl alcohol prepares benzaldehyde is as shown in Figure 6.It can be seen that with thermocatalyst compound quantity
It improves, the effect that benzyl alcohol selective oxidation generates benzaldehyde is in first to increase the trend reduced afterwards.When containing for thermocatalyst CAO
When amount reaches 50%, catalytic effect is best, and the conversion ratio of benzyl alcohol reaches 52.1%, and the yield of benzaldehyde reaches
51.6%, the selectivity of target product benzaldehyde is up to 99.0%.
Table 1
| Catalyst | Conversion ratio | Yield | Selectivity |
| CAO | 17.2% | 16.7% | 97.0% |
| CdS | 19.4% | 18.1% | 93.4% |
| 1%CAO/CdS | 35.6% | 35.1% | 98.6% |
| 5%CAO/CdS | 39.7% | 39.4% | 99.2% |
| 10%CAO/CdS | 38.1% | 37.8% | 99.4% |
| 20%CAO/CdS | 38.8 | 38.8% | 100% |
| 50%CAO/CdS | 52.1% | 51.6% | 99.0% |
| 80%CAO/CdS | 44.5% | 44.3% | 99.4% |
| 90%CAO/CdS | 40.9% | 40.7% | 99.5% |
| 95%CAO/CdS | 36.3% | 35.9% | 98.9% |
| 99%CAO/CdS | 27.9% | 27.5% | 98.6% |
By above-mentioned identical experimental method, the dosage of catalyst is changed to 0.05g, to single thermocatalyst CAO, single
Photochemical catalyst CdS the test of catalytic performance is carried out under conditions of illumination or 80 DEG C of oil baths.Fig. 7 is distinguished using CdS, CAO
Heating the work that benzaldehyde is prepared with selective oxidation benzyl alcohol under radiation of visible light (0.05g catalyst, 353.15K, 4h)
Property, with 50%CAO/CdS catalyst at radiation of visible light (0.1g catalyst, 353.15K, 4h) selective oxidation benzyl alcohol
Prepare the active comparison diagram of benzaldehyde.From fig. 6, it can be seen that after illumination 4h, 50%CAO/CdS catalysis oxidation benzyl alcohol
Active highest, the conversion ratio of benzyl alcohol and the yield of benzaldehyde have respectively reached 51.6% and 99.0%.However, single
One thermocatalyst CAO under the same conditions benzaldehyde yield be 16.7%, single photochemical catalyst CdS is in identical item
The yield of benzaldehyde is 18.1% under part.Activity data can be clearly seen that photochemical catalyst 50mg CdS is only being heated in Fig. 7
It is that no target product benzaldehyde generates in the case where not illumination, the yield of benzaldehyde is after illumination 4h condition
11.7%；Single 50mg thermocatalyst CAO yield of target product benzaldehyde in the case where only heating not illumination is
The yield of benzaldehyde is 11.0% after 10.8%, illumination 4h.It can be seen that 50%CAO/CdS selective oxidation benzyl alcohol generates
The ability of benzaldehyde is not that two monolithic catalyst catalytic effects simply sum it up.The experimental results showed that 50%CAO/CdS light
Thermocatalyst not only can significantly promote the conversion ratio of benzyl alcohol, and the selectivity of target product benzaldehyde is also very
Height.
Fig. 8 and Fig. 9 is DMPO-O respectively2 -The ESR of ESR signal map and DMPO-OH after illumination after illumination
Signal map.CdS, CAO and 50%CAO/CdS catalyst that Fig. 8 is shown DMPO-O after illumination 6min2 -ESR signal graph
Spectrum, can be clear that optical and thermal synergistic catalyst 50%CAO/CdS its DMPO-O after illumination 6min2 -Signal want
It is apparently higher than DMPO-O after single photochemical catalyst CdS and single thermocatalyst CAO illumination 6min2 -Signal.With Fig. 6
Middle activity data binding analysis it can be concluded that in entire reaction process O2 -Play the role of vital.And Fig. 9 is then
The ESR signal map of CdS, CAO and 50%CAO/CdS catalyst DMPO-OH after illumination 3min, can be apparent from Fig. 9
The ESR signal for seeing optical and thermal synergistic catalyst 50%CAO/CdS its DMPO-OH after illumination 3min almost without signal
Not the phenomenon that not occurring enhancing, so in conjunction with activity data analysis in Fig. 6 it can be concluded that OH is simultaneously in entire reaction process
Do not play an important role.
Figure 10 is the mechanism figure that optical and thermal synergistic catalyst selective oxidation benzyl alcohol generates benzaldehyde.It is compounded in light first
The thermocatalyst CAO of catalyst surface starts to interact with the alcoholic extract hydroxyl group of benzyl alcohol and H α under heating condition, to weaken
C-H α key and O-H key, secondly photochemical catalyst CdS can generate light induced electron and hole under illumination condition, electronics and be attached to catalysis
The O on agent surface2Effect forms active specy O2 -.Since thermocatalytic weakens C-H α key and O-H key, so O2 -The hole and
What can be more easier promotes benzyl alcohol oxidation dehydrogenation to become benzaldehyde.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. obtaining the optical and thermal synergistic catalyst of aromatic aldehyde for selective oxidation aromatic alcohol, it is characterised in that: the optical and thermal association
It with catalyst is combined by photochemical catalyst and thermocatalyst.
2. optical and thermal synergistic catalyst according to claim 1, it is characterised in that: the thermocatalyst is Cr2O3、CeO2、
ZnO、ZrO2、TiO2Or Cr2O3-Al2O3；The photochemical catalyst is CdS, ZnIn2S4、In2S3、CdIn2S4、CdLa2S4、CdxZn1- xS (x=0-1), Zn3In3S6、TiO2Or C3N4。
3. optical and thermal synergistic catalyst according to claim 1 or 2, it is characterised in that: in the optical and thermal synergistic catalyst
In, the quality of the thermocatalyst accounts for the 1%-99% of the photochemical catalyst quality.
4. optical and thermal synergistic catalyst according to claim 2, it is characterised in that: the optical and thermal synergistic catalyst is in light
The area load of catalyst CdS has thermocatalyst Cr2O3-Al2O3。
5. optical and thermal synergistic catalyst according to claim 4, it is characterised in that: in the optical and thermal synergistic catalyst,
The thermocatalyst Cr2O3-Al2O3Quality account for the 50% of the photochemical catalyst CdS mass.
6. the preparation method of optical and thermal synergistic catalyst described in a kind of any one of Claims 1 to 5, it is characterised in that: will
Photochemical catalyst and thermocatalyst are add to deionized water, and persistently stir 5-6h, are then centrifuged for, are dried, i.e. the collaboration of acquisition optical and thermal
Catalyst.
7. the application of optical and thermal synergistic catalyst described in a kind of any one of Claims 1 to 5, it is characterised in that: be used for conduct
Catalyst, selective catalytic oxidation aromatic alcohol obtain aromatic aldehyde.
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