CN110026211A - A kind of heterojunction composite and preparation method and application - Google Patents
A kind of heterojunction composite and preparation method and application Download PDFInfo
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- CN110026211A CN110026211A CN201910398291.7A CN201910398291A CN110026211A CN 110026211 A CN110026211 A CN 110026211A CN 201910398291 A CN201910398291 A CN 201910398291A CN 110026211 A CN110026211 A CN 110026211A
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- barium sulfate
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 108
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 43
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 29
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001802 infusion Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000010944 silver (metal) Substances 0.000 claims abstract description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 229960004217 benzyl alcohol Drugs 0.000 claims description 16
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 150000008040 ionic compounds Chemical class 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000006709 oxidative esterification reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 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
- 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
- B01J27/053—Sulfates
-
- 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
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
Present disclose provides a kind of heterojunction composite and preparation method and applications, the heterojunction composite is that several noble metal nano particles are adhered on barium sulfate surface, the partial size of the barium sulfate is 1~3 μm, the partial size of the noble metal nano particles is 3~10nm, and the noble metal is gold, silver or platinum.Preparation method are as follows: the compound containing M ion is attached to the surface of barium sulfate using infusion process, then M ion reduction that barium sulfate surface is contained to the compound of M ion is M nanoparticle；Wherein, M Ag, Au or Pt, the partial size of barium sulfate are 1~3 μm.The carrier using micron-sized barium sulfate as noble metal nano particles of disclosure heterojunction composite, micron order BaSO4With big specific surface area, the surface for adhering to barium sulfate in the micron-scale of noble metal nano particles more evenly can be enable, meanwhile, synergistic effect is generated with noble metal nano particles, improves the catalytic activity of noble metal nano particles.
Description
Technical field
The disclosure belongs to inorganic non-metallic functional material preparation technical field, is related to a kind of heterojunction composite and preparation
Method and application.
Background technique
Here statement only provides background information related with the disclosure, without necessarily constituting the prior art.
Noble metal catalyst refers to the noble metal that can change chemical reaction velocity and itself be not involved in reaction final product
Material.Nano-noble metal catalyst shows very high catalytic activity, stability and selectivity.In heterogeneous catalysis field,
Noble metal solid catalyst occupies an important position, they are widely used in petrochemical industry, fine chemistry industry, environment protection catalytic, life
And the fields such as biochemistry.Noble metal catalyst is commonly divided into homogeneous catalyst and heterogeneous catalyst according to the Nomenclature Composition and Structure of Complexes.
Noble metal exists in the form of the nano particle state or metal cluster of high dispersive in homogeneous noble metal catalyst, such as Au catalyst.When
After gold is made into the superfines of nanometer scale, specific surface area is greatly increased, so that nanogold particle and larger size
Golden watch reveals different chemical activity and catalytic performance, it is generally recognized that the surface characteristic, volume and quantum ruler of this and gold particle
The factors such as very little are closely and related.
However, recognizing according to the disclosed invention people research, the active high, stability of precious metal nano-particle catalyst
Feature good, catalytic performance is good.But dispersibility and loading of the noble metal nano particles on carrier are difficult to control accurately simultaneously
The disadvantages of.
Summary of the invention
In order to solve the deficiencies in the prior art, purpose of this disclosure is to provide a kind of heterojunction composite and preparation methods
With application, which can effectively solve the problem that the uneven problem of noble metal dispersion.
To achieve the goals above, the technical solution of the disclosure are as follows:
On the one hand, several noble metal nano particles, the barium sulfate are adhered in a kind of heterojunction composite, barium sulfate surface
Partial size be 1~3 μm, the partial sizes of the noble metal nano particles is 3~10nm, and the noble metal is gold, silver or platinum.
Carrier of the micron-sized barium sulfate as noble metal nano particles in the disclosure, firstly, micron order barium sulfate has
High-specific surface area can enable the surface for adhering to barium sulfate in the micron-scale of noble metal nano particles more evenly, to solve
The uneven problem of noble metal nano particles dispersion, and then solve the problems, such as easy to reunite when noble metal nano particles separation；Secondly, micro-
The barium sulfate of meter level can generate synergistic effect with noble metal nano particles, improve the catalytic activity of noble metal nano particles.
On the other hand, a kind of preparation method of heterojunction composite, it is using infusion process that the compound containing M ion is attached
On the surface of barium sulfate, then barium sulfate surface is contained the compound of M ion M ion reduction be M nanoparticle；Its
In, M Ag, Au or Pt, the partial size of barium sulfate are 1~3 μm.
The disclosure is easy to adsorb M ion using micron-sized barium sulfate, thus enable using infusion process barium sulfate more
Attachment M ion mostly more evenly, then by reduction, so that M ion reduction is M nanoparticle, so as to make noble metal receive
Rice corpuscles is capable of the surface of attachment barium sulfate in the micron-scale more evenly.
The heterojunction composite that the third aspect, a kind of above-mentioned heterojunction composite or above-mentioned preparation method obtain is being urged
Change the application in benzyl alcohol oxidation and/or esterification.
Fourth aspect, a kind of catalyst of benzyl alcohol oxidation esterification, active constituent are above-mentioned heterojunction composite
Or the heterojunction composite that above-mentioned preparation method obtains.
5th aspect, a kind of preparation method of benzoic ether add above-mentioned heterojunction composite using benzyl alcohol as raw material
Or the heterojunction composite that above-mentioned preparation method obtains, first catalytic phenylmethanol carries out oxidation reaction and obtains benzoic acid, then is catalyzed
Benzoic acid and alcohol carry out esterification and obtain benzoic ether.
The disclosure has the beneficial effect that
1. the carrier using micron-sized barium sulfate as noble metal nano particles of disclosure heterojunction composite, micron
Grade BaSO4With big specific surface area, the attachment of noble metal nano particles more evenly barium sulfate in the micron-scale can be enable
Surface, meanwhile, synergistic effect is generated with noble metal nano particles, improves the catalytic activity of noble metal nano particles.
2. the preparation method operating method of the heterojunction composite of the disclosure is simple, it is at low cost, there is universality, be easy to
Large-scale production.
3. the heterojunction composite of the disclosure can be with catalytic phenylmethanol oxidative esterification reaction, and uses the hetero-junctions compound
Material conversion ratio with higher and selectivity.
Detailed description of the invention
The Figure of description for constituting a part of this disclosure is used to provide further understanding of the disclosure, and the disclosure is shown
Meaning property embodiment and its explanation do not constitute the improper restriction to the disclosure for explaining the disclosure.
Fig. 1 is BaSO prepared by the embodiment of the present disclosure 14The low power transmission electron microscope picture of@Ag (figure medium scale is 50nm)；
Fig. 2 is BaSO prepared by the embodiment of the present disclosure 24The low power transmission electron microscope picture of@Au (figure medium scale is 50nm)；
Fig. 3 is BaSO prepared by the embodiment of the present disclosure 34The low power transmission electron microscope picture of@Pt (figure medium scale is 50nm)；
Fig. 4 is the benzyl alcohol oxidation esterification initial conversion and selective figure of the embodiment of the present disclosure 4；
Fig. 5 is the cycle-index figure of the benzyl alcohol oxidation esterification of the embodiment of the present disclosure 4.
Specific embodiment
It is noted that described further below be all exemplary, it is intended to provide further instruction to the disclosure.Unless another
It indicates, all technical and scientific terms used herein has usual with disclosure person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the disclosure.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Cause to reuse the lower deficiency of performance in view of the separation of existing precious metal nano-particle catalyst difficulty is easy to reunite, is
Solution technical problem as above, the present disclosure proposes a kind of heterojunction composite and preparation method and applications.
A kind of exemplary embodiment of the disclosure, provides a kind of heterojunction composite, and the attachment of barium sulfate surface is several
Noble metal nano particles, the partial size of the barium sulfate are 1~3 μm, and the partial size of the noble metal nano particles is 3~10nm, institute
Stating noble metal is gold, silver or platinum.
Carrier of the micron-sized barium sulfate as noble metal nano particles in the disclosure, firstly, micron order barium sulfate has
High-specific surface area can enable the surface for adhering to barium sulfate in the micron-scale of noble metal nano particles more evenly, to solve
The uneven problem of noble metal nano particles dispersion, and then solve the problems, such as easy to reunite when noble metal nano particles separation；Secondly, micro-
The barium sulfate of meter level can generate synergistic effect with noble metal nano particles, improve the catalytic activity of noble metal nano particles.
The another embodiment of the disclosure provides a kind of preparation method of heterojunction composite, using infusion process
Compound containing M ion is attached to the surface of barium sulfate, then barium sulfate surface is contained the M of the compound of M ion from
Son is reduced to M nanoparticle；Wherein, M Ag, Au or Pt, the partial size of barium sulfate are 1~3 μm.
The disclosure is easy to adsorb M ion using micron-sized barium sulfate, thus enable using infusion process barium sulfate more
Attachment M ion mostly more evenly, then by reduction, so that M ion reduction is M nanoparticle, so as to make noble metal receive
Rice corpuscles is capable of the surface of attachment barium sulfate in the micron-scale more evenly.
In one or more embodiments of the embodiment, the step of the infusion process are as follows: barium sulfate is dispersed to containing M
It is impregnated in the compound solution of ion, then the solvent in solution is removed.
In the series embodiment, the concentration of compound is 0.1~1.5mg/mL in the compound solution containing M ion.
In the series embodiment, the compound containing M ion is silver nitrate, gold chloride or chloroplatinic acid.
When using silver nitrate, the concentration of silver nitrate is 0.45~0.55mg/mL in solution.
When using gold chloride, the concentration of Chlorine in Solution auric acid is 0.95~1.05mg/mL.
When using chloroplatinic acid, the concentration of Chlorine in Solution platinic acid is 0.65~0.75mg/mL.
In the series embodiment, dip time is 40~80min.
When using silver nitrate, dip time is 45~55min.
When using gold chloride, dip time is 65~75min.
When using chloroplatinic acid, dip time is 45~55min.
In one or more embodiments of the embodiment, the reducing agent that M nanoparticle uses is reduced to as NaBH4。
In one or more embodiments of the embodiment, the step of being reduced to M nanoparticle are as follows: by surface contain M from
The barium sulfate of sub- compound is added in reducing agent solution, after ultrasonic reaction, is centrifuged.
In the series embodiment, the concentration of reducing agent is 5~15mg/mL in reducing agent solution.
In the series embodiment, ultrasonic time is 5~10min.
When using silver nitrate, ultrasonic time is 6.5~7.5min.
When using gold chloride, ultrasonic time is 7.5~8.5min.
When using chloroplatinic acid, ultrasonic time is 7.5~8.5min.
In one or more embodiments of the embodiment, step are as follows:
(1) by micron order BaSO4It is scattered in the salting liquid that a certain concentration contains M (M=Ag, Au, Pt) ion or compound
In, solvent evaporated (H in 150 DEG C of baking oven2O), stand, be cooled to room temperature；
(2) it disperses compound after drying in certain density reducing solution, ultrasound is allowed to sufficiently react, then again
Centrifuge separation；
(3) products therefrom is rinsed with deionized water, is dried to get BaSO4@M (M=Ag, Au, Pt) heterojunction material.
In the series embodiment, the number that water rinses in step (3) is 3 times.
Embodiment there is provided a kind of above-mentioned heterojunction composite or above-mentioned preparation methods to obtain for the third of the disclosure
Heterojunction composite catalytic phenylmethanol aoxidize and/or esterification in application.
Embodiment there is provided a kind of catalyst of benzyl alcohol oxidation esterification, active constituents for the 4th kind of the disclosure
The heterojunction composite obtained for above-mentioned heterojunction composite or above-mentioned preparation method.
Embodiment there is provided a kind of preparation methods of benzoic ether to add using benzyl alcohol as raw material for the 5th kind of the disclosure
In addition stating the heterojunction composite that heterojunction composite or above-mentioned preparation method obtain, first catalytic phenylmethanol aoxidize anti-
Benzoic acid should be obtained, then is catalyzed benzoic acid and alcohol progress esterification acquisition benzoic ether.
In one or more embodiments of the embodiment, step are as follows:
(1) heterojunction material, benzyl alcohol, cesium carbonate and methanol are uniformly mixed；
(2) air is filled under normal pressure into the system of step (1), is stirred under air-proof condition.
In order to be recycled to catalyst, the material after reaction is filtered, filtered precipitating is back
Receive catalyst.
In order to enable those skilled in the art can clearly understand the technical solution of the disclosure, below with reference to tool
The technical solution of the disclosure is described in detail in the embodiment of body.
Embodiment 1:
By 0.500g micron order BaSO4(purchase is in Aladdin Reagent Company；The ultra-fine barium sulfate that nano-scale is 1 μm) point
It dissipates in the AgNO of 20mL 0.5mg/mL3In solution, solvent evaporated (H in 150 DEG C of baking oven2O), 50min is stood, room is cooled to
Temperature.
Disperse the compound after drying in the NaBH of 5mL 10mg/mL4In solution, ultrasonic 7min is allowed to sufficiently react,
Then it is centrifugated again；
Products therefrom deionized water is rinsed 3 times, is dried to get BaSO4@Ag heterojunction material, such as Fig. 1.
By the BaSO of acquisition4@Ag heterojunction material is dissolved in concentrated nitric acid solution, and the solution for being made into 10mg/mL carries out ICP
Detection detects in solution and contains Ag+, Ag+Concentration is 0.059mg/L, demonstrates silver nano-grain in conjunction with Fig. 1 and is attached to BaSO4Table
Face.
Embodiment 2:
By 0.500g micron order BaSO4It is scattered in the HAuCl of 20mL 1.0mg/mL4In solution, it is evaporated in 150 DEG C of baking oven
Solvent (H2O), 70min is stood, is cooled to room temperature.
Disperse the compound after drying in the NaBH of 5mL 10mg/mL4In solution, ultrasonic 8min is allowed to sufficiently react,
Then it is centrifugated again；
Products therefrom deionized water is rinsed 3 times, is dried to get BaSO4@Au heterojunction material, such as Fig. 2.
By the BaSO of acquisition4@Au heterojunction material is dissolved in chloroazotic acid, and the solution for being made into 10mg/mL carries out ICP detection,
Contain Au in detection solution3+, Au3+Concentration is 0.047mg/L, demonstrates gold nano grain in conjunction with Fig. 2 and is attached to BaSO4Surface.
Embodiment 3:
By 0.500g micron order BaSO4It is scattered in the HPtCl of 20mL 0.7mg/mL6In solution, it is evaporated in 150 DEG C of baking oven
Solvent (H2O), 50min is stood, is cooled to room temperature.
Disperse the compound after drying in the NaBH of 5mL 10mg/mL4In solution, ultrasonic 8min is allowed to sufficiently react,
Then it is centrifugated again；
Products therefrom deionized water is rinsed 3 times, is dried to get BaSO4The heterojunction material of@Pt, such as Fig. 3.
By the BaSO of acquisition4@Pt heterojunction material is dissolved in concentrated nitric acid solution, and the solution for being made into 10mg/mL carries out ICP
Detection detects in solution and contains Pt5+, Pt5+Concentration is 0.040mg/L, demonstrates silver nano-grain in conjunction with Fig. 3 and is attached to BaSO4
Surface.
Embodiment 4:
BaSO4The oxidative esterification of@Au heterojunction material catalytic phenylmethanol obtains the reaction of methyl benzoate.
Specific steps are as follows:
(1) 30mgBaSO is weighed4@Au heterojunction material, 0.2g benzyl alcohol, 0.1303g cesium carbonate are placed in the round bottom of 30mL
In flask, the methanol of 10mL is added.
(2) air is filled under normal pressure into above-mentioned flask, is vigorously stirred under air-proof condition.
(3) it is passed through air in reaction process, reacts 4h, the mixture after reaction is extracted, is filtered to remove catalyst.
(4) above-mentioned filtrate is analyzed with chromatography of gases (CG).
The catalyst that step (3) filtering obtains is replaced to the 30mgBaSO in step (1)4@Au heterojunction material continues weight
Multiple above-mentioned (1), (2), (3) and (4) recycles 5 times, can obtain the characterization image such as Figure 4 and 5.
The foregoing is merely preferred embodiment of the present disclosure, are not limited to the disclosure, for the skill of this field
For art personnel, the disclosure can have various modifications and variations.It is all within the spirit and principle of the disclosure, it is made any to repair
Change, equivalent replacement, improvement etc., should be included within the protection scope of the disclosure.
Claims (10)
1. a kind of heterojunction composite, characterized in that several noble metal nano particles, the barium sulfate are adhered in barium sulfate surface
Partial size be 1~3 μm, the partial sizes of the noble metal nano particles is 3~10nm, and the noble metal is gold, silver or platinum.
2. a kind of preparation method of heterojunction composite, characterized in that will be adhered to containing the compound of M ion using infusion process
On the surface of barium sulfate, then M ion reduction that barium sulfate surface is contained to the compound of M ion is M nanoparticle；Wherein, M
For Ag, Au or Pt, the partial size of barium sulfate is 1~3 μm.
3. preparation method as claimed in claim 2, characterized in that the step of the infusion process are as follows: be dispersed to barium sulfate and contain
It is impregnated in the compound solution for having M ion, then the solvent in solution is removed；
Preferably, the concentration of compound is 0.1~1.5mg/mL in the compound solution containing M ion；
Preferably, the compound containing M ion is silver nitrate, gold chloride or chloroplatinic acid；
It is further preferred that the concentration of silver nitrate is 0.45~0.55mg/mL in solution when using silver nitrate；
It is further preferred that the concentration of Chlorine in Solution auric acid is 0.95~1.05mg/mL when using gold chloride；
It is further preferred that the concentration of Chlorine in Solution platinic acid is 0.65~0.75mg/mL when using chloroplatinic acid；
Preferably, dip time is 40~80min；
It is further preferred that dip time is 45~55min when using silver nitrate；
It is further preferred that dip time is 65~75min when using gold chloride；
It is further preferred that dip time is 45~55min when using chloroplatinic acid.
4. preparation method as claimed in claim 2, characterized in that be reduced to the reducing agent that M nanoparticle uses as NaBH4。
5. preparation method as claimed in claim 2, characterized in that the step of being reduced to M nanoparticle are as follows: M is contained on surface
The barium sulfate of ionic compound is added in reducing agent solution, after ultrasonic reaction, is centrifuged；
Preferably, the concentration of reducing agent is 5~15mg/mL in reducing agent solution；
Preferably, ultrasonic time is 5~10min；
It is further preferred that ultrasonic time is 6.5~7.5min when using silver nitrate；
It is further preferred that ultrasonic time is 7.5~8.5min when using gold chloride；
It is further preferred that ultrasonic time is 7.5~8.5min when using chloroplatinic acid.
6. preparation method as claimed in claim 2, characterized in that step is
(1) by micron order BaSO4It is scattered in a certain concentration to contain in the salting liquid of M ion or compound, be steamed in 150 DEG C of baking oven
Dry solvent stands, is cooled to room temperature；
(2) it disperses compound after drying in certain density reducing solution, ultrasound is allowed to sufficiently react, and is then centrifuged again
Separation；
(3) products therefrom is rinsed with deionized water, is dried to get BaSO4@M heterojunction material；
Preferably, the number that water rinses in step (3) is 3 times.
What 7. a kind of heterojunction composite described in claim 1 or any preparation method of claim 2~6 obtained
Application of the heterojunction composite in catalytic phenylmethanol oxidation and/or esterification.
8. a kind of catalyst of benzyl alcohol oxidation esterification, characterized in that active constituent is hetero-junctions described in claim 1
The heterojunction composite that composite material or any preparation method of claim 2~6 obtain.
9. a kind of preparation method of benzoic ether, characterized in that using benzyl alcohol as raw material, add described in claim 1 heterogeneous
Tie composite material or heterojunction composite that any preparation method of claim 2~6 obtains, first catalytic phenylmethanol into
Row oxidation reaction obtains benzoic acid, then is catalyzed benzoic acid and alcohol progress esterification acquisition benzoic ether.
10. preparation method as claimed in claim 9, characterized in that step are as follows:
(1) heterojunction material, benzyl alcohol, cesium carbonate and methanol are uniformly mixed；
(2) air is filled under normal pressure into the system of step (1), is stirred under air-proof condition.
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