CN109701565A - A bismuth oxyhalide-based metal thermal catalyst suitable for one-step synthesis of benzoin ether - Google Patents
A bismuth oxyhalide-based metal thermal catalyst suitable for one-step synthesis of benzoin ether Download PDFInfo
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- CN109701565A CN109701565A CN201910027380.0A CN201910027380A CN109701565A CN 109701565 A CN109701565 A CN 109701565A CN 201910027380 A CN201910027380 A CN 201910027380A CN 109701565 A CN109701565 A CN 109701565A
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- oxyhalogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 29
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 title 1
- -1 bismuthino Chemical group 0.000 claims abstract description 29
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000001308 synthesis method Methods 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 3
- 150000001455 metallic ions Chemical class 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003863 metallic catalyst Substances 0.000 description 6
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- 241000736148 Styrax Species 0.000 description 2
- 239000004870 Styrax Substances 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910018565 CuAl Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of oxyhalogen bismuthino metal thermocatalyst suitable for one-step synthesis method benzoin ethyl ether, the molecular compositions of the catalyst are as follows: M-BiOX, in formula: M=Au, Ag, Pd, Ru, Cu, Mg ...；X=Cl, Br, I.The oxyhalogen bismuth of body phase or nanometer is stirred with aqueous metallic ions and is uniformly dispersed, selects 500W xenon lamp for light irradiation 3h or more, obtains the oxyhalogen bismuthino thermocatalyst of different metal load capacity.The length and width of oxyhalogen bismuth are no more than 100nm, thickness about 20nm, surface uniform load having a size of 2 to 20nm metal nanoparticle.Base material oxyhalogen bismuth increases catalyst activity, reduces benzaldehyde catalyzing and condensing reaction energy barrier, while base material oxyhalogen bismuth has the characteristics that inexpensive, nontoxic, easy to handle, environmentally protective, has expanded application of the photo-reduction technology in terms of thermocatalyst synthesis.
Description
Technical field
The present invention relates to a kind of catalyst for synthesizing benzoin ethyl ether, more particularly to one kind to rest in peace suitable for one-step synthesis method
The oxyhalogen bismuthino metal thermocatalyst of fragrant ether.
Background technique
The chemical structure of benzoin ethyl ether is 1,2- diphenyl -2- alkoxy ethyl ketone, is a kind of white or light yellow needle
Shape crystal.It is a kind of important synthetic intermediate in pharmaceutical synthesis.Simultaneously as black light can be absorbed in it, thus often
Photosensitizer is used as to apply in printing industry, coatings industry etc..
In the prior art, traditional handicraft synthesis benzoin ethyl ether generally falls into two steps:
1, benzyl alcohol itself passes through benzoic conden-sation under the action of catalyst and forms styrax；
2, styrax and low-carbon alcohols synthesize benzoin ethyl ether under acidic catalyst effect.
Commonly used catalyst is cyanide or vitamin B1 in this technique, the former yield is high, but severe toxicity and " three
It is useless " processing difficulty, it is easy although the latter operates, saves material, be swift in response, target product yield is too low, and because of dimension
Raw element B1 and benzaldehyde are insoluble, other organic reagents need to be added and help to be uniformly mixed, this is with regard to a variety of by-products of simultaneous
The risk of generation.
In addition, domestic and international patent literature report is with phosphorus trichloride, alchlor, thionyl chloride, phosphorus oxychloride, phosgene etc.
The synthetic method of catalyst, but require ethyl alcohol significantly excessive in these techniques, and inevitably there are reaction time length, yield
The problems such as unstable, environmental pollution.
Later, researchers probed into NiAl/ environmentally protective, inexpensive, highly selective and with bigger serface
CuAl etc. is Ni-based and the preparation of alumina-base material one-step method synthesizes benzoin ethyl ether, but still remains the low problem of conversion ratio.
Summary of the invention
The object of the present invention is to provide a kind of oxyhalogen bismuthino metal thermocatalytics suitable for one-step synthesis method benzoin ethyl ether
Agent.
The purpose of the present invention is what is be achieved through the following technical solutions:
Oxyhalogen bismuthino metal thermocatalyst suitable for one-step synthesis method benzoin ethyl ether of the invention, selection is containing halogen family member
The oxyhalogen bismuth of element is base material, sensitive using response of the oxyhalogen bismuth to light, under the action of light, in-situ reducing metal salt solution
In metal ion, and finally obtain small size distribution oxyhalogen bismuthino metal thermocatalyst；
The element of the catalyst forms are as follows: M-BiOX, in formula: M=Au, Ag, Pd, Ru, Cu, Mg ...；X=Cl, Br, I.
As seen from the above technical solution provided by the invention, provided in an embodiment of the present invention for suitable for one-step method conjunction
At the oxyhalogen bismuthino metal thermocatalyst of benzoin ethyl ether, oxyhalogen bismuth is sensitive to the response of visible light, is also easy to produce light induced electron, because
This easily restores the metal in metal salt solution, forms the oxyhalide of small sized metallic catalyst load, this catalyst
Synthesizing mean is simple and efficient green.Oxyhalogen bismuth has the characteristics that inexpensive, nontoxic, environmentally friendly simultaneously, will substantially reduce catalyst
Pollution.
Detailed description of the invention
Fig. 1 is the mechanism signal of oxyhalogen bismuthino metal thermocatalyst one-step synthesis method benzoin ethyl ether in the embodiment of the present invention
Figure, in which: M=Au, Ag, Pd, Ru, Cu, Mg ...；X=Cl, Br, I.
Fig. 2 is oxyhalogen bismuthino metal fever catalyst preparation flow chart in the embodiment of the present invention.
Fig. 3 is the electron microscope of BiOCl base catalyst in the embodiment of the present invention, in which: (a) is Pd load phase BiOCl base
The scanning figure of catalyst；(b) transmission plot of nanometer BiOCl base catalyst is loaded for Pd.
Fig. 4 is the EDS electron spectrum of BiOCl base catalyst in the embodiment of the present invention, in which: (a) is Pd load phase
BiOCl base catalyst EDS electron spectrum；(b) the EDS electron spectrum of nanometer BiOCl base catalyst is loaded for Pd.
Specific embodiment
The embodiment of the present invention will be described in further detail below.What is be not described in detail in the embodiment of the present invention is interior
Appearance belongs to the prior art well known to professional and technical personnel in the field.
Oxyhalogen bismuthino metal thermocatalyst of the present invention for suitable for one-step synthesis method benzoin ethyl ether, preferably
Specific embodiment be:
Selecting the oxyhalogen bismuth containing halogen is base material, sensitive using response of the oxyhalogen bismuth to light, in the effect of light
Under, the metal ion in in-situ reducing metal salt solution, and finally obtain the oxyhalogen bismuthino metal thermocatalyst of small size distribution；
The element of the catalyst forms are as follows: M-BiOX, in formula: M=Au, Ag, Pd, Ru, Cu, Mg ...；X=Cl, Br, I.
The length and width of the oxyhalogen bismuth are 60nm to 7 μm, thickness is not more than 200nm, surface uniform load having a size of 2 to
The metal nanoparticle of 20nm.
The synthesis of the catalyst comprising steps of
Oxyhalogen bismuth is stirred with aqueous metallic ions and is uniformly dispersed, selects 500W xenon lamp for light irradiation, is adjusted
The concentration of irradiation time and solion obtains the oxyhalogen bismuthino thermocatalyst of different metal load capacity.
The irradiation time of the 500W xenon lamp is greater than or equal to 3h.
Oxyhalogen bismuthino metal thermocatalyst suitable for one-step synthesis method benzoin ethyl ether of the invention, utilizes oxyhalide
The metal ion in visible light generation light induced electron reduction ion salt solution is absorbed, the acquisition small sized metallic that can be simple and efficient is urged
The oxyhalide metallic catalyst of agent load.Wherein, the small size payload of metal greatly reduces the cost of catalyst.When with
When benzaldehyde is raw material, ethyl alcohol is solvent, which realizes the preparation of one step high-activity high-selectivity of benzoin ethyl ether.Such as figure
It is the mechanism schematic diagram of oxyhalogen bismuthino metal thermocatalyst one-step synthesis method benzoin ethyl ether shown in 1.Wherein: M=Au, Ag,
Pd,Ru,Cu,Mg……；X=Cl, Br, I.
The application designs for the first time to be loaded using on the halogen atom and oxyhalogen bismuth being easily detached from base material oxyhalogen bismuth
Metallic catalyst form strong nucleopilic reagent, to increase catalyst activity, reduce benzaldehyde catalyzing and condensing reaction energy barrier, have
The selectivity efficient for promoting reaction of effect carries out.Base material oxyhalogen bismuth has inexpensive, nontoxic, easy to handle, green simultaneously
The feature of environmental protection.One aspect of the present invention provides new approach and foundation for the green one-step method preparation of benzoin ethyl ether, another
Aspect has also expanded application of the photo-reduction technology in terms of thermocatalyst synthesis.
Specific embodiment:
This catalyst provides new effective way and thinking for the one-step method thermocatalytic preparation of benzoin ethyl ether.It is related to
To oxyhalogen bismuthino bottom have BiOCl, BiOBr, BiOI etc., the metal being related to has Pd, Au, Ag, Ru, Cu, Mg etc..Below will
Selecting chlorine oxygen bismuth (BiOCl) is base material, Pd is that metallic catalyst describes method process in detail.
As shown in Fig. 2, be oxyhalogen bismuthino metal fever catalyst preparation flow chart, comprising steps of
Select 500W xenon lamp for light source, by the chlorine oxygen bismuth of various concentration (body phase or nanometer) and sodium tetrachloropallate
Aqueous solution, which is stirred, to be uniformly dispersed, and adjusts xenon lamp irradiation time and solion concentration, can obtain different Pd load capacity
Chlorine bismuthyl thermocatalyst.
In order to characterize the pattern of product, the application has been the SEM and TEM (Fig. 3) of product, and (a) is negative for body phase BiOCl material
The SEM of the Pd catalyst of load schemes, and for body phase BiOCl having a size of micron order, the Pd nanoparticle size of area load is about 2-
20nm；It (b) is nanometer BiOCl Pt-supported catalyst, by can see in figure, the length and width of chlorine oxygen bismuth are no more than 100nm, thickness
About 20nm, surface have uniformly loaded the Pd nano particle that size is about 2.49nm.By interpretation of result it is found that either
Body phase or nano-scale chlorine oxygen bismuth material can pass through photoreduction met hod and obtain Pd supported catalyst.
In order to further determine the ingredient of product, the application has made the EDS map (Fig. 4) of respective material.By can be in figure
See, products therefrom is made of elements such as Bi, O, Cl, Pd.
Benefit in the same way, the application obtains a series of oxyhalogen bismuthino metal thermocatalysts, and select benzaldehyde for
Raw material, ethyl alcohol are solvent, and temperature is 100 degrees Celsius and has carried out heat catalysis.The results are shown in Table 1, under similarity condition, does not have
When having the load of Pd catalyst, individual chlorine oxygen bismuth does not have catalytic capability.After Pd load when reaction 5h, body phase
The conversion ratio of chlorine bismuthyl catalyst has reached 95.4%, and the selectivity of benzoin ethyl ether is 85.3%.And the chlorine of nano-scale
Conversion ratio of the oxygen bismuth catalyst in 5h has just reached 100%, and wherein the selectivity of benzoin ethyl ether has reached 97.9%.Also
It is to say, the oxyhalogen bismuthino metallic catalyst of nano-scale has higher activity and selectivity.The application has found simultaneously with nanometer
When oxyhalogen bismuth is base material, with the increase of halogen electronegativity under similarity condition, the activity and selectivity of reaction also with
Increase.Pd-3.3wt%-BiOI can reach 100% conversion ratio and selectivity in 3h.The polarity of halogen is stronger,
Nucleophilicity is stronger, this is also urged from reversely demonstrating segregative halogen in oxyhalogen bismuth and form effective nucleopilic reagent with Pd
Change the selectivity synthesis for accelerating benzoin ethyl ether.In order to further prove this point, the application utilizes same principle photo-reduction
It is prepared for Pd/TiO2And Pd/C3N4Thermocatalyst, discovery is to benzoin ethyl ether and does not have selectivity.That is, oxyhalogen bismuth
Halogen in base material plays conclusive effect in high activity and the high selectivity reaction of benzoin ethyl ether.
Table 1: different catalysts catalytic activity and selectivity comparison
The halogen and metallic catalyst that the present invention is easy to deviate from using oxyhalogen bismuthino bottom material form strong nucleopilic reagent,
Efficiently highly selective synthesis benzoin ethyl ether.Oxyhalogen bismuth can be the material that body phase material is also possible to nanoscale, wherein
The activity of the base material containing halogen of nano-scale is higher.In view of sensitivity of the oxyhalogen bismuth material to visible light absorbs, letter is utilized
Single photoreduction met hod can obtain the Metal Supported oxyhalogen bismuth-based catalysts of small size.Simultaneously base material oxyhalogen bismuth have it is low at
Originally, nontoxic, easy to handle, environmentally protective feature.One aspect of the present invention provides for the green one-step method preparation of benzoin ethyl ether
On the other hand new approach and foundation has also expanded application of the photo-reduction technology in terms of catalyst synthesis.The oxyhalogen being related to
There are BiOCl, BiOBr, BiOI etc. in bismuthino bottom, and the metal being related to has Pd, Au, Ag, Ru, Cu, Mg etc., specific embodiment be with
Body phase and nano-scale oxyhalogen bismuth are Pd/bulk BiOCl, Pd/BiOCl, Pd-/BiOBr, Pd/BiOI catalyst of substrate.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (4)
1. a kind of oxyhalogen bismuthino metal thermocatalyst suitable for one-step synthesis method benzoin ethyl ether, which is characterized in that selection contains
The oxyhalogen bismuth of halogen is base material, sensitive using response of the oxyhalogen bismuth to light, under the action of light, in-situ reducing metal
Metal ion in salting liquid, and finally obtain the oxyhalogen bismuthino metal thermocatalyst of small size distribution；
The element of the catalyst forms are as follows: M-BiOX, in formula: M=Au, Ag, Pd, Ru, Cu, Mg ...；X=Cl, Br, I.
2. the oxyhalogen bismuthino metal thermocatalyst according to claim 1 suitable for one-step synthesis method benzoin ethyl ether,
It is characterized in that, the length and width of the oxyhalogen bismuth are 60nm to 7 μm, thickness is not more than 200nm, and surface uniform load is having a size of 2
To the metal nanoparticle of 20nm.
3. the oxyhalogen bismuthino metal thermocatalyst according to claim 2 suitable for one-step synthesis method benzoin ethyl ether,
Be characterized in that, the synthesis of the catalyst comprising steps of
Oxyhalogen bismuth is stirred with aqueous metallic ions and is uniformly dispersed, selects 500W xenon lamp for light irradiation, adjustment irradiation
The concentration of time and solion obtain the oxyhalogen bismuthino thermocatalyst of different metal load capacity.
4. the oxyhalogen bismuthino metal thermocatalyst according to claim 3 suitable for one-step synthesis method benzoin ethyl ether,
It is characterized in that, the irradiation time of the 500W xenon lamp is greater than or equal to 3h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712612A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Method for preparing benzoin ethyl ether |
| US20130143731A1 (en) * | 2010-05-27 | 2013-06-06 | Beijing University Of Chemical Technology | Supported noble metal catalyst and process for preparing the same in situ |
| CN107790159A (en) * | 2017-09-28 | 2018-03-13 | 浙江理工大学 | Photochemical catalyst and its preparation and application of a kind of high selectivity catalysis oxidation alcohol into aldehyde |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712612A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Method for preparing benzoin ethyl ether |
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