CN106883108B - The method for being converted into aldehyde based on iridium nanoparticulate selective catalysis oxidation alcohol - Google Patents
The method for being converted into aldehyde based on iridium nanoparticulate selective catalysis oxidation alcohol Download PDFInfo
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- CN106883108B CN106883108B CN201710067522.7A CN201710067522A CN106883108B CN 106883108 B CN106883108 B CN 106883108B CN 201710067522 A CN201710067522 A CN 201710067522A CN 106883108 B CN106883108 B CN 106883108B
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- 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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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- 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
- C07C45/39—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 secondary hydroxyl group
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Abstract
The invention discloses the methods for being converted into aldehyde based on iridium nanoparticulate selective catalysis oxidation alcohol, belong to catalysis technical field.The method of the present invention is coating agent, NaBH using sodium citrate4Reducing agent is made, the water-soluble Ir NPs that diameter is 2.5 ± 0.5 nanometers has been synthesized.Since the Ir NPs of synthesis has high miller index surface { 200 }, { 220 } and { 311 } can be catalyzed DO oxidation alcohol at normal temperatures and pressures and generate corresponding aldehydes or ketones so its catalytic activity is very high.Ir NPs with type oxide enzymatic activity is expected to the substitute as biological oxidation enzyme, has potential application prospect in broader practice field.
Description
Technical field
The present invention relates to the methods for being converted into aldehyde based on iridium nanoparticulate selective catalysis oxidation alcohol, belong to catalysis technique neck
Domain.
Background technique
Whether in organic synthesis, fine chemistry industry, or in fuel cell field, selective oxidation alcohol generates corresponding aldehyde
Or ketone is all a very important process.Bichromate and permanganate are the conventional oxidation agent for aoxidizing alcohol and being changed into aldehyde, he
It is not only expensive, but also a large amount of heavy metal containing sewage can be generated.Currently, Ag or Cu that low toxicity is industrially widely used are catalyzed
Agent, catalytic air oxidation methanol generates formaldehyde, but only (600~700 DEG C) just can be carried out its conversion process at high temperature.One
A little metallic compounds and nano-particle catalyst have been synthesized, and catalysis dissolved oxygen (Dissolved oxygen, DO) aoxidizes alcohol
Become aldehydes or ketones, by-product only has water, but its catalytic oxidation process must have acetone, pyridine derivate, benzene fluoroform or chlorine
The toxic organic reagent such as benzene exists, very big to environmental hazard.
Make oxidant using DO, noble metal nanometer material makees catalyst, realizes aromatic series in water-alcohol two-phase system
The selective oxidation of alcohol, n-hexyl alcohol and n-amyl alcohol.Since the oxidizing potential of lower alcohol is higher than aromatic alcohols, such as methanol and second
Alcohol, therefore they are more difficult to be selectively oxidized.Relative to the basic crystal face of low index, the noble metal nano with high miller index surface
There are steps and defect on the surface of material, have more low level with atom, can be used as the active site of reaction, show Zhuo
Catalytic performance more.For example, the Pt with { 411 } high miller index surface it is nanocrystalline and with { hk0 } high miller index surface Pt-Cu and
Pt-Pd-Cu nanocages can be used for the electroxidation of methanol and ethyl alcohol.Currently, it is rudimentary to yet there are no catalysis DO oxidation at normal temperatures and pressures
Alcohol is converted into the relevant report of aldehydes or ketones.
Native enzyme can efficiently aoxidize alcohol under mild conditions and generate corresponding aldehydes or ketones, but its production process
Costly and time-consuming, purification process is also very complicated, and the variation of environment temperature and pH can all influence its stability and activity, this
A little defects limit the extensive use of native enzyme.And noble metal nanometer material analogue enztme can overcome these defects.Iridium nanometer
What grain Ir NPs (Iridium nanoparticles) was shown in terms of catalytic hydrogenation reaction and fuel cell superior urges
Change the interest that activity has attracted a large amount of scientific researchers.The research teams such as Su and our nearest research work verified Ir
NPs has good peroxidase activity, but about the oxidation enzymatic property of Ir NPs and catalysis DO selective oxidation
The method that alcohol is changed into aldehyde has not been reported.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of methods that catalysis DO oxidation alcohol is changed into aldehydes or ketones, specifically
It is related to simple and quick synthesis there is the Ir NPs, DO of oxide analogue enztme activity being oxidant, alcohol is oxidized to aldehydes or ketones.Tool
There are { 200 }, the Ir NPs of { 220 } and { 311 } high miller index surface can make coating agent, NaBH by sodium citrate4Make reducing agent letter
Single quickly synthesis.It has type oxide enzymatic property, at normal temperatures and pressures, can efficiently be catalyzed the change of DO selective oxidation alcohol
At corresponding aldehydes or ketones, and the injection of the energy such as any other light, electricity, heat is not needed.
Be changed into the methods of aldehydes or ketones the first purpose of the invention is to provide a kind of catalysis DO oxidation alcohol, the method with
Oxide analogue enztme is catalyst, DO is that oxidant carries out catalytic oxidation；The oxide analogue enztme is Ir NPs crystal.
In one embodiment, the noble metal Ir NPs that the oxide analogue enztme is 2.5 ± 0.5nm of particle size is brilliant
Body has { 200 }, { 220 } and { 311 } high miller index surface.
In one embodiment, the Ir NPs plane of crystal is by { 200 }, { 220 } and { 311 } high miller index surface packet
Quilt.
In one embodiment, the alcohol is lower alcohol.
In one embodiment, the alcohol includes methanol, ethyl alcohol, propyl alcohol, isopropanol etc..
In one embodiment, the method is catalyzed in the aqueous solution containing alcohol, is not necessarily to other co-catalysis
Agent.
In one embodiment, the method is to carry out catalysis reaction in normal temperature and pressure.
In one embodiment, O is used air as in the method2Source.
In one embodiment, the method is first to prepare certain density catalyst inventory liquid with water, is then added
Into alcohol, it is stirred to react a period of time after mixing.
In one embodiment, the final concentration of 0.1mg/mL~100mg/mL of the catalyst in the reaction system.
In one embodiment, the concentration of the catalyst inventory liquid is 0.2mg/mL~200mg/mL.
In one embodiment, the catalyst inventory liquid concentration is 3mg/mL.
In one embodiment, the catalyst inventory liquid and alcohol according to mixing in equal volume.
In one embodiment, the time of the reaction be 2~for 24 hours.
A second object of the present invention is to provide a kind of oxide analogue enztme, the oxide analogue enztme is particle size
The noble metal Ir NPs crystal of 2.5 ± 0.5nm has { 200 }, { 220 } and { 311 } high miller index surface.
In one embodiment, the Ir NPs plane of crystal is by { 200 }, { 220 } and { 311 } high miller index surface packet
Quilt.
Third object of the present invention is to provide the preparation method of the oxide analogue enztme, the method is by citric acid
Sodium solution is mixed with the salting liquid of Ir, and adjusts pH 7~9, under inert gas protection oil bath back flow reaction for a period of time, so
After NaBH is added4Solution closes heater switch, continues to be back to solution blackening, is added that ethyl alcohol is counter to be precipitated, be centrifuged, wash,
It is obtained by drying to arrive Ir NPs.
In one embodiment, the salting liquid of the Ir is IrCl3Solution.
In one embodiment, the sodium citrate, IrCl3、NaBH4Mass ratio be (8~12): (1~3): 1.
In one embodiment, the time of the oil bath back flow reaction is 15~25min, is to react to solution to become light
Yellow.
In one embodiment, the time for continuing back flow reaction is 25~35min.
In one embodiment, the oxide analogue enztme the preparation method is as follows:
The sodium citrate solution of 3mL 1% and the IrCl of 20mL 0.03%3Solution mixing, with the NaOH solution tune of 1M
Save pH to 7~9.In N2Under protection, which is placed in oil bath the 20min that flows back, solution becomes faint yellow, and it is fresh that 1mL is added
The NaBH of the 0.1M of preparation4Solution closes heater switch, continues the 30min that flows back, and solution colour blackening illustrates that Ir NPs is formed；
It is added that suitable ethyl alcohol is counter to be precipitated, and is centrifuged 5min at 3357rcf, precipitating is washed repeatedly with ethyl alcohol and is centrifuged 3 times,
Finally it is placed in a vacuum drying oven 45 DEG C of drying.
Advantages of the present invention and effect:
(1) preparation of Ir NPs, purification process are simple, large specific surface area, and catalytic activity is high, are expected to as oxide enzyme
Substitute.
(2) reuse rate of IrNPs is high, and after for several times, catalytic effect is not decreased obviously.
(3) IrNPs can be used for being catalyzed the more dysoxidizable lower alcohol of DO oxidation, such as methanol, ethyl alcohol, propyl alcohol and isopropanol.
(4) lower alcohol is converted into the reaction rate height of corresponding aldehydes or ketones, and selectivity is good.
(5) reaction condition is mild, and reaction process is simple, easy to operate.
(6) O is used air as in catalytic oxidation process2Source, it is not toxic without using toxic organic reagent
By-product generates, environmental sound, and any pollution is not present.
(7) catalytic process is not necessarily to co-catalyst, can carry out in normal temperature and pressure, the aqueous solution of alcohol.
Detailed description of the invention
The HRTEM picture of Fig. 1: (A) Ir NPs；(B) electron diffraction pattern of Ir NPs；(C) XRD diagram of IrNPs；
Fig. 2: the fluorescence pattern of (A) DPBF (a), DPBF-Ir NPs (b) and DPBF-Ir NPs-Vc (c)；(B)TMB-Ir
The UV-vis map of NPs (d) and TMB-Ir NPs- benzoquinones (e)；Wherein 5 μM of DPBF, Ir NPs 3 μ g/mL, Vc 2mM, TMB
100 μM, 100 μM of benzoquinones.
Specific embodiment
Below in conjunction with Detailed description of the invention a specific embodiment of the invention.Embodiments of the invention are only used to illustrate
A specific embodiment of the invention is not intended to limit the scope of the invention.After reading the content that the present invention lectures, art technology
Personnel can make various changes or modification to the present invention, and such equivalent forms equally fall within institute in the application the appended claims
The range of restriction.
The preparation and characterization of embodiment 1:Ir NPs oxide enzyme
(1) the IrCl of the sodium citrate solution of 3mL 1% and 20mL 0.03%3Solution mixing, with the NaOH solution of 1M
Adjust pH to 7~9.
(2) in N2Under protection, which is placed in oil bath the 20min that flows back, solution becomes faint yellow, and it is fresh that 1mL is added
The NaBH of the 0.1M of preparation4Solution closes heater switch, continues the 30min that flows back, and solution colour blackening illustrates that Ir NPs is formed.
(3) the suitable ethyl alcohol of addition is counter is precipitated, and is centrifuged 5min at 3357rcf, and precipitating is washed repeatedly with ethyl alcohol
It washs and is centrifuged 3 times, be finally placed in a vacuum drying oven 45 DEG C of drying.
(4) it weighs suitable Ir NPs crystal powder and is dissolved in the Ir NPs stock solution for preparing 3mg/mL in ultrapure water, use
It is about 1.8976mg/mL that ICP-MS, which measures Ir content,.
(5) table is carried out to the structure of Ir NPs with high-resolution electronic projection microscope (HRTEM) and X-ray diffraction (XRD)
Sign.As shown in Figure 1, that obtain is the HRTEM, electronic diffraction and XRD diagram of Ir NPs.
What can be removed from the HRTEM picture of Fig. 1 sees that Ir NPs is the spherical particle that partial size is about 2.5 ± 0.5nm.From
The HRTEM picture of amplification can obviously observe that the surface Ir NPs is made of different crystal faces, the electronic diffraction picture of Fig. 1 and
It is polycrystalline that XRD characterization, which further demonstrates Ir NPs, and crystal face includes { 111 }, { 200 }, { 220 } and { 311 }.Metal nano material
The sequence of the crystal face energy size of material is γ{111}< γ{100}< γ{110}< γ{hkl}, therefore speculate that oxygen molecule is easy to be adsorbed
{ 311 } crystal plane surface of Ir NPs come reduce its surface can, the oxygen molecule of absorption receives the electronics of Ir NPs and forms O2 ˉ,
O2 ˉLower alcohol can be aoxidized and form corresponding aldehydes or ketones.
Embodiment 2:Ir NPs catalysis DO oxidation lower alcohol is changed into corresponding aldehydes or ketones
(1) 3mg/mL Ir NPs stock solution is prepared with ultrapure water；
(2) isometric Ir NPs stock solution is added separately in methanol, ethyl alcohol, propyl alcohol and isopropanol, is uniformly mixed,
It is stirred at room temperature for 24 hours.
(3) solution after reaction is centrifuged, supernatant is taken to carry out GC analysis.
(4) conversion rate is measured.Table 1 is the conversion rate of alcohol.
As shown in Table 1, from the point of view of the conversion rate of lower alcohol, the catalytic efficiency of Ir NPs is very high, and alkyl chain is longer, alkane
The electronics that pushes away of base can be stronger, and conversion rate is higher, illustrate Ir NPs catalysis DO oxidation alcohol and substrate, Ir NPs and DO it
Between electronics transfer it is related.
Reaction solution is centrifuged at 3357rcf, obtained Ir NPs solid water and ethyl alcohol is washed repeatedly, is centrifuged,
Ir NPs is dried at 45 DEG C of vacuum oven later, i.e. recycling obtains IrNPs.The Ir NPs that recycling obtains is continued to use
The above method is catalyzed lower alcohol, the results show that conversion rate is still able to maintain 98% or so after reusing 10 times.Result above
Show reuse rate height, after for several times, catalytic effect is not decreased obviously.
The conversion rate of the lower alcohol under the catalytic action of Ir NPs of table 1
The verifying of embodiment 3:Ir NPs catalytic mechanism
(1) 3 parts of duplicate 1,3- diphenyl isobenzofuran (DPBF) solution are prepared, a copy of it solution constant volume
To 5mL, its fluorescence spectrum is measured.
(2) Ir NPs is added in second part of DPBF solution, constant volume to 5mL measures its fluorescence spectrum.
(3) ascorbic acid (Vc) and Ir NPs, same constant volume to 5mL, measurement are sequentially added in third part DPBF solution
Its fluorescence spectrum.
(4) two parts of identical TMB solution are prepared.
(5) suitable Ir NPs is added in wherein portion TMB solution, constant volume to 5mL measures its UV- after reacting 5min
Vis wave spectrum.
(6) suitable Ir NPs and benzoquinones solution, constant volume to 5mL, equally reaction 5min are added in another TMB solution
After measure its UV-vis wave spectrum.
DPBF is a kind of O2 ˉWith1O2Capturing agent, and other active oxygen radicals cannot be captured.As shown in Fig. 2, with
The addition of Ir NPs, the fluorescence intensity decline of DPBF, if Vc and IrNPs is added, the fluorescence intensity of DPBF do not decline
It is very serious, illustrate that the DO of IrNPs and solution is acted on, produces O2 ˉOr1O2.Benzoquinones is another O2 ˉScavenger, if in TMB
Benzoquinones is added in solution, then TMB will not be catalyzed the O that DO is generated by IrNPs2 ˉOxidation, illustrate the selective oxidation of lower alcohol with
O2 ˉGeneration it is related.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not intended to limit the invention, any to be familiar with this skill
The people of art can do various change and modification, therefore protection model of the invention without departing from the spirit and scope of the present invention
Enclosing subject to the definition of the claims.
Claims (6)
1. a kind of method that catalysis dissolved oxygen oxidation alcohol is changed into aldehydes or ketones, which is characterized in that the method is simulated with oxide
Enzyme is catalyst, dissolved oxygen is that oxidant carries out catalytic oxidation；Specifically, the method is first to prepare a certain concentration with water
Catalyst inventory liquid, be then added in alcohol, be stirred to react after mixing a period of time；Wherein, the oxide simulation
Enzyme is the iridium nano particle crystal of 2.5 ± 0.5nm of particle size, is had { 200 }, { 220 } and { 311 } high miller index surface；Institute
Stating alcohol is methanol, ethyl alcohol, propyl alcohol or isopropanol.
2. the method according to claim 1, wherein the catalyst in the reaction system final concentration of
0.1mg/mL~100mg/mL.
3. the method according to claim 1, wherein the method is to carry out catalysis reaction in normal temperature and pressure.
4. the method according to claim 1, wherein the method is urged in the aqueous solution containing alcohol
Change, is not necessarily to other co-catalysts.
5. the method according to claim 1, wherein using air as O in the method2Source.
6. the method according to claim 1, wherein the catalyst inventory liquid and alcohol according to mixing in equal volume.
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| CN111790449A (en) * | 2020-07-30 | 2020-10-20 | 泉州师范学院 | Iridium nanoparticle catalyst, preparation method thereof and application of iridium nanoparticle catalyst in catalytic reduction of nitro compound to amino compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731514A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731514A (en) * | 2016-01-28 | 2016-07-06 | 郑州航空工业管理学院 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
Non-Patent Citations (3)
| Title |
|---|
| Dual-Enzyme Characteristics of Polyvinylpyrrolidone-Capped Iridium Nanoparticles and Their Cellular Protective Effect against H2O2‑Induced Oxidative Damage;Hua Su等;《ACS Appl. Mater. Interfaces》;20151231;第8233-8242页 |
| Electrooxidation of Methanol on Iridium in Acidic Solutions: Electrocatalysis and Surface Characterization by Infrared Spectroscopy;Akiko Aramata等;《J.Phys.Chem.》;19871231;第91卷;第2309-2314页 |
| Facile synthesis of iridium nanoparticles with superior peroxidase-likeactivity for colorimetric determination of H2O2 and xanthine;Malin Cui等;《Sensors and Actuators B: Chemical》;20161127;第203-210页 |
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