CN104437484B - A kind of method synthesizing metal/metal oxide carrier nanometer catalyst - Google Patents
A kind of method synthesizing metal/metal oxide carrier nanometer catalyst Download PDFInfo
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- CN104437484B CN104437484B CN201410717299.2A CN201410717299A CN104437484B CN 104437484 B CN104437484 B CN 104437484B CN 201410717299 A CN201410717299 A CN 201410717299A CN 104437484 B CN104437484 B CN 104437484B
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Abstract
The invention discloses a kind of method synthesizing metal/metal oxide carrier nanometer catalyst, comprise the following steps: under the conditions of anaerobic and alkalescence, metal precursor, metal oxide precursor mix in dihydroxylic alcohols system and react, and isolated and purified after reaction obtain metal/metal oxide carrier nanometer catalyst.The present invention utilizes metal precursor, metal oxide precursor to react in alkalescence dihydroxylic alcohols system, one-step synthesis method metal/metal oxide carrier nanometer catalyst, and simple to operate, reaction condition is gentle, and the cycle is short.In the inventive method, dihydroxylic alcohols is solvent and reducing agent, it is not necessary to additionally add surfactant, and nano-catalyst particles will not be reunited, and particle diameter is little and is evenly distributed.
Description
Technical field
The present invention relates to field of inorganic nano material, be specifically related to a kind of synthesis metal/metal oxide support type
The method of nanocatalyst.
Background technology
Metal/metal oxide carrier nanometer catalyst is anti-for hydrogenation, oxidation, dehydrogenation, hydrogenation decomposition etc.
Should all show good catalytic performance, therefore the preparation method research of carrier nanometer catalyst is subject to always
To extensive concern.The preparation method of load type gold metal nano-particle mainly includes infusion process, coprecipitation at present
Deng.
Infusion process is to prepare one of the most traditional and modal method of loaded nano noble metal catalyst, will
Carrier impregnation is in the solution containing metal precursor, and then drying, roasting, reduction treatment can be catalyzed
Agent sample.The advantage of this method is simple to operate, it is easy to grasp.Shortcoming is prepared noble metal catalyst
Poor dispersion, easily reunite, particle diameter is big, particle diameter distribution width, thus affects its catalytic performance.
Coprecipitation be usually the most under certain condition by noble metal precursor body and the sun of metallic carrier that used from
Son precipitates simultaneously, be aged under certain pH value the precipitate that obtains of a period of time through filtering, washing,
It is dried, after roasting molding, obtains catalyst sample.The shortcoming of the sedimentation method is that dispersion is low, and embedding is in carrier
In noble metal in catalytic reaction, be difficult to play catalytic action, reduce the utilization rate of metal.
It addition, Chinese patent 200910154283.4 discloses a kind of load type metal catalyst, including oxidation
Thing carrier and the main metal being carried on oxide carrier and precious metal additive, it is by being carried on oxygen
Corresponding metal oxide precursor on compound carrier reduces under the temperature conditions of not higher than 500 DEG C
Obtain, specifically: first main metal precursor, precious metal additive presoma and macromolecular compound are dissolved
In a solvent；Then oxide carrier is entered in above-mentioned solution, obtain colloidal solid；Colloidal solid warp
Roasting, reduction, obtain load type metal catalyst.This technique needs multi-step to complete, and needs extra
Add auxiliary agent and macromolecular compound, relatively costly.
Summary of the invention
The invention provides a kind of method synthesizing metal/metal oxide carrier nanometer catalyst, solve existing
Method is had to need multi-step to complete, and the problem that the needs cost that additionally interpolation auxiliary agent and reducing agent cause is high.
A kind of method synthesizing metal/metal oxide carrier nanometer catalyst, will under the conditions of anaerobic and alkalescence
Metal precursor, metal oxide precursor hybrid reaction in dihydroxylic alcohols, after reaction completely, isolated and purified
Obtain metal/metal oxide carrier nanometer catalyst.
Dihydroxylic alcohols used by the present invention be in diethylene glycol, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol at least
One, dihydroxylic alcohols used is reaction dissolvent, is also reducing agent, and additionally dihydroxylic alcohols also functions to scattered effect,
Weaken the reunion of carrier nanometer catalyst in course of reaction.
As preferably, spent glycol is made to reach as high boiling solvent and reducing agent, reaction temperature
200 DEG C～250 DEG C, metal precursor, metal oxide precursor are well dispersed in system.
In reaction system, add at least one in sodium bicarbonate, potassium bicarbonate, ammonium hydrogen carbonate, add mesh
Be regulation reaction system basicity, make precipitated metal get off, be sodium bicarbonate as the alkali preferably added,
Its consumption is 1:100～700 with the mol ratio of metal precursor, and sodium bicarbonate is a kind of strong base-weak acid salt, can be steady
Set the tone and save reaction system basicity.
Metal precursor and mol ratio 1:2.0～48.0 of metal oxide precursor, before the metal-oxide of excess
Drive body to ensure that metal precursor is reacted completely, fully load is on an metal oxide, beneficially productivity
Improve.
Response time is 20min～40min, and metal precursor, metal oxide precursor are different, the response time
Different.
Obtain solid product after the liquid centrifugal segregation supernatant obtained after reaction, solid product water, have
After machine solvent respectively washed once, 60 DEG C～80 DEG C of vacuum constant temperatures are dried to obtain metal/metal oxide nano-catalytic
Agent, organic solvent used is at least one in acetone, ethanol and normal hexane.
Present invention also offers the metal/metal oxide manometer load-type catalyst grain that described method prepares
Footpath.
Described metal/metal oxide manometer load-type catalyst particle diameter is preferably 5nm～50nm.
Compared with prior art, the method have the advantages that the present invention utilizes metal precursor, gold
Belong to oxide precursor to react in alkalescence dihydroxylic alcohols system, one-step synthesis method metal/metal oxide support type
Nanocatalyst, simple to operate, reaction condition is gentle, and the cycle is short.In the inventive method, dihydroxylic alcohols is molten
Agent is again reducing agent, it is not necessary to additionally add surfactant, and nano-catalyst particles will not be reunited,
Particle diameter is little and is evenly distributed.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of the nano composite material that palladium is carried on zinc oxide.
Fig. 2 is transmission electron microscope (TEM) figure of the nano composite material that platinum is carried on zinc oxide.
Fig. 3 is transmission electron microscope (TEM) figure of the nano composite material that copper is carried on zinc oxide.
Fig. 4 is transmission electron microscope (TEM) figure of the nano composite material that gold is carried on zinc oxide.
Fig. 5 is transmission electron microscope (TEM) figure of the nano composite material that palladium is carried on cobalt oxide.
Detailed description of the invention
Embodiment 1: the preparation of palladium/zinc-oxide nano catalyst
The zinc acetate weighing 2mmol chlorine palladium acid sodium, 0.1g sodium bicarbonate and 5mmol joins 100ml tri-mouthfuls
In flask, in container, then add 45ml ethylene glycol, under nitrogen protection stirring condition, be warming up to 200 DEG C,
Back flow reaction 20min.Obtain the solid product of black after the liquid-like centrifugal segregation supernatant that will obtain, use
After water, acetone, ethanol, normal hexane respectively washed once, 70 DEG C of vacuum drying, gained pressed powder is Pd/ZnO.
Embodiment 2: the preparation of platinum/zinc-oxide nano catalyst
The zinc acetate weighing 1.25mmol chloroplatinic acid, 0.6g sodium bicarbonate and 15mmol joins 100ml tri-
In mouth flask, in container, then add 45ml ethylene glycol, be warming up under nitrogen protection stirring condition
200 DEG C, back flow reaction 25min.The solid of black is obtained after the liquid-like centrifugal segregation supernatant that will obtain
Product, after respectively washed once with water, acetone, ethanol, normal hexane, 80 DEG C of vacuum drying, gained solid powder
End is Pt/ZnO.
Embodiment 3: the preparation of copper/zinc-oxide nano catalyst
The zinc acetate weighing 1.25mmol Schweinfurt green, 0.4g sodium bicarbonate and 7.5mmol joins 100ml
In there-necked flask, in container, then add 60ml ethylene glycol, be warming up under nitrogen protection stirring condition
200 DEG C, back flow reaction 30min.The solid of black is obtained after the liquid-like centrifugal segregation supernatant that will obtain
Product, after respectively washed once with water, acetone, ethanol, normal hexane, 75 DEG C of vacuum drying, gained solid powder
End is Cu/ZnO.
Embodiment 4: the preparation of gold/zinc-oxide nano catalyst
The zinc acetate weighing 1.25mmol gold chloride, 0.5g sodium bicarbonate and 30mmol joins 100ml tri-
In mouth flask, in container, then add 45ml diethylene glycol, be warming up under nitrogen protection stirring condition
250 DEG C, back flow reaction 40min.The solid of black is obtained after the liquid-like centrifugal segregation supernatant that will obtain
Product, after respectively washed once with water, acetone, ethanol, normal hexane, 60 DEG C of vacuum drying, gained solid powder
End is Au/ZnO.
Embodiment 5: the preparation of palladium/cobalt oxide nanocatalyst
The zinc acetate weighing 2mmol chlorine palladium acid sodium, 0.8g sodium bicarbonate and 6mmol joins 100ml tri-mouthfuls
In flask, in container, then add 45ml1,2-propylene glycol, be warming up under nitrogen protection stirring condition
200 DEG C, back flow reaction 30min.The solid of black is obtained after the liquid-like centrifugal segregation supernatant that will obtain
Product, after respectively washed once with water, acetone, ethanol, normal hexane, 70 DEG C of vacuum drying, gained solid powder
End is Pd/Co3O4。
As Figure 1-5, prepare nano-catalyst particles and do not reunite, and even particle size distribution,
Size is all at below 50nm.
Claims (6)
1. the method synthesizing metal/metal oxide carrier nanometer catalyst, it is characterised in that comprise the following steps:
Under the conditions of anaerobic and alkalescence, metal precursor, metal oxide precursor are mixed in dihydroxylic alcohols system and reacts, instead
The most isolated and purified should obtain metal/metal oxide carrier nanometer catalyst；
Referring to add sodium bicarbonate under the conditions of described alkalescence in reaction system, its consumption with the mol ratio of metal precursor is
1:100～700；
Described metal precursor is at least one in chlorine palladium acid sodium, gold chloride, chloroplatinic acid, Schweinfurt green, described metal-oxide
Presoma is at least one in zinc acetate, cerous acetate, iron acetate, metal precursor and the mol ratio of metal oxide precursor
1:2.0～48.0；
Reaction temperature is 200 DEG C-250 DEG C, and the response time is 20min-40min.
The method of synthesis metal/metal oxide carrier nanometer catalyst the most according to claim 1, it is characterised in that
Described dihydroxylic alcohols is at least one in diethylene glycol, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol.
3. the method synthesizing metal/metal oxide carrier nanometer catalyst as claimed in claim 1, it is characterised in that
Described isolated and purified it is: after product removes supernatant by centrifugation, respectively with water and organic solvent washing, last vacuum is done
Dry, obtain metal/metal oxide carrier nanometer catalyst.
4. the method synthesizing metal/metal oxide carrier nanometer catalyst as claimed in claim 3, it is characterised in that
Described organic solvent is at least one in acetone, ethanol and normal hexane.
5. the metal/metal oxide carrier nanometer catalyst that method as described in claim 1-4 is arbitrary obtains.
6. metal/metal oxide carrier nanometer catalyst as claimed in claim 5, it is characterised in that particle diameter is
5nm-50nm。
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| CN109507251A (en) * | 2018-09-29 | 2019-03-22 | 中国科学院合肥物质科学研究院 | It palladium modification zinc oxide nanometer sheet, preparation method and its is applied in gas sensor |
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