CN104437484A - Method for synthesizing metal/metallic oxide loaded type nano-catalyst - Google Patents
Method for synthesizing metal/metallic oxide loaded type nano-catalyst Download PDFInfo
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- CN104437484A CN104437484A CN201410717299.2A CN201410717299A CN104437484A CN 104437484 A CN104437484 A CN 104437484A CN 201410717299 A CN201410717299 A CN 201410717299A CN 104437484 A CN104437484 A CN 104437484A
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Abstract
The invention discloses a method for synthesizing a metal/metallic oxide loaded type nano-catalyst. The method comprises the following steps: mixing a metal precursor and a metallic oxide precursor in a dihydric alcohol system for reaction under oxygen-free and alkaline conditions, and separating and purifying after the reaction to obtain the metal/metallic oxide loaded type nano-catalyst. According to the method, the metal precursor and the metallic oxide precursor react in the alkaline dihydric alcohol system to synthesize the metal/metallic oxide loaded type nano-catalyst by adopting a one-step method, the operation is simple, the reaction condition is mild and the period is short. Dihydric alcohol in the method can be used as a solvent and a reducing agent, a surface active agent is not required to be added additionally, nano-catalyst granules cannot be agglomerated, the particle size is small and the distribution is uniform.
Description
Technical field
The present invention relates to field of inorganic nano material, be specifically related to the method for a kind of synthetic metals/metal oxide supported type nanocatalyst.
Background technology
Metal/metal oxide carrier nanometer catalyst all shows good catalytic performance for reactions such as hydrogenation, oxidation, dehydrogenation, hydrogenation decomposition, and therefore preparation method's research of carrier nanometer catalyst is subject to extensive concern always.The preparation method of current load type gold metal nano-particle mainly comprises infusion process, coprecipitation etc.
Infusion process prepares one of the most traditional and modal method of loaded nano noble metal catalyst, and by carrier impregnation in the solution of containing metal presoma, then drying, roasting, reduction treatment can obtain catalyst sample.The advantage of this method is simple to operate, is easy to grasp.Shortcoming is obtained bad, the easy reunion of noble metal catalyst dispersiveness, particle diameter is large, domain size distribution is wide, thus affects its catalytic performance.
Coprecipitation is generally precipitated by the cation of noble metal precursor body with the metallic carrier adopted under certain condition simultaneously, under certain pH value the sediment that obtains of ageing a period of time after filtration, washing, dry, obtain catalyst sample after roasting is shaping.The shortcoming of the precipitation method is that decentralization is low, and embedding place noble metal is in the carrier difficult to play catalytic action in catalytic reaction, reduces the utilization rate of metal.
In addition, Chinese patent 200910154283.4 discloses a kind of load type metal catalyst, the main metal comprising oxide carrier and be carried on oxide carrier and precious metal additive, it obtains by the corresponding metal oxide precursor be carried on oxide carrier is carried out reduction under not higher than the temperature conditions of 500 DEG C, specifically: first main metal precursor, precious metal additive presoma and macromolecular compound are dissolved in a solvent; Then oxide carrier is entered into above-mentioned solution, obtain colloidal solid; Colloidal solid, through roasting, reduction, obtains load type metal catalyst.This technique needs multi-step to complete, and needs extra interpolation auxiliary agent and macromolecular compound, and cost is higher.
Summary of the invention
The invention provides the method for a kind of synthetic metals/metal oxide supported type nanocatalyst, solving existing method needs multi-step to complete, and the problem that the cost needing extra interpolation auxiliary agent and reducing agent to cause is high.
The method of a kind of synthetic metals/metal oxide supported type nanocatalyst, by metal precursor, metal oxide precursor hybrid reaction in dihydroxylic alcohols under anaerobic and alkali condition, after reacting completely, separation and purification obtains metal/metal oxide carrier nanometer catalyst.
The present invention's dihydroxylic alcohols used is at least one in diethylene glycol (DEG), ethylene glycol, 1,2-PD and 1,3-PD, dihydroxylic alcohols used is reaction dissolvent, also be reducing agent, dihydroxylic alcohols also plays the effect of dispersion in addition, weakens the reunion of carrier nanometer catalyst in course of reaction.
As preferably, make spent glycol as high boiling solvent and reducing agent, reaction temperature reaches 200 DEG C ~ 250 DEG C, and metal precursor, metal oxide precursor are well dispersed in system.
At least one in sodium acid carbonate, saleratus, carbonic hydroammonium is added in reaction system, adding object is regulate reaction system basicity, precipitated metal is got off, be sodium acid carbonate as preferred added alkali, the mol ratio of its consumption and metal precursor is 1:100 ~ 700, sodium acid carbonate is a kind of strong base-weak acid salt, and Absorbable organic halogens regulates reaction system basicity.
Mol ratio 1:2.0 ~ 48.0 of metal precursor and metal oxide precursor, excessive metal oxide precursor is in order to ensure metal precursor complete reaction, and abundant load on an metal oxide, is conducive to the raising of productive rate.
Reaction time is 20min ~ 40min, and metal precursor, metal oxide precursor are different, and the reaction time is different.
The centrifugal obtained after reaction obtains solid product after removing supernatant, solid product water, organic solvent respectively wash once, 60 DEG C ~ 80 DEG C vacuum constant temperature dryings obtain metal/metal oxide nanocatalyst, and organic solvent used is at least one in acetone, ethanol and n-hexane.
Present invention also offers the metal/metal oxide manometer load-type catalyst particle diameter that described method prepares.
Described metal/metal oxide manometer load-type catalyst particle diameter is preferably 5nm ~ 50nm.
Compared with prior art, the present invention has following beneficial effect: the present invention utilizes metal precursor, metal oxide precursor to react in alkaline dihydroxylic alcohols system, and one-step synthesis method metal/metal oxide carrier nanometer catalyst is simple to operate, reaction condition is gentle, and the cycle is short.In the inventive method, dihydroxylic alcohols is solvent and reducing agent, does not need additionally to add surfactant, and nano-catalyst particles can not be reunited, and particle diameter is little and be evenly distributed.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure that palladium is carried on the nano composite material on zinc oxide.
Fig. 2 is transmission electron microscope (TEM) figure that platinum is carried on the nano composite material on zinc oxide.
Fig. 3 is transmission electron microscope (TEM) figure that copper is carried on the nano composite material on zinc oxide.
Fig. 4 is transmission electron microscope (TEM) figure that gold is carried on the nano composite material on zinc oxide.
Fig. 5 is transmission electron microscope (TEM) figure that palladium is carried on the nano composite material on cobalt oxide.
Detailed description of the invention
Embodiment 1: the preparation of palladium/zinc-oxide nano catalyst
The zinc acetate taking the acid of 2mmol chlorine palladium sodium, 0.1g sodium acid carbonate and 5mmol joins in 100ml there-necked flask, then in container, adds 45ml ethylene glycol, is warming up to 200 DEG C, back flow reaction 20min under nitrogen protection stirring condition.To obtain the solid product of black after the liquid-like centrifugal segregation supernatant liquor obtained, respectively wash once with water, acetone, ethanol, n-hexane, 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 taking 1.25mmol chloroplatinic acid, 0.6g sodium acid carbonate and 15mmol joins in 100ml there-necked flask, then in container, adds 45ml ethylene glycol, is warming up to 200 DEG C, back flow reaction 25min under nitrogen protection stirring condition.To obtain the solid product of black after the liquid-like centrifugal segregation supernatant liquor obtained, respectively wash once with water, acetone, ethanol, n-hexane, 80 DEG C of vacuum drying, gained pressed powder is Pt/ZnO.
Embodiment 3: the preparation of copper/zinc-oxide nano catalyst
The zinc acetate taking 1.25mmol Schweinfurt green, 0.4g sodium acid carbonate and 7.5mmol joins in 100ml there-necked flask, then in container, adds 60ml ethylene glycol, is warming up to 200 DEG C, back flow reaction 30min under nitrogen protection stirring condition.To obtain the solid product of black after the liquid-like centrifugal segregation supernatant liquor obtained, respectively wash once with water, acetone, ethanol, n-hexane, 75 DEG C of vacuum drying, gained pressed powder is Cu/ZnO.
Embodiment 4: the preparation of gold/zinc-oxide nano catalyst
The zinc acetate taking 1.25mmol gold chloride, 0.5g sodium acid carbonate and 30mmol joins in 100ml there-necked flask, then in container, adds 45ml diethylene glycol (DEG), is warming up to 250 DEG C, back flow reaction 40min under nitrogen protection stirring condition.To obtain the solid product of black after the liquid-like centrifugal segregation supernatant liquor obtained, respectively wash once with water, acetone, ethanol, n-hexane, 60 DEG C of vacuum drying, gained pressed powder is Au/ZnO.
Embodiment 5: the preparation of palladium/cobalt oxide nanocatalyst
The zinc acetate taking the acid of 2mmol chlorine palladium sodium, 0.8g sodium acid carbonate and 6mmol joins in 100ml there-necked flask, then in container, adds 45ml1,2-propane diols, is warming up to 200 DEG C, back flow reaction 30min under nitrogen protection stirring condition.To obtain the solid product of black after the liquid-like centrifugal segregation supernatant liquor obtained, respectively wash once with water, acetone, ethanol, n-hexane, 70 DEG C of vacuum drying, gained pressed powder is Pd/Co
3o
4.
As Figure 1-5, prepare nano-catalyst particles and do not reunite, and even particle size distribution, particle size is all at below 50nm.
Claims (10)
1. the method for synthetic metals/metal oxide supported type nanocatalyst, it is characterized in that, comprise the following steps: under anaerobic and alkali condition, metal precursor, metal oxide precursor mix and react in dihydroxylic alcohols system, and after reaction, separation and purification obtains metal/metal oxide carrier nanometer catalyst.
2. the method for synthetic metals according to claim 1/metal oxide supported type nanocatalyst, is characterized in that, described dihydroxylic alcohols is at least one in diethylene glycol (DEG), ethylene glycol, 1,2-PD and 1,3-PD.
3. the method for synthetic metals according to claim 1/metal oxide supported type nanocatalyst, is characterized in that, reaction temperature is 200 DEG C ~ 250 DEG C, and the reaction time is 20min ~ 40min.
4. the method for synthetic metals according to claim 1/metal oxide supported type nanocatalyst, is characterized in that, add at least one in sodium acid carbonate, saleratus, carbonic hydroammonium in reaction system.
5. the method for synthetic metals according to claim 5/metal oxide supported type nanocatalyst, is characterized in that, in reaction system, add sodium acid carbonate, and the mol ratio of its consumption and metal precursor is 1:100 ~ 700.
6. the method for synthetic metals according to claim 1/metal oxide supported type nanocatalyst, it is characterized in that, metal precursor is at least one in chlorine palladium acid sodium, gold chloride, chloroplatinic acid, Schweinfurt green, metal oxide precursor is mol ratio 1:2.0 ~ 48.0 of at least one in zinc acetate, cerous acetate, ferric acetate, metal precursor and metal oxide precursor.
7. the method for synthetic metals/metal oxide supported type nanocatalyst as claimed in claim 1, it is characterized in that, described separation and purification is: product is after centrifugal segregation supernatant, use water and organic solvent washing respectively, last vacuum drying, obtains metal/metal oxide carrier nanometer catalyst.
8. the method for synthetic metals/metal oxide supported type nanocatalyst as claimed in claim 7, it is characterized in that, described organic solvent is at least one in acetone, ethanol and n-hexane.
9. the metal/metal oxide carrier nanometer catalyst that as described in as arbitrary in claim 1 ~ 8, method obtains.
10. metal/metal oxide carrier nanometer catalyst as claimed in claim 9, it is characterized in that, particle diameter is 5nm ~ 50nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108709884A (en) * | 2018-05-24 | 2018-10-26 | 南京工业大学 | Method for preparing glycosylated nano-gold by one-step method and application thereof |
| 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 |
| CN111715239A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of oxide-supported monatomic catalyst |
| CN115414931A (en) * | 2022-08-31 | 2022-12-02 | 北京工业大学 | Preparation method of Pd/ZnO catalyst for hydrogen production by methanol steam reforming |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008264761A (en) * | 2007-03-26 | 2008-11-06 | Mitsubishi Chemicals Corp | New alloy nano colloidal particle and chemical reaction using the same |
| CN103157519A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparing method for supported core-shell-structure catalyst for low-temperature fuel cell |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008264761A (en) * | 2007-03-26 | 2008-11-06 | Mitsubishi Chemicals Corp | New alloy nano colloidal particle and chemical reaction using the same |
| CN103157519A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparing method for supported core-shell-structure catalyst for low-temperature fuel cell |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108709884A (en) * | 2018-05-24 | 2018-10-26 | 南京工业大学 | Method for preparing glycosylated nano-gold by one-step method and application thereof |
| 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 |
| CN111715239A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of oxide-supported monatomic catalyst |
| CN115414931A (en) * | 2022-08-31 | 2022-12-02 | 北京工业大学 | Preparation method of Pd/ZnO catalyst for hydrogen production by methanol steam reforming |
| CN115414931B (en) * | 2022-08-31 | 2024-01-05 | 北京工业大学 | Preparation method of Pd/ZnO catalyst for preparing hydrogen by methanol steam reforming |
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