CN104689820A - Cobalt-based bimetallic catalyst with cylindrical structure as well as preparation method and application of cobalt-based bimetallic catalyst - Google Patents
Cobalt-based bimetallic catalyst with cylindrical structure as well as preparation method and application of cobalt-based bimetallic catalyst Download PDFInfo
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Abstract
The invention discloses a cobalt-based bimetallic catalyst with a cylindrical structure as well as a preparation method and application of the cobalt-based bimetallic catalyst. The cobalt-based bimetallic catalyst is prepared from the following steps: dissolving a cobalt source and a nickel source in a solvent to prepare a solution A; and adding a surfactant, a reducing agent and alkali in the solution A, and carrying out water bath heating treatment under the sealing condition to obtain the catalyst. The catalyst can be applied to reaction of catalyzing nitrobenzene hydrogenation, has a nanometer cylindrical structure, has the characteristics of good dispersion, stable structure, uniform morphology and size, exposure of high-activity crystal face, high reactivity to nitrobenzene hydrogenation and the like, is good in repeatability and is environmentally friendly due to mild conditions in the hydrogenation reaction process, also has the advantages of simplicity in preparation, good stability, easiness in separation of a product and the catalyst, convenience in recovery and utilization, easiness in activity and the like and has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of catalyst and method for making thereof and application, particularly relate to a kind of there is column structure cobalt-based bimetallic catalyst and method for making and application.
Background technology
Nano material, because of the bulk effect of its uniqueness, skin effect and quantum size effect, has the performances such as the electricity different from block materials, light, power, magnetic.And the application of these aspects and the size and dimension of nano material closely related.In recent years, along with the development of nanometer technology, the nano material of morphology controllable, because the physicochemical properties of its uniqueness, more and more receives the concern of every subjects researchers.So-called pattern includes two aspects exactly: size and dimension.As everyone knows, when the size of material little to certain degree time, its some physical parameters can change; And the homogeneous nano material of shape often can expose the surface with the identical indices of crystallographic plane, so just can obtain known surface characteristic.Large quantity research shows, has close inner link between the structure of nano material and its performance, the morphology controllable synthesis of research nano material for nano material Nature-Understanding and to widen its application significant.Such as in catalyticing research field, understand the relation between catalyst surface structure and its catalytic perfomance, having important directive significance to design and development effective catalyst, is the approach realizing above-mentioned target with the research that the metal nano material of compound with regular structure carries out surface texture-catalytic performance relation and mechanism of catalytic reaction for model catalyst.
In material science, form alloy by mixing two kinds of different metals and metal can be made to produce some new character, form bimetallic material.Compare with monometallic, in the composition and structural research of material, bimetallic composite nanometer particle has the character such as unique optics, catalysis and magnetic, and this is two kinds of synergistic results of metal owing to forming alloy.Owing to there is various combination, so the exploitation of bimetallic catalyst has huge potentiality.The second metal added can be noble metal or transition light metal.The monometallic method of most preparation can be used for preparing bimetallic.Due to the performance of bimetal nano material and its pattern closely related, so to realize these uniquenesses performance or acquired can better metal nano material, first must realize the controlledly synthesis of material morphology.But preparation size and the controlled nano particle of pattern (especially novel shape) and nanostructured are the difficult problem of and have challenge.The bimetal nano particles of the control synthesis reported mainly concentrates on noble metal and noble metal field, as these metals such as Au-Ag, Pt-Pd, Pt-Ni, Ag-Pd belong to VIII race (platinum, palladium, nickel) and IB race metal (gold, silver) more.The bimetallic material that noble metal and base metal form also has correlative study report, as Pt-Ni, Ag-Ni, Pd-Cu etc., the bimetal nano material that base metal and base metal synthesize then is studied less (as Ni-Co, Ni-Fe, Fe-Cu), and this is more unstable mainly due to this metalloid, easily reunite.
In recent years, bimetal nano catalysis material due to improve catalytic activity and selective etc. in important function and be subject to common concern, carry out regulating and controlling the different bimetallic material of synthesis preparation around factors such as bimetallic material composition, microstructures, study the performance of above-mentioned different bimetallic material in different catalytic reaction, attempt to find the catalyst material with more high activity, selective and stability, and attempt exploring the hot issue that new catalytic reaction and mechanism of catalytic reaction also become research.Certainly, the morphology controllable synthesis studying cobalt-based bimetallic material has important academic significance and industrial value.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of there is column structure cobalt-based bimetallic catalyst and method for making and application.This catalyst is a kind of morphology controllable and can be used for the column bimetallic catalyst of hydrogenation of chloronitrobenzene, it is prepared (as passed through at surfactant and reducing obtained in monohydric alcohol hydrothermal system) by liquid phase reduction etc., and preparation method of the present invention have simple to operate, reaction condition is gentle, product morphology controllable and the advantage such as stable, have a good application prospect.
For solving the problems of the technologies described above, cobalt-based bimetallic catalyst of the present invention, it is that method by comprising the steps is preparation-obtained:
Cobalt source and nickel source are dissolved in solvent, are prepared into solution A;
In solution A, add surfactant, reducing agent and alkali, and in confined conditions, carry out heating water bath process, obtain described catalyst.
Described cobalt source comprises: containing the salt of cobalt; Be preferably divalent cobalt, as this divalent cobalt comprises: one or more in cobalt chloride, cobalt nitrate or cobalt acetate etc.; Be preferably cobalt acetate (as Co (Ac)
24H
2o etc.).
Described nickel source comprises: nickeliferous salt; Be preferably divalent nickel salt, as this divalent nickel salt comprises: one or more in nickel chloride, nickel nitrate or nickel acetate etc.; Be more preferably nickel acetate (as Ni (Ac)
24H
2o etc.).
Nickel in described cobalt source, nickel source and the mol ratio of cobalt are preferably 0.5 ~ 2.
Described solvent comprises: monohydric alcohol; Wherein, this monohydric alcohol comprises: one or more in ethanol, propyl alcohol, butanols etc.; Preferably, this solvent is ethanol.
Described surfactant comprises: polyvinylpyrrolidone (PVP); Described polyvinylpyrrolidone comprises: one or more in PVP-K13-18, PVP-K23-27, PVP-K29-32 etc.; Be preferably PVP-K29-32.
Described reducing agent comprises: hydrazine hydrate; Be preferably the hydrazine hydrate solution of 40wt% ~ 85wt% (percetage by weight).
Described alkali comprises: inorganic base; Wherein, this inorganic base comprises: Na
2cO
3, one in NaOH etc. or its mixture; Be preferably NaOH.
Described catalyst is a kind of bimetallic cobalt-base catalyst with column structure, and the column diameters of this catalyst can be about 200 ~ 400nm, and length about 1 ~ 3 μm, structure is stable homogeneous comparatively.
In addition, for above-mentioned catalyst, the invention provides a kind of concrete preparation method of above-mentioned catalyst, comprise step:
1) preparation of reactant liquor
Above-mentioned cobalt source and above-mentioned nickel source are dissolved in above-mentioned solvent, are prepared into nickeliferous and solution A that is cobalt;
Wherein, the molar concentration of the cobalt in described solution A is preferably 0.05 ~ 0.2mol/L, is more preferably 0.1mol/L, and the molar concentration of nickel is according to molar concentration 50% ~ 200% modulation of the catalyst needs of preparation at cobalt, and namely the mol ratio of nickel and cobalt is 0.5 ~ 2.
2) surfactant, reducing agent and alkali is added
After above-mentioned surfactant, reducing agent and alkali are mixed to form mixed liquor, add in solution A, obtain solution B;
Wherein, the surfactant concentration in mixed liquor is 0.01 ~ 0.1mol/L, is preferably 0.4mol/L;
Reductant concentration in described mixed liquor is 1 ~ 10mol/L, is preferably 5.3mol/L;
Alkali concn in mixed liquor is 0.05mol/L ~ 1mol/L, is preferably 0.4mol/L;
The volume ratio of mixed liquor and solution A is 0.1 ~ 0.5, is preferably 0.25;
The method of described formation mixed liquor comprises: utilize ultrasonic carrying out mix and form mixed liquor;
The method of described interpolation is preferably and drips;
3) hydrothermal treatment consists
In confined conditions, by solution B at 100 ~ 200 DEG C, heating water bath process 5 ~ 20 hours;
Wherein, preferably, at 100 ~ 180 DEG C, heating water bath process 5 ~ 20 hours, more preferably heating water bath process 10 hours at 120 DEG C;
4) by step 3) washing of the product (precipitated product) that obtains is separated, dry, obtains the agent of cobalt-based Catalyzed by Pt/M Bimetallic Nano.
Wherein, the method for described washing comprises: with deionized water and absolute ethanol washing 4 ~ 6 times;
Vacuum drying 4 ~ 8 hours at the condition of described drying is preferably 50 ~ 60 DEG C, vacuum drying 4 ~ 8 hours at being more preferably 50 DEG C.
Moreover the present invention also provides the application of above-mentioned catalyst, be namely applied in the reaction of catalysis hydrogenation of chloronitrobenzene, wherein, the reaction condition of catalysis is preferably: reaction temperature 100 ~ 160 DEG C, H
2pressure 2 ~ 6MPa.
In the present invention, by adopting the certain density solution containing cobalt nickel as precursor liquid, add surfactant, reducing agent and alkali, mix under normal temperature, then moved in water heating kettle by mixed solution, hydrothermal treatment consists a period of time, after question response liquid cooling but, by centrifugal, washing, drying to process, catalyst of the present invention can be obtained.As under ethanol system, hydrazine hydrate, as reducing agent, utilizes hydrothermal reduction method to generate cobalt-based column bimetal nano catalyst, by XRD and SEM test display, the nano material of synthesis is cobalt-based bimetallic material, and the nanotopography of catalyst is column structure, and pattern is homogeneous.
Catalyst of the present invention has nanometer column structure and good dispersion, Stability Analysis of Structures, pattern size is homogeneous and expose high activity crystal face, p-nitrophenyl catalytic hydrogenation has the features such as higher reactivity, and hydrogenation process mild condition, catalyst is reproducible, environmental friendliness.Simultaneously, this catalyst have make simple, good stability, product and catalyst are easily separated, be convenient to advantages such as recycling, easily-activated, thus significantly improve equipment capacity and product quality, bring huge economic benefit, there is good industrial applications prospect.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and detailed description of the invention, the present invention is further detailed explanation:
Fig. 1 is SEM (ESEM) collection of illustrative plates of the catalyst of preparation in embodiment 1.
Fig. 2 is TEM (transmission electron microscope) collection of illustrative plates of the catalyst of preparation in embodiment 1.
Fig. 3 is XRD (X-ray diffraction) collection of illustrative plates of the catalyst of preparation in embodiment 1.
Fig. 4 is the nitrobenzene hydrogenation activity-time plot of the catalyst of preparation in embodiment 1.
Detailed description of the invention
Reagent involved in following examples is then commercially produced product if not otherwise specified.
Embodiment 1
Take 2mmol cobalt acetate (Co (Ac)
24H
2and 2mmol nickel acetate (Ni (Ac) O)
24H
2o), mixed dissolution is in 20mL ethanol, and under normal temperature condition, stirring and dissolving obtains uniform solution A.
Take 0.4g NaOH and 1mmol PVP-K29-32 again, the dropwise obtained, in 5mL 85wt% hydrazine hydrate, adds in solution A, is uniformly mixed, obtain solution B by ultrasonic dissolution.
The solution of gained is joined in 30ml water heating kettle, in confined conditions and at temperature 120 DEG C, heating water bath process 10 hours.Then, after question response temperature is cooled to room temperature, medication spoon scrapes atrament (product), uses deionized water and absolute ethanol washing 4-6 times respectively, finally by product vacuum drying 4 hours at 60 DEG C, obtains cobalt-based bimetallic column nanocatalyst.
Wherein, the SEM figure of this catalyst, as shown in Figure 1.As known in the figure, cobalt-based bimetallic column nanocatalyst of the present invention is better dispersed, and particle size is homogeneous, Stability Analysis of Structures, and it is { 111} face that cobalt-based bimetallic column nanocatalyst surface exposes crystal face.In addition, the column diameters of this catalyst is at about 200-400nm, and length is at about 1 ~ 3 μm.
In addition, as shown in Figure 2, though there is the overlap of column structure, but still can find out cobalt-based column structure clearly, diameter is probably also at about 200-400nm, and self assembly forms Cluster Structures.
In addition, the cobalt-based bimetallic catalyst that Fig. 3 shows column structure is then the mixture of face-centered cubic and close heap hexagonal structure, cobalt-based nano-pillar in 2 θ=41.8 °, 44.3 °, 47.4 °, 51.8 ° and corresponding (100), (111), (101), (200) and (110) face respectively, 76.2 ° of places.
Above-mentioned obtained catalyst, can be used in the catalytic reaction of hydrogenation of chloronitrobenzene preparing cyclohexane.Wherein, hydrogenation of chloronitrobenzene carries out in 100ml autoclave, take 2ml nitrobenzene and be dissolved in 60ml methyl alcohol, taking 0.18g catalyst joins in solution, and overall transformation enters reactor, repeatedly fills hydrogen, reaction condition is: T (temperature)=120 DEG C, P (H2 pressure)=3.0Mpa, carries out intermittent sampling in course of reaction, extracts reaction solution supernatant injection GC-MS and analyzes.As shown in Figure 4, compared to Ni, column structure cobalt-based bimetal nano catalyst demonstrates good catalytic activity to reaction result, within the equivalent responses time, have higher transformation efficiency.
Embodiment 2
Take 2mmol cobalt nitrate (Co (NO
3)
26H
2and 2mmol nickel acetate (Ni (Ac) O)
24H
2o), mixed dissolution is in 20mL propyl alcohol, and under normal temperature condition, stirring and dissolving obtains uniform solution A.
Take 0.4g NaOH and 1mmol PVP-K13-18 again, the dropwise obtained, in 5mL 45wt% hydrazine hydrate, adds in solution A, is uniformly mixed, obtain solution B by ultrasonic dissolution.
The solution of gained is joined in 30ml water heating kettle, in confined conditions and at temperature 110 DEG C, heating water bath process 20 hours.Then, after question response temperature is cooled to room temperature, medication spoon scrapes atrament (product), uses deionized water and absolute ethanol washing 4-6 times respectively, finally by product vacuum drying 8 hours at 50 DEG C, obtains cobalt-based bimetallic column nanocatalyst.
The column diameters of this catalyst is about 200 ~ 400nm, and length is at about 1 ~ 3 μm, and structure is stable homogeneous comparatively.
In addition, above-mentioned obtained catalyst, can be used in the catalytic reaction of hydrogenation of chloronitrobenzene preparing cyclohexane.Wherein, hydrogenation of chloronitrobenzene carries out in 100ml autoclave, takes 2ml nitrobenzene and is dissolved in 60ml methyl alcohol, taking 0.18g catalyst joins in solution, and overall transformation enters reactor, repeatedly replacing hydrogen, reaction condition can be: T (temperature)=110 DEG C, P (H
2pressure)=6Mpa.Result shows, good catalytic activity.
Embodiment 3
Take 2mmol cobalt nitrate (Co (NO
3)
26H
2and 2mmol nickel nitrate (Ni (NO O)
3)
26H
2o), mixed dissolution is in 20mL butanols, and under normal temperature condition, stirring and dissolving obtains uniform solution A.
Take 0.4g NaOH and 1mmol PVP-K23-27 again, the dropwise obtained, in 5mL 60wt% hydrazine hydrate, adds in solution A, is uniformly mixed, obtain solution B by ultrasonic dissolution.
The solution of gained is joined in 30ml water heating kettle, in confined conditions and at temperature 150 DEG C, heating water bath process 8 hours.Then, after question response temperature is cooled to room temperature, medication spoon scrapes atrament (product), uses deionized water and absolute ethanol washing 4-6 times respectively, finally by product vacuum drying 6 hours at 55 DEG C, obtains cobalt-based bimetallic column nanocatalyst.
The column diameters of this catalyst is about 200 ~ 400nm, and length is at about 1 ~ 3 μm, and structure is stable homogeneous comparatively.
In addition, above-mentioned obtained catalyst, can be used in the catalytic reaction of hydrogenation of chloronitrobenzene preparing cyclohexane.Wherein, hydrogenation of chloronitrobenzene carries out in 100ml autoclave, take 2ml nitrobenzene and be dissolved in 60ml methyl alcohol, taking 0.18g catalyst joins in solution, overall transformation enters reactor, repeatedly replacing hydrogen, reaction condition is: T (temperature)=130 DEG C, P (H2 pressure)=4Mpa.Result shows, good catalytic activity.
Embodiment 4
Take 3mmol nickel chloride and 2mmol cobalt chloride, mixed dissolution is in 20mL alcohol mixed liquor (ethanol: the volume ratio of propyl alcohol is 1:1), and under normal temperature condition, stirring and dissolving obtains uniform solution A.
Take Na again
2cO
3, NaOH and 1mmol PVP-K29-32, ultrasonic dissolution, in 5mL85% hydrazine hydrate, obtains solution (Na
2cO
30.6mol/L is with the concentration of NaOH), this dropwise is added in solution A, is uniformly mixed, obtain solution B.
The solution of gained is joined in 30ml water heating kettle, in confined conditions and at temperature 180 DEG C, heating water bath process 15 hours.Then, after question response temperature is cooled to room temperature, medication spoon scrapes atrament (product).The product obtained after hydrothermal treatment consists is used respectively deionized water and absolute ethanol washing 4-6 times, finally by product vacuum drying 5 hours at 52 DEG C, obtain cobalt-based bimetallic column nanocatalyst.
The column diameters of this catalyst is about 200 ~ 400nm, and length is at about 1 ~ 3 μm, and structure is stable homogeneous comparatively.
In addition, above-mentioned obtained catalyst, can be used in the catalytic reaction of hydrogenation of chloronitrobenzene preparing cyclohexane.Wherein, hydrogenation of chloronitrobenzene carries out in 100ml autoclave, take 2ml nitrobenzene and be dissolved in 60ml methyl alcohol, taking 0.18g catalyst joins in solution, overall transformation enters reactor, repeatedly replacing hydrogen, reaction condition is: T (temperature)=150 DEG C, P (H2 pressure)=5Mpa.Result shows, good catalytic activity.
Claims (10)
1. a cobalt-based bimetallic catalyst, is characterized in that: described catalyst is that the method by comprising the steps is preparation-obtained:
Cobalt source and nickel source are dissolved in solvent, are prepared into solution A;
In solution A, add surfactant, reducing agent and alkali, and in confined conditions, carry out heating water bath process, obtain described catalyst.
2. catalyst as claimed in claim 1, is characterized in that: described cobalt source comprises: containing the salt of cobalt;
Nickel source comprises: nickeliferous salt;
Nickel in cobalt source, nickel source and the mol ratio of cobalt are 0.5 ~ 2;
Solvent comprises: monohydric alcohol;
Surfactant comprises: polyvinylpyrrolidone;
Reducing agent comprises: hydrazine hydrate;
Alkali comprises: inorganic base.
3. catalyst as claimed in claim 2, is characterized in that: the described salt containing cobalt is divalent cobalt;
Nickeliferous salt is divalent nickel salt;
Monohydric alcohol comprises: one or more in ethanol, propyl alcohol, butanols;
Polyvinylpyrrolidone comprises: one or more in PVP-K13-18, PVP-K23-27, PVP-K29-32;
Hydrazine hydrate is the hydrazine hydrate solution of 40wt% ~ 85wt%.
Inorganic base comprises: Na
2cO
3, one in NaOH or its mixture.
4. catalyst as claimed in claim 3, is characterized in that: described divalent cobalt comprises: one or more in cobalt chloride, cobalt nitrate or cobalt acetate;
Divalent nickel salt comprises: one or more in nickel chloride, nickel nitrate or nickel acetate;
Solvent is ethanol;
Polyvinylpyrrolidone is PVP-K29-32;
Inorganic base is NaOH.
5. catalyst as claimed in claim 4, is characterized in that: described divalent cobalt is cobalt acetate;
Divalent nickel salt is nickel acetate.
6. catalyst as claimed in claim 1, is characterized in that: described catalyst is a kind of bimetallic cobalt-base catalyst with column structure, and the column diameters of this catalyst is 200 ~ 400nm, length 1 ~ 3 μm.
7. the preparation method of catalyst as claimed in claim 1, is characterized in that, comprise step:
1) cobalt source and nickel source are dissolved in solvent, are prepared into nickeliferous and solution A that is cobalt;
2), after surfactant, reducing agent and alkali being mixed to form mixed liquor, adding in solution A, obtain solution B;
3) in confined conditions, by solution B at 100 ~ 200 DEG C, heating water bath process 5 ~ 20 hours;
4) by step 3) washing of the product that obtains is separated, dry, obtains the agent of cobalt-based Catalyzed by Pt/M Bimetallic Nano.
8. method as claimed in claim 7, is characterized in that: the molar concentration of the cobalt in described solution A is 0.05 ~ 0.2mol/L; The mol ratio of nickel and cobalt is 0.5 ~ 2;
Step 2) in, the surfactant concentration in mixed liquor is 0.01 ~ 0.1mol/L; Reductant concentration in mixed liquor is 1 ~ 10mol/L; Alkali concn in mixed liquor is 0.05mol/L ~ 1mol/L; The volume ratio of mixed liquor and solution A is 0.1 ~ 0.5; The method forming mixed liquor comprises: utilize ultrasonic carrying out mix and form mixed liquor; The method of adding is for dripping;
Step 3) in, at 100 ~ 180 DEG C, heating water bath process 5 ~ 20 hours;
Step 4) in, the method for washing comprises: with deionized water and absolute ethanol washing 4 ~ 6 times; Dry condition is vacuum drying 4 ~ 8 hours at 50 ~ 60 DEG C.
9. method as claimed in claim 7, is characterized in that: the molar concentration of the cobalt in described solution A is 0.1mol/L;
Step 2) in, the surfactant concentration in mixed liquor is 0.4mol/L; Reductant concentration in described mixed liquor is 5.3mol/L; Alkali concn in mixed liquor is 0.4mol/L; The volume ratio of mixed liquor and solution A is 0.25;
Step 3) in, heating water bath process 10 hours at 120 DEG C;
Step 4) in, dry condition is vacuum drying 4 ~ 8 hours at 50 DEG C.
10. the application of the catalyst as described in any one of claim 1 ~ 6, is characterized in that: be applied in the reaction of catalysis hydrogenation of chloronitrobenzene, and wherein, the reaction condition of catalysis is: reaction temperature 100 ~ 160 DEG C, H
2pressure 2 ~ 6MPa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105081308A (en) * | 2015-08-24 | 2015-11-25 | 中国科学院上海高等研究院 | Curved-surface Pt-based nanometer bimetallic material with and preparation method and application thereof |
| CN105537624A (en) * | 2015-12-15 | 2016-05-04 | 中国科学院上海高等研究院 | Triangular ring Pd base material and preparing method and application of triangular ring Pd base material |
| CN106179353A (en) * | 2016-07-10 | 2016-12-07 | 北京化工大学 | A kind of application of load-type nickel copper alloy nanocatalyst and preparation method thereof and catalytic hydrogenation |
| CN108067232A (en) * | 2017-10-20 | 2018-05-25 | 天津大学 | The catalysis material CoNiO of high activity OER and ORR2And its synthetic method |
| CN109628074A (en) * | 2018-12-19 | 2019-04-16 | 常州大学 | A kind of preparation method and reducing crude oil viscosity material of reducing crude oil viscosity material |
| CN111115694A (en) * | 2020-01-21 | 2020-05-08 | 河南科技大学 | Preparation method of hollow Co-Fe LDH material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130087363A1 (en) * | 2011-10-11 | 2013-04-11 | Korea Institute Of Science And Technology | Metal nanowires with high linearity, method for producing the metal nanowires and transparent conductive film including the metal nanowires |
| CN103357410A (en) * | 2013-08-05 | 2013-10-23 | 上海中科高等研究院 | Nanometer nickel-based polyhedron catalyst used for aromatic ring hydrogenation, preparation method thereof and application thereof |
-
2015
- 2015-02-15 CN CN201510080881.7A patent/CN104689820B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130087363A1 (en) * | 2011-10-11 | 2013-04-11 | Korea Institute Of Science And Technology | Metal nanowires with high linearity, method for producing the metal nanowires and transparent conductive film including the metal nanowires |
| CN103357410A (en) * | 2013-08-05 | 2013-10-23 | 上海中科高等研究院 | Nanometer nickel-based polyhedron catalyst used for aromatic ring hydrogenation, preparation method thereof and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴孔林: "铁钴镍基二元合金微纳米结构的控制合成磁学及催化性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 陈慧玉: "金属纳米结构材料的研制", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN105537624A (en) * | 2015-12-15 | 2016-05-04 | 中国科学院上海高等研究院 | Triangular ring Pd base material and preparing method and application of triangular ring Pd base material |
| CN105537624B (en) * | 2015-12-15 | 2018-04-17 | 中国科学院上海高等研究院 | A kind of three square ring Pd sills and its preparation method and application |
| CN106179353A (en) * | 2016-07-10 | 2016-12-07 | 北京化工大学 | A kind of application of load-type nickel copper alloy nanocatalyst and preparation method thereof and catalytic hydrogenation |
| CN108067232A (en) * | 2017-10-20 | 2018-05-25 | 天津大学 | The catalysis material CoNiO of high activity OER and ORR2And its synthetic method |
| CN109628074A (en) * | 2018-12-19 | 2019-04-16 | 常州大学 | A kind of preparation method and reducing crude oil viscosity material of reducing crude oil viscosity material |
| CN111115694A (en) * | 2020-01-21 | 2020-05-08 | 河南科技大学 | Preparation method of hollow Co-Fe LDH material |
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