CN103263905A - Carbon black loaded lanthanum oxide nanocrystal composite catalyst and preparation method thereof - Google Patents
Carbon black loaded lanthanum oxide nanocrystal composite catalyst and preparation method thereof Download PDFInfo
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- CN103263905A CN103263905A CN2013101949777A CN201310194977A CN103263905A CN 103263905 A CN103263905 A CN 103263905A CN 2013101949777 A CN2013101949777 A CN 2013101949777A CN 201310194977 A CN201310194977 A CN 201310194977A CN 103263905 A CN103263905 A CN 103263905A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a carbon black loaded lanthanum oxide nanocrystal composite catalyst and a preparation method thereof. The catalyst has very high electrocatalytic activity and durability to an oxygen reduction reaction in an alkaline medium. The loaded catalyst is prepared from a soluble lanthanum salt, urea and carbon black, the pH value of a reaction solution is adjusted by using ammonia water, and meanwhile, a surfactant CTAB (Cetyl Trimethyl Ammonium Bromide) and ammonium sulfate are added during preparation so as to control the particle diameter of an oxide. The size of prepared rare-earth-metal lanthanum oxide nanocrystals is 2-10nm. Compared with loaded noble metal catalysts, such as silver, the catalyst has the characteristics of low cost, stable performance and the like.
Description
Technical field
The present invention relates to the rare earth nano material preparation field, particularly a kind of carbon black loadings lanthana rare earth catalyst and preparation method thereof.
Background technology
Nano lanthanum oxide is as important rare earth oxide, it is little to have size, specific area is big, characteristics such as active height, because the lanthanum element electronics transmits between positive trivalent and positive quadrivalent ion, so the lanthanum element electron exchange is very competent, oxidation reaction or reduction reaction take place in lanthanum element easily, the distinctive character of while nano material itself, it is quantum size effect, macro quanta tunnel effect, skin effect and small-size effect, chemical bond and the material internal on surface are inequality, thereby the surface atom coordination does not cause the surface-active position to increase entirely like this, form the different atomic steps of height, strengthened the reaction contact-making surface and strengthened adsorption capacity, La
2O
3Be widely used as auto-exhaust catalyst, petroleum refining catalyst, hydrogenation and Hydrobon catalyst, luminescent material, permanent-magnet material and high-performance ceramic etc. at home and abroad.
Based on an urgent demand of clean energy resource commercial applications such as fuel cell, metal-air battery, La
2O
3The hydrogen reduction electrocatalysis has been caused the interest that the scientific worker is bigger.In addition, consider that China Pt family metals resources is in great shortage and the situation of rare earth reserves and output based on rare earth resources, is given full play to resources advantage and the usefulness of rare earth, exploitation high activity La
2O
3Oxygen reduction electro-catalyst will have huge commercial Application background in fields such as alkaline fuel cell, chlorine industry, the senior electroxidation processing of sewage and vehicle exhaust processing.
Summary of the invention
Purpose of the present invention provides a kind of carbon black loadings lanthana rare earth catalyst and preparation method thereof on the one hand.Further, the purpose of this invention is to provide a kind of inexpensive, operating procedure is simple, particle diameter is controlled and be easy to the preparation method that suitability for industrialized production is applied to the support type rare earth oxide catalyst of catalytic oxygen reduction reaction.This catalyst has very high hydrogen reduction electro catalytic activity and durability in alkaline medium.
Support type rare earth metal lanthanum-oxides composite catalyst of the present invention is pressed powder, the nanocrystalline surface that evenly loads on the acidifying carbon black pellet dispersedly of the lanthanum-oxides of particle diameter 2～10nm, lanthanum-oxides load factor scope is 20%～200%, lanthanum-oxides nanocrystalline with the mass ratio acidifying carbon black be 0.2～2.By the gas reaction electrode that above-mentioned cheap catalyst is made, in alkaline medium, have very high oxygen reduction reaction electro catalytic activity and useful life longevity.
One aspect of the present invention relates to the preparation method of the nanocrystalline composite catalyst of a kind of carbon black loadings lanthanum-oxides, described catalyst is pressed powder, the nanocrystalline surface that loads on the acidifying carbon black pellet of the lanthanum-oxides of particle diameter 2～10nm, lanthanum-oxides load factor scope is 20%～200%, lanthanum-oxides nanocrystalline with the mass ratio acidifying carbon black be 0.2～2; It is characterized in that described preparation method comprises the steps:
(1) preparation 0.01 mol/L～0.1 mol/L solubility lanthanum saline solution, the carbon black of nitric acid acidifying is joined in the solution, add the ammonium sulfate of mass fraction 0.05% ~ 0.25% again as lanthanum-oxides grain size controlling agent, ultrasonic dispersion 5min～30min obtains containing the suspension of lanthanum salt, ammonium sulfate and acidifying carbon black;
(2) the urea precipitating reagent aqueous solution of preparation 0.01 mol/L～0.6 mol/L adds mass fraction and is 0.50% ~ 1.0% Surfactant CTAB as precipitation aid, and ultrasonic dispersion 5min～30min obtains containing the hydrolysis solution of precipitating reagent;
(3) the hydrolysis drips of solution with step (2) preparation is added in the suspension of step (1) preparation, the control bath temperature is at 65 ° of C～95 ° C, after dropwising, regulating mixed reaction solution pH value is 8～12, condensing reflux, the reaction time is 15min ~ 120min, then ultrasonic 20min ~ 80min.After reaction finishes, reacting liquid filtering, washing and drying, the rare-earth lanthanum oxide catalyst precursor pressed powder that obtains;
(4) lanthanum-oxides catalyst precursor pressed powder is heat-treated under the condition of argon gas as protective gas: at first the heating rate with 5～10 ° of C/min is warming up to 400 ° of C～500 ° C; secondly; after being warming up to 700 ° of C～1000 ° C with the heating rate of 2～8 ° of C/min again; behind insulation roasting 1.5h～5h; with the stove cooling, obtain the nanocrystalline composite catalyst of support type lanthanum-oxides.
In a preferred embodiment of the present invention, in above-mentioned steps (3), utilize concentrated ammonia solution as the pH conditioning agent.
In a preferred embodiment of the present invention, described solubility lanthanum salt is lanthanum chloride and/or lanthanum nitrate, and described carbon black is Vulcan XC-72, the acetylene black after Vulcan XC-72, acetylene black or process high temperature graphitization are handled.
The present invention also relates to the nanocrystalline composite catalyst of a kind of carbon black loadings lanthanum-oxides on the other hand, described catalyst is pressed powder, the nanocrystalline surface that loads on the acidifying carbon black pellet of the lanthanum-oxides of particle diameter 2～10nm, lanthanum-oxides load factor scope is 20%～200%, lanthanum-oxides nanocrystalline with the mass ratio acidifying carbon black be 0.2～2.
In a preferred embodiment of the present invention, carbon black carry the type lanthanum-oxides nanocrystalline by six sides mutually with cube mutually lanthanum sesquioxide or a kind of composition the wherein.
Described solubility lanthanum salt is lanthanum chloride and/or lanthanum nitrate, and described carbon black is Vulcan XC-72, the acetylene black after Vulcan XC-72, acetylene black or process high temperature graphitization are handled.
In a preferred embodiment of the present invention, it is characterized in that carbon black carry the type lanthanum-oxides nanocrystalline by six sides mutually with cube mutually lanthanum sesquioxide or a kind of composition the wherein.
The present invention also relates to a kind of electrode on the other hand, and it contains the nanocrystalline composite catalyst of above-mentioned carbon black loadings lanthanum-oxides.
The invention still further relates to above-mentioned electrode as the application of gas reaction electrode, described gas reaction electrode carries out the oxygen reduction reaction of electro-catalysis in alkaline medium.
The present invention adopts a kind of simple method to prepare the nanocrystalline composite catalyst of carbon black loadings lanthana, be used for the catalytic oxygen reduction reaction, by the gas reaction electrode that this cheap catalyst is made, in alkaline medium, have very high oxygen reduction reaction electro catalytic activity and useful life longevity.The technology cost is low, has especially reduced cost of material, and process is simple, easy to operate.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of embodiment 1 gained catalyst;
Fig. 2 is the transmission electron micrograph of embodiment 1 gained catalyst;
Fig. 3 is the tank voltage test curve that embodiment 1 gained Preparation of Catalyst becomes electrode;
Fig. 4 is the stable time-measuring electric potential test curve that embodiment 1 gained Preparation of Catalyst becomes electrode;
Fig. 5 is the durability cyclic voltammetric test curve that embodiment 1 gained nano-composite catalyst is prepared into electrode.
The specific embodiment
Embodiment 1
The preparation load capacity be 20% lanthanum-oxides nanocrystalline/the charcoal composite catalyst.
(1) at first adopt chemical precipitation method to prepare the nanocrystalline catalyst precursor of support type lanthanum-oxides:
(2) the lanthanum-oxides catalyst precursor pressed powder of step (1) preparation is heat-treated under the condition of argon gas as protective gas: at first the heating rate with 5～10 ° of C/min is warming up to 400 ° of C～500 ° C; secondly; after being warming up to 700 ° of C～1000 ° C with the heating rate of 2～8 ° of C/min again; behind insulation roasting 1.5h～5h, cool off with stove.Obtain the nanocrystalline composite catalyst of support type lanthanum-oxides.Composite catalyst is prepared into the gas reaction electrode carries out electro-chemical test.
The XRD collection of illustrative plates of the oxide nano rare earth composite catalyst of support type is seen Fig. 1, and the catalyst oxidation thing is La
2O
3, hexagonal structure is main.The TEM picture is seen Fig. 2 respectively, and the oxide uniform load is at carbon blacksurface, and particle diameter is less than 10nm.Nano-composite catalyst is prepared into the tank voltage test curve of electrode and sees Fig. 3, can be judged under actual working conditions by figure, and electrode potential calibration catalyst performance is good; 300mA/cm
2The timing curve that records under the fixed current condition is seen Fig. 4, and electrode stability is good as can be known; The electrode that is prepared into is carried out the test of cyclic voltammetry scan 1000 circle, the electric potential scanning scope be 0.5V～-1.0V, speed is seen Fig. 5 for the 50mV/s curve, durability of catalyst is good as can be known.
The preparation load capacity be 100% lanthanum-oxides nanocrystalline/the charcoal composite catalyst.
(1) at first adopt chemical precipitation method to prepare the nanocrystalline catalyst precursor of support type lanthanum-oxides:
Prepare 0.01 mol/L～0.1 mol/L solubility lanthanum saline solution, the 0.1629g carbon black of nitric acid acidifying is joined in the solution, add the ammonium sulfate of mass fraction 0.05% ~ 0.25% again as lanthanum-oxides grain size controlling agent, ultrasonic dispersion 5min～30min obtains containing the suspension of lanthanum salt, ammonium sulfate and acidifying carbon black;
With step
The hydrolysis drips of solution of preparation is added to step
In the suspension of preparation, fully mix.The control bath temperature after dropwising, utilizes concentrated ammonia solution as the pH conditioning agent at 65 ° of C～95 ° C, and regulating mixed reaction solution pH value is 8～12, condensing reflux, and the reaction time is 15min ~ 120min, then ultrasonic 20min ~ 80min.After reaction finishes, reacting liquid filtering, washing and drying, the rare-earth lanthanum oxide catalyst precursor pressed powder that obtains.
(2) the lanthanum-oxides catalyst precursor pressed powder of step (1) preparation is heat-treated under the condition of argon gas as protective gas: at first the heating rate with 5～10 ° of C/min is warming up to 400 ° of C～500 ° C; secondly; after being warming up to 700 ° of C～1000 ° C with the heating rate of 2～8 ° of C/min again; behind insulation roasting 1.5h～5h, cool off with stove.Obtain the nanocrystalline composite catalyst of support type lanthanum-oxides.
XRD collection of illustrative plates by the loaded nano rare earth oxide composite catalyst prepared determines that the composite catalyst oxide is La
2O
3, hexagonal structure be main and the oxide uniform load at carbon blacksurface, particle diameter is less than 10nm.The electrode that is prepared into carries out tank voltage, time-measuring electric potential and cyclic voltammetry scan 1000 circle tests under actual working conditions, functional, can determine catalyst activity, stability, good endurance.
Embodiment 3
The preparation load capacity be 200% lanthanum-oxides nanocrystalline/the charcoal composite catalyst.
(1) at first adopt chemical precipitation method to prepare the nanocrystalline catalyst precursor of support type lanthanum-oxides:
(2) the lanthanum-oxides catalyst precursor pressed powder of step (1) preparation is heat-treated under the condition of argon gas as protective gas: at first the heating rate with 5～10 ° of C/min is warming up to 400 ° of C～500 ° C; secondly; after being warming up to 700 ° of C～1000 ° C with the heating rate of 2～8 ° of C/min again; behind insulation roasting 1.5h～5h, cool off with stove.Obtain the nanocrystalline composite catalyst of support type lanthanum-oxides.
XRD collection of illustrative plates by the loaded nano rare earth oxide composite catalyst prepared determines that the composite catalyst oxide is La
2O
3, hexagonal structure be main and the oxide uniform load at carbon blacksurface, particle diameter is less than 10nm.The electrode that is prepared into carries out tank voltage, time-measuring electric potential and cyclic voltammetry scan 1000 circle tests under actual working conditions, functional, can determine catalyst activity, stability, good endurance.
Above embodiment shows and has described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification just illustrates principle of the present invention; rather than limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope.
Claims (10)
1. the preparation method of the nanocrystalline composite catalyst of carbon black loadings lanthanum-oxides, described catalyst is pressed powder, the nanocrystalline surface that loads on the acidifying carbon black pellet of the lanthanum-oxides of particle diameter 2～10nm, lanthanum-oxides load factor scope is 20%～200%, lanthanum-oxides nanocrystalline with the mass ratio acidifying carbon black be 0.2～2; It is characterized in that described preparation method comprises the steps:
(1) preparation 0.01 mol/L～0.1 mol/L solubility lanthanum saline solution, the carbon black of nitric acid acidifying is joined in the solution, add the ammonium sulfate of mass fraction 0.05%～0.25% again as lanthanum-oxides grain size controlling agent, ultrasonic dispersion 5min～30min obtains containing the suspension of lanthanum salt, ammonium sulfate and acidifying carbon black;
(2) the urea precipitating reagent aqueous solution of preparation 0.01 mol/L～0.6 mol/L adds mass fraction and is 0.50%～1.0% Surfactant CTAB as precipitation aid, and ultrasonic dispersion 5min～30min obtains containing the hydrolysis solution of precipitating reagent;
(3) the hydrolysis drips of solution with step (2) preparation is added in the suspension of step (1) preparation, the control bath temperature is at 65 ° of C～95 ° C, after dropwising, regulating mixed reaction solution pH value is 8～12, condensing reflux, reaction time is 15min～120min, then ultrasonic 20min～80min; After reaction finishes, reacting liquid filtering, washing and drying, the rare-earth lanthanum oxide catalyst precursor pressed powder that obtains;
(4) lanthanum-oxides catalyst precursor pressed powder is heat-treated under the condition of argon gas as protective gas: at first the heating rate with 5～10 ° of C/min is warming up to 400 ° of C～500 ° C; secondly; after being warming up to 700 ° of C～1000 ° C with the heating rate of 2～8 ° of C/min again; behind insulation roasting 1.5h～5h; with the stove cooling, obtain the nanocrystalline composite catalyst of support type lanthanum-oxides.
2. preparation method according to claim 1 is characterized in that, in step (3), utilizes concentrated ammonia solution as the pH conditioning agent.
3. preparation method according to claim 1 is characterized in that described solubility lanthanum salt is lanthanum chloride and/or lanthanum nitrate, and described carbon black is Vulcan XC-72, the acetylene black after Vulcan XC-72, acetylene black or process high temperature graphitization are handled.
4. according to any described preparation method of claim 1-3, it is characterized in that carbon black carry the type lanthanum-oxides nanocrystalline by six sides mutually with lanthanum sesquioxide cube mutually in a kind of or two kinds form.
5. nanocrystalline composite catalyst of carbon black loadings lanthanum-oxides, described catalyst is pressed powder, the nanocrystalline surface that loads on the acidifying carbon black pellet of the lanthanum-oxides of particle diameter 2～10nm, lanthanum-oxides load factor scope is 20%～200%, lanthanum-oxides nanocrystalline with the mass ratio acidifying carbon black be 0.2～2.
6. the nanocrystalline composite catalyst of carbon black loadings lanthanum-oxides according to claim 5, it is characterized in that described solubility lanthanum salt is lanthanum chloride and/or lanthanum nitrate, described carbon black is Vulcan XC-72, the acetylene black after Vulcan XC-72, acetylene black or process high temperature graphitization are handled.
7. according to claim 5 or the nanocrystalline composite catalyst of 6 described carbon black loadings lanthanum-oxides, it is characterized in that carbon black carry the type lanthanum-oxides nanocrystalline by six sides mutually with cube mutually lanthanum sesquioxide or a kind of composition the wherein.
8. according to the nanocrystalline composite catalyst of the claim 1-4 preparation-obtained carbon black loadings lanthanum-oxides of any described preparation method.
9. electrode, it contains any nanocrystalline composite catalyst of described carbon black loadings lanthanum-oxides of claim 5-8.
10. the described electrode of claim 9 is as the application of gas reaction electrode, and described gas reaction electrode carries out the oxygen reduction reaction of electro-catalysis in alkaline medium.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051721A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Preparation method and use of modified carbon black-LaMnO3 covalent composite material |
| CN104043453A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Supported cobaltosic oxide nanometer composite catalyst and use thereof |
| CN105689011A (en) * | 2016-02-29 | 2016-06-22 | 苏州莱特复合材料有限公司 | Petroleum processing catalyst and preparing method thereof |
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| US20080058201A1 (en) * | 2004-03-11 | 2008-03-06 | Gordon John H | Method of Diffusing a Catalyst for Electrochemical Oxygen Reduction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051721A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Preparation method and use of modified carbon black-LaMnO3 covalent composite material |
| CN104043453A (en) * | 2014-01-06 | 2014-09-17 | 北京化工大学 | Supported cobaltosic oxide nanometer composite catalyst and use thereof |
| CN104043453B (en) * | 2014-01-06 | 2015-12-09 | 北京化工大学 | A kind of support type cobaltosic oxide nano composite catalyst and application |
| CN104051721B (en) * | 2014-01-06 | 2016-05-11 | 北京化工大学 | A kind of modified carbon black-LaMnO3The preparation method of covalency composite and application thereof |
| CN105689011A (en) * | 2016-02-29 | 2016-06-22 | 苏州莱特复合材料有限公司 | Petroleum processing catalyst and preparing method thereof |
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