CN103977812A - Oxygen-reduction binary transition metal oxide catalyst and preparation method thereof - Google Patents
Oxygen-reduction binary transition metal oxide catalyst and preparation method thereof Download PDFInfo
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- CN103977812A CN103977812A CN201410228529.9A CN201410228529A CN103977812A CN 103977812 A CN103977812 A CN 103977812A CN 201410228529 A CN201410228529 A CN 201410228529A CN 103977812 A CN103977812 A CN 103977812A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to an oxygen-reduction binary transition metal oxide catalyst MxNyOz, wherein x is larger than or equal to 0.6 and less than or equal to 1.6, y is larger than or equal to 1.4 and less than or equal to 2.4, and z is larger than or equal to 2 and less than or equal to 4; M or N is one of manganese, ferrum, cobalt, nickel and zinc, and M and N are different metals. The oxygen-reduction binary transition metal oxide catalyst has the advantages of high efficiency, low cost, good stability, no pollution and easiness in industrial production.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method, relate to specifically a kind of oxygen reduction catalyst and preparation method based on transition metal oxide.
Background technology
New energy development and environmental protection are the significant challenge that national economy sustainable development faces.Fuel cell and metal-air battery power generation process do not relate to oxyhydrogen combustion, thereby are not subject to the restriction of Carnot cycle, and energy conversion rate is high; When generating, do not produce pollution, power generating modules, reliability is high, and assembling and maintenance are all very convenient, almost there is no noise when work, are considered to future automobile power and the most promising electrochmical power source of other vehicles, are subject to people's extensive concern.Wherein, the oxygen reduction reaction occurring on fuel cell and metal-air battery negative electrode is because relate to multielectron transfer process, and dynamics is slow, becomes the bottleneck of restriction battery efficiency.In order to improve the efficiency of oxygen reduction reaction on negative electrode, what use at present is containing the higher Pt/C catalyst of Pt amount.But Pt reserves rareness, expensive on the earth, seriously restrict the commercial applications of fuel cell and metal-air battery.Meanwhile, Pt catalyst easily, by evil in CO and sulfur-bearing organic molecule etc., shortens battery.Therefore, developing the new catalyst of alternative Pt, improve catalytic activity and the anti-CO poisoning capability of catalyst to oxygen reduction, reduce catalyst price, is emphasis and the focus of fuel cell and the research of metal-air battery cathod catalyst.
At present more existing reports about oxygen reduction catalyst patent.(the application number: a kind of 201310452053) reported synthetic oxygen reduction reaction eelctro-catalyst in enormous quantities method such as the Wang Xiaojuan of Peking University, transition metal salt and containing n-donor ligand are mixed according to certain mol proportion, use ball-milling method dry grinding said mixture, after dry grinding, under oxygen free condition, high-temperature calcination obtains oxygen reduction catalyst.The Ye Jianshan (publication number: CN101745426A) of East China University of Science discloses compound oxygen reduction electro-catalyst of nitrogenous carbon nano materials modified by macrocyclic compound and preparation method thereof.This catalyst has good catalytic activity and stability, can reach-0.1V of the spike potential of catalytic oxygen reduction reaction (vs.Ag/AgCl), and oxygen reduction peak current density can reach 3.4mA.cm
-2.The oxygen reduction catalyst that Changzhou Institute of Advanced Material, Beijing University of Chemical Technology's silver Fengxiang etc. (publication number: CN103035930A) disclose a kind of tool perovskite crystalline structure (is specially Ba
0.9co
0.7fe
0.2nb
0.1O3, La
0.6sr
0.4co
0.2fe
0.8O3, Pr
0.4sr
0.6co
0.2fe
0.7nb
0.1O3or Ba
0.5sr
0.5co
0.8fe
0.2O3), this catalyst is applied to lithium-air battery, can effectively reduce battery cost.
In above-mentioned patent or used and contain containing n-donor ligand, can cause catalyst high cost, uniformity is difficult to control; Or used various material with carbon elements, and cause catalyst stability poor, affect fuel cell or metal-air battery service life; Or used heavy metal, there are larger environmentally hazardous potentiality.
Summary of the invention
The object of this invention is to provide a kind of efficient, low cost, good stability, pollution-free, oxygen reduction binary oxide catalyts of transition metal of being easy to suitability for industrialized production and preparation method thereof.
Binary oxide catalyts of transition metal of the present invention is expressed as M
xn
yo
z, wherein 0.6≤x≤1.6; 1.4≤y≤2.4; 2≤z≤4, M or N are the one in manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), M and N are different metal.
Specific embodiment of the invention step is as follows:
(1) by soluble M slaine, solubility N slaine is soluble in water stirs, and obtains the mixed solution A of M slaine and N slaine, wherein M and N slaine total concentration are controlled between 1-20g/L;
(2) complexing agent, additive are added in mixed solution A successively, stir, obtain solution B; Wherein the concentration of complexometric reagent between 0.8-2.0g/L, additive concentration is between 1.6-3.0g/L;
(3) solution B is heated to 80-180 DEG C, reaction 2-16h, separated and collected obtains catalyst precursor;
(4) after catalyst precursor is dried at 60-120 DEG C, in certain atmosphere, be warming up to 200-800 DEG C, calcining 2-8h, obtains catalyst.
Complexing agent as above is ammonium fluoride, ammonium chloride, the one in ammonium nitrate;
Soluble M slaine as above and solubility N slaine are nitrate, halide salt or acetate.
Additive as above is the one in hexamethylenetetramine, urea, triethylenediamine.
Atmosphere is the one of air, argon gas or nitrogen as mentioned above.
Under normal temperature, oxygen reduction catalyst generally carries out linear scan test in the saturated KOH solution of oxygen, and by hydrogen reduction take-off potential, positive and negative and limiting current density size is carried out the active height of the catalytic reduction oxygen of evaluate catalysts.The take-off potential of at present best Pt/C catalyst (being 20% containing Pt) reduction oxygen is approximately-0.12Vvs.Ag/AgCl, and limiting current density can reach 3.4mA/cm
2.Can reach-0.13V of the take-off potential vs.Ag/AgCl of the catalyst reduction oxygen obtaining by this patent method, limiting current density also can reach 3.4mA/cm
2, show that this catalyst has the ability of good catalytic reduction oxygen, be expected to part and replace commercial Pt/C catalyst.
The present invention compared with prior art tool has the following advantages;
The present invention will not use containing n-donor ligand, material with carbon element and heavy metal, and this catalyst is a kind of transiton metal binary oxides obtaining by hydro-thermal method and heat treatment.This oxide particle size evenly, shows good oxygen reduction activity.Prepared by this catalyst easy, environmental protection, safety; Catalyst performance is good, stability is high, synthetic catalyst have cost low, be easy to large-scale industrialization produce, be a catalyst that has market application foreground.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but the invention is not restricted to embodiment.
Embodiment 1
1, take 0.5g iron chloride and 1.5g manganese chloride is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.5g ammonium chloride, 1.3g urea, joins in above-mentioned solution (A) successively, stirs and obtains solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 100 DEG C, isothermal reaction 12h;
4, by product centrifugation, and after drying at 120 DEG C, put into Muffle furnace argon atmosphere and be warming up to 600 DEG C, calcining 3h, obtains catalyst Fe
0.6mn
2.4o
3.2;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.19V that limiting current density is 2.7mA/cm
2.
Embodiment 2
1, take 0.5g cobalt acetate and 1.0g manganese acetate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.5 ammonium fluoride, 1.5g six methine four ammoniums, join in above-mentioned solution (A) successively, stir and obtain solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 120 DEG C, isothermal reaction 6h;
4, by product centrifugation, and after drying at 80 DEG C, put into Muffle furnace nitrogen atmosphere and be warming up to 600 DEG C, calcining 6h, obtains CATALYST Co
0.8mn
1.6o
2.4;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.12V that limiting current density is 3.4mA/cm
2.
Embodiment 3
1, take 0.5g cobalt nitrate and 0.25g nickel nitrate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.5g ammonium fluoride, 1.25g urea joins in above-mentioned solution (A) successively, stirs and obtains solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 120 DEG C, isothermal reaction 4h;
4, by product centrifugation, and after drying at 60 DEG C, put into Muffle furnace argon atmosphere and be warming up to 400 DEG C, calcining 3h, obtains catalyst n iCo
2o
4;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test demonstration, take-off potential is-0.13V that limiting current density is 3.3mA/cm
2.
Embodiment 4
1, take 0.8g cobalt acetate and 0.4g zinc acetate is scattered in 500ml water, stir and obtain solution (A);
2, take 0.7g ammonium chloride, 1 gram of triethylenediamine joins in above-mentioned solution (A), stir and obtain solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 100 DEG C, isothermal reaction 2h;
4, by product centrifugation, and after drying at 100 DEG C, put into Muffle furnace air atmosphere and be warming up to 200 DEG C, calcining 8h, obtains catalyst Z nCo
1.5o
2.5;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.15V that limiting current density is 2.8mA/cm
2.
Embodiment 5
1, take 0.6g zinc acetate and 1.3g manganese acetate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.6g ammonium nitrate, 1.2g six methine four ammoniums, join in above-mentioned solution (A) successively, stir and obtain solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 120 DEG C, isothermal reaction 6h;
4, by product centrifugation, and after drying at 80 DEG C, put into Muffle furnace air atmosphere and be warming up to 300 DEG C, calcining 6h, obtains catalyst Z n
0.6mn
1.4o
2;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.18V that limiting current density is 2.6mA/cm
2.
Embodiment 6
1, take 1.0 zinc nitrates and 1.7g ferric nitrate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.4g ammonium chloride, 1.0g urea, joins in above-mentioned solution (A) successively, stirs and obtains solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 140 DEG C, isothermal reaction 4h;
4, by product centrifugation, and 120
dEG Cafter drying under C, put into Muffle furnace air atmosphere and be warming up to 300 DEG C, calcining 5h, obtains catalyst Z n
1.2fe
1.6o
3.6;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.20V that limiting current density is 2.5mA/cm
2.
Embodiment 7
1, take 1g cobalt chloride and 1.6g iron chloride is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.6g ammonium nitrate, 0.8g six methine four ammoniums, join in above-mentioned solution (A) successively, stir and obtain solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 180 DEG C, isothermal reaction 2h;
4, by product centrifugation, and after drying at 80 DEG C, put into Muffle furnace nitrogen atmosphere and be warming up to 800 DEG C, calcining 2h, obtains CATALYST Co Fe
1.
4o
3.
1;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.14V that limiting current density is 3.2mA/cm
2.
Embodiment 8
1, take 1.2g nickel acetate and 1.9g manganese acetate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.8g ammonium chloride, 1.5g triethylenediamine, joins in above-mentioned solution (A) successively, stirs and obtains solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 80 DEG C, isothermal reaction 16h;
4, by product centrifugation, and after drying at 100 DEG C, put into Muffle furnace nitrogen atmosphere and be warming up to 600 DEG C, calcining 6h, obtains catalyst n i
1.2mn
1.8o
3;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.22V that limiting current density is 2.4mA/cm
2.
Embodiment 9
1, take 1.6g ferric nitrate and 0.7g nickel nitrate is dissolved in 500ml water, stir and obtain solution (A);
2, take 0.6g ammonium fluoride, 1.1g six methine four ammoniums, join in above-mentioned solution (A) successively, stir and obtain solution (B);
3, gained solution (B) is moved in hydrothermal reaction kettle, be heated to 100 DEG C, isothermal reaction 8h;
4, by product centrifugation, and after drying at 120 DEG C, put into Muffle furnace air atmosphere and be warming up to 400 DEG C, calcining 4h, obtains catalyst n iFe
1.
8o
3.
7;
5, on using above-mentioned 5mg catalyst cupport to glass-carbon electrode, as working electrode, taking Ag/AgCl as reference electrode, Pt is to electrode, at O
2in saturated 1M KOH solution, test its chemical property.Electrochemistry linear sweep test shows, take-off potential is-0.23V that limiting current density is 2.2mA/cm
2.
Claims (6)
1. an oxygen reduction binary oxide catalyts of transition metal, is characterized in that binary oxide catalyts of transition metal is expressed as M
xn
yo
z, wherein 0.6≤x≤1.6; 1.4≤y≤2.4; 2≤z≤4, M or N are the one in manganese, iron, cobalt, nickel, zinc, M and N are different metal.
2. the preparation method of a kind of oxygen reduction binary oxide catalyts of transition metal as claimed in claim 1, is characterized in that comprising the steps:
(1) by soluble M slaine, solubility N slaine is soluble in water stirs, and obtains the mixed solution A of M slaine and N slaine, wherein M and N slaine total concentration are controlled between 1-20g/L;
(2) complexing agent, additive are added in mixed solution A successively, stir, obtain solution B; Wherein the concentration of complexometric reagent between 0.8-2.0g/L, additive concentration is between 1.6-3.0g/L;
(3) solution B is heated to 80-180
0c, reaction 2-16h, separated and collected obtains catalyst precursor;
(4) by catalyst precursor at 60-120
0after drying under C, in certain atmosphere, be warming up to 200-800
0c, calcining 2-8h, obtains catalyst.
3. the preparation method of a kind of oxygen reduction binary oxide catalyts of transition metal as claimed in claim 2, is characterized in that described complexing agent is ammonium fluoride, ammonium chloride, the one in ammonium nitrate.
4. the preparation method of a kind of oxygen reduction binary oxide catalyts of transition metal as claimed in claim 2, is characterized in that described soluble M slaine and solubility N slaine are nitrate, halide salt or acetate.
5. the preparation method of a kind of oxygen reduction binary oxide catalyts of transition metal as claimed in claim 2, is characterized in that described additive is the one in hexamethylenetetramine, urea, triethylenediamine.
6. the preparation method of a kind of oxygen reduction binary oxide catalyts of transition metal as claimed in claim 2, is characterized in that described atmosphere is the one of air, argon gas or nitrogen.
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Cited By (2)
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CN109167074A (en) * | 2018-08-08 | 2019-01-08 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow additive Mn cobalt oxide nickel coated and preparation |
CN115007152A (en) * | 2022-07-22 | 2022-09-06 | 成都大学 | Catalyst for hydrogen production by hydrolysis, preparation method and application thereof |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109167074A (en) * | 2018-08-08 | 2019-01-08 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow additive Mn cobalt oxide nickel coated and preparation |
CN115007152A (en) * | 2022-07-22 | 2022-09-06 | 成都大学 | Catalyst for hydrogen production by hydrolysis, preparation method and application thereof |
CN115007152B (en) * | 2022-07-22 | 2023-11-21 | 成都大学 | Catalyst for hydrogen production by hydrolysis and preparation method and application thereof |
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Application publication date: 20140813 |