CN103611575A - Preparation method of catalyst containing imidazole and derivatives thereof - Google Patents
Preparation method of catalyst containing imidazole and derivatives thereof Download PDFInfo
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Abstract
The invention relates to preparation of a non-noble metal catalyst of a fuel battery, and aims to provide a preparation method of a catalyst containing imidazole and derivatives thereof. The preparation method of the catalyst containing imidazole and the derivatives thereof comprises the following steps: preparing a nitrogen-containing macroporous carbon material; and finally preparing an imidazole and derivatives modified nitrogen-containing macroporous carbon loaded transitional metal catalyst. By adopting a hydrothermal method to synthesize the catalyst provided by the invention, not only can catalyst particles which are consistent in dimension and uniform in distribution be obtained, but also the time for synthesizing the catalyst can be greatly shortened. Through grading calcining at different temperatures, through holes of macroporous carbon are smoother, the pore diameter distribution is more balanced, and the specific surface area is greater. The catalyst is good in conductivity, and the imidazole and derivatives modified layer increases the activity and stability of the catalyst, so that the catalyst is particularly suitable for a large current working condition. The synthesized non-noble metal catalyst can be used as a cathode catalyst for the fuel battery or an air battery, is low in cost, and facilitates popularization of fuel battery and air battery technologies.
Description
Technical field
The invention relates to the preparation of non-precious metal catalyst in fuel cell, particularly containing the preparation method of the catalyst of imidazole and its derivants.
Background technology
In recent years, due to the technology acquisition innovation breakthrough of fuel cell (Fuel Cell), add the multiple pressures such as environmental issue and energy deficiency and in succession arrive, the industries such as national governments and automobile, electric power, the energy are paid attention to the development of fuel cell technology gradually.Fuel cell is the new generation technology of high efficiency, low pollution, the diversification energy, and the electricity generation system of fuel cell, not only low than traditional fossil fuel cost, and there are cleaning, high efficiency benefit, more can, in conjunction with generation technologies such as nuclear energy, biological energy source, solar energy, wind energies, the energy be used to diversification, renewableization and continue to use.Fuel cell is used the fuel such as alcohols, natural gas, hydrogen, sodium borohydride, hydrazine to convert electric current to, and the fuel of inputting by the external world is energy source, can continue to produce electric power, does not need the program that discharges and recharges of secondary cell.During charging, as long as empty the container that is full of byproduct water, and then put into fuel fuel such as () alcohol.Fuel cell is exactly briefly a generator.Fuel cell is firepower, waterpower, outer the 4th kind of electricity-generating method of nuclear energy.
Development along with nanosecond science and technology, fuel cell has had great breakthrough technically, particularly the appearance of the proton exchange model of low-temperature operation makes fuel cell be able to be entered by unattainable space technological applications field the category of people's livelihood application, and PEMFC is extensively taken seriously one of the focus development technology that forms.Fuel cell power generation performance (power efficiency) depends primarily on electrode reaction and various ohmage.Compare with the oxidation reaction of fuel, the reduction reaction of oxygen is carried out difficulty.Conventionally low-temperature fuel cell all need to be take precious metal material as catalyst.Although traditional catalyst platinum excellent performance, scarcity of resources, selling at exorbitant prices, cause the universal difficulty of fuel cell technology.The non-precious metal catalyst research and development that substitute platinum have become focus and the key of fuel cell technology, and wherein, reducing oxygen reduction reaction (ORR) overpotential on negative electrode is one of fuel cell key technology.
Aspect non-precious metal catalyst research, nitrogen-doped carbon material has good catalytic activity to ORR, and the existence of hetero atom N or O on carbocyclic ring significantly improves the reaction speed of ORR.CNT, micropore and mesoporous carbon carry out forming graphite nitrogen (graphitic-N) and pyridine nitrogen (pyridinic-N) after N surface doping, the catalytic activity to ORR, and its performance is equivalent to city dealer's carbon supported platinum catalyst.Some nitrogen-containing compounds not only form graphite nitrogen and pyridine nitrogen with Co or the compound carbon supported catalyst of Fe as phthalocyanine (Pc), porphyrin on atomic scale or nanoscale, and also forming M-Nx(M is transition metal), ORR is had to remarkable catalytic action.Above result shows, forms nitrogen functional group and can obtain higher ORR catalytic activity on material with carbon element.At present the research of low-cost catalyst is mainly concentrated on to Transition Metal Cluster Compounds mixture catalyst, center containing macrocyclic compound catalyst and the metal carbide catalyst of transition metal; Nitride, sulfide, boride and silicide etc. also have report as Low-Temperature Fuel Cell Catalysts in addition, but the Performance Ratio of these catalyst is poor, studies also fewer.Great and market prospects are wide for the Research Significance of low-cost catalyst.
Summary of the invention
Main purpose of the present invention meets the development of non-precious metal catalyst, provides imidazole and its derivants to modify the preparation method of the carbon-supported transition-metal catalyst of nitrogenous macropore.For solving the problems of the technologies described above, solution of the present invention is:
Preparation method containing the catalyst of imidazole and its derivants is provided, for the preparation of imidazole and its derivants, modifies the carbon-supported transition-metal catalyst of nitrogenous macropore, comprise the following steps:
Steps A: get hydrophilic nano CaCO
3, urea, glucose is added in deionized water, then ultrasonic vibration mixes 30 minutes, urea and glucose is dissolved, nanometer CaCO
3formation suspension is uniformly dispersed, at 106 ℃, solidify and within 6 hours, form cured product, cured product is warming up to 500 ℃ under nitrogen atmosphere protection, constant temperature carbonization 2 hours, then at 900 ℃, constant temperature carbonization 2 hours, form carbonized product, at 80 ℃ by carbonized product successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water washing filter, at 120 ℃, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again;
Described hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100;
Step B: it is 100～400 orders that the nitrogenous macropore material with carbon element making in steps A is crushed to particle diameter, the nitrogenous macropore material with carbon element of getting after pulverizing is placed in hydrothermal reaction kettle, in hydrothermal reaction kettle, add imidazole and its derivants again, add the aqueous solution containing transition metal salt, then ultrasonic vibration mixed after 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100～300 ℃ of reactions 12 hours, filter, again with after washed with de-ionized water, vacuum drying at 90 ℃, obtain the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified,
The ratio of nitrogenous macropore material with carbon element, imidazole and its derivants, transition metal salt and water after described pulverizing is 2g:0.02～0.4g:1.2～6mmol:100mL; Described transition metal salt comprises nitrate, sulfate or the chloride of transition metal, and described transition metal is at least one in Pt, Pd, Ag, Mn, Fe, Co, Ni, Cu.
As further improvement, the hydrophilic nano CaCO in described steps A
3particle diameter be 15～40nm.
As further improvement, the hydrothermal reaction kettle in described step B adopts the hydrothermal reaction kettle that volume is 150mL.
As further improvement, (methylimidazole is as glyoxal ethyline, 4-methylimidazole for imdazole derivatives in the described step B imdazole derivatives that to be imidazoles obtain through alkylation or carboxylated, and mebendazole is the common imdazole derivatives of representativeness obtaining after imidazolidinyl, imidazolyl carboxylic acid as imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid be the imdazole derivatives obtaining after carboxylated).
The formation principle of nitrogenous macropore material with carbon element in the present invention:
Due to the mixture of glucose and urea and water azeotropic 106 ℃ time, at 106 ℃, glucose and urea generation polycondensation, solidify and be coated on Nano particles of calcium carbonate, and the polycondensation product of glucose and urea forms continuous phase.Be heated to 500 ℃ of polycondensation product generation carbonizations, form primary carbides, form fine and close solid content with nano-calcium carbonate.Be warming up to 900 ℃ of nano-calcium carbonates and decompose, CO
2in air release process, in solid content, form unobstructed air flue, form one-level through hole.Meanwhile, there is further carbonization in primary carbides, forms micropore, forms secondary through holes.In pickling and alkaline cleaning procedure subsequently, there is to decompose the rear calcium oxide forming and dissolve in nano-calcium carbonate, leaves three grades of through holes in material with carbon element.Due to CO
2originate from nano-calcium carbonate, therefore three grades of through holes must be connected with one-level through hole.By detecting, even through 900 ℃ of calcinings, in macropore carbon, still contain nitrogen element, this is that nitrogen fixation due to glucose and urea polycondensation product causes.
The present invention utilizes the characteristic of nitrogenous macropore carbon surface Nitrogen element, and by hydro-thermal method, the nitrogen on nitrogen and imidazole ring and transition metal M on macropore carbon surfaces externally and internally form coordinate bond, form M-Nx catalytic center.Compare with the single nitrogen element containing pyrrole ring of pyrroles or indoles, imidazoles contains two nitrogen, more easily forms M-Nx catalytic center with nitrogen and transition metal on macropore carbon surfaces externally and internally.When thering is high-specific surface area, possesses good electric conductivity.
Compared with prior art, the invention has the beneficial effects as follows:
1, adopt hydro-thermal method synthetic, the catalyst particle that not only can obtain consistent size, is evenly distributed, also can shorten catalyst generated time greatly.
2, glucose and urea admixture can obtain the nitrogenous macropore material with carbon element in surface as the presoma of macropore material with carbon element.
3, calcining stage by stage under different temperatures, the through hole of macropore carbon is more unobstructed, and pore-size distribution is more balanced, and specific area is larger.
4, catalyst good conductivity, imidazole and its derivants decorative layer increases activity and the stability of catalyst, is specially adapted to large current work situation.
5, synthetic non-precious metal catalyst can be used for the cathod catalyst of fuel cell or air cell, with low cost, be conducive to the universal of fuel cell and air cell technology, the electrokinetic cell that the fuel cell that the catalyst that contains imidazole and its derivants is cathod catalyst or air cell can be applicable to electric automobile.
Accompanying drawing explanation
Fig. 1 is the performance comparison figure of the fuel cell prepared of the fuel cell prepared in embodiment and commercially available platinum C catalyst.
The specific embodiment
Below in conjunction with accompanying drawing and the specific embodiment, the present invention is described in further detail:
Imidazoles is the five-membered heteroaromatic compounds that contains position nitrogen-atoms between two in molecular structure, and the not share electron pair of the 1-position nitrogen-atoms in imidazole ring participates in cyclic conjugated, and the electron density of nitrogen-atoms reduces, and the hydrogen on this nitrogen-atoms is easily left away with hydrogen ion form.Thereby imidazoles has faintly acid, can form salt with highly basic, and transition metal forms coordinate bond.
Nano-calcium carbonate claims again super fine calcium carbonate.The title of standard is calcium carbonate superfine powder.The most ripe industry of nano-calcium carbonate application is that plastics industry is mainly used in high-grade plastic products.Can improve the rheological characteristic of plastic matrix, improve its mouldability.As plastic filler, have toughened and reinforced effect, improve bending strength and the modulus of elasticity in static bending of plastics, heat distortion temperature and dimensional stability are also given plastics stagnant hot simultaneously.The industrial production process of nano-calcium carbonate is at certain density Ca (OH)
2suspension in pass into carbon dioxide and carry out carbonization.By to Ca (OH)
2the nucleation rate of the flow-control calcium carbonate nucleus of the temperature of suspension, carbon dioxide; In carbonization, to forming after certain nucleus number, by nucleus formation control, be converted into crystal growth and control, now add morphology regulation additives to control the growth rate of each crystal face, thereby it is controlled to reach pattern; By significantly improving the hydrophily of nano-calcium carbonate after processing containing surfactant.
The preparation method who contains the catalyst of imidazole and its derivants, modifies the carbon-supported transition-metal catalyst of nitrogenous macropore for the preparation of imidazole and its derivants, comprises the following steps:
Steps A: getting particle diameter is the hydrophilic nano CaCO of 15～40nm
3, urea, glucose is added in deionized water, and hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100, then ultrasonic vibration mixes 30 minutes, urea and glucose are dissolved and with nanometer CaCO
3be uniformly dispersed; at 106 ℃, solidify and within 6 hours, form cured product; cured product is warming up to 500 ℃ under nitrogen atmosphere protection, constant temperature carbonization 2 hours, then at 900 ℃; constant temperature carbonization 2 hours; form carbonized product, at 80 ℃ by carbonized product successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water washing under room temperature, filter; at 120 ℃, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again.
Step B: it is 100～400 orders that the nitrogenous macropore material with carbon element making in steps A is crushed to particle diameter, the nitrogenous macropore material with carbon element of getting after pulverizing is placed in the hydrothermal reaction kettle that volume is 150mL, in hydrothermal reaction kettle, add imidazole and its derivants again, add the nitrate containing transition metal, sulfate or the muriatic aqueous solution, transition metal is Pt, Pd, Ag, Mn, Fe, Co, Ni, at least one in Cu, and the nitrogenous macropore material with carbon element after making to pulverize, imidazole and its derivants, the ratio of transition metal salt and water is 2g:0.02～0.4g:1.2～6mmol:100mL.Then ultrasonic vibration mixed after 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100～300 ℃ of reactions 12 hours, filters, then with after washed with de-ionized water, vacuum drying at 90 ℃, obtains the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified.
The imdazole derivatives that to be imidazoles obtain through alkylation or carboxylated of imdazole derivatives wherein.Imidazoles is easy to generate derivative, and the approach of generation has alkyl substitution, quaternary ammonium reaction, halogenating reaction, carboxylation reaction and salinization etc.Conventional imdazole derivatives is the product after alkyl metalepsis.In addition, also has pyridine series, cyamelide series, hydroxy methylimidazole series, imidazoline series etc.The imdazole derivatives being obtained through alkylation by imidazoles has methylimidazole, methylimidazole, diethyl tetramethyl imidazoles, 4-methylimidazole and mebendazole etc., and the imdazole derivatives being obtained through carboxylated by imidazoles has imidazolyl carboxylic acid, imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid etc.
The following examples can make this professional professional and technical personnel's comprehend the present invention, but do not limit the present invention in any way.
Embodiment mono-: the preparation of macropore carbon
Getting particle diameter is the hydrophilic nano CaCO of 15～40nm
3with urea and each 8g of glucose, be added in 100mL deionized water, ultrasonic vibration mix within 30 minutes, make urea and glucose dissolve and with nanometer CaCO
3be uniformly dispersed; Then at 106 ℃, solidify 6 hours; Cured product is warming up to 500 ℃ under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again at 900 ℃, constant temperature carbonization 2 hours; At 80 ℃ by carbonized product successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration, deionized water washing, at 120 ℃, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element.
Embodiment bis-: imidazoles is modified the preparation of the carbon-supported noble metal catalyst of macropore
Getting particle diameter is the hydrophilic nano CaCO of 15～40nm
3with urea and each 8g of glucose, be added in 100mL deionized water, ultrasonic vibration mix within 30 minutes, make urea and glucose dissolve and with nanometer CaCO
3be uniformly dispersed; Then at 106 ℃, solidify 6 hours; Cured product is warming up to 500 ℃ under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again at 900 ℃, constant temperature carbonization 2 hours; At 80 ℃ carbonized product successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration, deionized water washing, at 120 ℃, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element.
It is 100～400 orders that nitrogenous macropore material with carbon element is crushed to particle diameter, get the nitrogenous macropore carbon of 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add imidazoles 0.02g as material modified, add respectively platinum chloride, palladium bichloride or liquor argenti nitratis ophthalmicus 100mL, include respectively platinum chloride, 3 mMs of palladium bichloride or silver nitrates, then ultrasonic vibration mixed after 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 100 ℃ of reactions 12 hours, filter, after washed with de-ionized water, after 90 ℃ of vacuum drying, can obtain respectively imidazoles and modify the carbon-supported platinum of nitrogenous macropore, palladium or silver catalyst.
Embodiment tri-: imidazoles is modified the preparation of the carbon-supported non-precious metal catalyst of nitrogenous macropore
Getting nitrogenous macropore material with carbon element that embodiment mono-makes, to be crushed to particle diameter be 100～400 orders, get 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add imidazoles 0.1g as material modified, add respectively copper chloride, nickelous sulfate, cobalt nitrate, iron chloride or manganese sulfate solution 100mL, containing copper chloride respectively, nickelous sulfate, cobalt nitrate, 1.2 mMs of iron chloride or manganese sulfates, ultrasonic vibration mixed after 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 200 ℃ of reactions 12 hours, filter, after washed with de-ionized water, after 90 ℃ of vacuum drying, can obtain respectively imidazoles and modify the carbon-supported copper of nitrogenous macropore, nickel, cobalt, iron or Mn catalyst.
Embodiment tetra-: imdazole derivatives is modified the preparation of the carbon-supported platinum-nickel alloy catalyst of nitrogenous macropore
It is 100～400 orders that the nitrogenous macropore material with carbon element that embodiment mono-is made is crushed to particle diameter, get the nitrogenous macropore carbon of 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add respectively 0.4g imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid, glyoxal ethyline, 4-methylimidazole or mebendazole are as material modified, add platinum chloride and nickelous sulfate mixed solution 100mL, include totally 6 mMs of platinum chloride and nickelous sulfates, ultrasonic vibration mixed after 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 300 ℃ of reactions 12 hours, filter, after washed with de-ionized water, after 90 ℃ of vacuum drying, can obtain respectively imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid, glyoxal ethyline, 4-methylimidazole, mebendazole is modified the carbon-supported platinum Raney nickel of nitrogenous macropore.
Embodiment five: fuel cell electrode preparation
The imidazoles making in embodiment bis-is modified to the carbon-supported platinum catalyst of nitrogenous macropore, the Nafion solution of 5wt% of take is binding agent, by Nafion solution and imidazoles, modify the carbon-supported platinum catalyst mass ratio of nitrogenous macropore 3:7 and be modulated into slurry, be coated on the carbon paper that hydrophobic processed, after drying, in the calcining of 150 ℃ of Muffle furnaces after one hour, naturally cool to room temperature and make anode of fuel cell.
The imidazoles of processing through hydrophobic is modified the carbon-supported platinum catalyst of nitrogenous macropore, the ptfe emulsion of 5wt% of take is binding agent, by ptfe emulsion and imidazoles, modify the carbon-supported platinum catalyst mass ratio of nitrogenous macropore and be modulated into slurry at 3: 7, be coated on the carbon paper that hydrophobic processed, after drying, in the calcining of 350 ℃ of Muffle furnaces after one hour, naturally cool to room temperature and make negative electrode.Then the perfluorinated sulfonic acid base resin solution that immerses 5wt%, dries the hydrophobicity negative electrode that rear formation has proton conduction.
Here adopt the alternative imidazoles of the carbon-supported transition-metal catalyst of nitrogenous macropore of all the other imidazole and its derivants modifications of preparing in above-described embodiment to modify the carbon-supported platinum catalyst of nitrogenous macropore, can make equally the electrode of fuel cell.
Embodiment six: imidazoles is modified fuel cell prepared by the carbon-supported catalyst of nitrogenous macropore
The imidazoles making in embodiment tri-is modified to the carbon-supported Co catalysts of nitrogenous macropore, the Nafion solution of 5wt% of take is binding agent, by Nafion solution and imidazoles, modify the carbon-supported platinum catalyst mass ratio of nitrogenous macropore 3:7 and be modulated into slurry, be coated on the carbon paper that hydrophobic processed, after drying, in the calcining of 150 ℃ of Muffle furnaces after one hour, naturally cool to room temperature and make anode of fuel cell.
The imidazoles of processing through hydrophobic is modified the carbon-supported Co catalysts of nitrogenous macropore, the ptfe emulsion of 5wt% of take is binding agent, by ptfe emulsion and imidazoles, modify the carbon-supported Co catalysts mass ratio of nitrogenous macropore and be modulated into slurry at 3: 7, be coated on the carbon paper that hydrophobic processed, after drying, in the calcining of 350 ℃ of Muffle furnaces after one hour, naturally cool to room temperature and make negative electrode.Then the perfluorinated sulfonic acid base resin solution that immerses 5wt%, dries the hydrophobicity negative electrode that rear formation has proton conduction.Prepare negative electrode and anode, selecting perfluorinated sulfonic resin (Nafion112) is dielectric film, and the catalyst layer of negative electrode and anode in opposite directions, forms sandwich structure with dielectric film, and hot-forming rear formation membrane electrode, is assembled into Proton Exchange Membrane Fuel Cells.
By the negative electrode making in embodiment five and anode, selecting perfluorinated sulfonic resin (Nafion112) is dielectric film, the catalyst layer of negative electrode and anode in opposite directions, form sandwich structure with dielectric film, hot-forming rear formation membrane electrode, be assembled into fuel cell, obtain modifying Proton Exchange Membrane Fuel Cells prepared by the carbon-supported platinum catalyst of nitrogenous macropore by imidazoles.
Fig. 1 is that imidazoles is modified fuel battery performance comparison diagram prepared by fuel cell prepared by the carbon-supported catalyst of nitrogenous macropore and commercially available platinum C catalyst.Wherein, in 1-embodiment five, the imidazoles of preparation is modified the power density curve of the hydrogen-oxygen fuel cell of the carbon-supported platinum catalyst electrode assembling of nitrogenous macropore, in 2-embodiment five, the imidazoles of preparation is modified the voltage polarizing curve of the hydrogen-oxygen fuel cell of the carbon-supported platinum catalyst electrode assembling of nitrogenous macropore, the imidazoles making in 3-embodiment tri-is modified the power density curve of the hydrogen-oxygen fuel cell of the carbon-supported Co catalysts electrode assembling of nitrogenous macropore, the imidazoles making in 4-embodiment tri-is modified the voltage polarizing curve of the hydrogen-oxygen fuel cell of the carbon-supported Co catalysts electrode assembling of nitrogenous macropore, the power density curve of the hydrogen-oxygen fuel cell of the commercially available platinum C catalyst of 5-electrode assembling, the voltage polarizing curve of the hydrogen-oxygen fuel cell of the commercially available platinum C catalyst of 6-electrode assembling.Operating temperature: 80 ℃, hydrogen and oxygen carry out respectively 80 ℃ of humidifications, and pressure is an atmospheric pressure.The transition metal loading of the negative electrode of three kinds of fuel cells and anode is 0.5mg/cm
2.
As seen from the figure, it is suitable that imidazoles is modified fuel battery performance prepared by fuel cell prepared by the carbon-supported Co catalysts of nitrogenous macropore and commercially available platinum C catalyst, and imidazoles is modified fuel cell prepared by the carbon-supported platinum catalyst of nitrogenous macropore and is better than fuel battery performance prepared by commercially available platinum C catalyst.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. contain the preparation method of the catalyst of imidazole and its derivants, for the preparation of imidazole and its derivants, modify the carbon-supported transition-metal catalyst of nitrogenous macropore, it is characterized in that, comprise the following steps:
Steps A: get hydrophilic nano CaCO
3, urea, glucose is added in deionized water, then ultrasonic vibration mixes 30 minutes, urea and glucose is dissolved, nanometer CaCO
3formation suspension is uniformly dispersed, at 106 ℃, solidify and within 6 hours, form cured product, cured product is warming up to 500 ℃ under nitrogen atmosphere protection, constant temperature carbonization 2 hours, then at 900 ℃, constant temperature carbonization 2 hours, form carbonized product, at 80 ℃ by carbonized product successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water washing filter, at 120 ℃, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again;
Described hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100;
Step B: it is 100～400 orders that the nitrogenous macropore material with carbon element making in steps A is crushed to particle diameter, the nitrogenous macropore material with carbon element of getting after pulverizing is placed in hydrothermal reaction kettle, in hydrothermal reaction kettle, add imidazole and its derivants again, add the aqueous solution containing transition metal salt, then ultrasonic vibration mixed after 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100～300 ℃ of reactions 12 hours, filter, again with after washed with de-ionized water, vacuum drying at 90 ℃, obtain the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified,
The ratio of nitrogenous macropore material with carbon element, imidazole and its derivants, transition metal salt and water after described pulverizing is 2g:0.02～0.4g:1.2～6mmol:100mL; Described transition metal salt comprises nitrate, sulfate or the chloride of transition metal, and described transition metal is at least one in Pt, Pd, Ag, Mn, Fe, Co, Ni, Cu.
2. the preparation method of the catalyst containing imidazole and its derivants according to claim 1, is characterized in that the hydrophilic nano CaCO in described steps A
3particle diameter be 15～40nm.
3. the preparation method of the catalyst containing imidazole and its derivants according to claim 1, is characterized in that, the hydrothermal reaction kettle in described step B adopts the hydrothermal reaction kettle that volume is 150mL.
4. the preparation method of the catalyst containing imidazole and its derivants according to claim 1, is characterized in that, the imdazole derivatives that to be imidazoles obtain through alkylation or carboxylated of the imdazole derivatives in described step B.
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| CN107308933A (en) * | 2017-08-15 | 2017-11-03 | 浙江大学 | A kind of application of high dispersive noble metal catalyst in electrochemistry evolving hydrogen reaction |
| CN109399603A (en) * | 2018-11-05 | 2019-03-01 | 大连理工大学 | A method of supercapacitor N doping porous charcoal is prepared using metal organic framework compound |
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