阅读说明：本技术 一种钴和氮掺杂三维有序多孔碳催化剂的制备方法 (A kind of preparation method of cobalt and the 3-D ordered multiporous C catalyst of N doping ) 是由 夏木西卡玛尔·买买提 乔孟飞 胡广志 王颖 伊力亚丝·*** 于 2019-09-05 设计创作，主要内容包括：本发明公开了一种钴和氮掺杂三维有序多孔碳催化剂的制备方法及用途,该方法先合成了不同粒径的PS球并将其制作成模板,将模板浸渍于含六水合硝酸钴和2-甲基咪唑的甲醇溶液中,模板上原位生长ZIF-67,使用四氢呋喃洗去模板,离心得到有序多孔ZIF-67前驱体,碳化处理后即得钴和氮掺杂三维有序多孔碳催化剂。所制备的催化剂为结构规则、颗粒分明的三维碳材料,具有有序孔道、高比表面积、较高的活性、较高稳定性等优点。该方法,对于合成孔隙可控、高的比表面积以及良好的耐久性的氧还原电催化材料提供了很大的可能性。所用原料皆易得且价格低廉,具有工业应用前景。(The invention discloses the Preparation method and uses of a kind of cobalt and the 3-D ordered multiporous C catalyst of N doping, this method has first synthesized the PS ball of different-grain diameter and has been made into template, template is impregnated in the methanol solution containing cabaltous nitrate hexahydrate and 2-methylimidazole, growth in situ ZIF-67 in template, template is washed away using tetrahydrofuran, it is centrifuged and obtains ordered porous ZIF-67 presoma, up to cobalt and the 3-D ordered multiporous C catalyst of N doping after carbonization treatment.Prepared catalyst is tactical rule, the three-dimensional carbon material of particle clearly, has many advantages, such as orderly duct, high-specific surface area, higher activity, higher stability.The hydrogen reduction electrocatalysis material of this method, the specific surface area and good durability controllable, high for synthesis hole provides a possibility that very big.It is raw materials used to be all easy to get and cheap, there is prospects for commercial application.)

1. the preparation method of a kind of cobalt and the 3-D ordered multiporous C catalyst of N doping, it is characterised in that follow these steps to carry out:

A, 50ml polystyrene solution is cleaned repeatedly with the NaOH solution of 10% mass fraction and deionized water, after cleaning Polystyrene solution is added in 1000ml flask, adds 1.5g polyvinylpyrrolidone and the mixing of 500ml deionized water, In Froth 20min under nitrogen, and then flow back at 92 DEG C of temperature in thermostatic mixer 40min；

B, the 50ml sodium peroxydisulfate solution of mass fraction 1% is rapidly joined into mixed liquor in step a, and continued at 92 DEG C of temperature 20h is persistently stirred with 400rpm, after being cooled to room temperature, suction filtration obtains the A Polystyrene Spheres Template of partial size 110nm；

C, the step b polystyrene moulding synthesized is impregnated in mass ratio is 1-4:4 containing cabaltous nitrate hexahydrate and 2-methylimidazole Methanol solution in, stand growth for 24 hours, obtain mixture；

D, it after the mixture for obtaining step c is dry at 40 DEG C of temperature, is dissolved in tetrahydrofuran solution, stirring and dissolving 12h, Centrifugation, and cleaned 3 times with tetrahydrofuran, blue powder is obtained after 110 DEG C of dryings of temperature；

E, step d is obtained into the lower carbonization treatment 2h of stream of nitrogen gas protection that blue powder is placed in 500 DEG C -700 DEG C of temperature, obtained most Final product has the cobalt and the 3-D ordered multiporous C catalyst of N doping of the cellular structure of three-dimensional order.

2. the purposes of the 3-D ordered multiporous C catalyst of cobalt and N doping obtained method according to claim 1, feature It is to be prepared into dispersion liquid and modifies in electrode surface, in electrocatalytic oxidation reduction reaction.

Technical field

With the development of economic society and the expansion of the size of population, nearly several century mankind have carried out largely fossil fuel Exploitation uses, this directly results in serious environmental problem and energy shortage problem.To cope with these problems, countries in the world all exist It is dedicated to researching and developing the energy conversion Land use systems of new clean energy resource or clean and effective, such as fuel cell, solar-electricity Pond, metal-air battery, lithium ion battery, supercapacitor etc..Compared to traditional internal combustion engine or other heat engines, combustion Expect that battery has higher energy density and energy conversion efficiency, this is because it directly converts electric energy for chemical energy, not by The limitation of Carnot cycle.Therefore, fuel cell is expected to play bigger effect in terms of following energy security.With society Fast development, we have increasing demand to clean reproducible energy, but as solar energy, wind energy, tide energy etc. are clear Clean renewable energy is generated in the form of non-rule.If generated without a kind of good energy storage mode in peak period The extra energy can only waste, this is unfavorable for save the cost and improving efficiency very much.Best settling mode is by volume The form that outer energy is converted to chemical energy (such as electrolysis water generation hydrogen) stores, and then passes through combustion in due course Chemical energy is converted to electric energy again by material battery.The utilization efficiency of clean reproducible energy just can be greatly improved in this way, alleviate the energy Crisis.As a kind of new energy conversion equipment, proton membrane fuel battery, which has been obtained in world wide, widely to be approved, and Commercialization propulsion is gradually carried out, but since anion-exchange membrane fuel cells develop slowly, people are striven to find More suitable substitute.Direct methanol fuel cell is to use methanol as fuel under alkaline condition, and compared to hydrogen, methanol is more Easily storage and processing, therefore direct methanol fuel cell has been invested in a large amount of research.Due to fuel battery negative pole oxygen reduction reaction Occur slowly, therefore research high performance cathodes oxygen reduction reaction catalyst carrys out driving a reaction and occurs to study as current fuel cell The big hot spot of the one of aspect.

Several aspects of investigating are usually required for the commercial practicability of the catalyst of fuel battery negative pole oxygen reduction reaction: one It is the overpotential size of oxygen reduction reaction, the smaller power consumption to react of usual overpotential is lower, also turns out the activity of catalyst It is higher；Second is that electronics transfer path, four electronics transfer paths are higher than two electronics transfer path efficiencies, and in two electron reactions Between product hydrogen peroxide may corrode catalyst, reduce catalyst activity, therefore advanced catalyst will avoid two electronics as possible The generation of reaction；Third is that methanol tolerance performance, direct methanol fuel cell is using methanol as fuel, however methanol may penetrate proton Exchange membrane reaches cathode and reaction is taken a turn for the worse；Fourth is that the stability being used for a long time, catalyst only has good durable Property could reduce cost, realize industrial-scale application.State-of-the-art promotion oxygen reduction reaction currently used commercially is urged Agent is the carbon material of the high-specific surface area of Pt nanometer particle load, mainly carbon black.But Pt is a kind of precious metal element, ground Reserves are few on ball, develop and at high cost, therefore the substitute products of developing low-cost are very necessary.It is wherein optimal representative It is metal-nitrogen-carbon structure catalyst, this metal (based on the transition metal with 3d unoccupied orbital) and nitrogen form coordination knot Structure has very high catalytic activity, and driving a reaction occurs usually in a manner of four electronics transfers.Common strategy is will be golden What category source, carbon source and the nitrogen source active site that pyrolysis at a certain temperature obtains that this metal and nitrogen are coordinated after mixing loaded Carbon nano-composite material.But the exposure of active site existing for prepared material leads to active low, active site easily quilt very little Stability caused by erosion falls off is poor, and catalyst coated causes electron-transport or proton transport rate low equal scarce in electrode surface Point.ZIF-67 is a kind of class zeolite imidazole frame structure material with permanent hole that Co ion and 2-methylimidazole are formed, It is still able to maintain its physical structure after high temperature cabonization not collapse, and Co and N coordination is good, with higher after carbonization treatment Stability sign activity and be used for a long time.But ZIF-67 usually has biggish particle, the catalyst being carbonized is a large amount of Active sites are buried, and only minority active sites in surface can play catalytic action, and the closs packing of this particle is unfavorable for electrode table Face mass transfer.In recent years, many researchers have done numerous studies to it, such as prepare the extra small ZIF-67 of partial size, or will ZIF-67 is directly grown on the active carbon material more than specific surface area macrovoid (such as porous carbon, carbon nanotube, graphene), this It is a little to attempt all to improve its hydrogen reduction catalytic performance to a certain extent.

The present invention is based on the current ZIF-67 series derivatives material there are the problem of, in conjunction with research achievement in recent years, wound The property made proposes a kind of strategy of growth in situ in hard template, has synthesized ordered porous ZIF-67 material, has obtained after carbonization Derivative as catalyst be applied to fuel battery negative pole redox reactions.The catalyst had both inherited traditional ZIF-67 and had spread out The advantages that high latent active of raw catalyst and stability, and overcome the disadvantages of its active site is few and mass transfer ability is poor.Electricity Chemical property test shows that the catalyst all shows higher catalytic activity, stability and resisted under alkalinity and acid condition Methanol ability, and mainly driving a reaction carries out in a manner of four electronics transfers.Compared to what is obtained after traditional ZIF-67 carbonization Catalyst, the catalyst performance that this research obtains have the raising of several times.

Summary of the invention

Present invention aims at provide the preparation method and use of a kind of cobalt and the 3-D ordered multiporous C catalyst of N doping On the way.This method has first synthesized the PS ball of different-grain diameter and has been made into template, template is impregnated in containing cabaltous nitrate hexahydrate and In the methanol solution of 2-methylimidazole, growth in situ ZIF-67 in template washes away template using tetrahydrofuran, and centrifugation obtains orderly Porous ZIF-67 presoma, up to cobalt and the 3-D ordered multiporous C catalyst of N doping after carbonization treatment.Prepared catalyst For the three-dimensional carbon material that tactical rule, particle are clearly demarcated, there is orderly duct, high-specific surface area, higher activity, higher stability The advantages that.This method, the hydrogen reduction electrocatalysis material of the specific surface area and good durability controllable, high for synthesis hole Provide a possibility that very big.It is raw materials used to be all easy to get and cheap, there is prospects for commercial application.

A kind of preparation method of the 3-D ordered multiporous C catalyst of cobalt and N doping of the present invention, follow these steps into Row:

A, 50ml polystyrene solution is cleaned repeatedly with the NaOH solution of 10% mass fraction and deionized water, will be cleaned Polystyrene solution afterwards is added in 1000ml flask, adds 1.5g polyvinylpyrrolidone and 500ml deionized water is mixed It closes, froth 20min under a nitrogen, and then flow back at 92 DEG C of temperature in thermostatic mixer 40min；

B, the 50ml sodium peroxydisulfate solution of mass fraction 1% is rapidly joined into mixed liquor in step a, and continued in temperature 92 20h is stirred persistently with 400rpm at DEG C, after being cooled to room temperature, suction filtration obtains the A Polystyrene Spheres Template of partial size 110nm；

C, the step b polystyrene moulding synthesized is impregnated in mass ratio is 1-4:4 containing cabaltous nitrate hexahydrate and 2- methyl In the methanol solution of imidazoles, stands growth for 24 hours, obtain mixture；

D, it after the mixture for obtaining step c is dry at 40 DEG C of temperature, is dissolved in tetrahydrofuran solution, stirring and dissolving 12h, centrifugation, and cleaned 3 times with tetrahydrofuran, blue powder is obtained after 110 DEG C of dryings of temperature；

E, step d is obtained into the lower carbonization treatment 2h of stream of nitrogen gas protection that blue powder is placed in 500 DEG C -700 DEG C of temperature, obtained There is the cobalt and the 3-D ordered multiporous C catalyst of N doping of the cellular structure of three-dimensional order to final product.

The purposes of cobalt and the 3-D ordered multiporous C catalyst of N doping that the method obtains, it is characterised in that prepared It at dispersion liquid and modifies in electrode surface, in electrocatalytic oxidation reduction reaction.

A kind of Preparation method and use of the 3-D ordered multiporous C catalyst of cobalt and N doping of the present invention, this method It has first synthesized the PS ball of different-grain diameter and has been made into template, template is impregnated in the methanol containing cobalt nitrate and 2-methylimidazole In solution, growth in situ ZIF-67 in template washes away template using tetrahydrofuran, and centrifugation obtains ordered porous ZIF-67 forerunner Body, nitrogen atmosphere are protected after carbonization treatment up to cobalt and the 3-D ordered multiporous C catalyst of N doping.The characteristics of this method are as follows: system For the polystyrene spheres of 110nm partial size and it is prepared into template, growth in situ ZIF-67 in template, due to the work of template With the ZIF-67 of formation has ordered porous structural, and hole knot is adjustable.The catalyst material that carbonization treatment obtains maintains forerunner Bodily form looks, it may have 3-D ordered multiporous structure.Cobalt, nitrogen are dispersed in carbon substrate, and mainly with the coordination of cobalt nitrogen Form exists, and has high latent active.This 3-D ordered multiporous structure provides big specific surface area, so that more urging Change active sites to be exposed, aperture abundant is conducive to mass transfer in solution.The catalyst preparation is modified at dispersion liquid in electricity Pole surface has good catalytic effect for redox reactions.Preparing reaction mass used in material is to be easy to get, is inexpensive Common raw material.

Electrochemical property test is done to the catalyst that this method obtains, shows the catalyst under alkalinity and acid condition all Higher catalytic activity, stability and methanol tolerance ability are shown, and the mainly driving a reaction in a manner of four electronics transfers It carries out.Compared to the catalyst obtained after traditional ZIF-67 carbonization, the catalyst performance that the present invention obtains has the raising of several times, Excellent performance and stabilization, raw material is cheap and easy to get, and the catalyst that the present invention obtains is suitable for large-scale business application.

Compared with existing technique, the method for the invention has apparent different:

1. method of the present invention needs first to prepare the monodisperse polystyrene ball of 110nm partial size, and passes through centrifugation Or the mode of filtering is fabricated to template；

2. template is impregnated in the methanol solution containing cobalt nitrate and 2-methylimidazole, growth is stood for 24 hours, being formed has three-dimensional The ZIF-67 monocrystalline of orderly pore structure；

3. its good pore structure still is maintained after the three-dimensional order pore structure ZIF-67 carbide of preparation, big Specific surface area exposes more catalytic active sites, and aperture abundant is conducive to mass transfer in solution, substantially increases catalyst Catalytic performance；

4. on the one hand the method for the invention synthesis cobalt and the 3-D ordered multiporous C catalyst of N doping inherit original work Skill obtains the advantages of catalyst, on the other hand the durability that active sites have high latent active and work long hours overcomes again The deficiency of original handicraft product, it is few to improve the exposure of its active sites, the disadvantage of mass transfer ability difference.

5. electrochemical test data shows that the catalyst of this method synthesis has several times compared to prior art properties of product Raising, activity be more than business Pt/C.

Detailed description of the invention

Fig. 1 is the polystyrene spheres scanning electron microscope (SEM) photograph prepared in the embodiment of the present invention 1；

Fig. 2 is the scanning electron microscope of ordered porous the ZIF-67 presoma and final catalyst that prepare in the embodiment of the present invention 3 Figure, wherein a is 3-D ordered multiporous ZIF-67；B is Co-NOPC-3/4-500；

Fig. 3 is that the X-ray of the cobalt and the 3-D ordered multiporous C catalyst of N doping that prepare in the embodiment of the present invention 3,4,5 is spread out Figure is penetrated, wherein a is Co-NOPC-3/4-500；B is Co-NOPC-3/4-600；C is Co-NOPC-3/4-700；

Fig. 4 is the rotational circle of the cobalt and the 3-D ordered multiporous C catalyst of N doping that prepare in the embodiment of the present invention 3,4,5 Disc electrode polarization curve, disc rotation speed 1600rpm, wherein a is Co-NOPC-3/4-500；B is Co-NOPC-3/4-600； C is Co-NOPC-3/4-700；

Fig. 5 is the Co-NOPC-3/4-500 catalyst prepared in the embodiment of the present invention 3 and Pt/C at 0.85V (vs.RHE) The stability and methanol tolerance aptitude tests of lower redox reactions, 10ml methanol are added in the 0.1MKOH solution of 100ml, Middle a is Co-NOPC-3/4-500；B is Pt/C；

Fig. 6 is the rotation of the cobalt and the 3-D ordered multiporous C catalyst of N doping that prepare in the embodiment of the present invention 1,2,3,6 Disk electrode polarization curve, disc rotation speed 1600rpm, wherein a is Co-NOPC-1/4-500；B is Co-NOPC-2/4- 500；C is Co-NOPC-4/4-500；D is Co-NOPC-3/4-500.

Specific embodiment

Below by specific embodiment, the invention will be further described: