CN103332687B - A kind of take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron - Google Patents
A kind of take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron Download PDFInfo
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Abstract
Take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, the present invention relates to the synthetic method of the nitrogen co-doped graphitization nano carbon of boron.The present invention to solve the complicated process of preparation of the nitrogen co-doped graphitization nano carbon of existing boron, severe reaction conditions, boron and nitrogen content low, yield poorly, cost is high, thus is difficult to the problem realizing suitability for industrialized production.Method: one, pre-treatment; Two, presoma is prepared; Three, carbonizing treatment; Four, acid treatment.The biomass that the present invention adopts occurring in nature abundant are carbon source, and preparation technology is simple, reduces the synthesis cost of material; By the material ratio of feed change, can regulate and control the content of nitrogen, boron in the finished product and degree of graphitization, meet the needs of different field; The uniform composition of biomass, makes functionalization ion be dispersed in biomass well, therefore product pattern and character homogeneous.The present invention prepares the nitrogen co-doped graphitization nano carbon of boron for the preparation of carbon source.
Description
Technical field
The present invention relates to the synthetic method of the nitrogen co-doped graphitization nano carbon of boron.
Background technology
Fuel cell has that energy density is high, efficiency of conversion is high and advantages of environment protection, is therefore considered to the most promising energy conversion device.Cathodic oxygen reduction kinetics is relatively slower, and it is the key determining fuel battery performance.So far, precious metals pt and Pt base alloy are the most effective oxygen reduction catalysts.But, due to expensive, poor durability, the scarcity of resources of precious metals pt, limit the commercial applications of fuel cell.Therefore, current research person is devoted to develop cheap non noble metal oxygen reduction catalyst.
The carbon material of base metal doping has excellent oxygen reduction reaction activity and the ability of resisting CO poisoning due to it, is therefore considered to a kind of cheapness, is expected to the efficient oxygen reduction reaction catalyzer of alternative precious metal.The carbon material (N-CNTs, N-Graphene etc.) of N, B codoped, has excellent ORR electro catalytic activity, the preferably feature such as weather resistance and environmental friendliness, has potential application prospect.Usual employing chemical Vapor deposition process prepares the carbon material of this kind of doping, and required conversion unit is complicated, and productive rate is low, boron N doping amount is uncontrollable, and cost is higher.Therefore, be necessary that a kind of method that is simple, low cost of development synthesizes the catalyzer of the nitrogen co-doped graphitization nano carbon non noble metal oxygen reduction reaction of highly active boron.
In sum, the nitrogen co-doped graphitization nano carbon of existing boron exist complicated process of preparation, severe reaction conditions, the structure heterogeneity of product, boron and nitrogen content uncontrollable, yield poorly, cost is high, thus is difficult to the problem realizing suitability for industrialized production.
Summary of the invention
The present invention to solve the complicated process of preparation of the nitrogen co-doped graphitization nano carbon of existing boron, severe reaction conditions, boron and nitrogen content low, yield poorly, cost is high, thus be difficult to the problem realizing suitability for industrialized production, and to provide a kind of take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron.
Take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, specifically carry out according to following steps:
One, chemical method is adopted to carry out pre-treatment to biomass;
Two, the biomass after step one being processed join in solvent, add the compound containing boron, the compound of nitrogen element and graphitization catalyst again, again temperature be 25 DEG C ~ 60 DEG C, stirring velocity stirs 2h ~ 10h under being 80r/min ~ 200r/min condition, then at temperature is 80 DEG C ~ 110 DEG C by solvent evaporate to dryness, obtain presoma;
Three, carbonizing treatment: presoma step 2 obtained is under protection of inert gas, and to control heat-up rate be 2 DEG C/min ~ 15 DEG C/min, and be warming up to 600 DEG C ~ 1200 DEG C, soaking time is 30min ~ 300min, obtains carbonized product;
Four, acid treatment: carbonized product step 3 obtained joins in acid solution and carries out acid treatment, controlling the acid treatment time is 4h ~ 12h, the pH being washed with distilled water to washing lotion is again 7, then vacuum-drying 4h ~ 16h under temperature is 60 DEG C ~ 100 DEG C conditions, obtain the nitrogen co-doped graphitization nano carbon of boron, namely completing with biomass is the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, and wherein, the mass ratio of carbonized product and acid solution is 1:(30 ~ 100).
The invention has the beneficial effects as follows: the first, the biomass that the present invention adopts occurring in nature abundant are carbon source, and preparation technology is simple, therefore greatly reduces the synthesis cost of material; The second, by the material ratio of feed change, can regulate and control the content of nitrogen, boron in the finished product and degree of graphitization, therefore can meet the needs of different field; 3rd, the uniform composition of biomass, makes functionalization ion be dispersed in biomass well, therefore product pattern and character homogeneous.
The present invention prepares the nitrogen co-doped graphitization nano carbon of boron for the preparation of carbon source.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the nitrogen co-doped graphitization nano carbon of boron prepared by embodiment one; Wherein a is the crystallographic plane diffraction peak of (002) crystal face, and b is the crystallographic plane diffraction peak of (100) crystal face;
The x-ray photoelectron spectroscopy figure of the nitrogen co-doped graphitization nano carbon of boron prepared by Fig. 2 embodiment one; Wherein a is the power spectrum peak of boron, and b is the power spectrum peak of carbon, and c is the power spectrum peak of nitrogen.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is a kind of take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, specifically carries out according to following steps:
One, chemical method is adopted to carry out pre-treatment to biomass;
Two, the biomass after step one being processed join in solvent, add the compound containing boron, the compound of nitrogen element and graphitization catalyst again, again temperature be 25 DEG C ~ 60 DEG C, stirring velocity stirs 2h ~ 10h under being 80r/min ~ 200r/min condition, then at temperature is 80 DEG C ~ 110 DEG C by solvent evaporate to dryness, obtain presoma;
Three, carbonizing treatment: presoma step 2 obtained is under protection of inert gas, and to control heat-up rate be 2 DEG C/min ~ 15 DEG C/min, and be warming up to 600 DEG C ~ 1200 DEG C, soaking time is 30min ~ 300min, obtains carbonized product;
Four, acid treatment: carbonized product step 3 obtained joins in acid solution and carries out acid treatment, controlling the acid treatment time is 4h ~ 12h, the pH being washed with distilled water to washing lotion is again 7, then vacuum-drying 4h ~ 16h under temperature is 60 DEG C ~ 100 DEG C conditions, obtain the nitrogen co-doped graphitization nano carbon of boron, namely completing with biomass is the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, and wherein, the mass ratio of carbonized product and acid solution is 1:(30 ~ 100).
Present embodiment beneficial effect: the first, the biomass that the present invention adopts occurring in nature abundant are carbon source, and preparation technology is simple, therefore greatly reduces the synthesis cost of material.The second, by the material ratio of feed change, can regulate and control the content of nitrogen, boron in the finished product and degree of graphitization, therefore can meet the needs of different field.3rd, the uniform composition of biomass, makes functionalization ion be dispersed in biomass well, therefore product pattern and character homogeneous.
Embodiment two: present embodiment and embodiment one unlike: described in step one, pretreated step is as follows: biomass are joined the aqueous solution that massfraction is the potassium hydroxide of 10% ~ 35%, salt aqueous acid that the aqueous solution that massfraction is the sodium hydroxide of 10% ~ 35%, massfraction are 10% ~ 35%, massfraction be 10% ~ 35% nitre aqueous acid or massfraction be in the aqueous solution of the potassium permanganate of 10% ~ 35%, under activation temperature is 90 DEG C ~ 190 DEG C conditions, activate 3h ~ 8h again, complete pre-treatment.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one unlike: the biomass described in step one are coconut husk, maize straw, palm hull, bagasse, the stem or leaf of cattail, bamboo or wood chip.Other is identical with embodiment one.
Embodiment four: present embodiment and embodiment one unlike: the graphitization catalyst described in step 2 is iron nitrate, iron trichloride, ferrous chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, nickelous nitrate, nickelous chloride, the Tripotassium iron hexacyanide, yellow prussiate of potash, potassium cobalticyanide, nickel potassium cyanide or three oxalic acid close potassium ferrite.Other is identical with embodiment one.
Embodiment five: present embodiment and embodiment one unlike: the compound containing boron in step 2 is sodium tetraborate, copper borate, zinc borate, Sodium Tetraborate, Sodium peroxoborate, boric acid, fluoroboric acid, ammonium borofluoride, fluoroborate, nickel fluoborate, Sodium tetrafluoroborate, potassium fluoborate, fluoroboric acid cobalt or zinc fluoroborate.Other is identical with embodiment one.
Embodiment six: present embodiment and embodiment one unlike: the compound containing nitrogen element in step 2 is nitric acid, cyanamide, trimeric cyanamide or urea.Other is identical with embodiment one.
Embodiment seven: present embodiment and embodiment one unlike: in step 2, the mass ratio of biomass and solvent is 1:(10 ~ 30), the mass ratio of biomass and graphitization catalyst is 1:(0.3 ~ 5), compound containing boron and the mass ratio of graphitization catalyst are 1:(0.8 ~ 6), compound containing boron is 1:(0.3 ~ 2.5 with the mass ratio of compound containing nitrogen element), wherein solvent is one or both mixing by any ratio in water and dehydrated alcohol.Other is identical with embodiment one.
Embodiment eight: present embodiment and embodiment one unlike: in step 3, rare gas element is mixing of being mixed by any ratio of one or both in nitrogen and argon gas, and flow is 60mL/min ~ 300mL/min.Other is identical with embodiment one.
Embodiment nine: present embodiment and embodiment one unlike: in step 4, acid treatment is stirring at room temperature or reflux.Other is identical with embodiment one.
Embodiment ten: present embodiment and embodiment one unlike: in step 4, acid solution is hydrochloric acid soln, salpeter solution or acetum, and the mass concentration of acid solution is 6% ~ 20%.Other is identical with embodiment one.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one:
The present embodiment is a kind of take biomass as the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron, specifically carries out according to following steps:
One, 6g maize straw being joined massfraction is in the aqueous solution of the sodium hydroxide of 25%, then activates 3h under activation temperature is 120 DEG C of conditions;
Two, the maize straw after step one being processed is added to the water, add containing boric acid, urea and nickel potassium cyanide again, again temperature be 35 DEG C, stirring velocity stirs 4h under being 120r/min condition, then at temperature is 105 DEG C by solvent evaporate to dryness, obtain presoma, wherein, the mass ratio of maize straw and water is 1:20, the mass ratio of maize straw and nickel potassium cyanide is 1:0.4, and the mass ratio of boric acid and nickel potassium cyanide is 1:3;
Three, carbonizing treatment: under nitrogen protection, control heat-up rate is 4 DEG C/min to presoma step 2 obtained, and be warming up to 800 DEG C, soaking time is 60min, obtains carbonized product;
Four, acid treatment: the carbonized product that step 3 is obtained join 150mL mass concentration be in the salpeter solution of 20% temperature be 110 DEG C of conditions next time stream carry out acid treatment, controlling the returned acid treatment time is 6h, the pH being washed with distilled water to washing lotion is again 7, then vacuum-drying 6h under temperature is 90 DEG C of conditions, obtain the nitrogen co-doped graphitization nano carbon of boron, namely completing with biomass is the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron.
As shown in Figure 1, wherein a is the crystallographic plane diffraction peak of (002) crystal face to the X-ray diffraction spectrogram of the nitrogen co-doped graphitization nano carbon of boron prepared by the present embodiment, and b is the crystallographic plane diffraction peak of (100) crystal face; As can be seen from Figure 1, (002) and (100) amount crystal face there is obvious crystallographic plane diffraction peak, illustrates that this material has graphitized carbon structure.The x-ray photoelectron spectroscopy figure of the nitrogen co-doped graphitization nano carbon of boron prepared by the present embodiment as shown in Figure 2, as can be seen from Figure 2 has the power spectrum peak of obvious nitrogen, boron, carbon, and wherein a is the power spectrum peak of boron, and b is the power spectrum peak of carbon, and c is the power spectrum peak of nitrogen; Illustrate that surface sample is the nitrogen co-doped carbon material of boron.
Claims (1)
1. be the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron with biomass, it is characterized in that what the method was specifically carried out according to following steps:
One, 6g maize straw being joined massfraction is in the aqueous solution of the sodium hydroxide of 25%, then activates 3h under activation temperature is 120 DEG C of conditions;
Two, the maize straw after step one being processed is added to the water, add containing boric acid, urea and nickel potassium cyanide again, again temperature be 35 DEG C, stirring velocity stirs 4h under being 120r/min condition, then at temperature is 105 DEG C by solvent evaporate to dryness, obtain presoma, wherein, the mass ratio of maize straw and water is 1:20, the mass ratio of maize straw and nickel potassium cyanide is 1:0.4, and the mass ratio of boric acid and nickel potassium cyanide is 1:3;
Three, carbonizing treatment: under nitrogen protection, control heat-up rate is 4 DEG C/min to presoma step 2 obtained, and be warming up to 800 DEG C, soaking time is 60min, obtains carbonized product;
Four, acid treatment: the carbonized product that step 3 is obtained join 150mL mass concentration be in the salpeter solution of 20% temperature be 110 DEG C of conditions next time stream carry out acid treatment, controlling the returned acid treatment time is 6h, the pH being washed with distilled water to washing lotion is again 7, then vacuum-drying 6h under temperature is 90 DEG C of conditions, obtain the nitrogen co-doped graphitization nano carbon of boron, namely completing with biomass is the method that carbon source prepares the nitrogen co-doped graphitization nano carbon of boron.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456554A (en) * | 2009-01-06 | 2009-06-17 | 黑龙江大学 | Method for preparing graphitization nano carbon |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN103112854A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method |
| CN103112845A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing boron and nitrogen co-doped graphitized nano-carbon by using ion-exchange resin |
-
2013
- 2013-07-11 CN CN201310293898.1A patent/CN103332687B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456554A (en) * | 2009-01-06 | 2009-06-17 | 黑龙江大学 | Method for preparing graphitization nano carbon |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
| CN103050714A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Nano carbon doped electrocatalyst for fuel cell, and application of nano carbon doped electrocatalyst |
| CN103112854A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method |
| CN103112845A (en) * | 2013-01-31 | 2013-05-22 | 黑龙江大学 | Method for synthesizing boron and nitrogen co-doped graphitized nano-carbon by using ion-exchange resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621959A (en) * | 2018-11-22 | 2019-04-16 | 长沙理工大学 | Amorphous boric acid cobalt nanorod efficiently analyses the preparation method and application of oxygen elctro-catalyst |
| CN109621959B (en) * | 2018-11-22 | 2021-08-06 | 长沙理工大学 | Preparation method and application of amorphous cobalt borate nanorod high-efficiency oxygen evolution electrocatalyst |
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