CN104961119A - Preparation method of boron and nitrogen co-doped hollow carbon nanocage - Google Patents
Preparation method of boron and nitrogen co-doped hollow carbon nanocage Download PDFInfo
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Abstract
The invention relates to a simple, safe and environmentally-friendly method for massively preparing a high-quality boron and nitrogen co-doped hollow carbon nanocage. The method comprises the following steps: decomposing and breaking basic magnesium carbonate or magnesium carbonate placed in a tubular furnace at a certain reaction temperature to generate magnesium oxide nanoparticles; carrying C, B and N sources (such as benzene, pyridine and dimethylamine broane) into the high temperature reaction zone of the tubular furnace by Ar or N2 or another inert gas flow, and carbonizing and wrapping the surface of in situ generated magnesium oxide nanoparticles to form a MgO@BCN structure; and carrying out hydrochloric acid or diluted sulfuric acid treatment to remove the core of MgO in order to obtain the boron and nitrogen co-doped hollow carbon nanocage with high purity and high quality (such as good graphitization degree, high specific surface area, large pore volume and high meso-porous rate). The performances of the boron and nitrogen co-doped hollow carbon nanocage can be controlled by regulating the reaction temperature, the raw material flow amount and the reaction time. The basic magnesium carbonate or magnesium carbonate used as an important precursor is cheap, can be easily recycled, and can reduce the cost.
Description
Technical field
The present invention relates to a kind of with the carbon containings such as magnesium basic carbonate (or magnesiumcarbonate) and benzene, pyridine, pyrroles, dimethylamine broane and nitrogen, boron compound for precursor, the bitter earth nano particle produced with magnesium basic carbonate or magnesiumcarbonate decomposition in situ, for template, prepares the method for the nitrogen co-doped hollow nano cages of high-quality boron in a large number.
Background technology
Character such as the novel structure of carbon fullerene and nanotube and unique optical, electrical, magnetic and cause the extensive attention of people, and excite people and explore other carbon nano-structured interest (R.H.Baughman, et al.Science 2002,297,787).Hollow nano cages has unique physicochemical property, and there are some researches show, it is expected to be applied to numerous areas (Anvar A.Zakhidov, the et al.Science 1998,282,897 such as catalysis, the energy, separation, optics; S.Han, et al.Adv.Mater.2003,15,1922; Ajayan Vinu et al., J.Porous Mater 2006,13,379; J.J.Niu, et al.J.Phys.Chem.C 2007,111,10329).Up to the present, people have developed several technological lines to prepare hollow nano cages, such as: (the S.Han such as arc process, laser evaporization method, Plasma Polymerization, chemical vapor deposition method (CVD), supercritical fluid method, et al.Adv.Mater.2003,22: 1922; Y.M.Ma, et al.Carbon.2005,8,1667; J.Y.Miao, et al.Carbon 2004,42,813; J.Cao, et al.J.Nanoparticle Res.2004,6,447).A common feature of above-mentioned synthetic method is that synthesis hollow nano cages generally needs template, and the material as template has (G.Hu, et al., Chem.Commun.2002,1948 such as metallics, high score bulbec and SiO2 ball; J.Jang, et al.Chem.Mater.2003,15,2109; J.Jang, et al.Adv.Mater.2002,14,1390).Its principal character is the carbon paste capsule first forming core/shell structure, then selects suitable physico-chemical process that core is removed according to inner nuclear material, finally obtains hollow nano cages.Polymer-based nanocages is also needed to carry out high temperature cabonization process.Because above method relates to complicated multistep process, and some technique uses the poisonous or disagreeableness reagent of environment, and therefore these techniques more or less also exist unfavorable factor.
According to the literature, N doping can the structure of modulation carbon nanotube effectively, acid-basicity, reactive behavior and electroconductibility etc., contribute to the catalyzer preparing excellent property, for example: nitrogen-doped carbon nanometer pipe (NCNTs) does not need metal supported catalyst just to show redox reactions (ORR) catalytic activity more much higher than Pt/C catalyzer and stability [(a) K.Gong, et al.Science 323, 60 (2009). (b) Y.F.Tang, et al.J.Am.Chem.Soc.131, 13200 (2009). (c) Z.Chen, et al.J.Phys.Chem.C 113, 21008 (2009) .], be that the Pt base nano-composite catalyst of vector construction has excellent electrocatalysis characteristic (methanol oxidation and hydrogen reduction) [(a) S.J.Jiang with nitrogen-doped carbon nanometer pipe, et al.Adv.Mater.21, 4953 (2009). (b) B.Yue, et al.J.Mater.Chem.18, 1747 (2008). (c) M.Gross, Chemistry World (China edition) C4 (2008). (d) Y.W.Ma, et al.J.Phys.Chem.C 112, ].Our seminar reports boron doped carbon nanometer pipe and also has good oxygen reduction catalytic activity [L.Yang, etal.Angew.Chem.Int.Ed.50,7132 (2011)] recently.And the synergy that boron nitrogen binary codoped can utilize boron and nitrogen is carried out to carbon nanotube, effectively improve its electrocatalysis characteristic [S.Wang, et al.Angew.Chem.Int.Ed.50,11756 (2011)].From the angle of support of the catalyst, carbon based nanotube still comes with some shortcomings, main manifestations is specific surface area (specific surface area of many walls carbon based nanotube only has tens of to 100 m2/g usually) less than normal, because generally speaking high specific surface area is more conducive to the dispersion of catalytic active species.In addition, doped carbon nanometer pipe normally Bamboo-shaped, granules of catalyst not easily enters space in pipe, and its abundant internal surface is difficult to effective utilization.And carbon-based nano cage is expected to these deficiencies overcoming carbon based nanotube just.
200410024700.0 " method of mass preparing hollow nanometer carbon cages " discloses a kind of method of mass preparing hollow nanometer carbon cages.For technical field of nanometer material preparation.First solid carbon nanocages is prepared: metal carbonyls liquid and the even proportioning of low-carbon (LC) class organic liquid are obtained reaction soln and be placed in volumetric flask, main reactor heats up, and pass into rare gas element, reaction soln is sprayed into by main reactor top through electronic peristaltic pump, in main reactor bottoms collector, obtains the solid carbon nanocages being enclosed with metallics; Then hollow nano cages is prepared: the solid carbon nanocages obtained is placed in pure nitric acid or pure nitric acid and distilled water mixing solutions, this miscellany is placed in ultrasonator and carries out sonic oscillation; By the mixture heating after vibration, and add recirculated water reflux cooling; Again mixture adding distil water is diluted, until solution is in neutral or close neutral, then leaves standstill and solid matter is deposited and outwells upper liquid, dry immediately, obtain hollow nano cages.
200510110213.0 " methods of mass preparing hollow nanometer carbon cages " disclose a kind of method of mass preparing hollow nanometer carbon cages, for technical field of nanometer material preparation.First this invention prepares solid carbon nanocages: metal carbonyls liquid and the even proportioning of low-carbon (LC) class organic liquid are obtained reaction soln and be placed in volumetric flask, main reactor is heated up, and pass into rare gas element, reaction soln is sprayed into by main reactor end injector through electronic peristaltic pump, in main reactor afterbody product collector, obtains the solid carbon nanocages being enclosed with metallics; Then prepare hollow nano cages: by the solid carbon nanocages atmospheric oxidation obtained, be then placed in pure hydrochloric acid or pure hydrochloric acid and distilled water mixing solutions and carry out sonic oscillation; Mixture after vibration is added deionized water rinsing, filtration, until solution is in neutral or close neutral, then leaves standstill and solid matter is deposited and outwells upper liquid, dry immediately, obtain hollow nano cages.
200610024088.6 " methods of solid-state preparing great amount of hollow nanometer carbon cage " disclose a kind of method of solid-state preparing great amount of hollow nanometer carbon cage, for technical field of nanometer material preparation.The amorphous carbon precursor having iron catalyst uniform particle to distribute is prepared in this invention first in a large number, then precursor is heat-treated and obtain hollow nano cages by solid state reaction, finally hollow nano cages is carried out subsequent disposal removing catalyzer, obtain final product.
It should be noted that above patented method relates to complicated multistep process, and some technique uses the poisonous or disagreeableness reagent of environment, and be difficult to batch preparation, therefore these techniques more or less also exist unfavorable factor.
200810023448.X " method of mass preparing hollow nano cages in high quality " disclose a kind of with magnesium basic carbonate (or magnesiumcarbonate) with the carbonaceous organic material such as benzene, ethanol for precursor, the bitter earth nano particle produced with magnesium basic carbonate or magnesiumcarbonate decomposition in situ for template, the method for mass preparing hollow nano cages in high quality.The nano cages utilizing the method to synthesize has shown superior performance [K.Xie, et al.Adv.Mater.24,347 (2012)] as super capacitor material.
Up to the present, there is not yet the report of the nitrogen co-doped nano cages aspect of boron.This patent intends open one with carbon containing, boron, nitrogen compounds such as magnesium basic carbonate (or magnesiumcarbonate) and benzene, dimethylamine broane, pyridines for precursor, the bitter earth nano particle produced with magnesium basic carbonate or magnesiumcarbonate decomposition in situ, for template, prepares the method for the nitrogen co-doped hollow nano cages of high-quality boron in a large number.
Summary of the invention
The object of this invention is to provide simpler, the safer preparation method of the nitrogen co-doped hollow nano cages of a kind of boron.
Concrete technical scheme of the present invention is as follows:
A preparation method for the nitrogen co-doped hollow nano cages of high-quality boron, step comprises:
(1) the boron nitrogen co-doped carbon-coating parcel bitter earth nano particle of nucleocapsid structure is prepared:
Get magnesium basic carbonate or magnesiumcarbonate joins in reaction tubes, uniform spreading falls apart, and put into tube furnace, then deflating is filled with rare gas element, as N
2and Ar; Under atmosphere of inert gases, temperature of reaction is warmed up to 700 DEG C ~ 1100 DEG C gradually, introduces C and B, N source steam, under the protection of 10-500sccm rare gas element, reacts 5 ~ 240 minutes; Described C and B, N source gas bring tube furnace reaction zone into through inert gas flow, and the bitter earth nano particle surface carbonization generated in position is also wrapped up, and form MgO BCN structure; After above-mentioned reaction terminates under the protection of rare gas element, in reaction tubes, temperature is down to room temperature;
(2) the nitrogen co-doped hollow nano cages of boron is prepared:
From reaction tubes, collect powder, be placed in enough hydrochloric acid or sulfuric acid soaks 5-720 minute, remove the kernel of MgO, filter, with deionized water wash to neutral, dry, obtain the nitrogen co-doped hollow nano cages of boron (BN-CNCs).
In step (1), reaction tubes is placed in the central area of tube furnace.
In step (1), rare gas element is argon gas or nitrogen.
In step (1), the best in quality flow of rare gas element is 50-100sccm; Optimum reacting time is 10 ~ 60 minutes.
In step (1), the temperature rise rate of temperature of reaction is per minute 5-50 DEG C.
In step (1), C source comprises benzene and ethanol etc.
In step (1), N source comprises pyridine, quadrol, acetonitrile, benzylamine, ammonia etc., and dimethylamine broane is as B, N source, and triphenyl-boron also can as B source.
In step (1), the molar ratio range of C, B, N source gas and carrier gas is 0.01-5.0.
In step (1), the content of N species is adjustable at 0-12%, and the content of B species is adjustable at 0-10%, B, N content and existence and presoma and depositing temperature closely related.
In step (1), described tube furnace is in temperature control tube furnace.
In step (1), reaction tubes is reaction tubes, alundum tube, vitrified pipe or stainless steel tube.
In step (1), as magnesium basic carbonate or the magnesiumcarbonate of important precursor, easy recycling, can reduce costs, this process environmental protection.
In step (2), the structure of process middle acid substance to the nitrogen co-doped nano cages of boron removing template does not have destruction.
Device required for the present invention mainly contain CVD depositing system, gas distributing system and vacuum system three part composition, the relationship and function of its each several part is as follows: (1) CVD system comprises the reaction chamber made by reaction tubes and is placed in tube furnace, the corundum boat being placed with magnesium basic carbonate or magnesiumcarbonate is placed in reaction chamber center, and the temperature of vitellarium can regulate and control.(2) gas distributing system, is made up of gas circuit and mass flowmeter, is connected to one end of growth room, utilizes it can regulate precursor kind, input.(3) vacuum system, the vacuum tightness of growth regulation indoor and reacting gas pressure.
In the present invention, MgO kernel only need soak and can remove with hydrochloric acid or dilute sulphuric acid.
Feature of the present invention is as follows:
The proposed by the invention original position template method preparing the nitrogen co-doped hollow nano cages of boron, it is characterized in that as the MgO nanoparticle of template it being that temperature-rise period decomposes by magnesium basic carbonate or magnesiumcarbonate generation of breaking, carbon and boron, nitrogenous source are wrapped to form MgO@BCN structure at its surface carbonation, and kernel MgO easily removes.
The preparation method of the nitrogen co-doped hollow nano cages of a kind of high-quality boron proposed by the invention, it is characterized in that not needing to use metal catalyst, MgO is template and catalyzer, and it is easy to remove.
The preparation method of the nitrogen co-doped hollow nano cages of a kind of high-quality boron proposed by the invention, is characterized in that product purity is high, substantially free from foreign meter, has the advantages such as specific surface area is high, pore volume is large, mesoporous rate is high, degree of graphitization is good.
The preparation method of the nitrogen co-doped hollow nano cages of a kind of high-quality boron proposed by the invention, it is characterized in that by regulation and control growth temperature, material flow and growth time etc., regulate and control the performance (as specific surface area, pore volume, size distribution etc.) of product.
The preparation method of the nitrogen co-doped hollow nano cages of a kind of high-quality boron proposed by the invention, is characterized in that all can preparing the nitrogen co-doped hollow nano cages of boron by change carbon source, boron source, nitrogenous source.
The preparation method of the nitrogen co-doped hollow nano cages of a kind of high-quality boron proposed by the invention, is characterized in that the magnesium basic carbonate as important precursor or magnesiumcarbonate, and cheap, easy recycling, can reduce costs, environmental protection.
Accompanying drawing explanation
Fig. 1 removes typical high-resolution electron microscopy (HRTEM) photo of boron nitrogen-doped carbon nanocages (BN-CNCs) before and after MgO template
Electronic Speculum (TEM) photo (a) BN-CNC700 of the nitrogen co-doped nano cages of the boron prepared under Fig. 2 differing temps, (b) BN-CNC750, (c) BN-CNC800, (d) BN-CNC850, (e) BN-CNC900, (f) BN-CNC1000.
The total spectrogram of XPS of Fig. 3 typical boron nitrogen-doped carbon nanocages and B, N spectrum
Embodiment
Below in conjunction with accompanying drawing and embodiment, the inventive method is described.
The method that the present invention prepares the nitrogen co-doped hollow nano cages of boron is as follows, first the reaction tubes being placed with magnesium basic carbonate or magnesiumcarbonate is placed in above-mentioned growth room, under the protection of 10-500sccm Ar or N2 gas, be heated to 700-1100 DEG C.Then carbon source and boron, nitrogen source gas (as benzene, methane, acetylene or ethanol etc.) and boron nitrogenous source solution (as dimethylamine broane, triphenyl-boron, pyridine, quadrol, acetonitrile, ammonia etc.) are introduced reaction chamber; reaction 5-240min; under the protection of Ar or N2 gas, be cooled to room temperature, collect the powder in reaction tubes.This powder is placed in enough hydrochloric acid or sulfuric acid stirs for some time, filters, washing, to dry, MgO template can be removed.Optimum temps of the present invention is the flow of 700-1000 DEG C, Ar gas is 50-100sccm (sccm), and growth time is 10-60min.
Embodiment 1 is with the benzole soln of 0.05g/ml dimethylamine broane for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon atmosphere, (50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 10 DEG C, with the benzole soln 0.020ml/min of constant-flux pump input 0.05g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from reaction tubes; the dilute hydrochloric acid being placed in 1mol/L soaks 1 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is 0.27%, nitrogen content about 2.8%.Specific surface area can reach 1650m
2g
-1, pore volume can reach 3.90cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 2 is with the benzole soln of 0.10g/ml dimethylamine broane for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in alundum tube, and uniform spreading falls apart, and puts into tube furnace central area, then inflated with nitrogen and finding time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 10 DEG C under nitrogen atmosphere, with the benzole soln 0.020ml/min of constant-flux pump input 0.10g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of nitrogen (50sccm); powder is collected from alundum tube; the dilute hydrochloric acid being placed in 0.1mol/L soaks 12 hours; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is 8.34%, nitrogen content about 12.57%.Specific surface area can reach 1480m
2g
-1, pore volume can reach 3.50cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 3 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in vitrified pipe, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon atmosphere, (50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 10 DEG C, with the benzole soln 0.020ml/min of constant-flux pump input 0.20g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from vitrified pipe; the hydrochloric acid being placed in 10mol/L soaks 5 minutes; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents about 9.48%, nitrogen content about 12.57%.Specific surface area can reach 950m
2g
-1, pore volume can reach 3.20cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 4 is with the pyridine solution of 0.2g/ml triphenyl-boron for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in vitrified pipe, and uniform spreading falls apart, and puts into tube furnace central area, then inflated with nitrogen and finding time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 10 DEG C under nitrogen atmosphere, with the pyridine solution 0.020ml/min of constant-flux pump input 0.2g/ml triphenyl-boron, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of nitrogen (50sccm); powder is collected from vitrified pipe; the hydrochloric acid being placed in 5mol/L soaks 0.5 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain N doping hollow nano cages; Boron contents about 1.32%, nitrogen content is about 4.47%.Specific surface area can reach 1300m
2g
-1, pore volume can reach 3.30cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 5 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 800 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in alundum tube, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon atmosphere, (50sccm) is warmed up to 800 DEG C with the temperature rise rate of per minute 10 DEG C, with the benzole soln 0.020ml/min of constant-flux pump input 0.20g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from alundum tube; the dilute hydrochloric acid being placed in 1mol/L soaks 0.5 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 7%, nitrogen content about 10%.Specific surface area can reach 1100m
2g
-1, pore volume can reach 2.50cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 6 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 850 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in vitrified pipe, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon gas atmosphere is enclosed, (50sccm) is warmed up to 850 DEG C with the temperature rise rate of per minute 10 DEG C, with the benzole soln 0.020ml/min of constant-flux pump input 0.20g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from vitrified pipe; the dilute hydrochloric acid being placed in 1mol/L soaks 1 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 6%, nitrogen content about 8%.Specific surface area can reach 800m
2g
-1, pore volume can reach 2.20cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 7 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 900 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesiumcarbonate joins in vitrified pipe, and uniform spreading falls apart, and puts into tube furnace central area, then inflated with nitrogen and finding time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 900 DEG C with the temperature rise rate of per minute 10 DEG C under nitrogen atmosphere, with the benzole soln 0.020ml/min of constant-flux pump input 0.20g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of nitrogen (50sccm); powder is collected from vitrified pipe; the dilute hydrochloric acid being placed in 1mol/L soaks 2 hours; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 5%, nitrogen content about 7%.Specific surface area 400m
2g
-1, pore volume 1.80cm
3g
-1, particle diameter is about 10 ~ 50nm, and mesoporous rate is higher than 99.3%.
Embodiment 8 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 950 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon atmosphere, (50sccm) is warmed up to 950 DEG C with the temperature rise rate of per minute 10 DEG C, inputs the benzole soln 0.020ml/min of 0.20 g/ml dimethylamine broane with constant-flux pump, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from reaction tubes; the dilute hydrochloric acid being placed in 1mol/L soaks 3 hours; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents about 3%, nitrogen content about 4%.Specific surface area 300m
2g
-1, pore volume 1.10cm
3g
-1, particle diameter is about 10 ~ 50nm, and mesoporous rate is higher than 99.3%.
Embodiment 9 is with the benzole soln of 0.20g/ml dimethylamine broane for precursor, and temperature of reaction is 1000 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesiumcarbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace central area, then inflated with nitrogen and finding time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 1000 DEG C with the temperature rise rate of per minute 10 DEG C under nitrogen atmosphere, with the benzole soln 0.020ml/min of constant-flux pump input 0.20g/ml dimethylamine broane, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of nitrogen (50sccm); powder is collected from reaction tubes; the dilute hydrochloric acid being placed in 1mol/L soaks 1 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 2%, nitrogen content about 3%.Specific surface area 150m
2g
-1, pore volume 0.70cm
3g
-1, particle diameter is about 10 ~ 150nm, and mesoporous rate is higher than 99.3%.
Embodiment 10 is with the dimethylamine broane pyridine solution of 0.2g/ml for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 60min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon gas or nitrogen atmosphere, (50sccm) is warmed up to 1100 DEG C with the temperature rise rate of per minute 5 DEG C, with the dimethylamine broane pyridine solution 0.020ml/min of constant-flux pump input 0.2g/ml, reacts 60 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas or nitrogen (50sccm); powder is collected from reaction tubes; the dilute hydrochloric acid being placed in 1mol/L soaks 1 hour; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents about 1.27%, nitrogen content 10.34%.Specific surface area can reach 1020m
2g
-1, pore volume can reach 0.3 cm
3g
-1, particle diameter is about 30 ~ 200nm, and mesoporous rate is higher than 99.5%.
Embodiment 11 is with the dimethylamine broane pyridine solution of 0.4g/ml for precursor is for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 20min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in stainless steel tube, and uniform spreading falls apart, and puts into tube furnace central area, then applying argon gas and finding time 3-5 time with mechanical pump repeatedly.Under argon atmosphere, (50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 10 DEG C, is precursor 0.020ml/min, reacts 20 minutes with the dimethylamine broane pyridine solution of constant-flux pump input 0.2g/ml.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from stainless steel tube; the dilute sulphuric acid being placed in 0.1mol/L soaks 12 hours; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 3.4%, nitrogen content about 11.4%.Specific surface area can reach 950m
2g
-1, pore volume can reach 0.27cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Embodiment 12 is with the ethylenediamine solution of 0.2g/ml dimethylamine broane for precursor, and temperature of reaction is 700 DEG C, and the reaction times is 10min, the nitrogen co-doped hollow nano cages of original position template synthesis boron.
Taking a certain amount of magnesium basic carbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace central area, then inflated with nitrogen and finding time 3-5 time with mechanical pump repeatedly.(50sccm) is warmed up to 700 DEG C with the temperature rise rate of per minute 20 DEG C under nitrogen atmosphere, with the ethylenediamine solution 0.020ml/min of constant-flux pump input 0.2g/ml dimethylamine broane, reacts 10 minutes.Reaction terminates rear boiler tube and drops to room temperature in the protection of argon gas (50sccm); powder is collected from reaction tubes; the dilute sulphuric acid being placed in 0.5mol/L soaks 6 hours; filter; with deionized water repetitive scrubbing to neutral, 110 DEG C of oven dry, obtain the nitrogen co-doped hollow nano cages of boron; Boron contents is about 4%, nitrogen content about 11%.Specific surface area can reach 1780m
2g
-1, pore volume can reach 4.20cm
3g
-1, particle diameter is about 10 ~ 40nm, and mesoporous rate is higher than 99.5%.
Claims (8)
1. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that:
Comprise two steps, wherein step (1) prepares the boron of nucleocapsid structure nitrogen co-doped carbon-coating parcel bitter earth nano particle: get magnesium basic carbonate or magnesiumcarbonate joins in reaction tubes, and uniform spreading falls apart, and puts into tube furnace; Then deflate and be filled with rare gas element, Bubbling method introduces volatility C source, boracic and nitrogenous source steam, and under the protection of 10-500sccm atmosphere of inert gases, temperature of reaction is warmed up to 700 ~ 1100 DEG C gradually, and the reaction times is 5 ~ 240 minutes; Described volatility C source, boracic and nitrogenous source steam bring described tube furnace reaction zone into through inert gas flow, and the bitter earth nano particle surface carbonization generated in position is also wrapped up, and form MgO@BCN structure;
After above-mentioned reaction terminates under the protection of rare gas element, in described reaction tubes, temperature is down to room temperature;
Wherein step (2) prepares the nitrogen co-doped hollow nano cages of boron:
From described reaction tubes, collect powder, the hydrochloric acid or the dilute sulphuric acid that are placed in 0.1 ~ 10mol/L soak 5 ~ 720 minutes, remove the kernel of MgO, filter, and with deionized water wash to neutral, dry, obtain the nitrogen co-doped hollow nano cages of boron (BNCNC).
2. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), described reaction tubes is placed in the central area of tube furnace.
3. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), and the mass rate of described rare gas element is 50-200sccm; The described reaction times is 10-60 minute; Rare gas element is argon gas or nitrogen.
4. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), and the temperature rise rate of described temperature of reaction is per minute 5-50 DEG C.
5. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), C source comprises benzene, ethanol, and dimethylamine broane can be used as boracic and nitrogenous source, and nitrogenous source can also adopt pyridine, pyrroles, acetonitrile etc.
6. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), and described tube furnace is temperature programmed control tube furnace.
7. a preparation method for the nitrogen co-doped hollow nano cages of boron, is characterized in that: in step (1), and described reaction tubes is that silica tube, alundum tube, vitrified pipe, stainless steel tube are wherein a kind of.
8. a preparation method for the nitrogen co-doped hollow nano cages of boron, it is characterized in that: the content of N species is adjustable at 0-12%, the content of B species is adjustable at 0-10%, B, N content and existence and presoma and depositing temperature closely related.
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