CN103193223A - Controllable synthetic method of graphitized carbon spheres with hollow structure - Google Patents

Controllable synthetic method of graphitized carbon spheres with hollow structure Download PDF

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CN103193223A
CN103193223A CN2013101133538A CN201310113353A CN103193223A CN 103193223 A CN103193223 A CN 103193223A CN 2013101133538 A CN2013101133538 A CN 2013101133538A CN 201310113353 A CN201310113353 A CN 201310113353A CN 103193223 A CN103193223 A CN 103193223A
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salt
acid
carbon
high temperature
nanometers
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尹诗斌
罗林
黄飞
闫爱华
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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Abstract

The invention provides a controllable synthetic method of graphitized carbon spheres with a hollow structure. The controllable synthetic method comprises the following steps of: (1) dissolving a carbon source, soluble metal salts and a catalyst in deionized water according to proportioning, stirring till completely dissolving, transferring to a hydrothermal reaction kettle for hydro-thermal synthesis, and washing, filtering and drying precipitates to obtain primary products; (2) reducing the primary products at a high temperature in a high-temperature reaction furnace under the production of gas; and (3) placing the products obtained through reduction in an acid solution for soaking, and washing, filtering and drying to obtain the graphitizing carbon spheres with the hollow structure. The graphitizing carbon spheres with the hollow structure have the advantages that the morphology is uniform, the carbon shells are of microcellular structures, the interiors of the carbon spheres are of mesoporous support structures, the graphitization degree is good, and the like. The graphitizing carbon spheres can be used in numerous fields of high-efficiency catalytic conversion, energy source storage and transition, medicine release control, matter adsorption and separation and the like. An invented formwork-free hydrothermal synthesis technology is simple and controlled and can be used for large-scale production.

Description

Controllable synthesis method with hollow structure graphitized carbon ball
Technical field
The present invention relates to a kind of synthetic method of nano hollow carbon ball, particularly a kind of controllable synthesis method with hollow structure graphitized carbon ball.
Background technology
The nano hollow carbon ball is a kind of special carbon material, have high chemical stability, lower density, good thermostability and biocompatibility, not only can be used as electrode materials, support of the catalyst, gas storage medium, lubricant, material fractionation by adsorption, drug sensor, medicine and release template of control, artificial cell, preparation other materials etc., also as various fields such as dyestuff, rubber strongthener, lightweight structural materials, attracted increasing concern.
Hollow carbon sphere is mainly by the preparation of methods such as organism Pintsch process, chemical vapour deposition, medium reduction, laser distillation, arc-over, template self-assembly at present.These methods will be carried out under hot conditions usually, long reaction time, and energy consumption is big, and not only apparatus expensive, complicated operation, cost are higher, and hollow ball shape irregularity productive rate low-purity is not high, has directly influenced suitability for industrialized production and the application thereof of hollow carbon sphere.Therefore explore the technology of low temperature mass preparation hollow carbon sphere, not only help to inquire into theoretically the formation mechanism of hollow carbon sphere, and supply raw materials for its performance of research, help to promote the widespread use of hollow ball.
The synthetic method of hollow carbon sphere generally speaking can be concluded and be divided into two classes, template and no template, and wherein template is most widely used general.Its advantage is that pore passage structure and pattern are controlled, can design the hollow material of synthetic different sizes and pattern by size and the shape of adjusting template.It is template that aluminium meso-porous silica core-shell structure ball is mixed in the ZL200910055527.3 employing, and furfuryl alcohol is carbon source, has prepared small-size meso-porous hollow carbon sphere with removing template silicon-dioxide after its polymerization, the carbonization.ZL200910198399.8 provides a kind of vacuum nano to build the method for preparing the magnetic kernel medium hole hollow carbon sphere, based on the mesoporous SiO 2 hollow ball, by the air pressure inside and outside the change hollow ball, the source of iron solution of different concns is injected in the hollow core, after the thermal treatment furfuryl alcohol is poured on the hollow ball, with utilizing sodium hydroxide solution to remove silica template after its polymerization, the carbonization, obtain having the meso-porous hollow carbon sphere of magnetic kernel.In the whole process of preparation, at first to synthesize template and then will remove the material that template is synthesized at last and do not contain template.This has just caused three problems, and one is to synthesize and remove template to cause the production preparation process of whole material loaded down with trivial details, is unfavorable for that large-scale material is synthetic, has increased cost; Another problem is that the hollow material rate ratio is lower; The 3rd, last in removing the process of template, if the strength of materials deficiency that covers may cause structural collapse to cause the synthetic failure of material.
At these shortcomings of template, people explore no template and synthesize hollow carbon material.
ZL200410024700.0, ZL200610027992.2 and ZL200510110213.0 mix the back with metal carbonyls liquid and adopt chemical Vapor deposition process to prepare the nano cages with hollow structure with low-carbon (LC) class organic liquid.Nanjing University's (application number 201210062927.9) is catalyzer with magnesiumcarbonate, adopts chemical Vapor deposition process to prepare the hollow nano cages that nitrogen mixes.Though chemical Vapor deposition process is operated fairly simple, synthetic material shape irregularity, these materials in use tend to show the unstable of structure and the unhomogeneity of performance.Shandong University's (application number 200810015929.6) with oxygen-bearing organic matter as carbon source, the reactor of packing into after mixing with metallic zinc, 500~600 ° of C reactions 4~8 hours obtain the nano hollow carbon ball after pickling.Because adopt metallic zinc as catalyzer and template, the internal diameter variable range of hollow ball is very little.After Heilongjiang University's (application number 201210128545.1) adopts trimeric cyanamide powder and formaldehyde solution hydro-thermal to synthesize again the method for Pintsch process prepared nitrogenous greying hollow carbon sphere, trimeric cyanamide had wherein not only served as template but also as carbon source.Though this method need not be added template and catalyzer in synthetic process, owing to the limitation of trimeric cyanamide powder itself, limited the internal diameter of this hollow carbon sphere equally.ZL200910111112.3 is dissolved in source of iron in the lower alcohol, and mix with the toluene solution that contains tribromophenol or chlorophenesic acid, add the thermal synthesis of nitrogenous source high-temperature water afterwards and obtain the hollow Nano carbon balls of hydroxyl and amino functional, but because the later stage lacks pyroprocessing, be difficult to obtain graphited hollow carbon sphere.
The hot method of solvent (water) is synthetic the have compound of special construction and performance and the effective ways of novel material.Adopt water or organic solvent as reaction medium, mixing raw material reacts, and obtains carbon material behind the high temperature cabonization.(Nano-architecturesoforderedhollowcarbonspheresfilledwith carbonwebsby template-freecontrollablesynthesis such as Hu Zhuofeng, ZhuofengHu, etal.Nanotechnology, 2012,23 (48): be raw material with glucose and sodium stannate 1-10.), hydro-thermal has been synthesized the hollow carbon sphere of Adjustable structure.But the carbon ball that this synthetic method obtains does not have graphite carbon to be existed.
Summary of the invention
It is simple that the object of the invention provides a kind of technology, with low cost, the controllable synthesis method with hollow structure graphitized carbon ball that product purity is high.
The object of the present invention is achieved like this, this controllable synthesis method, and step is:
Step (1) hydrothermal preparation nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in the deionized water according to mol ratio, are stirred to fully that to be transferred to the hydrothermal reaction kettle hydro-thermal after the dissolving synthetic, sediment undergoes washing, filtration, drying with obtaining obtain primary products;
The high temperature reduction of step (2) carbon ball
In high temperature reaction stove with the primary products high temperature reduction under gas shield that obtains;
Step (3) preparation hollow plumbago carbon ball
After the product that high temperature reduction is obtained places acidic solution to soak, cleaning, filtration, drying, the graphitized carbon ball that namely obtains having hollow structure;
Carbon source in the step (1) is organic carbon source, as wherein any one of glucose, sucrose, chitosan, urea, thiocarbamide, polyvinyl alcohol, polyoxyethylene glycol, polystyrene, phenol, Resorcinol, polyacrylonitrile or toluene;
Soluble metallic salt in the step (1) is the metal-salt of stanniferous or the metal-salt that contains zinc, dissolves in pure water or acidity or the basic solution of 20~100 ° of C; Wherein the metal-salt of stanniferous is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; The metal-salt that contains zinc is wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
Described catalyzer in the step (1) is the metal-salt of iron content or contains the metal-salt of cobalt or nickeliferous metal-salt, dissolves in pure water or acidity or the basic solution of 20~100 ° of C; The metal-salt of described iron content is wherein any one of iron(ic) chloride, ferric sulfate, iron nitrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ironic acetate, ferric fluoride, ferric ammonium citrate, ironic citrate or Hexacyanoferrate potassium; The described metal-salt that contains cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Xiao Suangu, ammonium cobaltous sulfate or sodium cobaltinitrite; Nickeliferous metal-salt is wherein any one of nickelous bromide, nickelous acetate, single nickel salt, nickelous chloride, nickel ammonium sulfate, nickelous nitrate, nickel sulfamic acid, nickelous fluoride or nickelous carbonate;
The proportioning of the carbon source in the step (1), soluble metallic salt, catalyzer is mol ratio 5~300:1:0.1~50; Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product;
Hydro-thermal synthesis temperature in the step (1) is 100~300 ℃, hydro-thermal generated time 2~36 hours;
The reagent that is used in step (1) and the step (3) cleaning is the deionized water of acetone or alcohol or 20~100 ° of C, and purging method is filtration or centrifugal, and drying is 1~24 hour under 60~300 ° of C vacuum-dryings or protection of inert gas; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, the helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in the step (2) is a kind of or its mixture in nitrogen, argon gas, helium, hydrogen, the ammonia, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium, hydrogen, ammonia is more than or equal to 99.99%, and gas flow is 5~500 ml/min;
Step (2) but in the high temperature reaction stove time variable control heat up, can feed gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cool off; Sample is placed the middle section of high temperature reaction stove, and High Temperature Furnaces Heating Apparatus can be retort furnace, tube furnace or microwave oven, and cavity material can be quartz, corundum, pottery, stainless steel or insulating brick;
The temperature of high temperature reduction is 500~3200 ° of C in the step (2), and the recovery time is 0.1~36 hour, and heat-up rate is 0.1~50 ° of C of per minute;
Acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid iodide, bromic acid, perchloric acid, Periodic acid, hyperbromic acid, permanganic acid, dichromic acid strong inorganic acid and mixes aqueous acid in the step (3), guarantees that the pH value of solution value is less than mixing with arbitrary proportion under 7 the prerequisite;
The product that earlier high temperature reduction is obtained before soaking in the step (3) and acidic solution are ultrasonic or mix to being uniformly dispersed, and soak 0.1~48 hour in 20~100 ° of C temperature ranges, then mixed solution are diluted cleaning and filtering, and filtrate recycling recycling.
Beneficial effect, owing to adopted such scheme, the preparation method of this hollow structure graphitized carbon ball, products obtained therefrom purity height, free from foreign meter substantially, pattern is even, the carbon shell has microvoid structure, carbon ball inside has the mesoporous carbon supporting structure, degree of graphitization is good.By regulating the ratio that carbon source and ratio or the kind of soluble metallic salt are controlled the inner/outer diameter of hollow carbon sphere, and micropore and mesoporous ratio.By ratio and the high temperature reduction temperature control degree of graphitization of adjusting catalyzer.Soluble metallic salt and catalyzer as presoma are cheap, and recycling easily can reduce cost environmental protection.Hollow structure graphitized carbon ball has and the diverse characteristic of conventional graphite material, can be used as support of the catalyst and be used for the efficient catalytic conversion, be used for energy storage and conversion as electrode materials, be used for medicine as pharmaceutical carrier and release control, being used for storage hydrogen as the gas storage medium separates with gas trapping, as filtering adsorbing material be used for separating substances, as template for the preparation of other nano materials, as electrode materials, be used for various fields such as rubber and resin enhancing as conductive agent as the lightweight strongthener.
Advantage: technology is simple, with low cost, the product purity height, the hollow structure graphitized carbon ball that makes have pattern evenly, the carbon shell has that microvoid structure, carbon ball inside have the mesoporous carbon supporting structure, degree of graphitization is good, can be used for efficient catalytic conversion, energy storage and conversion, medicine is released control, material fractionation by adsorption, atmosphere storage various fields.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 70 ° of C vacuum-dryings of reaction product after 12 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 25 ° of C of 12mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 224 nanometers, internal diameter 140 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 420 square metres of every grams of specific surface area, the greying ratio is 98.9%.
The soluble metallic salt that adds is the metal-salt of stanniferous or the metal-salt that contains zinc, and the fusing point of this two classes salt is very low, flows out from the carbon shell easily during heat, forms to have mesoporous hollow carbon.
Adding catalyzer is in order to reduce graphitization temperature, to reach the purpose that cuts down the consumption of energy.
Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product.
Control heat-up rate well, the too fast structure that can not obtain wishing of heat-up rate, heat-up rate is crossed slowly can cause energy dissipation.
The acidic solution that adopts can not produce destruction to the structure of graphitized carbon material, therefore do not have concentration limit, but had better not use strong solution, but concentration can not be too low, otherwise can cause the removal decrease in efficiency.
Embodiment 2: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 3 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 25 ° of C of 12mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 94 nanometers, internal diameter 71 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 521 square metres of every grams of specific surface area, the greying ratio is 97.8%.
Embodiment 3: at first with 4.0 gram glucose, 0.21 gram sodium stannate, 0.22 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 9 hours are filtered reaction product, remove impurity with 50 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 25 ° of C of 12mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 125 nanometers, internal diameter 104 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 530 square metres of every grams of specific surface area, the greying ratio is 98.7%.
Embodiment 4: at first with 4.0 gram glucose, 1.07 gram sodium stannates, 1.08 gram iron(ic) chloride, mol ratio 5:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 150 ° of C vacuum-dryings of reaction product after 2 hours, place 700 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 75 ° of C of 1mol/L sulfuric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 123 nanometers, internal diameter 115 nanometers, the ratio of external diameter/internal diameter is 1.1, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 572 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 5: at first with 8.0 gram glucose, 0.24 gram sodium stannate, 0.24 gram iron(ic) chloride mol ratio 50:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 6 hours except detin and iron by 50 ° of C of 15mol/L nitric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 117 nanometers, internal diameter 65 nanometers, the ratio of external diameter/internal diameter is 1.8, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 594 square metres of every grams of specific surface area, the greying ratio is 98.3%.
Embodiment 6: at first with 6.0 gram glucose, 0.12 gram sodium stannate, 0.36 gram iron(ic) chloride, mol ratio 75:1:3, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, air-cooled to room temperature, soak 2 hours except detin and iron by 80 ° of C of 15mol/L nitric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 200 nanometers, internal diameter 80 nanometers, the ratio of external diameter/internal diameter is 2.5, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 440 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 7: at first with 8.0 gram glucose, 0.12 gram sodium stannate, 0.6 gram iron(ic) chloride, mol ratio 100:1:5, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 900 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 1mol/L perchloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 133 nanometers, internal diameter 45 nanometers, the ratio of external diameter/internal diameter is 3.0, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 498 square metres of every grams of specific surface area, the greying ratio is 97.7%.
Embodiment 8: at first with 10.0 gram glucose, 0.1 gram sodium stannate, 0.5 gram iron(ic) chloride, mol ratio 150:1:5, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 15 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 800 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 5mol/L hyperbromic acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 200 nanometers, internal diameter 67 nanometers, the ratio of external diameter/internal diameter is 3.0, pore size (0.7 nanometer, 1.1 nanometer) mesoporous size 4.7 nanometers, the about 453 square metres of every grams of specific surface area, the greying ratio is 98.3%.
Embodiment 9: at first with 4.0 gram glucose, 0.19 gram stannous sulfate, the 0.29 gram Tripotassium iron hexacyanide, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 8 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 10 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except detin and iron by 80 ° of C of 1mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 224 nanometers, internal diameter 140 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 420 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 10: at first with 8.0 gram sucrose, 0.17 gram zinc acetate, 0.23 gram Cobaltous diacetate, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 6 hours are filtered reaction product, remove impurity with 100 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 20 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except dezincify and cobalt by 80 ° of C of 1mol/L sulfuric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 130 nanometers, internal diameter 85 nanometers, the ratio of external diameter/internal diameter is 1.5, carbon shell pore size (0.9 nanometer, 1.3 nanometers), carbon is examined mesoporous size 5.0 nanometers, the about 451 square metres of every grams of specific surface area, the greying ratio is 99.9%.
Embodiment 11: at first with 8.0 gram sucrose, 0.13 gram zinc chloride, 1.16 gram nickelous acetates, mol ratio 25:1:5, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 50 ° of C washed with de-ionized water.With under 150 ° of C argon shields of reaction product dry 1 hour; place 1200 ° of C heating of high temperature process furnances 0.5 hour again; 10 ° of C per minutes of heat-up rate; 10 milliliters of per minutes of argon flow amount; after naturally cooling to room temperature; soak 1 hour except dezincify and nickel by 80 ° of C of 2mol/L phosphoric acid; obtain having the graphitized carbon ball of hollow structure, its external diameter 100 nanometers, internal diameter 75 nanometers; the ratio of external diameter/internal diameter is 1.3; carbon shell pore size (0.9 nanometer, 1.3 nanometers), carbon is examined mesoporous size 5.0 nanometers; the about 518 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 12: at first with 8.0 gram urea, 0.69 gram tin tetrachloride, 1.1 gram iron(ic) chloride, mol ratio 50:1:2, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reaction after 4 hours is carried out reaction product centrifugal, removes impurity with 100 ° of C washed with de-ionized water.With dry 1 hour of the following 150 ° of C of reaction product nitrogen protection; place 1000 ° of C heating of high temperature process furnances 1 hour again; 10 ° of C per minutes of heat-up rate; 10 milliliters of per minutes of helium gas flow; after naturally cooling to room temperature; soak 1 hour except detin and iron by 80 ° of C of 1mol/L hydrochloric acid; obtain having the graphitized carbon ball of hollow structure, its external diameter 141 nanometers, internal diameter 105 nanometers; the ratio of external diameter/internal diameter is 1.4; carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers; the about 497 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 13: at first with 8.0 gram urea, 0.29 gram zinc sulfate, 2.11 gram cobalt chloride, mol ratio 75:1:5, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 20 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 2 hours except dezincify and cobalt by 50 ° of C of 5mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 135 nanometers, internal diameter 110 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.9 nanometer, 1.3 nanometers), carbon is examined mesoporous size 5.0 nanometers, the about 543 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 14: at first with 8.0 gram thiocarbamides, 1.12 gram sodium stannates, 1.14 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 230 ° of C reactions after 2 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 2 hours, place 1000 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 50 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 1 hour except detin and iron by 80 ° of C of 12mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 107 nanometers, internal diameter 85 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 631 square metres of every grams of specific surface area, the greying ratio is 98.9%.
Embodiment 15: at first with 8.0 gram thiocarbamides, 0.37 gram sodium stannate, 3.33 gram cobalt chloride, mol ratio 75:1:10, deionized water in 40 milliliters, move into 50 milliliters hydrothermal reaction kettle after stirring, 190 ° of C reactions after 2 hours are filtered reaction product, remove impurity with 80 ° of C washed with de-ionized water.With 120 ° of C vacuum-dryings of reaction product after 2 hours, place 1200 ° of C heating of high temperature process furnances 1 hour again, 10 ° of C per minutes of heat-up rate, 15 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 1 hour except detin and cobalt by 50 ° of C of 3mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 133 nanometers, internal diameter 90 nanometers, the ratio of external diameter/internal diameter is 1.5, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 507 square metres of every grams of specific surface area, the greying ratio is 99.9%.
Embodiment 16: at first with 8.0 gram thiocarbamides, 1.12 gram sodium stannates, 1.0 gram cobalt chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 900 ° of C heating of high temperature process furnances 2 hours again, 5 ° of C per minutes of heat-up rate, 10 milliliters of per minutes of hydrogen flowing quantity, after naturally cooling to room temperature, by 5mol/L sulfuric acid/mixed in hydrochloric acid acid, volume ratio 1:3,50 ° of C soak 1 hour except detin and cobalt, obtain having the graphitized carbon ball of hollow structure, its external diameter 143 nanometers, internal diameter 114 nanometers, the ratio of external diameter/internal diameter is 1.3, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 489 square metres of every grams of specific surface area, the greying ratio is 98.3%.
Embodiment 17: at first with 8.0 gram thiocarbamides, 1.12 gram sodium stannates, 5.0 gram cobalt chloride, mol ratio 25:1:5, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 5 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 1300 ° of C heating of high temperature process furnances 0.5 hour again, 5 ° of C per minutes of heat-up rate, 15 milliliters of per minutes of nitrogen flow, recirculated water cools off to room temperature, soak 2 hours except detin and cobalt by 50 ° of C of 2mol/L bromic acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 148 nanometers, internal diameter 123 nanometers, the ratio of external diameter/internal diameter is 1.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 465 square metres of every grams of specific surface area, the greying ratio is 99.8%.
Embodiment 18: at first with 8.0 gram polyoxyethylene glycol, 0.12 gram sodium stannate, 0.13 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 160 ° of C reactions after 12 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of argon flow amount, after naturally cooling to room temperature, soak 2 hours except detin and iron by 50 ° of C of 4mol/L hydrochloric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 330 nanometers, internal diameter 103 nanometers, the ratio of external diameter/internal diameter is 3.2, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 375 square metres of every grams of specific surface area, the greying ratio is 98.3%.
Embodiment 19: at first with 8.0 gram glucose, 0.33 gram zinc acetate, 0.48 gram iron(ic) chloride, mol ratio 25:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 180 ° of C reactions after 4 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 700 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except dezincify and iron by 25 ° of C of 6mol/L nitric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 154 nanometers, internal diameter 107 nanometers, the ratio of external diameter/internal diameter is 1.4, carbon shell pore size (0.9 nanometer, 1.3 nanometers), carbon is examined mesoporous size 5.0 nanometers, the about 476 square metres of every grams of specific surface area, the greying ratio is 97.8%.
Embodiment 20: at first with 8.0 gram sucrose, 0.14 gram potassium stannate, 0.13 gram iron(ic) chloride, mol ratio 50:1:1, be dissolved in 40 milliliters deionized water, move into 50 milliliters hydrothermal reaction kettle after stirring, 170 ° of C reactions after 5 hours are filtered reaction product, remove impurity with 25 ° of C washed with de-ionized water.With 100 ° of C vacuum-dryings of reaction product after 4 hours, place 800 ° of C heating of high temperature process furnances 3 hours again, 5 ° of C per minutes of heat-up rate, 30 milliliters of per minutes of nitrogen flow, after naturally cooling to room temperature, soak 12 hours except detin and iron by 25 ° of C of 5mol/L nitric acid, obtain having the graphitized carbon ball of hollow structure, its external diameter 195 nanometers, internal diameter 124 nanometers, the ratio of external diameter/internal diameter is 1.6, carbon shell pore size (0.7 nanometer, 1.1 nanometers), carbon is examined mesoporous size 4.7 nanometers, the about 433 square metres of every grams of specific surface area, the greying ratio is 98.7%.
The discussion of front and description are giving an example of the specific embodiment of the invention, but they do not mean that the restriction that is subjected to this operation.According to the present invention, many improvement and change apparent to those skilled in the art.Claim comprises all equivalence descriptions, defines scope of the present invention.

Claims (1)

1. controllable synthesis method with hollow structure graphitized carbon ball is characterized in that: this controllable synthesis method, and step is:
Step (1) hydrothermal preparation nucleocapsid structure carbon ball
Carbon source, soluble metallic salt, catalyzer are dissolved in the deionized water according to mol ratio, are stirred to fully that to be transferred to the hydrothermal reaction kettle hydro-thermal after the dissolving synthetic, sediment undergoes washing, filtration, drying with obtaining obtain primary products;
The high temperature reduction of step (2) carbon ball
In high temperature reaction stove with the primary products high temperature reduction under gas shield that obtains;
Step (3) preparation hollow plumbago carbon ball
After the product that high temperature reduction is obtained places acidic solution to soak, cleaning, filtration, drying, the graphitized carbon ball that namely obtains having hollow structure;
Carbon source in the step (1) is organic carbon source, as wherein any one of glucose, sucrose, chitosan, urea, thiocarbamide, polyvinyl alcohol, polyoxyethylene glycol, polystyrene, phenol, Resorcinol, polyacrylonitrile or toluene;
Soluble metallic salt in the step (1) is the metal-salt of stanniferous or the metal-salt that contains zinc, dissolves in pure water or acidity or the basic solution of 20~100 ° of C; Wherein the metal-salt of stanniferous is wherein any one of sodium stannate, potassium stannate, stannous sulfate, stannous oxalate, tindichloride or tin tetrachloride; The metal-salt that contains zinc is wherein any one of zinc acetate, zinc iodide, zinc fluoride, zinc chloride, zinc sulfate, zinc phosphate or zinc nitrate;
Described catalyzer in the step (1) is the metal-salt of iron content or contains the metal-salt of cobalt or nickeliferous metal-salt, dissolves in pure water or acidity or the basic solution of 20~100 ° of C; The metal-salt of described iron content is wherein any one of iron(ic) chloride, ferric sulfate, iron nitrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ferrous sulfate, iron protochloride, ferrous ammonium sulphate, ironic acetate, ferric fluoride, ferric ammonium citrate, ironic citrate or Hexacyanoferrate potassium; The described metal-salt that contains cobalt is wherein any one of Cobaltous diacetate, rose vitriol, cobalt chloride, Xiao Suangu, ammonium cobaltous sulfate or sodium cobaltinitrite; Nickeliferous metal-salt is wherein any one of nickelous bromide, nickelous acetate, single nickel salt, nickelous chloride, nickel ammonium sulfate, nickelous nitrate, nickel sulfamic acid, nickelous fluoride or nickelous carbonate;
The proportioning of the carbon source in the step (1), soluble metallic salt, catalyzer is mol ratio 5~300:1:0.1~50; Under the certain situation of carbon source content, the inner/outer diameter ratio that can regulate hollow ball by the ratio of adjusting soluble metallic salt is by the ratio of regulating catalyzer and the degree of graphitization that the high temperature reduction temperature is adjusted final product;
Hydro-thermal synthesis temperature in the step (1) is 100~300 ℃, hydro-thermal generated time 2~36 hours;
The reagent that is used in step (1) and the step (3) cleaning is the deionized water of acetone or alcohol or 20~100 ° of C, and purging method is filtration or centrifugal, and drying is 1~24 hour under 60~300 ° of C vacuum-dryings or protection of inert gas; Wherein rare gas element is a kind of or its mixture in nitrogen, argon gas, the helium, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium is more than or equal to 99.99%;
Gas in the step (2) is a kind of or its mixture in nitrogen, argon gas, helium, hydrogen, the ammonia, and proportioning is any, and wherein the purity of nitrogen, argon gas, helium, hydrogen, ammonia is more than or equal to 99.99%, and gas flow is 5~500 ml/min;
Step (2) but in the high temperature reaction stove time variable control heat up, can feed gas shield, adopts air-cooled or recirculated water or shallow-layer refrigerated water cool off; Sample is placed the middle section of high temperature reaction stove, and High Temperature Furnaces Heating Apparatus can be retort furnace, tube furnace or microwave oven, and cavity material can be quartz, corundum, pottery, stainless steel or insulating brick;
The temperature of high temperature reduction is 500~3200 ° of C in the step (2), and the recovery time is 0.1~36 hour, and heat-up rate is 0.1~50 ° of C of per minute;
Acidic solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acid iodide, bromic acid, perchloric acid, Periodic acid, hyperbromic acid, permanganic acid, dichromic acid strong inorganic acid and mixes aqueous acid in the step (3), guarantees that the pH value of solution value is less than mixing with arbitrary proportion under 7 the prerequisite;
The product that earlier high temperature reduction is obtained before soaking in the step (3) and acidic solution are ultrasonic or mix to being uniformly dispersed, and soak 0.1~48 hour in 20~100 ° of C temperature ranges, then mixed solution are diluted cleaning and filtering, and filtrate recycling recycling.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101224883A (en) * 2008-02-03 2008-07-23 山东大学 Method for preparing hollow carbon balls
CN101264878A (en) * 2008-04-29 2008-09-17 山东大学 All-purpose technique for preparing nano hollow carbon sphere
CN101314467A (en) * 2008-06-20 2008-12-03 大连理工大学 One-step synthesis method for hollow carbon case
CN102637533A (en) * 2012-04-27 2012-08-15 黑龙江大学 Method for preparing nitrogenous graphitized hollow carbon microspheres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101224883A (en) * 2008-02-03 2008-07-23 山东大学 Method for preparing hollow carbon balls
CN101264878A (en) * 2008-04-29 2008-09-17 山东大学 All-purpose technique for preparing nano hollow carbon sphere
CN101314467A (en) * 2008-06-20 2008-12-03 大连理工大学 One-step synthesis method for hollow carbon case
CN102637533A (en) * 2012-04-27 2012-08-15 黑龙江大学 Method for preparing nitrogenous graphitized hollow carbon microspheres

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHOUFENG HU ET AL: "Nano-architectures of ordered hollow carbon spheres filled with carbon webs by temple-free controllable synthesis", 《NANOTECHNOLOGY》, vol. 23, 6 November 2012 (2012-11-06), pages 1 - 10 *
张慧娟等: "SnO2/中空洋葱状碳纳米复合材料的制备及电化学性能", 《物理化学学报》, vol. 26, no. 5, 31 May 2010 (2010-05-31), pages 1259 - 1263 *

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Application publication date: 20130710