CN104923275B - A kind of method of porous charcoal carried metal carbide - Google Patents
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Abstract
The invention discloses a kind of methods of porous charcoal carried metal carbide, belong to technical field of nanometer material preparation.The characteristic of homogeneous mixture system can be formed under certain condition using ammonium salt or nitride, carbohydrate and metal salt, porous charcoal is formed in situ after dehydration is carbonized, then passing through high-temperature heat treatment makes metal form carbide to prepare the nano metal carbide material for forming porous charcoal load.The present invention can obtain load capacity, particle size and composition loaded nano material controllable simultaneously by synthesis conditions such as feed change proportioning, reaction time and heat treatment temperatures.Entire technique has many advantages, such as that operation is simple, of low cost and abundant raw material is easy to get, and the nano metal carbide material of obtained porous charcoal load has broad application prospects in all various aspects such as Industrial Catalysis, water process and electrochemistry.
Description
Technical field
The present invention provides a kind of methods of porous charcoal carrying transition metal carbide, belong to nano material preparation technology neck
Domain.Excellent urge all is shown in catalytic hydrogenation and dehydrogenation reaction, the isomerization of hydrocarbon and the reactions such as aromatisation and electro-catalysis
Change performance.
Background technology
Nano material refer to be made of superfine crystal grain, characteristic dimension size nanometer scale (~ 100nm) solid material
Material.Nano material possesses the performance not available for many conventional materials, including optical property, electromagnetic property, thermodynamic property,
Quantum mechanics performance etc., due to these performances, nano material is widely used in the fields such as lubrication, photoelectricity, magnetic recording, catalysis.So
And due to its high surface energy, the easily spontaneous reunion of nano particle greatly limits the nano effect of nano material, reduces it
Application field and effect.Therefore nano material generally requires carrier, and porous material is a kind of by being mutually communicated or closed cavity
The material of network structure is constituted, porous charcoal is ideal catalyst carrier, can hinder the reunion of loaded particle, provide
The transfer passage of reaction solution, and the diffusion for generating substance is promoted, big specific surface area contributes to catalyst and reactant
Contact, is one of indispensable important materials in modern industry.The preparation of porous charcoal is generally by hard template method and soft mode
Plate method synthesizes, it is considered to be synthesis porous charcoal most successful and most efficient method.The metal carbide material of porous charcoal load exists
All various aspects such as catalysis, water process, ceramics and electrochemistry all have broad application prospects.
Carbide is to be often referred to metal or the nonmetallic binary compound with carbon composition.It can be divided into gold from attribute of an element
Belong to carbide and non-metallic carbide, there is very high fusing point and hardness, high thermal stability and mechanical stability, be in room
Under temperature almost resistance to various chemical attacks the features such as substance.In addition, it also has the electricity similar with its base metal, magnetism
Matter, exactly these properties make them be widely used in machine cut, mineral mining, manufacture wear-resistant and high-temperature component and core
The fields such as reactor.Metal carbides refer to that metal is combined the compound to be formed with carbon, since the presence of surface carbon changed
The electron surface characteristic for crossing metal, is allowed to the characteristic of the catalyst similar to noble metals such as platinum, ruthenium, iridium, Levy in 1973 etc.
[Levy R B, Boudart M. et al catalysis[J]. science, 1973, 181(4099): 547-549.]
It was found that tungsten carbide has the property of Pt in series reaction, to be increasingly becoming one of the hot spot of catalytic field research.Currently, golden
Belong to carbide catalyst in ammonia synthesis decomposition, the hydrofinishing of oil product, hydrocarbon isomerization, selection plus hydrogen dehydrogenation reaction, methane
It is demonstrated by excellent catalytic performance in the reactions such as partial oxidation and preparing synthetic gas by reforming, F- T synthesis.Meanwhile China is tungsten, molybdenum
Resource big country, tungsten ore reserves account for 55% or more of whole world gross reserves, and the Precious Metals Resources such as China's platinum, palladium are very poor, if
Noble metal problem in short supply can be made up using the abundant metals resources in China, it will generated to Chinese national economy construction
Larger impact.
Traditional method for preparing carbide is developed from powder metallurgy industry, and Jiang G, Zhuang H etc. exists
[Jiang G, Zhuang HCeramics international, 2004, 30(2):185-190.] in by metal, metal
Hydride or metal oxide and suitable carbon react in protective atmosphere or reducing atmosphere, and reaction temperature is usually very high, for
Tungsten carbide, temperature are higher than 1500K.Preparation process is cumbersome, and the product specific surface of preparation is low, purity is low while of high cost.Together
When, preparing carbide, also there are many new methods, mainly there is the hot hydrogen reduction method of high-temperature synthesis, carbon and chemical vapour deposition technique.It is high
Warm synthetic method refers to the volatilizable metal of evaporation or metal oxide in the low pressure vessel of hydrocarbon-containifirst, to be carbonized
Object, [Leclercq L, Imura K, Yoshida S, the et al. Preparation of such as Leclercq L
Catalysts II [J] B. Delmon, Ed, 1978,627.] with the method obtained specific surface area reach 40m2/ g is left
Right WC and MoOxCy, but the shortcomings that this method is that condition is not easy to control, synthetic quantity is small.The hot hydrogen reduction method of carbon is to use metal salt
The impregnated carrier of solution metal under reducibility gas atmosphere is combined to form carbide with carbon source, and Mordenti etc. exists
[Mordenti D, Brodzki D, Journal of solid state chemistry, 1998, 141(1): 114-
120.] in, by ammonium molybdate solution Immesion active carbon, hydrogen temperature programmed reduction is then used, being averaged for Activated Carbon Supported is prepared for
The Mo of grain size 14nm2C, the method preparation condition is mildly easily operated, and the carrier only loaded is restricted.Chemical vapor deposition
Method is to react the technology for generating solid deposited object in gas phase or gas-solid interface using the substance of gaseous state or steam-like.Giraudon
Et al. in [Giraudon J M, Devassine P, Leclercq L, et al. Journal of materials
science,1998, 33(5):1369-1377.] in the metallo-organic compound containing W and C be presoma, in H2Atmosphere
That 600 DEG C of deposition 2h of lower normal pressure are obtained is the W of pure phase hexagonal closs packing2The major advantage of C, this method are that depositing temperature is low.Separately
Outside, the novel preparation method of carbide also has microwave method, thermal decomposition method, ultrasonic synthetic method and solid-state exchange reaction method etc..
In terms of porous charcoal supports the preparation method of nano material, generally also using direct dipping process and microwave chemical
Former method.Direct dipping process is by porous carbon material direct impregnation in metal salt solution, then through drying and being thermally treated resulting in more
The nano material of hole charcoal load.Infusion process is widely used, but the grain size for nano-particle, component and distribution in the carrier
Lack effective regulation and control.Microwave chemical reduction method is that study physics under microwave field action and chemistry using microwave technology anti-
It answers.Cao Yanbing etc. [Cao Yanbing, Hu Guorong etc., Microwave carbothermic Li2FeSiO4/C,
Functional material 2010 (6) .990-993].With Li2CO3, FeOOH, Nano-meter SiO_22For raw material, polyvinyl alcohol and superconduction carbon are carbon source,
Li has been synthesized using microwave carbon thermal synthesis method2FeSiO/C materials.Microwave chemical method research object compares limitation, the metal of bulk
Microwave heating, but metal catalyst powder or particle can not possibly be carried out, microwave heating can be carried out.
In recent years, some research groups report easily has been prepared porous carbon composite material using self-assembly method.
[Liu R, et al. (2007) the .Chemistry of Materials 20 (3) such as Zhao:1140-1146.] with solubility
Phenolic resin is presoma, and the TiO of ordered mesoporous carbon load is obtained by organic and inorganic self assembly2With TiC composite materials.Yao
Deng [Yao J, et al. (2009) .Carbon47 (2):436-444.] using resorcinol as carbon source, magnetic has directly been prepared
Separable ordered mesoporous carbon/Ni the composite materials of property.[Ji Z., et al. (2009) .Carbon 47 (9) such as Ji: 2194-
2199.] it is total to assemble method using three components, is prepared for ordered mesoporous carbon/Ru composite materials of high-specific surface area, and have studied it
Catalytic action to benzene hydrogenation.This method for synthesis of silica-base material it is very ripe, but synthesize carbon material still need into
One step is furtherd investigate, and this method is difficult to be widely used in the preparation that various charcoals carry metal/metal oxide composite material.
That often there is synthetic routes is long for the synthetic method of traditional porous charcoal load nano material, and template agent is of high cost,
The problems such as post-processing is seriously polluted, thus be difficult to realize mass produce.The pore passage structure of high-area carbon, and the metal that supports
Or the parameters such as size, component, crystalline phase and loading of metal carbides are difficult to be controlled simultaneously.In addition, prior synthesizing method
Since the limitation of preparation method can not be widely used in the preparation of various nano metal carbides.Therefore, exploitation is a kind of simple
It is easy, the preparation method of efficient porous charcoal carried metal carbide composite material, and charcoal can be controlled in the synthesis process
The parameters such as the pore passage structure of carrier and the size of nano-particle, component, crystalline phase and loading, for answering extensively for such material
With great impetus will be generated.
Invention content
It is an object of the invention to develop a kind of simple pervasive easy porous charcoal carried metal carbide composite material
Preparation method, this method can be widely suitable for the synthesis of numerous charcoal carried metal carbide.
The present invention utilizes carbon source, ammonium salt（Or nitride）It forms molten homogeneous system under certain condition with metal salt, makes
Metal salt is obtained to be evenly distributed in mixed system.Secondly heating mixed system makes carbohydrate be carbonized to obtain porous charcoal, and metal is promoted to live
Property component be evenly distributed in porous charcoal, and under protection gas or reducing atmosphere after high-temperature heat treatment, last gained sample is logical
Cross porous charcoal carried metal carbide composite material.
The present invention specific implementation step be：A kind of method of porous charcoal supported nano-gold category carbide material, under
State step progress：
1）By carbon source and ammonium salt（Or nitride）By 1:100~100:1 mass ratio, ammonium salt（Or nitride）With metal salt
According to 1:10~10:1 mass ratio mixes and milled processed, forms uniform reaction system；
2）By step（1）In obtained homogeneous system at a temperature of 500-1000 DEG C, and in protection gas or reducibility gas
Middle heat treatment 5-10h so that carbon source dehydration carbonization, and react generation metal carbides and obtain dark brown solid, i.e. porous charcoal
The metal carbide material of load.
In above-mentioned technical proposal, it is preferable that step（1）The metal salt be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
Nitrate, halide, the secondary chlorine of Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg
At least one of hydrochlorate, acetate, oxalates, phosphate or sulfate；
In above-mentioned technical proposal, it is preferable that step（1）Middle carbon source is glucose, fructose, sucrose, maltose, lactose, shallow lake
At least one of powder and dextrin.
In above-mentioned technical proposal, it is preferable that step（1）Middle ammonium salt or nitride are the organic nitrogen-contg. compounds such as urea element, guanidine, amidine
At least one of object.
In above-mentioned technical proposal, step（1）The mass ratio of middle carbon source and ammonium salt is 1:100~100:1, it is preferable that carbon source and
The mass ratio of ammonium salt is 20:1；Step（2）The mass ratio of middle carbon source and metal salt is 1:10~10:1, it is preferable that carbon source and metal
The mass ratio of salt is 1:5；
In above-mentioned technical proposal, it is preferable that step（2）Described in protection gas be nitrogen, argon gas, at least one in helium
Kind；Step（2）Described in the gaseous mixture that reducibility gas is hydrogen or carbon monoxide volume fraction is 5% ~ 10%, gaseous mixture
In Balance Air be at least one of nitrogen or argon gas.
The present invention utilizes carbon source, ammonium salt（Nitride）Form molten homogeneous system under certain condition with metal salt so that
Metal salt is evenly distributed in mixed system.Later, at high temperature so that carbon source dehydration is carbonized, while metal component is uniformly distributed
In high-area carbon and carbide is formed, charcoal carried metal carbide is obtained finally by high-temperature heat treatment.The present invention can be used for
Numerous metal carbide materials are loaded, size is 5-100 nm and monodispersity is high, by adjusting synthesis condition, can be controlled
Composition and loading of metal carbides etc..The synthetic method belongs to anhydrous system, can to avoid prior synthesizing method due to
Metal salt solution hydrolyze and caused by synthesize it is difficult.In addition, the present invention also has synthetic route simply and the advantages such as of low cost,
Therefore possess huge application prospect in all various aspects such as Industrial Catalysis, water process.
Description of the drawings
Fig. 1 is that porous charcoal made from embodiment 1 loads Mo2The XRD diagram of C.
Fig. 2 is that porous charcoal made from embodiment 1 loads Mo2The TEM of C schemes.
Fig. 3 is that porous charcoal made from embodiment 10 loads Fe3The XRD diagram of C.
Fig. 4 is that porous charcoal made from embodiment 10 loads Fe3The TEM of C schemes.
Fig. 5 is embodiment 2, the porous charcoal of different material ratio made from example 3 and example 4 loads Mo2The XRD diagram of C.
Specific implementation mode
With reference to specific embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto.
Embodiment 1：Porous charcoal loads Mo2C
Synthesis material：Glucose, urea element, ammonium molybdate
（1）Weigh 1 g glucose, 0.01 g ureas element and 0.1g H24Mo7N6O24·4H2O in a 100 mL beakers,
Later by beaker drug with uniformly, and forming molten condition at a certain temperature after mortar grinder 20min；
（2）It will（1）Described in mixture as in crucible slot, be placed in tube furnace, by sample at 800 DEG C, N2Condition
Lower calcining 5 hours, obtains dark brown bulk solids, and it is that porous charcoal loads molybdenum carbide to measure XRD（Mo2C）.
Embodiment 2：Porous charcoal loads Mo2C
Synthesis material：Glucose, urea element, ammonium molybdate
（1）Weigh 0.02 g glucose, 2 g ureas elements and 0.2g H24Mo7N6O24·4H2O in a 100 mL beakers,
Later by beaker drug with after mortar grinder 30min uniformly, be thermally formed molten condition；
（2）It will（1）Described in mixture as in crucible slot, be placed in tube furnace, by sample at 800 DEG C, N2Item
It is calcined 6 hours under part, obtains dark brown bulk solids, it is that porous charcoal loads molybdenum carbide to measure XRD（Mo2C）, display sample carbonization
Object grain size is about 6nm.
Embodiment 3：Porous charcoal loads Mo2C
Synthesis material：Glucose, urea element, ammonium molybdate
（1）Weigh 0.03 g glucose, 0.3 g ureas element and 3g H24Mo7N6O24·4H2O in a 100 mL beakers,
Heating stirring forms molten condition；
（2）It will（1）Described in mixture as in crucible slot, be placed in tube furnace, by sample at 800 DEG C, N2Item
It is calcined 6 hours under part, obtains dark brown bulk solids, it is that porous charcoal loads molybdenum carbide to measure XRD（Mo2C）.
Experimental example 4：Porous charcoal loads Mo2C
（1）2 g glucose, 0.1g ureas element are weighed in a 100 mL beakers, heating stirring is uniform, then weighs 0.5g
H24Mo7N6O24·4H2O continues heating stirring, forms molten condition；
（2）It will（1）Described in mixture as in crucible slot, be placed in tube furnace, by sample at 800 DEG C, N2Item
It is calcined 6 hours under part, obtains dark brown bulk solids, grind and handle, it is that porous charcoal loads molybdenum carbide to measure XRD（Mo2C）.
Experimental example 5：Porous charcoal load C oC
Synthesis material：Glucose, urea element, Co (NO3)2·6H2O（Cobalt nitrate）
（1）Weigh 10g glucose, 0.1g ureas element, 0.01 g Co (NO3)2·6H2O is in a 100 mL beakers, later
Reagent in beaker is persistently ground into 10 min until drug forms molten condition in beaker with mortar.
（2）Mixture in beaker is placed in as in small crucible in quartz ampoule later, in 5%H2In 700 under the conditions of/Ar
It is heat-treated 7 hours at DEG C, obtains dark brown bulk solids, XRD is shown as the cobalt carbide of porous charcoal load（CoC）.
Experimental example 6：Porous charcoal loads WC
Synthesis material：Fructose, guanidine, (NH4)10H2 (W2O7)6（Ammonium tungstate）
（1）100 g fructose and 1 g guanidines are weighed in a 100 mL beakers, material in the cup mortar grinder will be burnt later
30min, heating stirring form melting mixing state.
（2）It weighs and 7g (NH4)10H2 (W2O7)6It is added（1）Described in mixed system, persistently stir 10min；
（3）Later, substance is put in crucible, is placed in tube furnace at 1000 DEG C, in N2Under the conditions of be heat-treated 8 hours, obtain
WC is loaded to porous charcoal（Tungsten carbide）.
Experimental example 7：Porous charcoal loads ZrC
Synthesis material：Lactose, guanidine, Zr (NO3) 45H2O（Zirconium nitrate）
（1）10 g lactose and 2 g guanidines are weighed in a 100 mL beakers, material in the cup mortar grinder will be burnt later
20min forms melting mixing state.
（2）It weighs and is added with 0.1g Zr (NO3) 45H2O（1）Described in mixed system, persistently grind 5min；
（3）Later, substance is put in crucible, is placed in tube furnace at 800 DEG C, 5%H2It is heat-treated 10 hours under the conditions of/Ar,
Obtain porous charcoal load ZrC（Zirconium carbide）.
Experimental example 8：Porous charcoal loads TaC
Synthesis material：Starch, urea element, ethanol tantalum
（1）15g starch, 1 g ureas element and 0.8g ethanol tantalums are weighed in a 100 mL beakers, material in the cup will be burnt later
With mortar grinder 30min, melting mixing state is formed.
（2）Later, substance is put in crucible, is placed in tube furnace at 850 DEG C, 5%H2It is heat-treated 6 hours under the conditions of/Ar,
Obtain porous charcoal load TaC（Ramet）.
Experimental example 9：Porous charcoal supported V C
Synthesis material：Fructose, guanidine, NH4VO3（Ammonium metavanadate）
（1）5g fructose, 0.7g guanidines and 1g ammonium metavanadates are weighed in a 100 mL beakers, material in the cup will be burnt later and used
Mortar grinder 10min forms molten state.
（2）Later, substance is put in crucible, is placed in tube furnace at 800 DEG C, in N2Under the conditions of be heat-treated 7 hours, obtain
Porous charcoal supported V C（Vanadium carbide）.
Experimental example 10：Porous charcoal loads Fe3C
Synthesis material：Fructose, urea element, Fe (NO3)2·9H2O（Ferric nitrate）
（1）Weigh 1g fructose, 0.1g ureas element and 1g Fe (NO3)2·9H2O is in a 100 mL beakers, later by beaker
Middle substance mortar grinder 10min, heating stirring forms molten state at 120 DEG C.
（2）Later, substance is put in crucible, is placed in tube furnace at 800 DEG C, in N2Under the conditions of be heat-treated 7 hours, obtain
Porous charcoal loads Fe3C（Cementite）.
Experimental example 11：Porous charcoal loads Fe3C
Synthesis material：Glucose, urea element, Fe (NO3)2·9H2O（Ferric nitrate）
（1）Weigh 0.5g glucose, 2g ureas element and 1g Fe (NO3)2·9H2O is in a 100 mL beakers, at 100 DEG C
Lower heating stirring forms molten state.
（2）Later, substance is put in crucible, is placed in tube furnace at 850 DEG C, in 5%H2Heat treatment 6 is small under the conditions of/Ar
When, obtain porous charcoal load Fe3C（Cementite）.
Claims (4)
1. a kind of method of porous charcoal supported nano-gold category carbide material, it is characterised in that carry out as steps described below：
（1）Carbon source, nitride are pressed 1:100~100:1 mass ratio, carbon source is with metal salt according to 1:10~10:1 mass ratio is mixed
Close placed in the vessel, stirring 10-60 min under the conditions of certain temperature so that the complete melting mixing of solid forms uniform body
System；Wherein, carbon source is at least one of glucose, fructose, sucrose, maltose, lactose, starch and dextrin；Nitride is urea
At least one of element, guanidine, amidine；
（2）By step（1）In obtained mixture be heat-treated 5-10h at a temperature of 500-1000 DEG C so that carbon source dehydration carbonization
Obtain dark brown solid；The heat treatment process protects gas or reducing atmosphere to enclose lower progress in inertia；
（3）By step（2）In dark brown solid obtained suitably ground, obtain porous charcoal load nano metal carbide
Material.
2. a kind of method of porous charcoal supported nano-gold category carbide material according to claim 1, it is characterised in that its
Middle step（1）The metal salt be selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag,
Nitrate, halide, hypochlorite, acetate, oxalates, phosphate or the sulphur of Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg
At least one of hydrochlorate.
3. a kind of method of porous charcoal supported nano-gold category carbide material according to claim 1, it is characterised in that its
Middle step（1）The mass ratio of middle carbon source and nitride is 20:1；The mass ratio of carbon source and metal salt is 1:5；Step（2）Described in
Heat treatment temperature be 800 DEG C；The heat treatment time is 5h.
4. a kind of method of porous charcoal supported nano-gold category carbide material according to claim 1, it is characterised in that its
Middle step（2）Described in protection gas be nitrogen, argon gas, at least one of helium；Step（2）Described in reducibility gas
The gaseous mixture for being 5% ~ 10% for hydrogen or carbon monoxide volume fraction, the Balance Air in gaseous mixture be in nitrogen or argon gas extremely
Few one kind.
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