CN104923275A - Method for preparing porous carbon supported metal carbide - Google Patents
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Abstract
The inventiondiscloses a method for preparing porous carbon supported metal carbide, and belongs to the technical field of nano-material preparation. The method utilizes the characteristic that a uniformly mixed system can be formed between an ammonium salt, a nitride or a saccharide and a metal salt, and comprises the following steps: carrying out dehydration and carbonization to form porous carbon in situ; carrying out high-heat treatment to ensure that metal is converted into a carbide, namely the porous carbon supported metal carbide material. Through change of synthesis conditions such as raw material ratio, reaction time and heat treatment temperature, the capacity, the particle size and the composition of the obtained supported nanomaterial can be controlled simultaneously. The method has the advantages that the whole process is simple to operate and easy to apply; the cost is low; the raw materials are rich and easy to get; the obtained porous carbon supported metal carbide material is wide in application prospect in various fields such as industrial catalysis, water treatment and electrochemistry.
Description
Technical field
The invention provides a kind of method of porous charcoal carrying transition metal carbide, belong to technical field of nanometer material preparation.Excellent catalytic performance is all shown in the isomerization and the reaction such as aromatisation and electro-catalysis of catalytic hydrogenation and dehydrogenation reaction, hydrocarbon.
Background technology
Nano material refer to be made up of superfine crystal grain, characteristic dimension size is at the solid material of nanometer scale (~ 100nm).Nano material has the performance not available for many conventional materials, and comprise 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.But due to its high surface energy, the very easily spontaneous reunion of nano particle, greatly limit the nano effect of nano material, reduces its application and effect.Therefore nano material often needs carrier, porous material is a kind of material being made up of network structure mutually through or closed cavity, porous charcoal is ideal catalyst carrier, the reunion of institute's loaded particle can be hindered, the transfer passage of reaction solution is provided, facilitate again and generate the diffusion of material, large specific area contributes to contacting of catalyst and reactant, is one of indispensable important materials in modern industry.The preparation of porous charcoal is generally by hard template method and soft template method synthesis, is considered to the most successful and most effective method of synthesizing porous charcoal.The metal carbide material of porous charcoal load all has broad application prospects in all many-sides such as catalysis, water treatment, pottery and electrochemistry.
Carbide is often referred to metal or the nonmetal binary compound formed with carbon.Can be divided into metal carbides and non-metallic carbide from attribute of an element, have very high fusing point and hardness, high heat endurance and mechanical stability, be the material of the at room temperature almost feature such as resistance to various chemical attacks.In addition, it also has the electricity similar with its base metal, magnetic property, and these character make them be widely used in the wear-resistant and field such as high-temperature component and nuclear reactor of machine cut, mineral mining, manufacture just.Metal carbides refer to that metal is combined the compound formed with carbon, existence due to surface carbon changes the electron surface characteristic of transition metal, make it the characteristic of the catalyst being similar to the noble metals such as platinum, ruthenium, iridium, [the Levy R B such as Levy in 1973, Boudart M. et al catalysis [J]. science, 1973,181 (4099): 547-549.] find that tungsten carbide has the character of Pt in series reaction, thus become one of focus of catalytic field research gradually.At present, metal carbide catalyst has showed excellent catalytic performance in the hydrofinishing of ammonia synthesis decomposition, oil product, hydrocarbon isomerization, selec-tive hydrogenation dehydrogenation reaction, methane portion oxidation and the reaction such as preparing synthetic gas by reforming, F-T synthesis.Simultaneously, China is tungsten, Mo resource big country, tungsten ore reserves account for more than 55% of whole world gross reserves, and the Precious Metals Resources such as China's platinum, palladium are very poor, if the abundant metals resources of China can be utilized to make up noble metal problem in short supply, considerable influence will be produced to Chinese national economy construction.
Traditional method preparing carbide develops from powder metallurgy industry; Jiang G; Zhuang H etc. are at [Jiang G; Zhuang HCeramics international; 2004,30 (2): 185-190.] reacted in protective atmosphere or reducing atmosphere by metal, metal hydride or metal oxide and appropriate carbon in, reaction temperature is usually very high; for tungsten carbide, temperature is higher than 1500K.Preparation process is loaded down with trivial details, and the product specific surface of preparation is low, purity is low, and cost is high simultaneously.Meanwhile, preparing carbide also has many new methods, mainly contains high-temperature synthesis, the hot hydrogen reduction method of carbon and chemical vapour deposition technique.High-temperature synthesis refers to the low pressure vessel volatilizable metal of interior evaporation or metal oxide that are used in hydrocarbon-containifirst, thus obtain carbide, [the Leclercq L such as Leclercq L, Imura K, Yoshida S, et al. Preparation of Catalysts II [J]. B. Delmon, Ed, 1978,627.] obtain specific area by the method and reach 40m
2wC and MoO of about/g
xc
y, but the shortcoming of this method to be condition wayward, synthetic quantity is little.The hot hydrogen reduction method of carbon is combined with carbon source with the impregnated carrier of metal salt solution metal under reducibility gas atmosphere to form carbide, Mordenti etc. are at [Mordenti D, Brodzki D, Journal of solid state chemistry, 1998,141 (1): 114-120.] in, by ammonium molybdate solution Immesion active carbon, then use hydrogen temperature programmed reduction, prepare the Mo of the average grain diameter 14nm of Activated Carbon Supported
2c, the method preparation condition gentleness is easy to operation, and the carrier of just load is restricted.Chemical vapour deposition technique utilizes the material of gaseous state or steam-like in gas phase or gas-solid interface, react the technology generating solid deposited thing.The people such as Giraudon are at [Giraudon J M, Devassine P, Leclercq L, et al. Journal of materials science, 1998,33 (5): 1369-1377.] metallo-organic compound containing W and C is used to be presoma in, at H
2that under atmosphere, normal pressure 600 DEG C deposition 2h obtains is the W of pure phase hexagonal closs packing
2c, the major advantage of the method is that depositing temperature is low.In addition, the novel preparation method of carbide also has microwave method, thermal decomposition method, ultrasonic synthetic method and solid-state exchange reaction method etc.
In the preparation method supporting nano material in porous charcoal, what generally adopt is direct dipping process and microwave chemical reducing process.Direct dipping process is by porous carbon material direct impregnation in metal salt solution, and then drying and heat treatment obtain the nano material of porous charcoal load.Infusion process is widely used, but lacks effective regulation and control for the particle diameter of nano particle, component and distribution in the carrier.Microwave chemical reducing process utilizes microwave technology to study the physical and chemical reaction under microwave field effect.Cao Yanbing etc. [Cao Yanbing, Hu Guorong etc., Microwave carbothermic Li2FeSiO4/C, functional material 2010 (6) .990-993].With Li
2cO
3, FeOOH, Nano-meter SiO_2
2for raw material, polyvinyl alcohol and superconduction carbon are carbon source, adopt microwave carbon thermal synthesis method to synthesize Li
2feSiO/C material.Microwave chemical method research object compares limitation, and the metal of bulk can not carry out heating using microwave, but metal catalyst powder or particle, can heating using microwave be carried out.
In recent years, some research groups report and adopt self-assembly method to prepare porous carbon composite material easily.Zhao etc. [Liu R, et al. (2007) .Chemistry of Materials 20 (3): 1140-1146.] are presoma with resol resin, are obtained the TiO of ordered mesoporous carbon load by organic and inorganic self assembly
2with TiC composite.Yao etc. [Yao J, et al. (2009).
carbon
47 (2): 436-444.] take resorcinol as carbon source, directly prepared magnetic separable ordered mesoporous carbon/Ni composite.Ji etc. [Ji Z., et al. (2009).
carbon 47 (9): 2194-2199.] adopt three components altogether assemble method, prepare the ordered mesoporous carbon/Ru composite of high-specific surface area, and have studied its catalytic action to benzene hydrogenation.The method is very ripe for the synthesis of silica-base material, but synthesis material with carbon element still needs further further investigation, and the method is difficult to be widely used in the preparation that various charcoal carries metal/metal oxide composite.
It is long that the synthetic method of traditional porous charcoal loaded with nano material often also exists synthetic route, and the problems such as template agent cost is high, and post-processed is seriously polluted, are thus difficult to realize large-scale production.The pore passage structure of high-area carbon, and the parameter such as the size of the metal supported or metal carbides, component, crystalline phase and loading is difficult to be controlled simultaneously.In addition, prior synthesizing method can not be widely used in the preparation of various nano metal carbide due to the restriction of preparation method.Therefore, exploitation is a kind of simple, the preparation method of efficiency much higher hole charcoal carried metal carbide composite material, and the pore passage structure of high-area carbon and size, component, the parameter such as crystalline phase and loading of nano particle can be controlled in building-up process, the extensive use for such material will produce great impetus.
Summary of the invention
The object of the invention is to the preparation method developing a kind of simple pervasive easy porous charcoal carried metal carbide composite material, the method can be applicable to the synthesis of numerous charcoal carried metal carbide widely.
The present invention utilizes carbon source, ammonium salt (or nitride) and slaine to form molten homogeneous system under certain condition, and slaine is evenly distributed in mixed system.Secondly heating mixed system makes carbohydrate carbonization obtain porous charcoal, impels metal active constituent to be evenly distributed in porous charcoal, and under protection gas or reducing atmosphere after high-temperature heat treatment, last gained sample is by porous charcoal carried metal carbide composite material.
Specific embodiment of the invention step is: a kind of method of porous charcoal loaded with nano metal carbide material, carries out according to following step:
1) by carbon source and ammonium salt (or nitride) mass ratio by 1:100 ~ 100:1, ammonium salt (or nitride) mixes and milled processed according to the mass ratio of 1:10 ~ 10:1 with slaine, forms uniform reaction system;
2) by the homogeneous system that obtains in step (1) at 500-1000 DEG C of temperature; and protecting heat treatment 5-10h in gas or reducibility gas; make carbon source dehydration carbonization, and reaction generation metal carbides obtain dark brown solid, i.e. the metal carbide material of porous charcoal load.
In technique scheme, preferably, the slaine described in step (1) is selected from least one in the nitrate of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, halide, hypochlorite, acetate, oxalates, phosphate or sulfate;
In technique scheme, preferably, in step (1), carbon source is at least one in glucose, fructose, sucrose, maltose, lactose, starch and dextrin.
In technique scheme, preferably, in step (1), ammonium salt or nitride are at least one in the nitrogen-containing organic compounds such as urea element, guanidine, amidine.
In technique scheme, in step (1), the mass ratio of carbon source and ammonium salt is 1:100 ~ 100:1, and preferably, the mass ratio of carbon source and ammonium salt is 20:1; In step (2), the mass ratio of carbon source and slaine is 1:10 ~ 10:1, and preferably, the mass ratio of carbon source and slaine is 1:5;
In technique scheme, preferably, the protection gas described in step (2) is at least one in nitrogen, argon gas, helium; Reducibility gas described in step (2) is hydrogen or carbon monoxide volume fraction is the gaseous mixture of 5% ~ 10%, and the Balance Air in gaseous mixture is at least one in nitrogen or argon gas.
The present invention utilizes carbon source, ammonium salt (nitride) and slaine to form molten homogeneous system under certain condition, and slaine is evenly distributed in mixed system.Afterwards, at high temperature make carbon source to dewater carbonization, simultaneously metal component to be evenly distributed in high-area carbon and to form carbide, obtains charcoal carried metal carbide finally by high-temperature heat treatment.The present invention may be used for the numerous metal carbide material of load, and it is of a size of 5-100 nm and monodispersity is high, by regulating synthesis condition, can control the composition of metal carbides and loading etc.This synthetic method belongs to anhydrous system, can avoid the synthesis difficulty that prior synthesizing method causes due to metal salt solution hydrolysis.In addition, the present invention also has the advantages such as synthetic route is simple and with low cost, therefore has huge application prospect in all many-sides such as Industrial Catalysis, water treatment.
Accompanying drawing explanation
Fig. 1 is the porous charcoal load Mo that embodiment 1 obtains
2the XRD figure of C.
Fig. 2 is the porous charcoal load Mo that embodiment 1 obtains
2the TEM figure of C.
Fig. 3 is the porous charcoal load Fe that embodiment 10 obtains
3the XRD figure of C.
Fig. 4 is the porous charcoal load Fe that embodiment 10 obtains
3the TEM figure of C.
Fig. 5 is the porous charcoal load Mo of the different material ratio that embodiment 2, example 3 and example 4 obtains
2the XRD figure of C.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but protection scope of the present invention is not limited thereto.
Embodiment 1: porous charcoal load Mo
2c
Synthesis material: glucose, urea element, ammonium molybdate
(1) 1 g glucose, 0.01 g urea element and 0.1g H is taken
24mo
7n
6o
244H
2o in 100 mL beakers, afterwards by beaker medicine with after mortar grinder 20min evenly, and form molten condition at a certain temperature;
(2) by mixture described in (1) as in crucible groove, and be placed in tube furnace, by sample at 800 DEG C, N
2calcine 5 hours under condition, obtain pitchy bulk solids, recording XRD is porous charcoal load molybdenum carbide (Mo
2c).
Embodiment 2: porous charcoal load Mo
2c
Synthesis material: glucose, urea element, ammonium molybdate
(1) 0.02 g glucose, 2 g urea element and 0.2g H are taken
24mo
7n
6o
244H
2o in 100 mL beakers, afterwards by beaker medicine with after mortar grinder 30min evenly, add thermosetting molten condition;
(2) by mixture described in (1) as in crucible groove, and be placed in tube furnace, by sample at 800 DEG C, N
2calcine 6 hours under condition, obtain pitchy bulk solids, recording XRD is porous charcoal load molybdenum carbide (Mo
2c), show sample carbide particle diameter is about 6nm.
Embodiment 3: porous charcoal load Mo
2c
Synthesis material: glucose, urea element, ammonium molybdate
(1) 0.03 g glucose, 0.3 g urea element and 3g H is taken
24mo
7n
6o
244H
2o, in 100 mL beakers, adds thermal agitation, forms molten condition;
(2) by mixture described in (1) as in crucible groove, and be placed in tube furnace, by sample at 800 DEG C, N
2calcine 6 hours under condition, obtain pitchy bulk solids, recording XRD is porous charcoal load molybdenum carbide (Mo
2c).
Experimental example 4: porous charcoal load Mo
2c
(1) take 2 g glucose, 0.1g urea element in 100 mL beakers, heating stirs, and then takes 0.5g H
24mo
7n
6o
244H
2o, continues to add thermal agitation, forms molten condition;
(2) by mixture described in (1) as in crucible groove, and be placed in tube furnace, by sample at 800 DEG C, N
2calcine 6 hours under condition, obtain pitchy bulk solids, grind and process, recording XRD is porous charcoal load molybdenum carbide (Mo
2c).
Experimental example 5: porous charcoal load C oC
Synthesis material: glucose, urea element, Co (NO
3)
26H
2o(cobalt nitrate)
(1) 10g glucose, 0.1g urea element, 0.01 g Co (NO is taken
3)
26H
2reagent mortar in beaker, in 100 mL beakers, is continued grinding 10 min until medicine forms molten condition in beaker by O afterwards.
(2) after by mixture in beaker as in monkey, and be placed in quartz ampoule, at 5%H
2heat treatment 7 hours at 700 DEG C under/Ar condition, obtain pitchy bulk solids, XRD is shown as the cobalt carbide (CoC) of porous charcoal load.
Experimental example 6: porous charcoal load WC
Synthesis material: fructose, guanidine, (NH
4)
10h
2(W
2o
7)
6(ammonium tungstate)
(1) take 100 g fructose and 1 g guanidine in 100 mL beakers, afterwards by the mortar grinder 30min of material in beaker, add thermal agitation and form melting mixing state.
(2) take and 7g (NH
4)
10h
2(W
2o
7)
6add in mixed system described in (1), Keep agitation 10min;
(3) after, material is put in crucible, is placed in tube furnace at 1000 DEG C, at N
2heat treatment 8 hours under condition, obtains porous charcoal load WC(tungsten carbide).
Experimental example 7: porous charcoal load ZrC
Synthesis material: lactose, guanidine, Zr (NO3) 45H2O(zirconium nitrate)
(1) take 10 g lactose and 2 g guanidines in 100 mL beakers, afterwards by the mortar grinder 20min of material in beaker, form melting mixing state.
(2) take and add in mixed system described in (1) with 0.1g Zr (NO3) 45H2O, continue grinding 5min;
(3) after, material is put in crucible, is placed in tube furnace at 800 DEG C, 5%H
2heat treatment 10 hours under/Ar condition, obtains porous charcoal load ZrC(zirconium carbide).
Experimental example 8: porous charcoal load TaC
Synthesis material: starch, urea element, ethanol tantalum
(1) take 15g starch, 1 g urea element and 0.8g ethanol tantalum in 100 mL beakers, afterwards by the mortar grinder 30min of material in beaker, form melting mixing state.
(2) after, material is put in crucible, is placed in tube furnace at 850 DEG C, 5%H
2heat treatment 6 hours under/Ar condition, obtains porous charcoal load TaC(ramet).
Experimental example 9: porous charcoal supported V C
Synthesis material: fructose, guanidine, NH
4vO
3(ammonium metavanadate)
(1) take 5g fructose, 0.7g guanidine and 1g ammonium metavanadate in 100 mL beakers, afterwards by the mortar grinder 10min of material in beaker, form molten state.
(2) after, material is put in crucible, is placed in tube furnace at 800 DEG C, at N
2heat treatment 7 hours under condition, obtains porous charcoal supported V C(vanadium carbide).
Experimental example 10: porous charcoal load Fe
3c
Synthesis material: fructose, urea element, Fe (NO
3)
29H
2o(ferric nitrate)
(1) 1g fructose, 0.1g urea element and 1g Fe (NO is taken
3)
29H
2o, in 100 mL beakers, afterwards by the mortar grinder 10min of material in beaker, adds thermal agitation and forms molten state at 120 DEG C.
(2) after, material is put in crucible, is placed in tube furnace at 800 DEG C, at N
2heat treatment 7 hours under condition, obtains porous charcoal load Fe
3c(cementite).
Experimental example 11: porous charcoal load Fe
3c
Synthesis material: glucose, urea element, Fe (NO
3)
29H
2o(ferric nitrate)
(1) 0.5g glucose, 2g urea element and 1g Fe (NO is taken
3)
29H
2o, in 100 mL beakers, adds thermal agitation and forms molten state at 100 DEG C.
(2) after, material is put in crucible, is placed in tube furnace at 850 DEG C, at 5%H
2heat treatment 6 hours under/Ar condition, obtains porous charcoal load Fe
3c(cementite).
Claims (6)
1. a method for porous charcoal loaded with nano metal carbide material, is characterized in that carrying out according to following step:
1) by carbon source, ammonium salt (or nitride) by the mass ratio of 1:100 ~ 100:1, carbon source and slaine mix according to the mass ratio of 1:10 ~ 10:1 to be put in a reservoir, under uniform temperature condition, stir 10-60 min, solid is mixed completely, form uniform system;
2) the mixture heat treatment 5-10h at 500-1000 DEG C of temperature will obtained in step 1), makes carbon source dehydration carbonization obtain dark brown solid; This heat treatment process is carried out under inertia protection gas or reducing gases atmosphere;
3) by step 2) in obtained dark brown solid suitably grind, obtain the nano metal carbide material of porous charcoal load.
2. the method for a kind of porous charcoal carried metal carbide material according to claim 1, is characterized in that the slaine wherein described in step (1) is selected from least one in the nitrate of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, halide, hypochlorite, acetate, oxalates, phosphate or sulfate.
3. the method for a kind of porous charcoal carried metal carbide material according to claim 1, is characterized in that wherein the middle carbon source of step (1) is at least one in glucose, fructose, sucrose, maltose, lactose, starch and dextrin.
4. the method for a kind of porous charcoal carried metal carbide material according to claim 1, is characterized in that wherein the middle ammonium salt of step (1) or nitride are at least one in the nitrogen-containing organic compounds such as urea element, guanidine, amidine.
5. the method for a kind of porous charcoal carried metal carbide material according to claim 1, it is characterized in that the mass ratio of the wherein middle carbon source of step (1) and ammonium salt is 1:100 ~ 100:1, preferably, the mass ratio of carbon source and ammonium salt is 20:1; In step (2), the mass ratio of carbon source and slaine is 1:10 ~ 10:1, and preferably, the mass ratio of carbon source and slaine is 1:5;
The method of a kind of porous charcoal carried metal carbide material according to claim 1, is characterized in that wherein the heat treatment temperature described in step (2) is between 500-1000 DEG C, and preferably, under protection gas, heat treatment temperature is 800 DEG C; Heat treatment time described in step (2) is 5-10h, and preferably, under protection gas, heat treatment time is 5h.
6. the method for a kind of porous charcoal carried metal carbide material according to claim 1, is characterized in that wherein the protection gas described in step (2) is at least one in nitrogen, argon gas, helium; Reducibility gas described in step (2) is hydrogen or carbon monoxide volume fraction is the gaseous mixture of 5% ~ 10%, and the Balance Air in gaseous mixture is at least one in nitrogen or argon gas.
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