CN101367521A - Synthesis of stephanoporate molybdenum carbide nano-wire - Google Patents
Synthesis of stephanoporate molybdenum carbide nano-wire Download PDFInfo
- Publication number
- CN101367521A CN101367521A CNA2008102011062A CN200810201106A CN101367521A CN 101367521 A CN101367521 A CN 101367521A CN A2008102011062 A CNA2008102011062 A CN A2008102011062A CN 200810201106 A CN200810201106 A CN 200810201106A CN 101367521 A CN101367521 A CN 101367521A
- Authority
- CN
- China
- Prior art keywords
- stephanoporate
- molybdenum carbide
- molybdenum
- carbide nano
- synthetic method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to the technical field of the nanometer material, and relates to a method for synthesizing the porous molybdenum carbide nanometer wire, and adopts the following steps: molybdate is dissolved in the water, and the mol concentration of the molybdenum atom is 0.02 to 1.5 mol/L; organic amine is filled in, and the mol ratio between the organic amine and the molybdenum atom is 20.0 to 1.0: 1; inorganic acid is dropped into the solution, and the pH value is adjusted to be 3 to 6 until the white precipitate appears; the reaction solution is moved into an oil bath with the temperature of 30 to 60 DEG C to be reacted for 6 to 24 hours; (5) the product is washed, pumped, filtered and dried; the product is baked in the inert gases atmosphere at the temperature of 675 to 750 DEG C for 4 to 10 hours. The invention has the advantages that abundant nanometer hole structure is arranged between the nanometer particles, the granularity of the molybdenum carbide is small, the molybdenum carbide has rich porous structure and large specific surface area, the carbon on the surface is small, thereby favoring the secondary assembling of the catalyst and having wide application fields; the productivity can reach 95 percent or more; the conditions are simple and easy to be controlled; the preparation efficiency is high; the invention has favorable application and industrialization prospect.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of synthetic method of stephanoporate molybdenum carbide nano-wire.
Background technology
With the molybdenum carbide is electronic structure and catalytic performance, anti-sulphur and the anti-carboloy forming property of the transition metal carbide catalyst of representative owing to its unique class precious metal, and good thermostability, becoming over nearly one, 20 year has one of catalytic material of application prospect most.Particularly grow to even greater heights at the cry efficient and the greenization utilization that is accompanied by oil price rise fast, the energy and resource in recent years, carbides catalytic performance and the exploitation of catalyzed reaction have newly further been caused people's attention.In addition, because the carbide synthesis material comparatively cheaply is easy to get, saving the precious metal precious resources, it is also significant to reduce the catalyzed reaction cost.The related reaction of molybdenum carbide catalyst has at present comprised that water-gas shift, methane and lower carbon number hydrocarbons steam and CO 2 reformation, methanol vapor are reformed, methanol electro-oxidizing is used for direct methanol fuel cell, fischer-tropsch synthetic, alcohol mixture is synthetic, the isomerization of the hydrogenating desulfurization of oil product and hydrodenitrification, olefin metathesis, hydrogenation/dehydrogenation, hydro carbons, aromizing etc., in the energy and chemical industry catalyzed reaction, shown great potential (R.B.Levy, M.Boudart, Science, 1977,181,547; E.V.Rebrov, S.A.Kuznetsov, M.H.J.M.de Croon, J.C.Schouten, Catal.Today, 2007,125,88; A.R.S.Darujati, W.J.Thomson, Appl.Catal.A:General, 2005,296,139; R.Barthos, F.Solymosi, J.Catal.2007,249,289; H.X.Zhong, H.M.Zhang, Y.M.Liang, J.L.Zhang, M.R.Wang, X.L.Wang, J.Power.Sources, 2007,164,572; J.Rasko, J.Kiss, Appl.Catal.A:General, 2003,253,427; M.L.Xiang, D.B.Li, H.J.Qi, W.H.Li, B.Zhong, Y.H.Sun YH, Fuel, 2007,86,1298; G.L.Parks, M.L.Pease, A.W.Burns, K.A.Layman, M.E.Bussell, X.Q.Wang, J.Hanson, J.A.Rodriguez, J.Catal., 2007,246,277; M.Lewandowski, A.Szymanska-Kolasa, P.Da Costa, C.Sayag, Catal.Today, 2007,119,31; G.Boskovic G, P.Putanov, K.Foettinger, H.Vinek H, Appl.Catal.A:General, 2007,317,175; X.Y.Li, D.Ma, L.M.Chen, X.H.Bao.Catal.Lett., 2007,116,63; A.F.Lamic, T.L.H.Pham, C.Potvin, J.M.Manoli, G.Djega-Mariadassou, J.Mol.Catal.A, 2005,237,109; A.Szechenyi, F.Solymosi, J.Phys.Chem.C, 2007,111,9509.).For example, methane and lower carbon number hydrocarbons are reformed will be for Sweet natural gas efficiently utilizes, and developing clean hydrogen source and carbon monoxide resource provides the basis; Alcohol mixture synthesizes and synthetic grade of fischer-tropsch again will be for making full use of non-oil carbon back resource, development green fuel aspect provides the basis, and with transition metal such as molybdenums the carbide catalyst of representative in the application of a series of hydrotreatments such as the hydrogenating desulfurization of oil or coal resource, hydrodenitrification, to solve environmental problem industrial and that motor vehicle emission causes possibility is provided for producing clean fuel.
From bibliographical information, the synthetic method of molybdenum carbide catalytic material approximately can be divided into following a few class at present: 1) high temperature cabonization method (1500 ~ 2000 ℃), by metal species (oxide compound of molybdenum) and C, CO carbonization at high temperature, there are shortcomings such as temperature height, area carbon are serious, particle sintering.2) CVD and plasma sputtering method, the method for utilizing CVD or plasma sputtering are deposited as nano particle after with Mo species and the gasification of C species again, exist high temperature, atmosphere to require shortcomings such as height, cost costliness.3) temperature programming reaction method (TPR) is by MoO
3(or molybdenum nitride) is at CH
4/ H
2(perhaps C
2H
4/ H
2) slowly heating carbonization in the gas mixture, this method is the method that is most widely used in the synthetic document of carbon current compound catalyst, but because reactor product exists area carbon, reaction inhomogeneous, and H
2Dangerous explosive, shortcomings such as volume production difficulty.4) the hot hydrogenation of carbon (carbothermal hydrogenation) method compares with programmed temperature method, and this method is based on the high dispersing MoO of the charcoal/superpolymer aerosol load of multiple-wall carbon nanotube or high-ratio surface
3(or soluble molybdenum compound) directly utilizes carrier carbon source and the loaded article surface reaction in hydrogen atmosphere, helps improving dispersity, reduces temperature of reaction, improves specific surface, but still can not eliminate some difficult problem in the programmed temperature method gas-solid phase reaction fully.5) solution reaction utilizes strong reductant KBH at organic system
4Deng reducing, react complicated, operational difficulty, output is little.6) utilize the metal precursor cracking, comprise organometallics and the methods such as mixture cracking of utilizing ammonium molybdate and hexamethylenetetramine, the former presoma preparation is complicated, and entire operation is crossed the range request inert atmosphere, the condition harshness; Latter's precursor construction is indeterminate, is unfavorable for products perfection, and is mixed with Mo in the product
2N impurity; Particle is big.Also have microwave method, ultrasonic dispersing [to wait report in addition, but exist output little equally, react insufficient, a difficult problem (R B.Levy.Advanced Materials in Catalysis (eds.Burton J J. such as the product particle is bigger, Garten R L) .New York:Academic Press, 1977; M.Saito, R.B.Anderson.J.Catal., 1980,63,438; M.J.Ledoux, C.Phamr Huu.Catal.Today, 1992,15,263; P.Ronsheim, A.Mazza, A.N.Christensen, Plasma Chem.Plasma Process, 1981,1,135; T.Miyao, I.Shishikura, M.Matsuoka, M.Nagal, S.T.Oyama.Appl.Catal.A:General, 1997,165,419; J.X.Wang, S.F.Ji, J.Yang, Q.L.Zhu, S.B.Li.Catal.Comm., 2005,6,389; T.C.Xiao, A.P.E.York, V.C.Williams, H.Al-Megren, A.Hanif, X.Y.Zhou, M.L.H.Green.Chem.Mater.2000,12,3896; Y.Z.Li, Y.N.Fan, Y.Chen.J.Solid State Chem.2003,170,135; X.L.Li, Y.D.Li, Chem.Eur.J.2004,10,433; H.M.Wang, X.H.Wang, M.H.Zhang, X.Y.Du, W.Li, K.Y.Tao, Chem.Mater.2007,19,1801; S.R.Vallance, S.Kingman, D.H.Gregory.Chem.Commun., 2007,742; N.A.Dhas, A.Gedanken.Chem.Mater.1997,9,3144.).
Therefore, it is big to utilize new synthetic method to prepare specific surface, and area carbon is few, and the nano silicon carbide molybdenum new catalytic agent material of controllable size, is one of the most interesting research topic in this field at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of synthetic method of stephanoporate molybdenum carbide nano-wire of simple and easy to control, economical rationality; Another technical problem to be solved is to provide a kind of abundant stephanoporate molybdenum carbide nano-wire of character that utilizes synthetic method to make.
The present invention solves the problems of the technologies described above the technical scheme of being taked: a kind of synthetic method of stephanoporate molybdenum carbide nano-wire comprises the steps: in regular turn
(1) with the molybdate molybdate solution that obtains soluble in water, the volumetric molar concentration of molybdenum atom is 0.02～1.5mol/L;
(2) organic amine is injected molybdate solution, the mol ratio of organic amine and molybdenum atom is 20.0～1.0:1;
(3) dropping inorganic acid in the solution is regulated pH to 3～6, to the white precipitate appearance, makes reaction solution;
(4) reaction solution moves in 30～60 ℃ the oil bath, reacted 6～24 hours, product;
(5) product washing suction filtration, oven dry, concrete, washing can be adopted absolute ethanol washing number time, 50 ℃ of bake out temperatures.
(6) roasting in inert atmosphere, 675～750 ℃ of maturing temperatures, roasting time 4～10 hours obtains stephanoporate molybdenum carbide nano-wire.
Stephanoporate molybdenum carbide nano-wire of the present invention, its specific surface height, area carbon is few, and avtive spot is many, and keeps good 1-dimention nano pattern, and the needs that are beneficial at actual catalyzed reaction carry out surface modification and assembling, have potentiality to be exploited and application prospect.
In the molybdate solution of above-mentioned steps (1), the volumetric molar concentration of molybdenum atom is specifically as follows 0.02,0.05, and 0.1,0.2,0.25,0.3,0.4,0.5,0.55,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4 or 1.5mol/L;
The mol ratio of organic amine and molybdenum atom is 20.0,18.0,16.0,14.0 in the above-mentioned steps (2), 12.0,10.0,8.0,6.0,4.0,2.0 or 1.0:1;
Dropping inorganic acid in the above-mentioned steps (3) is regulated pH and is specifically as follows 3,3.5,4,4.5,5,5.5 or 6;
Oil bath temperature is specifically as follows 30,35,40,45,50,55 or 60 ℃ in the above-mentioned steps (4); Reaction times is specifically as follows 6,8, and 10,12,15,18,20,22 or 24 hours;
The maturing temperature of above-mentioned steps (6) is specifically as follows 675,680, and 690,700,710,720,730,740 or 750 ℃, roasting time is specifically as follows 4,5,6,8 or 10 hours.
On the basis of such scheme, the molybdate in the step (1) is ammonium molybdate, Sodium orthomolybdate or potassium molybdate.
On the basis of such scheme, the organic amine in the step (2) is aniline, imidazoles or hexanediamine.
On the basis of such scheme, the mineral acid in the step (3) is hydrochloric acid, nitric acid or sulfuric acid.
On the basis of such scheme, the inert atmosphere in the step (6) is argon gas, nitrogen or helium.
It is as follows to the invention provides preferred synthetic method:
On the basis of such scheme, in the molybdate solution of step (1), the volumetric molar concentration of molybdenum atom is 0.2～1.0mol/L.
On the basis of such scheme, in the step (2), the mol ratio of organic amine and molybdenum atom is 4.0～2.0:1.
On the basis of such scheme, the mineral acid in the step (3) is a hydrochloric acid, and volumetric molar concentration is 1.0～5.0mol/L.
On the basis of such scheme, the maturing temperature in the step (6) is 720～730 ℃, constant temperature time 5～8 hours.
Preferred ammonium molybdate (the NH of described molybdate
4)
6Mo
7O
244H
2O, purity 99.99%.
Organic amine is an aniline, analytical pure.
The invention has the beneficial effects as follows:
The stephanoporate molybdenum carbide nano-wire of the inventive method preparation is made up of the molybdenum carbide nanoparticle, also has abundant nano-pore structure between the nanoparticle, molybdenum carbide particles by the stephanoporate molybdenum carbide nano-wire of the inventive method preparation is little, and has abundant meso-hole structure between the particle, specific surface area is big, area carbon is few, helps the exposure of reactant diffusion and active sites; Simultaneously, the 1-dimention nano pattern also helps the secondary assembling of catalyzer, creation has the multilevel ordered catalytic material of unique space structure, so fine chemistry industry catalyzed reactions such as this stephanoporate molybdenum carbide nano-wire is expected to synthesize at benzene hydrogenation, Fischer-Tropsch, hydrogenating desulfurization/denitrogenation, alcohols decomposing hydrogen-production, with fuel cell electrode catalytic material, transmitter, and use in the fields such as electricity and magnetics material;
The inventive method productive rate is very high, reaches more than 95%, and preparation condition is simple and easy to control, and the processing condition cost is low, the preparation efficiency height, and quality product and yield rate height have good application and industrialization prospect.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) figure of stephanoporate molybdenum carbide nano-wire product A of the present invention.
Fig. 2 is transmission electron microscope (TEM) figure of product A of the present invention.
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) figure of product A of the present invention.
Fig. 4 is X-ray powder diffraction (XRD) figure of product A of the present invention.
Fig. 5 is the isothermal nitrogen adsorption figure of product A of the present invention.
Fig. 6 is the graph of pore diameter distribution of product A of the present invention.
Fig. 7 is scanning electron microscope (SEM) figure of product B of the present invention.
Fig. 8 is transmission electron microscope (TEM) figure of product B of the present invention.
Fig. 9 is X-ray powder diffraction (XRD) figure of product B of the present invention.
Figure 10 is scanning electron microscope (SEM) figure of products C of the present invention.
Figure 11 is transmission electron microscope (TEM) figure of products C of the present invention.
Figure 12 is scanning electron microscope (SEM) figure of product D of the present invention.
Figure 13 is transmission electron microscope (TEM) figure of product D of the present invention.
Embodiment
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.24g ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (the about 0.35mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) 1.90g aniline is injected ammonium molybdate solution (aniline and the about 2.92:1 of molybdenum atom mol ratio);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product A.
The scanning electron microscope of product A (SEM) figure absorbs on Philips XL30 D6716 instrument, and as shown in Figure 1, product A has one dimension wire pattern as can be seen.
The transmission electron microscope of product A (TEM) figure absorbs on JEOL JEM-2010 instrument, and as shown in Figure 2, observing nano wire is that (10～15nm) assemble by the molybdenum carbide nano particle.
The high-resolution-ration transmission electric-lens of product A (HRTEM) figure (Fig. 3) proves that the molybdenum carbide particles surface is very clean, does not almost have carbon distribution.
The X-ray powder diffraction of product A (XRD) figure carries out on Rigaku D/Max-IIA type X-ray diffractometer, as shown in Figure 4, the product A of gained is characterized, and proves that product is the Mo of hexagonal system
2C (JCPDS:35-0787).
The isothermal nitrogen adsorption line chart (Fig. 5) of product A shows that its specific surface area is 51.3m
2/ g, and shown that at pore distribution figure (Fig. 6) aperture mainly concentrates on the 3.5nm place.
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (volumetric molar concentration of molybdenum atom is 0.02mol/L) in the 20ml distilled water;
(2) (aniline and molybdenum atom mol ratio are 4.0～2.0:1) aniline to be injected ammonium molybdate solution;
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product A '.
Embodiment 3
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (volumetric molar concentration of molybdenum atom is 1.5mol/L) in the 20ml distilled water;
(2) (aniline and molybdenum atom mol ratio are 4.0～2.0:1) aniline to be injected ammonium molybdate solution;
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product A ".
Embodiment 4
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.24g ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (the about 0.35mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) aniline is injected ammonium molybdate solution (aniline and molybdenum atom mol ratio are 20.0:1);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product A ' ".
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.24g ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (the about 0.35mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) aniline is injected ammonium molybdate solution (aniline and molybdenum atom mol ratio are 1.0:1);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product A " ".
Embodiment 6
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.24g ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (the about 0.35mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) the 1.02g imidazoles is injected ammonium molybdate solution (imidazoles and the about 2.14:1 of molybdenum atom mol ratio);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH5～6, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 60 ℃ the oil bath, reacted 24 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 750 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire product B.
The SEM figure (Fig. 7) of product B proves and utilizes imidazoles, also getable nano wire product.The TEM figure (Fig. 8) of product B shows that this nano wire also has vesicular structure, and the XRD figure of B (Fig. 9) proves that this nano wire also is a molybdenum carbide.
Embodiment 7
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.24g ammonium molybdate (NH
4)
6Mo
7O
244H
2O is dissolved in and obtains ammonium molybdate solution (the about 0.35mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) with 1.66g 1, the 6-hexanediamine injects ammonium molybdate solution (1,6-hexanediamine and the about 2.04:1 of molybdenum atom mol ratio);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains the stephanoporate molybdenum carbide nano-wire products C.
Embodiment 8
A kind of synthetic method of stephanoporate molybdenum carbide nano-wire is characterized in that comprising the steps:
(1) with 1.67g Sodium orthomolybdate Na
2MoO
42H
2O is dissolved in and obtains sodium molybdate solution (the about 0.3mol/L of the volumetric molar concentration of molybdenum atom) in the 20ml distilled water;
(2) 1.90g aniline is injected ammonium molybdate solution (aniline and the about 3.4:1 of molybdenum atom mol ratio);
(3) dropwise add the hydrochloric acid of 1.0mol/L in the solution, regulate pH4～5, occur to white precipitate, make reaction solution;
(4) reaction solution moves among 50 ℃ the oil bath, reacted 6 hours, product;
(5) product is through absolute ethanol washing several and suction filtration, 50 ℃ of oven dry;
(6) at last with product roasting in argon gas stream, 725 ℃ of maturing temperatures, roasting time 5 hours obtains stephanoporate molybdenum carbide nano-wire product D.
As SEM, the TEM figure (Figure 10,11) of products C and SEM, the TEM figure (Figure 12,13) of product D, show that this method has universality, be fit to other organic amine (1, the 6-hexanediamine) and molybdenum source (Sodium orthomolybdate) equally.
Because the molybdenum carbide particles of such molybdenum carbide nano wire is little, and has abundant meso-hole structure between the particle, specific surface is big, and area carbon is few, helps the exposure of reactant diffusion and active sites; Simultaneously, the 1-dimention nano pattern also helps the secondary assembling of catalyzer, creation has the multilevel ordered catalytic material of unique space structure, fine chemistry industry catalyzed reactions such as this nano wire is expected to synthesize at benzene hydrogenation, Fischer-Tropsch, hydrogenating desulfurization/denitrogenation, alcohols decomposing hydrogen-production, with fuel cell electrode catalytic material, transmitter, and use in the fields such as electricity and magnetics material.Because this product has above potential using value, and preparation condition is simple and easy to control, the processing condition cost is low, the preparation efficiency height, and quality product and yield rate height, so this product has good application and industrialization prospect.In addition, this method has universality, can form and organic amine carbon content and type (as straight-chain paraffin, aromatic hydrocarbon etc.) etc. the control institute molybdenum carbide catalytic material that obtains composition and character, the catalysis behavior of further catalyzer that modulation forms by further regulating the molybdenum source.To this method systematic study, the novel energy catalyzed conversion carbides catalytic material with class precious metal performance not only can be provided, and the synthetic method and the Catalyst Design of material had wide significance.
Claims (10)
1. the synthetic method of a stephanoporate molybdenum carbide nano-wire comprises the steps: in regular turn
(1) with the molybdate molybdate solution that obtains soluble in water, the volumetric molar concentration of molybdenum atom is 0.02～1.5mol/L;
(2) organic amine is injected molybdate solution, the mol ratio of organic amine and molybdenum atom is 20.0～1.0:1;
(3) dropping inorganic acid in the solution is regulated pH to 3～6, to the white precipitate appearance, makes reaction solution;
(4) reaction solution moves in 30～60 ℃ the oil bath, reacted 6～24 hours, product;
(5) product washing suction filtration, oven dry;
(6) roasting in inert atmosphere, 675～750 ℃ of maturing temperatures, roasting time 4～10 hours obtains stephanoporate molybdenum carbide nano-wire.
2. the synthetic method of stephanoporate molybdenum carbide nano-wire according to claim 1, it is characterized in that: the molybdate in the step (1) is ammonium molybdate, Sodium orthomolybdate or potassium molybdate.
3. the synthetic method of stephanoporate molybdenum carbide nano-wire according to claim 1 and 2, it is characterized in that: in the molybdate solution of step (1), the volumetric molar concentration of molybdenum atom is 0.2～1.0mol/L.
4. the synthetic method of stephanoporate molybdenum carbide nano-wire according to claim 1, it is characterized in that: the organic amine in the step (2) is aniline, imidazoles or hexanediamine.
5. according to the synthetic method of claim 1 or 4 described stephanoporate molybdenum carbide nano-wires, it is characterized in that: in the step (2), the mol ratio of organic amine and molybdenum atom is 4.0～2.0:1.
6. the synthetic method of stephanoporate molybdenum carbide nano-wire according to claim 1, it is characterized in that: the mineral acid in the step (3) is hydrochloric acid, nitric acid or sulfuric acid.
7. according to the synthetic method of claim 1 or 6 described stephanoporate molybdenum carbide nano-wires, it is characterized in that: the mineral acid in the step (3) is a hydrochloric acid, and volumetric molar concentration is 1.0～5.0mol/L.
8. the synthetic method of stephanoporate molybdenum carbide nano-wire according to claim 1, it is characterized in that: the inert atmosphere in the step (6) is argon gas, nitrogen or helium.
9. according to the synthetic method of claim 1 or 8 described stephanoporate molybdenum carbide nano-wires, it is characterized in that: the maturing temperature in the step (6) is 720～730 ℃, constant temperature time 5～8 hours.
10. the stephanoporate molybdenum carbide nano-wire that makes at the synthetic method of one of claim 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102011062A CN101367521A (en) | 2008-10-13 | 2008-10-13 | Synthesis of stephanoporate molybdenum carbide nano-wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102011062A CN101367521A (en) | 2008-10-13 | 2008-10-13 | Synthesis of stephanoporate molybdenum carbide nano-wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101367521A true CN101367521A (en) | 2009-02-18 |
Family
ID=40411556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102011062A Pending CN101367521A (en) | 2008-10-13 | 2008-10-13 | Synthesis of stephanoporate molybdenum carbide nano-wire |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101367521A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829588A (en) * | 2010-05-27 | 2010-09-15 | 复旦大学 | Synthetic method of load type molybdenum carbide catalyst |
| CN101899318A (en) * | 2010-07-23 | 2010-12-01 | 浙江大学 | Method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation |
| CN102086302B (en) * | 2009-12-04 | 2012-08-01 | 复旦大学 | Preparing method for molybdenum oxide - polyaniline composite nanowire and nanotube |
| RU2489351C2 (en) * | 2011-10-04 | 2013-08-10 | Учреждение Российской академии наук Институт химии твердого тела Уральского отделения РАН | Method of producing molybdenum carbide nanoparticles |
| CN103240108A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Molybdenum carbide catalyst for hydrogen generation of methanoic acid and preparation method of molybdenum carbide catalyst |
| CN103657633A (en) * | 2013-11-19 | 2014-03-26 | 大连理工大学 | Preparation method and application of eggshell type molybdenum carbide catalyst |
| CN104707636A (en) * | 2015-02-02 | 2015-06-17 | 北京大学 | Pt/alpha-MoC1-x supported catalyst, and synthesis method and application thereof |
| CN105529474A (en) * | 2016-01-22 | 2016-04-27 | 复旦大学 | Graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and preparation method thereof |
| CN106925314A (en) * | 2017-04-24 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | A kind of nickel assisted cryogenic synthesizes the method for molybdenum carbide elctro-catalyst |
| CN106964362A (en) * | 2017-04-10 | 2017-07-21 | 中国科学技术大学 | Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application |
| CN107311176A (en) * | 2017-08-07 | 2017-11-03 | 太原理工大学 | A kind of preparation method of order mesoporous carbonization molybdenum |
| CN107866249A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | For citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol |
| CN108455524A (en) * | 2018-01-18 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of application of transition metal carbide |
| CN109482212A (en) * | 2018-11-12 | 2019-03-19 | 大连理工大学 | A kind of preparation and its biomass hydrogenation deoxidation application of low temperature self assembly molybdenum carbide nano-wire catalyst |
| CN110201693A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
| CN114216936A (en) * | 2021-12-20 | 2022-03-22 | 湖北工业大学 | Preparation method and application of cubic phase molybdenum carbide nanowire gas sensor |
| CN115228491A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide |
-
2008
- 2008-10-13 CN CNA2008102011062A patent/CN101367521A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086302B (en) * | 2009-12-04 | 2012-08-01 | 复旦大学 | Preparing method for molybdenum oxide - polyaniline composite nanowire and nanotube |
| CN101829588B (en) * | 2010-05-27 | 2013-01-30 | 复旦大学 | Synthetic method of load type molybdenum carbide catalyst |
| CN101829588A (en) * | 2010-05-27 | 2010-09-15 | 复旦大学 | Synthetic method of load type molybdenum carbide catalyst |
| CN101899318A (en) * | 2010-07-23 | 2010-12-01 | 浙江大学 | Method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation |
| RU2489351C2 (en) * | 2011-10-04 | 2013-08-10 | Учреждение Российской академии наук Институт химии твердого тела Уральского отделения РАН | Method of producing molybdenum carbide nanoparticles |
| CN103240108B (en) * | 2013-05-22 | 2015-09-30 | 南京工业大学 | A kind of formic acid hydrogen manufacturing molybdenum carbide catalyst and preparation method thereof |
| CN103240108A (en) * | 2013-05-22 | 2013-08-14 | 南京工业大学 | Molybdenum carbide catalyst for hydrogen generation of methanoic acid and preparation method of molybdenum carbide catalyst |
| CN103657633A (en) * | 2013-11-19 | 2014-03-26 | 大连理工大学 | Preparation method and application of eggshell type molybdenum carbide catalyst |
| CN103657633B (en) * | 2013-11-19 | 2015-10-28 | 大连理工大学 | The preparation method of eggshell type molybdenum carbide catalyst and application |
| CN104707636A (en) * | 2015-02-02 | 2015-06-17 | 北京大学 | Pt/alpha-MoC1-x supported catalyst, and synthesis method and application thereof |
| CN105529474A (en) * | 2016-01-22 | 2016-04-27 | 复旦大学 | Graphene wrapped ultra-dispersed nano molybdenum carbide electro-catalysis hydrogen producing catalyst and preparation method thereof |
| CN105529474B (en) * | 2016-01-22 | 2019-01-15 | 复旦大学 | The super-dispersed nano molybdenum carbide electro-catalysis catalyst for preparing hydrogen and preparation method thereof of graphene package |
| CN107866249B (en) * | 2016-09-26 | 2021-12-28 | 中国石油化工股份有限公司 | Molybdenum carbide catalyst for preparing nerol and geraniol by hydrogenating citral |
| CN107866249A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | For citral Hydrogenation nerol and the molybdenum carbide catalyst of geraniol |
| CN106964362A (en) * | 2017-04-10 | 2017-07-21 | 中国科学技术大学 | Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application |
| CN106925314B (en) * | 2017-04-24 | 2019-10-15 | 中国科学院上海硅酸盐研究所 | A kind of method of nickel assisted cryogenic synthesis molybdenum carbide elctro-catalyst |
| CN106925314A (en) * | 2017-04-24 | 2017-07-07 | 中国科学院上海硅酸盐研究所 | A kind of nickel assisted cryogenic synthesizes the method for molybdenum carbide elctro-catalyst |
| CN107311176A (en) * | 2017-08-07 | 2017-11-03 | 太原理工大学 | A kind of preparation method of order mesoporous carbonization molybdenum |
| CN107311176B (en) * | 2017-08-07 | 2019-04-05 | 太原理工大学 | A kind of preparation method of order mesoporous carbonization molybdenum |
| CN108455524A (en) * | 2018-01-18 | 2018-08-28 | 中国科学院理化技术研究所 | A kind of application of transition metal carbide |
| CN109482212A (en) * | 2018-11-12 | 2019-03-19 | 大连理工大学 | A kind of preparation and its biomass hydrogenation deoxidation application of low temperature self assembly molybdenum carbide nano-wire catalyst |
| CN109482212B (en) * | 2018-11-12 | 2020-11-13 | 大连理工大学 | Preparation of low-temperature self-assembled molybdenum carbide nanowire catalyst and application of catalyst in biomass hydrodeoxygenation |
| CN110201693A (en) * | 2019-06-14 | 2019-09-06 | 陕西科技大学 | A kind of molybdenum carbide catalyst and its preparation method and application |
| CN115228491A (en) * | 2021-04-23 | 2022-10-25 | 中国科学院大连化学物理研究所 | High-dispersion rhodium-based catalyst, preparation method thereof and application thereof in preparation of ethanol from carbon dioxide |
| CN114216936A (en) * | 2021-12-20 | 2022-03-22 | 湖北工业大学 | Preparation method and application of cubic phase molybdenum carbide nanowire gas sensor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101367521A (en) | Synthesis of stephanoporate molybdenum carbide nano-wire | |
| CN101829588B (en) | Synthetic method of load type molybdenum carbide catalyst | |
| CN109174085B (en) | Atomic-level dispersed palladium-based nano-diamond/graphene composite material catalyst and preparation method and application thereof | |
| CN103936008A (en) | Synthesis method of nano-molybdenum carbide | |
| Wang et al. | Ammonia from photothermal N2 hydrogenation over Ni/TiO2 catalysts under mild conditions | |
| CN102600876B (en) | Preparation method of carbon onion loaded transition metal carbide nano composite | |
| CN110841661A (en) | Preparation method and application of 1T-2H molybdenum disulfide @ cadmium sulfide composite nanomaterial | |
| Zhang et al. | g‐C3N4 Nanosheet Nanoarchitectonics: H2 Generation and CO2 Reduction | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN113101933A (en) | Supported nickel-cobalt bimetallic nano catalyst and application thereof in catalyzing selective hydrogenation reaction of vanillin | |
| CN111672521A (en) | Transition metal monoatomic material and preparation method and application thereof | |
| CN112609197B (en) | Preparation method of two-dimensional lamellar carbon-based molybdenum carbide composite material | |
| CN107233890A (en) | A kind of nickel-base catalyst of attapulgite load of zinc modification and its preparation method and application | |
| Ma et al. | Two-dimensional transition metal dichalcogenides for electrocatalytic nitrogen fixation to ammonia: Advances, challenges and perspectives. A mini review | |
| CN109499592B (en) | Preparation method of nanorod molybdenum carbide/molybdenum dioxide composite material | |
| CN110876950B (en) | Composite material containing metal hydroxide, preparation method and application thereof | |
| CN114984952B (en) | Carbon-coated copper material and preparation method and application thereof | |
| CN113277514A (en) | Transition metal carbide Mo2Preparation method of material C | |
| CN114471658A (en) | Temperature-controlled bifunctional atomic-level dispersed metal g-C3N4Method for preparing photocatalyst | |
| CN113145114B (en) | Supported noble metal boride catalyst and preparation method and application thereof | |
| CN104525210A (en) | Method for preparing MWCNTs-supported copper and cerium catalyst by using iron, cobalt and nickel as matrix | |
| CN112591754B (en) | Preparation method of carbon nanocage coupled molybdenum carbide quantum dot nanocomposite | |
| Luo et al. | Ni-Ni3P/SiO2 Catalyst for Highly Selective Production of Silicon Tetrachloride via Silicon Hydrochlorination | |
| Hao et al. | Selective Hydrogenation of 5-Hydroxymethylfurfural to 2, 5-Dimethylfuran Over Popcorn-Like Nitrogen-Doped Carbon-Confined CuCo Bimetallic Catalyst | |
| CN114100682B (en) | Lupin She Yizhi junction photocatalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090218 |