CN1774389A - Nano-structured metal-carbon composite and process for preparation thereof - Google Patents
Nano-structured metal-carbon composite and process for preparation thereof Download PDFInfo
- Publication number
- CN1774389A CN1774389A CNA2004800103708A CN200480010370A CN1774389A CN 1774389 A CN1774389 A CN 1774389A CN A2004800103708 A CNA2004800103708 A CN A2004800103708A CN 200480010370 A CN200480010370 A CN 200480010370A CN 1774389 A CN1774389 A CN 1774389A
- Authority
- CN
- China
- Prior art keywords
- metal
- carbon composite
- nanostructured
- carbon
- precursor
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/935—Carbides of alkali metals, strontium, barium or magnesium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
Disclosed are a nano-structured metal-carbon composite and a process for preparation thereof. More specifically, a nano-structured metal-carbon composite is prepared by continuously impregnating a transition metal precursor and a carbon precursor into a nano template and reacting the resultant mixture at high temperature. In the composite according to the present invention, metal is regularly multi-dispersed in a size of less than 1 nano meter, and metal and carbon are chemically bonded, thereby exhibiting the highly excellent hydrogen storage capacity.
Description
Technical field
The present invention relates generally to metal-carbon composite of a kind of nanostructured and preparation method thereof, be specifically related to a kind of metal-carbon composite with nanostructured of excellent hydrogen storage ability, and the method for the metal-carbon composite of preparation nanostructured, comprise the preparation nano template, in this nano template, immerse metal precursor and carbon precursor in succession, the structure that obtains is reacted.
Background of invention
Different with generally well-known amorphous carbon, CNT or sheet carbon possess hydrogen storage ability.The hydrogen storage ability of carbon is with the surface area and the proportional increase of pore volume of carbon.Because this specific character only occurs to the temperature range of liquid nitrogen (196 ℃) at low temperature, so be difficult to use hydrogen storage ability among the visitor commercial.Yet, have relative small surface area and show excellent hydrogen storage ability than the CNT of small pore volume or carbon nano-fiber.
For improving hydrogen storage ability, various metals are added in the CNT.For example, the CNT of adding alkali metal such as lithium is compared with common CNT and is had higher hydrogen storage ability.Under 200～400 ℃ temperature or at room temperature, and under atmospheric pressure, be known that the CNT by 100wt%, CNT can store the hydrogen of about 14～20wt%.In addition, the storage of hydrogen and emit circulation and can repeat, and can not reduce storage capacity.The main material of CNT is a methane, and CNT has specific laminated structure, and its open edge can carry out hydrogen effectively and absorb.The catalyst that the alkali metal that adds absorbs as hydrogen.
Because the adding of different metal, the carbon of ad hoc structure such as fullerene or CNT can show conductor or characteristic of semiconductor.Because the physics that hydrogen absorbs or the variation of chemical characteristic add transition metal in the carbon of said structure such as Pt is significant.
Yet producing highly purified fullerene or CNT in a large number needs big cost, by transition metal being added to the extremely difficult electronic structure that changes carbon in the carbon structure.
Because carbon is the material of stabilizer pole, seldom be disclosed so have the composite and preparation method thereof of the true nano-structured of metal-carbon chemical bond.As the conventional method of the composite for preparing nanostructured, preparation and heat treatment Organometallic precursor are as (PPh
3)
2Pt (C
2H
4) method be known (JACS 1992,114,769).Yet, be preparation or buy expensive precursor as (PPh in the shortcoming of above-mentioned conventional method
3)
2Pt (C
2H
4).In addition, be well known that the metal-carbon composite by the nanostructured of above-mentioned conventional method preparation comprises the Pt-C chemical bond.
Brief Description Of Drawings
Fig. 1 is the results of structural analysis of the metal-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 2 is the XRD analysis result of the metal-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 3 is the pore structure analysis result of the metal-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 4 is the EXAFS analysis result of the metal-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 5 is the storage hydrogen thermoisopleth (hydrogen absorption-desorption experiment result) of the platinum-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 6 is the hydrogen storage ability experimental result of the platinum-carbon composite of the nanostructured that obtains from embodiment 1.
Fig. 7 is the storage hydrogen thermoisopleth (hydrogen absorption-desorption experiment result) of the copper-carbon composite of the nanostructured that obtains from embodiment 3.
Fig. 8 is the storage hydrogen thermoisopleth (hydrogen absorption-desorption experiment result) of the nickel-carbon composite of the nanostructured that obtains from embodiment 4.
Fig. 9 is the storage hydrogen thermoisopleth (hydrogen absorption-desorption experiment result) of the magnesium-carbon composite of the nanostructured that obtains from embodiment 5.
Figure 10 is the storage hydrogen thermoisopleth (hydrogen absorption-desorption experiment result) of the cobalt-carbon composite of the nanostructured that obtains from embodiment 6.
Figure 11 is the hydrogen storage ability experimental result (J.Mat.Chem.2003,13,209) of the routine CNT that is used for Chu Qing.
Preferred embodiment describes in detail
Technical task
The objective of the invention is to address the above problem, a kind of metal-carbon composite of nanostructured promptly is provided, this material can mix transition metal such as platinum in the mode of simple economy with the mesoporous carbon with porous nanometer structure except fullerene or CNT, change the electronic structure of carbon easily, and at room temperature have excellent hydrogen storage ability, its preparation method also is provided.
Technical scheme
For achieving the above object, use nano template to prepare the metal-carbon composite of nanostructured.Here, this nano template is selected from silica, aluminium oxide or its mixture, preferred silica.
In the metal-carbon composite of nanostructured of the present invention, the carbon precursor of this metal-carbon composite is selected from furfuryl alcohol, dextrose plus saccharose.Preferably, this carbon precursor is a sucrose.
In the metal-carbon composite of nanostructured of the present invention, this metal-carbon composite comprises at least a following metal: Pt, Ru, Cu, Ni, Mg, Co, the W of being selected from, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Li, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B.In addition, this metal precursor is selected from
, (NH
3)
6RuCl
3, CuCl
2, Ni (NO
3)
2, Mg (NO
3)
2, CoCl
2, (NH
4)
6W
12O
39, FeCl
3Or FeCl
3(NH
4)
3, IrCl
6, RhCl
3, AgCl, NH
4AuCl
4, OsCl
3, CrCl
2, MoCl
5, VCl
3, TaCl
5, ZrCl
4, HfCl
4, Li
2CO
3, NaCl, KCl, Be (CH
3COCHCOCH
3)
2, CaCl
2, BaCl
2, MnCl
2, Pd (NO
3)
2, TiCl
4, ZnCl
2, AlCl
3, Ga
2Cl
4, SnCl
4, PbCl
2, SbCl
3, SeCl
4, TeCl
4, CsCl, RbCl, SrCl
2, CeCl
3, PrCl
3, NdCl
3, SmCl
3, ReCl
3And BCl
3
In the metal-carbon composite of nanostructured of the present invention, press total restatement of metal-carbon composite, contained amount of metal is that 1～95wt% and institute's phosphorus content are 5～99wt%.Preferably, press total restatement of metal-carbon composite, contained amount of metal is that 4～36wt% and institute's phosphorus content are 64～96wt%.
In the metal-carbon composite of nanostructured of the present invention, press total restatement of metal-carbon composite, institute's platinum containing amount is that 0.2～44wt% and institute's phosphorus content are 56～99.8wt%.Preferably, press total restatement of metal-carbon composite, institute's platinum containing amount is that 2～34wt% and institute's phosphorus content are 66～98wt%.
In one embodiment, a kind of method for preparing the metal-carbon composite of nanostructured comprises:
The preparation process of preparation nano template;
The calcination step of the nano template of calcination preparation;
Use metal precursor metal to be immersed the immersion step of the nano template of calcination;
In immersion adding and the blend step that adds the carbon precursor in the nano template of metal and evenly mix the carbon precursor arranged;
Make add and blend step in the reactions steps that reacts of the mixture that makes;
The carburising step of the reactant mixture that carbonization obtains; And
From the carbonization mixture that obtains, remove the removal step of nano template.
In the methods of the invention, nano template is selected from silica, aluminium oxide or its mixture, and preferably, nano template is a silica.
In the methods of the invention, reactions steps is carried out under 100～160 ℃ temperature, and carburising step carries out under 800～1000 ℃ temperature.
In the methods of the invention, the carbon precursor is selected from furfuryl alcohol, dextrose plus saccharose.Preferably, the carbon precursor is a sucrose.
In the methods of the invention, metal-carbon composite comprises at least a following metal: Pt, Ru, Cu, Ni, Mg, Co, the W of being selected from, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Li, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B, metal precursor is selected from (NH
3)
4Pt (NO
3)
2, (NH
3)
6RuCl
3, CuCl
2, Ni (NO
3)
2, Mg (NO
3)
2, CoCl
2, (NH
4)
6W
12O
39, FeCl
3Or FeCl
3(NH
4)
3, IrCl
6, RhCl
3, AgCl, NH
4AuCl
4, OsCl
3, CrCl
2, MoCls, VCl
3, TaCl
5, ZrCl
4, HfCl
4, Li
2CO
3, NaCl, KCl, Be (CH
3COCHCOCH
3)
2, CaCl
2, BaCl
2, MnCl
2, Pd (NO
3)
2, TiCl
4, ZnCl
2, AlCl
3, Ga
2Cl
4, SnCl
4, PbCl
2, SbCl
3, SeCl
4, TeCl
4, CsCl, RbCl, SrCl
2, CeCl
3, PrCl
3, NdCl
3, SmCl
3, ReCl
3And BCl
3
The metal-carbon composite of nanostructured disclosed by the invention uses nano template to prepare.For nano template used among the embodiment 1～7, mainly use SBA-15 type silica, but also can use MCM-48 type silica.In addition, can use the mixture of aluminium oxide, aluminium oxide and silica.
Preferably, the carbon precursor of metal-carbon composite is selected from furfuryl alcohol, dextrose plus saccharose.More preferably, use sucrose, because can make the more carbon nano-array of perfect structure like this.
Preferably, this metal-carbon composite comprises at least a following metal: Pt, Ru, Cu, Ni, Mg, Co, the W of being selected from, Fe, Ir, Rh, Ag, Au, Os, Mo, Mo, V, Ta, Zr, Hf, Li, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B.Here, at least a metal finger can comprise one of above-mentioned metal, perhaps can comprise one or more above-mentioned metals.For example use (NH respectively
3)
4Pt (NO
3)
2(NH
3)
6RuCl
3As the precursor of platinum and ruthenium, one of platinum and ruthenium or Pt-Ru can immerse nano template.
In the metal-carbon composite of disclosed nanostructured, metal-carbon composite comprises at least a following metal: Pt, Ru, Cu, Ni, Mg, Co, the W of being selected from, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Li, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B.Here, press total restatement of metal-carbon composite, contained at least a amount of metal is that 1～95wt% and institute's phosphorus content are 5～99wt%.For having more excellent hydrogen storage ability, preferably press total restatement of metal-carbon composite, contained amount of metal is that 4～36wt% and institute's phosphorus content are 64～96wt%.
In the metal-carbon composite of nanostructured, press total restatement of metal-carbon composite, institute's platinum containing amount is that 0.2～44wt% and institute's phosphorus content are 56～99.8wt%.For having more excellent hydrogen storage ability, preferably press total restatement of metal-carbon composite, institute's platinum containing amount is that 2～34wt% and institute's phosphorus content are 66～98wt%.
In the metal-carbon composite process of preparation nanostructured, after in the single reactor of nano template, immersing catalyst metal precursor and carbon precursor continuously, react, wherein nano template is selected from silica, aluminium oxide or its mixture, thus this method very economical.After the reaction, the mixture that carbonization obtains is removed nano template then.Therefore, can obtain having the new composite of metal and carbon chemical bond.This composite shows excellent hydrogen storage ability.
As mentioned above, the present inventor has prepared a kind of new composite, wherein by reaction and heating in vacuum metal precursor and carbon precursor bonding in nano template less than the metal and the carbon of 1 nanometer, and confirm that physics by adjusting carbon and chemical characteristic can be with storing hydrogen in ultra-fine holes, thereby finished the present invention.Depend on metal species, the material that obtains not only can be used for Chu Qing, and can be used for various catalyst reactions and electronic material.
Preferred embodiment
Be described in more detail the preferred embodiments of the invention below in conjunction with accompanying drawing.
Embodiment 1
A. prepare nano template (MCM-48)
At 80 ℃ of 1M NaOH (77.5g) and Ludox HS40 (22.5g) that stir and mix preheating down, the mixture that obtains is as silica source (nano template precursor).The silica material of above-mentioned preparation, softex kw (CTMABr) and C
12EO
4The ratio of being mixed into is 5SiO
2: 1.25Na
2O: 0.85CTMABr: 0.15C
12EO
4: 400H
2The gel mixture of O.The gel mixture that obtains was reacted 60 hours.Add small amount of acetic acid, making the at first mixture pH of reaction that obtains is 10.Secondly, the mixture that obtains reacted 40 hours in 100 ℃ heating furnace, thereby obtained nano template (MCM-48).The MCM-48 of above-mentioned preparation only for open preparation method, uses following nano template SBA-15 in an embodiment.
B. prepare nano template (SBA-15)
At room temperature stir and mix the hydrochloric acid 1.6M (380mL) and the BASF Co. of preheating, the Pluronic P123 (10g) of Ltd..In the mixture that obtains, add tetraethyl orthosilicate (TEOS) (22g), and stir.Subsequently, the mixture in that 80 ℃ of following polymerizations obtain to remove surfactant, uses then.
C. use nano template to prepare the Pt-C composite of nanostructured
After the nano template (SBA-15) that 300 ℃ of following calcination obtain from preparation method B, the Pt precursor solution is added in the nano template, thereby immerses by 1g nano template 67wt%Pt.The mixture that obtains dewaters with vacuum desiccator.Here, (NH
3)
4Pt (NO
3)
2As the Pt precursor.Contain the solution of Pt precursor and nano template by vacuum drying, the immersion process evenly is immersed in the nano template Pt precursor.Subsequently, with sucrose (2.5g), sulfuric acid (0.28g) and water (10g) are added in the mixture that obtains.Then, the mixture that obtains reacted 6 hours down at 100 ℃ and 160 ℃ respectively, and carbonization in 900 ℃ vacuum atmosphere.The fusion nano template, and with the fluoracid aqueous solution of dilution it is removed, washing, thus the Pt-C composite of nanostructured obtained.
Use nano template to prepare the metal-carbon composite of nanostructured
Behind 300 ℃ of following sintering, use the vacuum desiccator preparation to use respectively, Cu, Ni, Mg, the mixture that Co and W immerse in nano template (SBA-15) that embodiment 1 obtains by 1g nano template 24wt%Ru.For Ru, Cu, Ni, Mg, Co and W precursor use (NH respectively
3)
6RuCl
3, CuCl
2, Ni (NO
3)
2, Mg (NO
3)
2, CoCl
2, (NH
4)
6W
12O
39Subsequently, with sucrose (2.5g), sulfuric acid (0.28g) and water (10g) are added in the mixture that obtains, and evenly mix.Then, the mixture that obtains reacted 6 hours down at 100 ℃ and 160 ℃ respectively, and carbonization in 900 ℃ vacuum atmosphere.The fusion nano template, and with the dilution the fluoracid aqueous solution it is removed, washing, thereby obtain the ruthenium-carbon composite (embodiment 2) of nanostructured, copper-carbon composite (embodiment 3), nickel-carbon composite (embodiment 4), magnesium-carbon composite (embodiment 5), cobalt-carbon composite (embodiment 6) and tungsten-carbon composite (embodiment 7).
Carry out the real structure of platinum-carbon composite (embodiment 1) of using the nanostructured of nano template preparation entirely with checking of following analysis.
For the structure of platinum-carbon composite of analyzing nanostructured, use transmission microscopy (TEM), x-ray diffractometer (XRD), hole analyzer, the X-radiation absorption fine structure (EXAFS) of expansion.
Fig. 1 shows the observed result of the platinum-carbon composite that uses the nanostructured that TEM obtains from embodiment 1.As shown in Figure 1, the metal-carbon composite of observing disclosed nanostructured has three-dimensional structure.
Fig. 2 is the XRD analysis result of the platinum-carbon composite of the nanostructured that obtains from embodiment 1.Because the XRD analysis result of the metal-carbon composite of disclosed nanostructured is identical with SBA-15, therefore observe the shape that disclosed composite has duplicated nano template.Experimental result supports that the platinum-carbon composite of nanostructured is a three-dimensional structure.
Fig. 3 is the pore structure analysis result of the platinum-carbon composite of the nanostructured that obtains from embodiment 1.Fig. 3 shows that disclosed composite has by micropore and mesoporous a large amount of pores of forming less than 1 nanometer.By calculating from absorption isotherm, observed BET surface area is about 1700m
2/ g.
Fig. 4 is the EXAFS analysis result of the platinum-carbon composite of the nanostructured that obtains from embodiment 1, and the analysis result of conventional platinum-carbon composite.Curve A and D show the result of disclosed platinum-carbon composite, and curve B and C show the result of conventional composite.Table 1 shows the EXAFS graphic simulation result of Fig. 4 analysis result.
Table 1EXAFS graphic simulation result
| Sample | The Pt-Pt bond number | The Pt-C bond number | Pt-Pt bond distance (nm) | Pt-C bond distance (nm) | |
| A | The Pt-C composite (1) of nanostructured | 4.31 | 2.73 | 0.2735 | 0.2041 |
| B | Pt/C(1) | 9.58 | 0.2757 | ||
| C | Pt/C(2) | 9.71 | 0.2757 | ||
| D | The Pt-C composite (2) of nanostructured | 2.78 | 2.12 | 0.2736 | 0.2041 |
As shown in table 1, Pt-C bond number in the Pt-C composite (2) of the Pt-C composite (1) of nanostructured and nanostructured and the bond distance curve A and the D of the analysis result of Fig. 4 (respectively corresponding to) be can be determined at, and Pt-C bond number and the bond distance curve B and the C of the analysis result of Fig. 4 (respectively corresponding to) in conventional Pt/C (1) and Pt/C (2), can not be measured.Can clearly be seen that from The above results metal and carbon mix simply in conventional composite, and in the Pt-C of disclosed nanostructured composite, metal and carbon mix simply not, less than the platinum and the carbon geochemistry bonding of 1 nanometer.Less than 1 nanometer fine holes the time, also has new chemical bonding structure even promptly be known that disclosed composite.Therefore, the stable chemical bond of metal and carbon is represented the novel characteristic structure of the Pt-C composite of disclosed nanostructured.
Although the material that carbon is normally stable, if by change architectural characteristic shown in the present, carbon also can be used as suitable material so.Because the metal-carbon composite of the nanostructured of disclosed use nano template can make up with various metallochemistries, so the carbon in the composite shows different qualities.For example, regulate valence band in the catalyst, might water-splitting produce hydrogen so if some metal is added to.Because use the metal-carbon composite with superior electrical conductivity to cut down the consumption of energy in the preparation of semiconductor element, therefore disclosed composite can be used for the delicate elements process.In addition, if because metal and bond with carbon, carbon can transmit the sensitiveness electron reaction so, so carbon can be used in the preparation of fine sensor.
According to above-mentioned analysis result, the Pt-C composite of disclosed nanostructured is the three-dimensional structure with nano-scale, less than the Pt of 1 nanometer and the carbon geochemistry bonding of 2 or 3 dimensions, and is polydisperse.
Carry out hydrogen absorption/desorption experiment, study the hydrogen storage ability of the metal-carbon composite of the nanostructured of in embodiment 1～7, using the nano template preparation.
(86.1mg) is placed in the stainless steel reactor with sample, the residual volume of assaying reaction device.Pressurize with hydrogen and to measure equalizing pressure.At room temperature experimentize, experimental result shows in Fig. 5～10.
Fig. 5 shows the repeated hydrogen adsorption/desorption result of carrying out under 15atm in the Pt-C of disclosed nanostructured composite.Fig. 6 shows that the hydrogen in the Pt-C of disclosed nanostructured composite absorbs the result under 80atm.Figure 11 shows the experimental result (J.Mat.Chem.2003,13,209) of conventional CNT, with the hydrogen storage ability of the Pt-C composite of discloseder nanostructured and the hydrogen storage ability of conventional CNT.
As shown in figure 11, the about 0.25wt% of the hydrogen storage ability of conventional CNT under 30atm.Yet, the Pt-C composite of the disclosed nanostructured shown in Fig. 5 shows excellent hydrogen storage ability, about 1.8wt% (referring to Fig. 5) under 17atm, about 9.8wt% is (referring to Fig. 6 under 80atm, by changing the pressure of equilibrium state, change the molal quantity that hydrogen absorbs, obtain result of calculation, PV=nRT).
Fig. 7～Figure 10 uses the storage hydrogen thermoisopleth of the copper-carbon composite that obtains from embodiment 3, hydrogen absorption-desorption experiment result under 10atm, nickel-the carbon composite that obtains from embodiment 4, magnesium-the carbon composite that obtains from embodiment 5, the storage hydrogen thermoisopleth of the cobalt-carbon composite that obtains from embodiment 6.
In Fig. 7～Figure 10, copper-the carbon composite that obtains from embodiment 3 shows excellent hydrogen storage ability, about 0.9wt%, nickel-the carbon composite that obtains from embodiment 4 shows excellent hydrogen storage ability, about 1.05wt%, the magnesium-carbon composite that obtains from embodiment 5 shows excellent hydrogen storage ability, about 1.12wt%, cobalt-the carbon composite that obtains from embodiment 6 shows excellent hydrogen storage ability, about 1.35wt%.
Although do not show among the figure, the ruthenium-carbon composite that obtains from embodiment 2 and embodiment 7 and the tungsten-carbon composite hydrogen storage ability that under 10atm, shows excellence respectively, about respectively 1.01% and about 1.43%.
By the mode similar, use nano template to prepare metal-carbon composite (embodiment 8～45), except using following precursor, as FeCl to embodiment 1～7
3Or FeCl
3(NH
4)
3, IrCl
6, RhCl
3, AgCl, NH
4AuCl
4, OsCl
3, CrCl
2, MoCl
5, VCl
3, TaCl
5, ZrCl
4, HfCl
4, Li
2CO
3, NaCl, KCl, Be (CH
3COCHCOCH
3)
2, CaCl
2, BaCl
2, MnCl
2, Pd (NO
3)
2, TiCl
4, ZnCl
2, AlCl
3, Ga
2Cl
4, SnCl
4, PbCl
2, SbCl
3, SeCl
4, TeCl
4, CsCl, RbCl, SrCl
2, CeCl
3, PrCl
3, NdCl
3, SmCl
3, ReCl
3And BCl
3, other metals Fe for example accordingly, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Li, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B, and analyze subsequently.Therefore, comprise that in use what show is metal and carbon geochemistry bonding in the metal-carbon composite that the nano template of these metals prepares, composite shows excellent hydrogen storage ability.Table 2 shows under the hydrogen balance pressure of 10atm, the hydrogen storage ability of the metal-carbon composite that obtains from embodiment 8～45.Should be appreciated that these results record under 10atm hydrogen balance pressure, the hydrogen storage ability of metal-carbon composite can raise with hydrogen balance pressure and increase.For example, reveal at material list under the situation of conventional hydrogen storage ability, their hydrogen storage ability under 6MPa (about 59atm) less than 0.1wt% (' Hydrogen storagecapacity of commercially available carbon materials at roomtemperature ', people such as H.Kajiura, APPLIED PHYSICS LETTERS, 2003.02.17, Vol.82, No.7).Yet, as shown in table 2, even disclosed metal-carbon composite also has excellent hydrogen storage ability under 10atm.Therefore, be appreciated that hydrogen storage ability is more excellent under high pressure.
The storage hydrogen experimental result of [table 2] metal-carbon composite (embodiment 8～45)
| Embodiment | The metal of metal-carbon composite | Tenor (wt%) | Hydrogen storage content (wt%) |
| 8 | Fe | 21 | 0.4 |
| 9 | | 5 | 0.6 |
| 10 | Rh | 8 | 0.7 |
| 11 | Ag | 11 | 0.3 |
| 12 | Au | 7 | 0.8 |
| 13 | | 2 | 1.1 |
| 14 | | 20 | 0.9 |
| 15 | Mo | 31 | 0.7 |
| 16 | V | 22 | 0.1 |
| 17 | | 4 | 0.2 |
| 18 | Zr | 8 | 0.5 |
| 19 | | 3 | 0.1 |
| 20 | | 4 | 1.5 |
| 21 | | 3 | 1.3 |
| 22 | | 5 | 1.2 |
| 23 | Be | 31 | 0.4 |
| 24 | Ca | 27 | 0.2 |
| 25 | Ba | 32 | 0.1 |
| 26 | | 10 | 0.6 |
| 27 | Pd | 41 | 1.2 |
| 28 | Ti | 39 | 1.0 |
| 29 | Zn | 21 | 0.2 |
| 30 | Al | 16 | 0.5 |
| 31 | Ga | 22 | 0.4 |
| 32 | Sn | 22 | 0.1 |
| 33 | Pb | 31 | 0.3 |
| 34 | Sb | 13 | 0.5 |
| 35 | Se | 21 | 0.3 |
| 36 | Te | 18 | 0.6 |
| 37 | Cs | 22 | 0.5 |
| 38 | | 5 | 0.4 |
| 39 | Sr | 15 | 0.2 |
| 40 | Ce | 21 | 0.4 |
| 41 | | 9 | 0.8 |
| 42 | | 5 | 0.5 |
| 43 | Sm | 13 | 0.6 |
| 44 | Re | 5 | 1.0 |
| 45 | B | 31 | 1.2 |
Although can make various modifications and variations, in accompanying drawing and explanation, describe embodiment for example in detail to the present invention.Yet, should be appreciated that, the invention is not restricted to specific disclosed form.But the present invention covers modification, equivalent and selection mode in all the spirit and scope of the present invention in claims limit.
Industrial usability
As previously mentioned, metal-carbon composite of the nanostructured of embodiment of the present invention and preparation method thereof has improved storage hydrogen efficiency and hydrogen storage ability. Therefore, the field that composite and method are applicable to various storages and use hydrogen, wherein hydrogen is clean energy, in the storage of the hydrogen fuel in the fuel automobile and hydrogen supply material, fuel automobile is conducted extensive research now, therefore provide effective scheme for the energy resource consumption and the pollution that cause owing to the use fossil fuel. In addition, depend on used metal species, disclosed composite can be used for electronic material and different catalysts reaction.
In addition, according to metal-carbon composite of nanostructured and preparation method thereof, because metal precursor and carbon precursor all immerse in the nano template, so composite can prepare in the situation of modifier not having. Therefore, disclosed method is simpler and more economical than the method that routine prepares CNT.
Claims (19)
1. metal-carbon composite that uses the nanostructured of nano template preparation.
2. the metal-carbon composite of nanostructured as claimed in claim 1, wherein this nano template is selected from silica, aluminium oxide or its mixture.
3. the metal-carbon composite of nanostructured as claimed in claim 2, wherein this nano template is a silica.
4. the metal-carbon composite of nanostructured as claimed in claim 1, wherein the carbon precursor of this metal-carbon composite is selected from furfuryl alcohol, dextrose plus saccharose.
5. the metal-carbon composite of nanostructured as claimed in claim 4, wherein this carbon precursor is a sucrose.
6. as the metal-carbon composite of each described nanostructured of claim 1～5, wherein this metal-carbon composite comprises at least a following metal: Pt, Ru, Cu, Ni, Mg, Co, W, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Limitations, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and the B of being selected from.
7. the metal-carbon composite of nanostructured as claimed in claim 6, wherein this metal precursor is selected from (NH
3)
4Pt (NO
3)
2, (NH
3)
6RuCl
3, CuCl
2, Ni (NO
3)
2, Mg (NO
3)
2, CoCl
2, (NH
4)
6W
12O
39, FeCl
3Or FeCl
3(NH
4)
3, IrCl
6, RhCl
3, AgCl, NH
4AuCl
4, OsCl
3, CrCl
2, MoCl
5, VCl
3, TaCl
5, ZrCl
4, HfCl
4, Li
2CO
3, NaCl, KCl, Be (CH
3COCHCOCH
3)
2, CaCl
2, BaCl
2, MnCl
2, Pd (NO
3)
2, TiCl
4, ZnCl
2, AlCl
3, Ga
2Cl
4, SnCl
4, PbCl
2, SbCl
3, SeCl
4, TeCl
4, CsCl, RbCl, SrCl
2, CeCl
3, PrCl
3, NdCl
3, SmCl
3, ReCl
3And BCl
3
8. as the metal-carbon composite of each described nanostructured of claim 1～7, wherein press total restatement of metal-carbon composite, contained amount of metal is 1～95wt%, and institute's phosphorus content is 5～99wt%.
9. the metal-carbon composite of nanostructured as claimed in claim 8 is wherein pressed total restatement of metal-carbon composite, and contained amount of metal is 4～36wt%, and institute's phosphorus content is 64～96wt%.
10. as the metal-carbon composite of claim 6 or 7 described nanostructureds, wherein press total restatement of metal-carbon composite, institute's platinum containing amount is 0.2～44wt%, and institute's phosphorus content is 56～99.8wt%.
11. the metal-carbon composite of nanostructured as claimed in claim 10 is wherein pressed total restatement of metal-carbon composite, institute's platinum containing amount is 2～34wt%, and institute's phosphorus content is 66～98wt%.
12. a method for preparing the metal-carbon composite of nanostructured comprises:
The preparation process of preparation nano template;
The calcination step of the nano template of calcination preparation;
Use metal precursor metal to be immersed the immersion step of the nano template of calcination;
Have in the nano template of metal in immersion, add carbon precursor and even adding and the blend step that mixes the carbon precursor;
Make add and blend step in the reactions steps that reacts of the mixture that makes;
The carburising step of the reactant mixture that carbonization obtains; And
From the carbonization mixture that obtains, remove the removal step of nano template.
13. method as claimed in claim 12, wherein this nano template is selected from silica, aluminium oxide or its mixture.
14. method as claimed in claim 13, wherein this nano template is a silica.
15. method as claimed in claim 12, wherein reactions steps is carried out under 100～160 ℃ temperature, and carburising step carries out under 800～1000 ℃ temperature.
16. as each described method of claim 12～15, wherein this carbon precursor is selected from furfuryl alcohol, dextrose plus saccharose.
17. method as claimed in claim 16, wherein this carbon precursor is a sucrose.
18. as each described method 12～17 of claim, wherein this metal-carbon composite comprises at least a be selected from following metal Pt, Ru, Cu, Ni, Mg, Co, W, Fe, Ir, Rh, Ag, Au, Os, Cr, Mo, V, Ta, Zr, Hf, Limitations, Na, K, Be, Ca, Ba, Mn, Pd, Ti, Zn, Al, Ga, Sn, Pb, Sb, Se, Te, Cs, Rb, Sr, Ce, Pr, Nd, Sm, Re and B.
19. method as claimed in claim 18, wherein this metal precursor is selected from (NH
3)
4Pt (NO
3)
2, (NH
3)
6RuCl
3, CuCl
2, Ni (NO
3)
2, Mg (NO
3)
2, CoCl
2, (NH
4)
6W
12O
39, FeCl
3Or FeCl
3(NH
4)
3, IrCl
6, RhCl
3, AgCl, NH
4AuCl
4, OsCl
3, CrCl
2, MoCl
5, VCl
3, TaCl
5, ZrCl
4, HfCl
4, Li
2CO
3, NaCl, KCl, Be (CH
3COCHCOCH
3)
2, CaCl
2, BaCl
2, MnCl
2, Pd (NO
3)
2, TiCl
4, ZnCl
2, AlCl
3, Ga
2Cl
4, SnCl
4, PbCl
2, SbCl
3, SeCl
4, TeCl
4, CsCl, RbCl, SrCl
2, CeCl
3, PrCl
3, NdCl
3, SmCl
3, ReCl
3And BCl
3
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20030024319 | 2003-04-17 | ||
| KR1020030024319 | 2003-04-17 | ||
| KR1020030058480 | 2003-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1774389A true CN1774389A (en) | 2006-05-17 |
Family
ID=36760898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800103708A Pending CN1774389A (en) | 2003-04-17 | 2004-04-16 | Nano-structured metal-carbon composite and process for preparation thereof |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100624084B1 (en) |
| CN (1) | CN1774389A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862062A (en) * | 2014-04-11 | 2014-06-18 | 南京大学 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
| CN105413726A (en) * | 2015-12-08 | 2016-03-23 | 上海师范大学 | Base catalyst embedded into carbon material as well as preparation method and application thereof |
| CN112143932A (en) * | 2020-09-10 | 2020-12-29 | 深圳金斯达应用材料有限公司 | Copper-based palladium coating bonding lead and manufacturing method thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100931825B1 (en) * | 2007-09-12 | 2009-12-15 | 충남대학교산학협력단 | Lithium cobalt oxide nanotube structure using carbon template sacrificial method and method for manufacturing same |
| KR101827626B1 (en) | 2016-04-11 | 2018-03-23 | 인하대학교 산학협력단 | Method for manufacturing formaldehyde from methanol and formaldehyde manufactured by the same |
| KR20220120728A (en) | 2021-02-22 | 2022-08-31 | 아머스 주식회사 | Coating composite for capturing and storing hydrogen gas under normal temperature and pressure |
| WO2023248242A1 (en) * | 2022-06-23 | 2023-12-28 | Anna University, Chennai | A method for synthesis of carbon-silica-metal composite and combination thereof |
-
2003
- 2003-08-23 KR KR1020030058480A patent/KR100624084B1/en not_active IP Right Cessation
-
2004
- 2004-04-16 CN CNA2004800103708A patent/CN1774389A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103862062A (en) * | 2014-04-11 | 2014-06-18 | 南京大学 | Composite material of copper nano particles evenly doped with submicron carbon spheres and one-step synthesis method thereof |
| CN105413726A (en) * | 2015-12-08 | 2016-03-23 | 上海师范大学 | Base catalyst embedded into carbon material as well as preparation method and application thereof |
| CN112143932A (en) * | 2020-09-10 | 2020-12-29 | 深圳金斯达应用材料有限公司 | Copper-based palladium coating bonding lead and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100624084B1 (en) | 2006-09-19 |
| KR20040090377A (en) | 2004-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6854531B2 (en) | electrode | |
| CN105776174B (en) | A kind of poroid carbon nanosheet of N doping and its preparation method and application | |
| JP2007519165A (en) | Nanostructured metal-carbon composite for electrode catalyst of fuel cell and production method thereof | |
| CN1781604A (en) | Mesoporous carbon composite containing carbon nanotube | |
| CN108716008A (en) | Three-dimensional ferronickel layered double-hydroxide array and its room temperature preparation method and application | |
| CN108754531A (en) | A kind of preparation method of the nano combined electrocatalysis material containing Co and Ru bimetallic carbon | |
| CN105826572A (en) | N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof | |
| CN107834078B (en) | Different-atom-doped honeycomb porous carbon material and preparation method thereof | |
| Muthurasu et al. | Ruthenium nanoparticles integrated bimetallic metal–organic framework electrocatalysts for multifunctional electrode materials and practical water electrolysis in seawater | |
| Wang et al. | MOF-templated nitrogen-doped porous carbon materials as efficient electrocatalysts for oxygen reduction reactions | |
| CN110292939A (en) | A kind of iridium nanocluster and its preparation method and application of double carbon confinements | |
| Rehman et al. | Controllable synthesis of a porous PEI-functionalized Co3O4/rGO nanocomposite as an electrochemical sensor for simultaneous as well as individual detection of heavy metal ions | |
| CN1774389A (en) | Nano-structured metal-carbon composite and process for preparation thereof | |
| KR100752265B1 (en) | Nano-structured metal-carbon composite for electrode catalyst of fuel cell and process for preparation thereof | |
| JP2006228502A (en) | Electrode catalyst for fuel cell, its manufacturing method, and electrode and fuel cell using the same | |
| US20060240256A1 (en) | Nano-structured metal-carbon composite and process for preparation thereof | |
| CN110277565B (en) | Platinum-indium catalyst for fuel cell and preparation method and application thereof | |
| Ye et al. | An ingeniously assembled metal–organic framework on the surface of FeMn co-doped Ni (OH) 2 as a high-efficiency electrocatalyst for the oxygen evolution reaction | |
| Sun et al. | Ternary ZnCo2O4 nanowire electrode materials for high-capacitance and flexible electrochemical capacitors | |
| Tasviri et al. | Nanosized NiFeSe 2/NiCo 2 O 4 hierarchical arrays on Ni foam as an advanced electrocatalyst for hydrogen generation | |
| CN110180594B (en) | Preparation method of electrocatalyst | |
| Pimonova et al. | Iron-/nitrogen-doped electrocatalytically active carbons for the oxygen reduction reaction with low amounts of cobalt | |
| Liu et al. | Two-dimension on two-dimension growth: hierarchical Ni 0.2 Mo 0.8 N/Fe-doped Ni 3 N nanosheet array for overall water splitting | |
| CN115570143B (en) | Low-platinum high-entropy alloy nano-particle and preparation method and application thereof | |
| Ji et al. | N-doped carbon as a promoted substrate for Ir nanoclusters toward hydrogen oxidation in alkaline electrolytes |
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 |