CN100444953C - Heterostructure material of hydrotalcite and carbon nanotube and its prepn process - Google Patents
Heterostructure material of hydrotalcite and carbon nanotube and its prepn process Download PDFInfo
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- CN100444953C CN100444953C CNB2007100985427A CN200710098542A CN100444953C CN 100444953 C CN100444953 C CN 100444953C CN B2007100985427 A CNB2007100985427 A CN B2007100985427A CN 200710098542 A CN200710098542 A CN 200710098542A CN 100444953 C CN100444953 C CN 100444953C
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Abstract
The present invention provides one kind of heterostructure material of hydrotalcite and carbon nanotube and its preparation process. Carbon nanotube and bridging molecule L-cysteine are first added into alkali solution and the mixture solution of soluble bivalent metal salt and trivalent metal salt is then added to produce co-precipitation reaction to prepare hydrotalcite. During the reaction, the -NH2 end of L-cysteine existing in positively charged -NH3+ combines stably with the negatively charged -COO- and -O- radicals in the surface of carbon nanotube while the -SH end of L-cysteine and the metal ion in the hydrotalcite layer form coordinate bond, so that hydrotalcite is assembled onto carbon nanotube by means of the bridging effect. The present invention can raise the dispersivity of hydrotalcite particle and the active center, and the obtained heterostructure material is homogeneous, stable, strong in binding force and adjustable in assembled amount.
Description
Technical field
The invention belongs to the technical field of material structure preparation and assemble method.Be specifically related to hydrotalcite/carbon nanotube heterojunction structure material and preparation method thereof, adopt the resulting system of the method to have Stability Analysis of Structures, good dispersion, characteristics that composition is adjustable.
Background technology
CNT be a class have hollow tubular structure, than the carbon-based material of bigger serface, because its particular structure characteristics and physicochemical characteristics, have broad application prospects at numerous areas such as absorption, photoelectricity, Chu Qing, the energy, catalysis, wherein a class important use is as catalyst carrier, be used for specific catalytic reaction, improve catalytic performance.After simple processing of CNT process and the finishing, its outer surface will connect functional groups such as many hydroxyls, carboxyl, and these electronegative groups can form more stable composite construction system by electrostatic force with having electropositive molecule or group.
Document Q.Hong, et al.J.Mater.Chem.2001,11,2378.B.Yoon, et al.J.Am.Chem.Soc.2005,127,17174. have introduced the surface that metal nanoparticle (Pd, Pt, Ag, Au) that the method for utilizing liquid phase or microemulsion will have catalytic activity is assembled in CNT.Document X.-R.Ye, et al.J.Mater.Chem.2004,14,908. have introduced and utilize supercritical fluid processes that metal nanoparticle is loaded on the CNT.These methods need the preparation condition of strict control, and the package assembly stability that obtains is bad.
Hydrotalcite (LDHs) is an anionoid type layered inorganic functional material, and in the LDHs crystal structure, metal ion evenly distributes on laminate in a certain way, has formed specific chemical composition and structure.Because uniformity and the Modulatory character of LDHs on chemical composition and microstructure, so this class material is the good precursor of preparation catalyst.But because in the intensification roasting process, the hydrotalcite laminate caves in gradually, agglomeration between particle, has caused that particle bad dispersibility, specific surface reduce, the activated centre number reduces, and then influences catalytic activity.This has limited the application of LDHs material as catalyst precarsor to a great extent.In order to overcome this shortcoming, improve the dispersiveness of LDHs precursor, the gathering of minimizing active particle, be necessary LDHs is assembled on a kind of outstanding catalyst carrier, thereby improve the dispersiveness of LDHs, the reunion of reduction product of roasting, expose more activated centre, to strengthen its catalytic activity.Simple mixing or composite pathway can cause the compound system structural homogeneity after the assembling poor, and unstable, and under the condition that is subjected to external force or heating, compound system can produce the phenomenon of mutual disengaging.Therefore be necessary to develop special assembling means, make that the compound system after the assembling has good dispersion, structure homogeneous and stable characteristics.At present, utilizing the bridging molecule of being with functional group that hydrotalcite is assembled in the method that obtains the composite heterogenous junction structure on the CNT does not appear in the newspapers.
Summary of the invention
The objective of the invention is to be contained on the CNT by effective assemble method controllable groups, obtain a kind of novel function heterogeneous structure material forming adjustable hydrotalcite.This structure has not only improved the dispersiveness in hydrotalcite activated centre, and the compound system after the assembling has advantages such as Stability Analysis of Structures, the assembling amount is adjustable.
Hydrotalcite (LDHs) is an anionoid type stratiform functional material, and its chemical composition is expressed as [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+Can be Mg
2+, Ni
2+, Co
2+, Zn
2+, Fe
2+, Cu
2+Deng divalent metal; M
3+Be Al
3+, Cr
3+, Ga
3+, In
3+, Fe
3+Deng trivalent metal cation; A
N-Be interlayer anion, as CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, C
6H
4(COO)
2 2-Etc. inorganic, organic ion or complex ion.Because therefore the structural homogeneity of LDHs and the adjustable sex change of composition are the good precursors of preparation catalyst material.In order to improve the dispersiveness of LDHs precursor, the reunion of active particle and the minimizing of catalytic active center after the reduction roasting, be necessary to utilize catalyst carrier to pass through specific assemble method, in preparation process the LDHs controllable groups is contained on the carrier, form even, stable new function heterojunction structure, to avoid influencing catalytic performance owing to the gathering of LDHs particle.At this problem, the present invention proposes at the LDHs synthesis phase, introduces catalyst carrier---and the CNT of modification and have the bridging molecule of multi-functional group, utilize the L-cysteine as the bridging molecule.In the aqueous solution L-cysteine-NH
2End is with-NH
3 +Form exists, and has electronegative-COO by electrostatic interaction and surface
-And O
-The CNT stable bond of group; Simultaneously the L-cysteine-SH can form stable coordinate bond with the metal ion on the hydrotalcite laminate, utilize the interaction between functional group that synthetic LDHs molecule effectively, controllably is assembled on the carbon nanotube carrier like this, form evenly assembling, stable composite heterogenous junction structure.
The concrete preparation method of this hydrotalcite/carbon nanotube heterojunction structure material is as follows:
A. CNT is packed into and be with in the reaction vessel of condensing unit, adding 10-20ml concentration by every gram CNT is 65% red fuming nitric acid (RFNA), under recirculated water condensation condition with vlil 3-10 hour, after backflow is finished, treat that it is chilled to room temperature and carries out suction filtration, spend deionised water to neutral, it is dry to put into 60 ℃ of baking ovens, collects the CNT that obtains modifying.
Used CNT is: external diameter 20-100nm, the multi-walled carbon nano-tubes of length 1-15 μ m.The material carbon nanotube was heated in 65% red fuming nitric acid (RFNA) reflow treatment 5-10 hour, so not only can make carbon nano tube surface modify functional group such as hydroxyl, the carboxyl etc. of going up some, also can remove catalyst granules remaining in the raw material.
B. solubility divalent metal salt and trivalent metal salt are dissolved in that preparation contains M in the deionized water
2+And M
3+Mixing salt solution, M wherein
2+Molar concentration be 0.1-1.0M, M
3+Molar concentration be 0.05-0.5M, M
2+With M
3+Mol ratio be 2-5: 1, preferable mol ratio is 2-3: 1; Wherein the acid ion in the mixing salt solution is NO
3 -, Cl
-Or SO
4 2-In the 1-2 kind; M
2+Be Co
2+, Ni
2+, Mg
2+, Zn
2+Or Cu
2+In a kind or 2 kinds, preferably Co
2+Or Ni
2+, M
3+Be Al
3+, Cr
3+, Fe
3+, Ga
3+Or In
3+In a kind or 2 kinds, preferably Al
3+Or Fe
3+
With preparing mixed ammonium/alkali solutions in NaOH and the soluble sodium salt adding deionized water, wherein naoh concentration is 0.4-2.8M, and the soluble sodium salinity is 0.1-1.0M; Soluble sodium salt is any one in sodium carbonate, sodium chloride, sodium nitrate or the sodium sulphate;
Be the additional liquid of NaOH of 0.4-2.8M in addition with NaOH and deionized water configuration molar concentration.
C. the mixed ammonium/alkali solutions with step B preparation adds in the reactor of band stirring, the CNT and the L-cysteine that at room temperature add modified while stirring, wherein the mass ratio of CNT that is added and divalent metal salt is 0.05-0.1: 1, and L-cysteine and M
2+Mol ratio be 0.5-4: 1; After treating fully dissolving, the mixing salt solution of step B preparation is added drop-wise in the above-mentioned reactor, and dropping sodium is replenished liquid, the pH value of control solution is between 7-11, after salting liquid to be mixed drips, temperature is risen to crystallization temperature 40-65 ℃ by room temperature, crystallization 2-20 hour, reaction finishes the back suction filtration, be washed till neutrality with deionized water, use absolute ethanol washing 3-5 time again, at last filter cake is put into 60 ℃ of baking oven vacuum drying 6-24h, promptly obtain hydrotalcite/CNT assembling heterogeneous structure material;
The sample that obtains is characterized with XRD and transmission electron microscope (TEM), (002) characteristic peak (seeing Fig. 1, Fig. 2) that has obviously occurred (003), (006) and (110) and the CNT of corresponding hydrotalcite on Fig. 1, Fig. 2 XRD spectra, the structure of these characteristic peak explanation hydrotalcites and the structure of CNT are not destroyed after assembling.The hydrotalcite that can be observed sheet from TEM is assembled in carbon nano tube surface, and the average grain size of hydrotalcite is at 10-50nm (seeing Fig. 3, Fig. 4).
The present invention has following remarkable result:
A. by electrostatic interaction and cooperate and bond function between functional group, hydrotalcite effectively can be assembled in carbon nano tube surface, the compound system after the assembling is even, stable.
B. by changing the use amount of bridging molecule L-cysteine, can regulate the assembling amount of hydrotalcite on CNT, therefore assembling measurer has Modulatory character.
C. the The Nomenclature Composition and Structure of Complexes of hydrotalcite has Modulatory character, can be assembled on the CNT forming different hydrotalcites.
D. hydrotalcite is assembled on the CNT, can improves the dispersiveness of hydrotalcite particle, expose more activated centre, thereby overcome the drawback that causes the activated centre decreased number because of particle aggregation.
Description of drawings
Fig. 1. be assembled in the XRD spectra of carbon nano tube surface for the cobalt aluminium carbonate type hydrotalcite of embodiment 1 preparation.
Fig. 2. be assembled in the XRD spectra of carbon nano tube surface for the nickel aluminium nitrate anion type hydrotalcite of embodiment 2 preparations.
Fig. 3. be assembled in the TEM figure (length of the scale is 333nm among the figure) of carbon nano tube surface for the cobalt aluminium carbonate hydrotalcite of embodiment 1 preparation.
Fig. 4. be assembled in the TEM figure (length of the scale is 67nm among the figure) of carbon nano tube surface for the nickel aluminium nitrate anion hydrotalcite of embodiment 2 preparations.
The specific embodiment
Embodiment one
The CNT of getting 3g length and be 5～15 μ m diameters and be 40～60nm is packed in the there-necked flask, adding 100ml concentration is 65% nitric acid, add hot reflux 6h, after backflow is finished, be chilled to room temperature and carry out suction filtration, and spend deionised water to neutral, and put into 60 ℃ of dry 12h of baking oven then, collect the CNT that obtains modifying.
With 4.3655g Co (NO
3)
26H
2O and 1.8756g Al (NO
3)
39H
2O joins deionized water preparation mixing salt solution, the wherein Co (NO of the 100ml degassing
3)
26H
2O and Al (NO
3)
39H
2The molar concentration of O is respectively 0.15M and 0.05M, in addition with 1.600g NaOH and 1.0599g Na
2CO
3Join the deionized water preparation mixed-alkali solution of the 100ml degassing, wherein NaOH and Na
2CO
3Molar concentration is respectively 0.4M and 0.1M, this mixed-alkali solution is poured in the four-hole bottle, the L-cysteine that adds 0.5g CNT and 0.015mol again, stirring at room slowly drips mixing salt solution, when pH=10.5 then to evenly, fixed intact with the NaOH refill droplet of 0.6M until the mixing salt solution titration, the water-bath heating is 60 ℃ then, crystallization 6h, and entire reaction course is carried out under the condition of logical nitrogen.Reaction finishes the back suction filtration, is washed till neutrality with the deionized water that outgases, and uses absolute ethanol washing again 3 times, at last filter cake is put into 60 ℃ of dry 12h of vacuum drying oven and is obtained product.
Can observe (003), (006) and (110), the characteristic peak of (113) and the diffraction maximum of CNT (002) of hydrotalcite by the XRD spectra of Fig. 1, calculated by the Scherrer equation that grain size is 19nm on (003) direction, crystallite dimension is 27nm on (110) direction.Can observe the hydrotalcite uniform crystal particles by Fig. 3 transmission electron microscope photo and be assembled on the CNT, show that prepared structure is hydrotalcite/carbon nanotube heterojunction structure.
Embodiment two
With 3g length is 5～15 μ m, diameter is that the CNT of 20～40nm is packed in the there-necked flask, adding 100ml concentration is 65% nitric acid, add hot reflux 8h, after backflow is finished, be chilled to room temperature and carry out suction filtration, and spend deionised water to neutral, put into 60 ℃ of dry 12h of baking oven then, collect the CNT that obtains modifying.
With 9.3056g Ni (NO
3)
26H
2O and 6.0021g Al (NO
3)
39H
2O joins deionized water preparation mixing salt solution, the wherein Ni (NO of the 80ml degassing
3)
26H
2O, Al (NO
3)
39H
2The molar concentration of O is respectively 0.4M, 0.2M, in addition with 3.840g NaOH and 2.7197g NaNO
3Join the deionized water preparation mixed-alkali solution of the 80ml degassing, wherein NaOH and NaNO
3Molar concentration is respectively 1.2M and 0.4M, the L-cysteine that adds 1g CNT and 0.03mol after being poured into this mixed-alkali solution in the four-hole bottle, stirring at room is to even, slowly drip mixing salt solution then, when pH=10, fixed intact until the mixing salt solution titration with the NaOH refill droplet of 1.6M, the water-bath heating is 60 ℃ then, crystallization 6h, entire reaction course is carried out under the condition of logical nitrogen.Reaction finishes the back suction filtration, is washed till neutrality with the deionized water that outgases, and uses absolute ethanol washing again 4 times, at last filter cake is put into 60 ℃ of dry 15h of vacuum drying oven and is obtained product.
Can observe (003), (006) and (110), the characteristic peak of (113) and the diffraction maximum of CNT (002) of hydrotalcite by the XRD spectra of Fig. 2, calculated by the Scherrer equation that grain size is 8nm on (003) direction, crystallite dimension is 17nm on (110) direction.Can observe the hydrotalcite uniform crystal particles by Fig. 4 transmission electron microscope photo and be assembled on the CNT, show that prepared structure is hydrotalcite/carbon nanotube heterojunction structure.
Embodiment three
With 2g length is 5～15 μ m, diameter is that the CNT of 20～40nm is packed in the there-necked flask, adding 80ml concentration is 65% nitric acid, add hot reflux 5h, after backflow is finished, be chilled to room temperature and carry out suction filtration, and spend deionised water to neutral, put into 60 ℃ of dry 12h of baking oven then, collect the CNT that obtains modifying.
With 14.2620g NiCl
26H
2O and 5.4060g FeCl
39H
2O joins deionized water preparation mixing salt solution, the wherein NiCl of the 100ml degassing
26H
2O, FeCl
39H
2The molar concentration of O is respectively 0.6M, 0.2M, in addition 6.4000g NaOH and 2.3376g NaCl are joined the deionized water preparation mixed-alkali solution that 100ml outgases, wherein NaOH and NaCl molar concentration are respectively 1.6M and 0.4M, the L-cysteine that adds 0.8g CNT and 0.06mol after being poured into this mixed-alkali solution in the four-hole bottle, stirring at room is to even, slowly drip mixing salt solution then, when pH=8, fixed intact with the NaOH refill droplet of 2M until the mixing salt solution titration, the water-bath heating is 65 ℃ then, crystallization 8h, entire reaction course is carried out under the condition of logical nitrogen.Reaction finishes the back suction filtration, is washed till neutrality with the deionized water that outgases, and uses absolute ethanol washing again 3 times, at last filter cake is put into 60 ℃ of dry 18h of vacuum drying oven and is obtained product.
Observe (003), (006) and (110), the characteristic peak of (113) and the diffraction maximum of CNT (002) of hydrotalcite by XRD, can get the size of crystal grain on (003) direction by the calculating of Scherrer equation is 15nm, and the size on (110) direction is 29nm.Can observe the hydrotalcite uniform crystal particles by transmission electron microscope and be assembled on the CNT, show that prepared structure is hydrotalcite/carbon nanotube heterojunction structure.
Embodiment four
With 5g length is 5～15 μ m, diameter is that the CNT of 40～60nm is packed in the there-necked flask, adding 100ml concentration is 65% nitric acid, add hot reflux 6h, after backflow is finished, be chilled to room temperature and carry out suction filtration, and spend deionised water to neutral, put into 60 ℃ of dry 12h of baking oven then, collect the CNT that obtains modifying.
With 6.9847g Co (NO
3)
26H
2O, 2.0512g Mg (NO
3)
26H
2O and 6.0021g Al (NO
3)
39H
2O joins deionized water preparation mixing salt solution, the wherein Co (NO3) of the 80ml degassing
26H
2O, Mg (NO
3)
26H
2O and Al (NO
3)
39H
2The molar concentration of O is respectively 0.3M, 0.1M, 0.2M, in addition with 3.8400gNaOH and 2.7197gNaNO
3Join the deionized water preparation mixed-alkali solution of the 80ml degassing, wherein NaOH and NaNO
3Molar concentration is respectively 1.2M and 0.4M, the L-cysteine that adds 0.5g CNT and 0.03mol after being poured into this mixed-alkali solution in the four-hole bottle, stirring at room is to even, slowly drip mixing salt solution then, when pH=10.5, fixed intact until the mixing salt solution titration with the NaOH refill droplet of 1.5M, the water-bath heating is 50 ℃ then, crystallization 16h, entire reaction course is carried out under the condition of logical nitrogen.Reaction finishes the back suction filtration, is washed till neutrality with the deionized water that outgases, and uses absolute ethanol washing again 3 times, at last filter cake is put into 60 ℃ of dry 18h of vacuum drying oven and is obtained product.
Can detect (003), (006) and (110), the characteristic peak of (113) and the diffraction maximum of CNT (002) of hydrotalcite by XRD, calculating crystal grain size on (003) direction by the Scherrer equation is 18nm, and the size on (110) direction is 34nm.Can observe the hydrotalcite uniform crystal particles by transmission electron microscope and be assembled on the CNT, show that prepared structure is hydrotalcite/carbon nanotube heterojunction structure.
Embodiment five
With 3g length is 1～2 μ m, diameter is that the CNT of 60～100nm is packed in the there-necked flask, adding 100ml concentration is 65% nitric acid, add hot reflux 6h, after backflow is finished, be chilled to room temperature and carry out suction filtration, and spend deionised water to neutral, put into 60 ℃ of dry 12h of baking oven then, collect the CNT that obtains modifying.
With 11.6412g Co (NO
3)
26H
2O, 5.6269g Al (NO
3)
39H
2O and 8.4302g Fe
2(SO
4)
39H
2O joins deionized water preparation mixing salt solution, the wherein Co (NO of the 100ml degassing
3)
26H
2O, Al (NO
3)
39H
2O and Fe
2(SO
4)
39H
2The molar concentration of O is respectively 0.4M, 0.15M, 0.15M, in addition with 5.6000g NaOH and 8.5212gNa
2SO
4Join deionized water preparation mixed ammonium/alkali solutions, the wherein NaOH and the Na of the 100ml degassing
2SO
4Molar concentration is respectively 1.4M and 0.6M, the L-cysteine that adds 0.8g CNT and 0.04mol after being poured into this mixed-alkali solution in the four-hole bottle, stirring at room is to even, slowly drip mixing salt solution then, when pH=9.5, fixed intact until the mixing salt solution titration with the NaOH refill droplet of 1.5M, the water-bath heating is 60 ℃ then, crystallization 8h, entire reaction course is carried out under the condition of logical nitrogen.Reaction finishes the back suction filtration, is washed till neutrality with the deionized water that outgases, and uses absolute ethanol washing again 4 times, at last filter cake is put into 60 ℃ of dry 12h of vacuum drying oven and is obtained product.
(003), (006) and (110), the characteristic peak of (113) and the diffraction maximum of CNT (002) that occur hydrotalcite in the XRD spectrum of this product, calculate to such an extent that crystal grain size on (003) direction is 21nm by the Scherrer equation, the size on (110) direction is 35nm.Can observe the hydrotalcite uniform crystal particles by transmission electron microscope and be assembled on the CNT, show that prepared structure is hydrotalcite/carbon nanotube heterojunction structure.
Claims (5)
1. hydrotalcite/carbon nanotube heterojunction structure preparation methods, concrete steps are as follows:
A. CNT is packed into and be with in the reaction vessel of condensing unit, adding 10-20ml concentration by every gram CNT is 65% red fuming nitric acid (RFNA), under recirculated water condensation condition with vlil 3-10 hour, after backflow is finished, treat that it is chilled to room temperature and carries out suction filtration, spend deionised water to neutral, it is dry to put into 60 ℃ of baking ovens, collects the CNT that obtains modifying;
B. solubility divalent metal salt and trivalent metal salt are dissolved in that preparation contains M in the deionized water
2+And M
3+Mixing salt solution, M wherein
2+Molar concentration be 0.1-1.0M, M
3+Molar concentration be 0.05-0.5M, M
2+With M
3+Mol ratio be 2-5: 1; Acid ion in the mixing salt solution is NO
3 -, Cl
-Or SO
4 2-In a kind or 2 kinds; M
2+Be Co
2+, Ni
2+, Mg
2+, Zn
2+, Cu
2+In a kind or 2 kinds, M
3+Be Al
3+, Cr
3+, Fe
3+, Ga
3+, In
3+In a kind or 2 kinds;
With preparing mixed ammonium/alkali solutions in NaOH and the soluble sodium salt adding deionized water, wherein naoh concentration is 0.4-2.8M, and the soluble sodium salinity is 0.1-1.0M; Soluble sodium salt is any one in sodium carbonate, sodium chloride, sodium nitrate or the sodium sulphate;
Be the additional liquid of NaOH of 0.4-2.8M in addition with NaOH and deionized water preparation molar concentration;
C. the mixed ammonium/alkali solutions with step B preparation adds in the reactor of band stirring, the CNT and the L-cysteine that at room temperature add modified while stirring, wherein the mass ratio of the CNT of the modified that is added and divalent metal salt is 0.05-0.1: 1, and L-cysteine and M
2+Mol ratio be 0.5-4: 1; After treating fully dissolving, the mixing salt solution of step B preparation is added drop-wise in the above-mentioned reactor, and dropping sodium is replenished liquid, the pH value of control solution is between 7-11, after salting liquid to be mixed drips, temperature is risen to crystallization temperature 40-65 ℃ by room temperature, crystallization 2-20 hour, reaction finishes the back suction filtration, is washed till neutrality with deionized water, uses absolute ethanol washing 3-5 time again, at last filter cake is put into 60 ℃ of baking oven vacuum drying 6-24h, promptly obtain hydrotalcite/carbon nanotube heterojunction structure material, this material is that the hydrotalcite of sheet is assembled in carbon nano tube surface, and the average grain size of hydrotalcite is at 10-50nm.
2. hydrotalcite according to claim 1/carbon nanotube heterojunction structure preparation methods is characterized in that, used CNT is that external diameter is that 20-100nm and length are the multi-walled carbon nano-tubes of 1-15 μ m.
3. hydrotalcite according to claim 1/carbon nanotube heterojunction structure preparation methods is characterized in that the described M of step B
2+With M
3+Mol ratio be 2-3: 1; M
2+Be Co
2+Or Ni
2+, M
3+Be Al
3+Or Fe
3+
4. hydrotalcite/carbon nanotube heterojunction structure material is characterized in that this material is to adopt claim 1,2 or 3 described method preparations.
5. hydrotalcite according to claim 4/carbon nanotube heterojunction structure material, the hydrotalcite that it is characterized in that being assembled in carbon nano tube surface is a laminated structure, average grain size is at 10-50nm.
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| CN1438072A (en) * | 2003-03-03 | 2003-08-27 | 清华大学 | Catayst for preparing carbon-nano tube |
| CN1579622A (en) * | 2003-07-31 | 2005-02-16 | 北京化工大学 | High dispersion copper base oxidation catalyst prepared by intercalation precursor and its preparing method |
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2007
- 2007-04-20 CN CNB2007100985427A patent/CN100444953C/en not_active Expired - Fee Related
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| JPH11139815A (en) * | 1997-11-07 | 1999-05-25 | Canon Inc | Carbon nanotube device and its manufacture |
| CN1438072A (en) * | 2003-03-03 | 2003-08-27 | 清华大学 | Catayst for preparing carbon-nano tube |
| CN1579622A (en) * | 2003-07-31 | 2005-02-16 | 北京化工大学 | High dispersion copper base oxidation catalyst prepared by intercalation precursor and its preparing method |
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| 插层组装超分子结构有机物柱撑阴离子层状材料. 孟锦宏等.化学通报，第66卷第2期. 2003 |
| 插层组装超分子结构有机物柱撑阴离子层状材料. 孟锦宏等.化学通报，第66卷第2期. 2003 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103386306A (en) * | 2013-08-07 | 2013-11-13 | 上海师范大学 | Cu/CuxO/TiO2 heterojunction visible light catalyst, as well as preparation method and application thereof |
| CN103386306B (en) * | 2013-08-07 | 2015-05-20 | 上海师范大学 | Cu/CuxO/TiO2 heterojunction visible light catalyst, as well as preparation method and application thereof |
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| CN101066526A (en) | 2007-11-07 |
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