CN114797864A - Preparation method of catalyst for growth of small-diameter bulk-phase single-walled carbon nanotube - Google Patents
Preparation method of catalyst for growth of small-diameter bulk-phase single-walled carbon nanotube Download PDFInfo
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- CN114797864A CN114797864A CN202110082993.1A CN202110082993A CN114797864A CN 114797864 A CN114797864 A CN 114797864A CN 202110082993 A CN202110082993 A CN 202110082993A CN 114797864 A CN114797864 A CN 114797864A
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
Abstract
The invention provides a catalyst for the growth of a small-diameter bulk single-walled carbon nanotube, a preparation method thereof and a preparation method of the small-diameter single-walled carbon nanotube. The catalyst of the invention effectively limits the size of metal catalyst particles by using the complexing agent, the catalyst carrier is easy to remove, the subsequent application of the carbon nano tube is convenient, the process is simple, and the prepared carbon nano tube has smaller diameter and narrower tube diameter distribution.
Description
Technical Field
The invention relates to a preparation method of a carbon material growth catalyst, in particular to a preparation method of a small-diameter bulk-phase single-walled carbon nanotube growth catalyst.
Background
The structurally controllable growth of single-walled carbon nanotubes is a key challenge in high-end applications such as quantum devices, bioimaging, electronics, optoelectronics, and the like. The band gap width of the semiconductor single-walled carbon nanotube is directly related to the tube diameter. The band gap can be regulated and controlled by controlling the diameter of the single-walled carbon nanotube so as to meet the requirements of corresponding application. For example, for near infrared bioluminescence imaging, single-walled carbon nanotubes with a tube diameter of 0.8-1.2nm can emit fluorescence in the near infrared 2-region window of biological tissue. For a single photon light source in a quantum device, the single-walled carbon nanotube with the tube diameter of 0.9-1.2nm has a proper light-emitting wavelength. In the single-walled carbon nanotube thin film field effect transistor, the size and uniformity of the band gap of the carbon nanotube directly affect the performance of the device. In single-walled carbon nanotube-fullerene solar cells, the internal quantum efficiency of the cell decreases as the diameter of the carbon nanotube increases, which means that only small diameter carbon nanotubes are suitable for use in such solar cells. Meanwhile, the bulk carbon nanotubes with small diameters are easier to disperse in solution, so that the method is more suitable for separating and obtaining the carbon nanotubes with different conductivities and chiral indexes by a solution phase separation means.
In the process of growing single-walled carbon nanotubes by Chemical Vapor Deposition (CVD), two key factors for controlling the diameter of the carbon nanotubes are mainly used, one is the regulation and control of the size distribution of catalyst particles, and the other is the control of CVD conditions. First, the size distribution of the catalyst directly affects the diameter distribution of the carbon nanotubes. The zeolite, magnesia, alumina, mesoporous silica and the like can be synthesized into nano-particles with uniform and controllable size by a solution chemical method, and the nano-particles can be used as a catalyst or a catalyst precursor to grow the carbon nano-tube with controllable diameter. The size of the nano particles can be effectively controlled by using long-chain carboxylic acid or amine molecules as a protective agent or using apoferritin, dendritic polymers, block copolymers and the like as a nano reactor, so that a uniform carbon nano tube catalyst precursor can be synthesized. The catalyst support can generally serve to stabilize the size of the catalyst and limit catalyst agglomeration.
In the prior art, porous materials such as zeolite, mesoporous silica and the like are commonly used as catalyst carriers, and although the porous structure plays a role in limiting the size of the catalyst, the zeolite and the mesoporous silica carrier are difficult to remove, which brings certain inconvenience to the preparation and application of the carbon nanotube.
Disclosure of Invention
Based on the above technical background, the present inventors have conducted intensive studies and, as a result, found that: a catalyst precursor is prepared from a compound containing an element A, a catalyst carrier and a complexing agent, and then the metal catalyst prepared by burning and reduction can be used for growing a bulk-phase single-walled carbon nanotube with a small diameter.
The first aspect of the invention provides a catalyst for the growth of a small-diameter bulk-phase single-walled carbon nanotube, which is prepared from a compound containing an element A, a catalyst carrier and a complexing agent, wherein the element A is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium.
A second aspect of the present invention provides a method for preparing the catalyst of the first aspect of the present invention, comprising the steps of:
step 1, preparing a catalyst precursor by adopting a compound containing an element A, a catalyst carrier and a complexing agent;
step 2, preparing a catalyst by firing and reduction;
the element A is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium;
the compound containing the element A is selected from one or more of water-soluble salts containing the element A;
the catalyst carrier is selected from oxides of magnesium, aluminum, silicon, calcium and the like or mixed oxides and carbonates thereof, various zeolites, boron nitride and the like;
particularly, complexing agent molecules can coordinate metal ions of the element A, so that hydrolysis of the metal ions is inhibited, and agglomeration of the metal ions is reduced, so that the prepared metal catalyst particles can keep smaller and uniform size, and the growth of the small-diameter single-walled carbon nanotube is facilitated;
the complexing agent is selected from one or more of ammonia water, methylamine, pyridine, oxalate, phenanthroline, ethylenediamine, ethylene diamine tetraacetic acid or salts thereof, sodium tripolyphosphate, triethanolamine and sodium pyrophosphate.
A third aspect of the present invention is to provide a use of the catalyst according to the first aspect of the present invention or the catalyst for the growth of small-diameter bulk single-walled carbon nanotubes prepared by the preparation method of the second aspect of the present invention, which can be used for the preparation of small-diameter bulk single-walled carbon nanotubes.
The fourth aspect of the present invention is to provide a method for preparing a small-diameter bulk single-walled carbon nanotube, comprising the steps of:
step a, adding a catalyst into a tubular furnace, and raising the furnace temperature to the growth temperature of the carbon nano tube;
and b, introducing a carbon source to prepare the carbon nano tube.
The invention provides a small-diameter bulk-phase single-walled carbon nanotube growth catalyst and a small-diameter bulk-phase single-walled carbon nanotube prepared by the same, which have the following advantages: the catalyst carrier is easy to remove, the subsequent application of the carbon nano tube is facilitated, the preparation efficiency is high, the prepared carbon nano tube has a small diameter and narrow tube diameter distribution (the diameter distribution is 0.9-1.2 nm), and the method is suitable for being applied to the fields of near-infrared bioluminescence imaging, quantum device single photon light sources and the like.
Drawings
FIG. 1 shows Raman spectra of 532nm laser wavelength of carbon nanotubes prepared in comparative example 2 and comparative example 3 according to the present invention;
FIG. 2 shows Raman spectra of the laser wavelength of 633nm of the carbon nanotubes prepared in comparative example 2 and comparative example 3 according to the present invention;
FIG. 3 shows Raman spectra of 532nm in laser wavelength of carbon nanotubes prepared in comparative example 2, comparative example 4 and comparative example 5 according to the present invention;
FIG. 4 shows Raman spectra of the carbon nanotubes prepared by comparative examples 2, 4 and 5 of the present invention having a laser wavelength of 633 nm;
FIG. 5 shows Raman spectra of the carbon nanotubes prepared by comparative examples 2, 6, 7, 8, 9, 10, 11 and 12 according to the present invention at a laser wavelength of 532 nm;
FIG. 6 shows Raman spectra of the carbon nanotubes prepared by comparative examples 2, 6, 7, 8, 9, 10, 11 and 12 according to the present invention at a laser wavelength of 633 nm;
FIG. 7 shows Raman spectra of 532nm in laser wavelength of carbon nanotubes obtained in comparative example 2, comparative example 13, comparative example 14, comparative example 15 and comparative example 16 according to the present invention;
FIG. 8 shows Raman spectra of the carbon nanotubes obtained in comparative example 2, comparative example 13, comparative example 14, comparative example 15 and comparative example 16 of the present invention at a laser wavelength of 633 nm;
FIG. 9 shows Raman spectra of 532nm laser wavelength of the carbon nanotubes prepared in comparative example 2 and example 2 according to the present invention;
FIG. 10 shows Raman spectra of the laser wavelength of 633nm of the carbon nanotubes prepared in comparative example 2 and example 2 according to the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the invention provides a catalyst for growing a small-diameter bulk single-walled carbon nanotube, which is prepared from a compound containing an element A, a catalyst carrier and a complexing agent.
The compound containing the element A is selected from one or more of water-soluble salts containing the element A, preferably one or more of sulfate, nitrate and acetate containing the element A, and more preferably selected from sulfate containing the element A.
The element A in the invention is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium, preferably selected from one or more of iron, cobalt, nickel, copper, manganese and molybdenum, and more preferably selected from one or two of iron, cobalt and nickel.
The catalyst carrier is selected from one or more of magnesia, alumina, silica, calcium oxide, magnesium carbonate, aluminum carbonate, silicon carbonate, calcium carbonate, zeolite and boron nitride, preferably from one or more of magnesia, Y-type zeolite and silica, and more preferably from magnesia.
The molar ratio of the catalyst carrier to the compound containing the element A is (30-70): 1, preferably the molar ratio is (40-60): 1, more preferably the molar ratio is (45-55): 1. When a bimetal is used in the A element-containing compound, the molar ratio of the two metals is preferably 1: 1.
The complexing agent is selected from one or more of ammonia water, methylamine, pyridine, oxalate, phenanthroline, ethylenediamine, ethylene diamine tetraacetic acid or salt thereof, sodium tripolyphosphate, triethanolamine and sodium pyrophosphate, preferably selected from one or more of oxalate, ethylene diamine tetraacetic acid or salt thereof and sodium tripolyphosphate, and more preferably is ethylene diamine tetraacetic acid or ethylene diamine tetraacetic acid sodium salt.
The amount of the complexing agent added is 1 to 15 times, preferably 2 to 10 times, more preferably 4 to 7 times, for example 5 times, the molar amount (the molar amount, i.e., the number of moles in the present invention) of the molar amount of the compound containing the element a.
The catalyst according to the invention is prepared by a process comprising the steps of:
step 1, preparing a catalyst precursor by adopting a compound containing an element A, a catalyst carrier and a complexing agent;
and 2, preparing the catalyst by burning and reducing.
A second aspect of the present invention provides a method for preparing a catalyst for small-diameter bulk single-walled carbon nanotube growth according to the first aspect of the present invention, the method comprising the steps of:
step 1, preparing a catalyst precursor by adopting a compound containing an element A, a catalyst carrier and a complexing agent;
step 2, preparing a catalyst through firing and reduction;
this step is specifically described and illustrated below.
Step 1, preparing a catalyst precursor by adopting a compound containing an element A, a catalyst carrier and a complexing agent.
The catalyst precursor is prepared by mixing and post-treating a compound containing an element A and a catalyst carrier. Before mixing, the compound containing the element A and the catalyst carrier are dissolved in water and then mixed.
After the compound containing the element A is dissolved in water, the molar concentration of the element A is 0.1-1 mmol/mL, preferably 0.1-0.5 mmol/mL, and more preferably 0.1-0.2 mmol/mL.
The compound containing the element A is selected from one or more of water-soluble salts containing the element A, preferably one or more of sulfate, nitrate and acetate containing the element A, and more preferably selected from sulfate containing the element A.
In the preparation process, the compound containing the element A needs to be dissolved in water to prepare a solution, and then the solution is mixed with the catalyst carrier, so that the compound containing the element A is a water-soluble salt, the compound containing the element A can be hydrolyzed in the later evaporation process after being dissolved in water, the more severe the hydrolysis degree is, the more serious the agglomeration degree is, the larger the particle size of the formed catalyst is, the larger the diameter of the carbon nano tube is caused, the lower the hydrolysis degree of sulfate is, and the smaller the diameter of the prepared carbon nano tube is.
The element A in the invention is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium, preferably selected from one or more of iron, cobalt, nickel, copper, manganese and molybdenum, and more preferably selected from one or two of iron, cobalt and nickel.
The present inventors have found that the use of a bimetallic catalyst system, such as iron and cobalt, is effective in increasing the growth efficiency of carbon nanotubes while reducing the tube diameter and tube diameter distribution of the carbon nanotubes, as compared to a single metal catalyst.
The catalyst carrier is selected from one or more of magnesia, alumina, silica, calcium oxide, magnesium carbonate, aluminum carbonate, silicon carbonate, calcium carbonate, zeolite and boron nitride, preferably selected from one or more of magnesia, Y-type zeolite and silica, and more preferably selected from magnesia.
The porous catalyst carrier can limit the size of the catalyst through a pore passage with nanometer size so as to control the pipe diameter of the carbon nano tube, but porous structure carriers such as zeolite and the like are difficult to remove, which brings certain inconvenience to the subsequent application of the carbon nano tube, and magnesium oxide as the catalyst carrier can be removed by soaking in dilute acid, so that the method is very simple and convenient, the pipe diameter of the prepared carbon nano tube is small, and simultaneously the magnesium oxide can effectively control the sizes of iron and cobalt particles, so that the prepared carbon nano tube has small pipe diameter and narrow distribution.
Dispersing a catalyst carrier in water, wherein the concentration of the catalyst carrier is 0.05-1 g/mL, preferably the concentration of the catalyst carrier is 0.07-0.5 g/mL, and more preferably the concentration of the catalyst carrier is 0.1-0.2 g/mL.
The molar ratio of the catalyst carrier to the compound containing the element A is (30-70): 1, preferably the molar ratio is (40-60): 1, more preferably the molar ratio is (45-55): 1. When the catalyst is a bimetallic catalyst, the molar ratio of the two metals is preferably 1: 1.
According to a preferred embodiment of the present invention, a complexing agent is further added during the preparation of the catalyst precursor, and the present inventors have found that the added complexing agent can coordinate with metal ions such as iron and cobalt, thereby inhibiting the hydrolysis thereof, reducing the agglomeration thereof, and limiting the size of the catalyst particles, so that the size of the prepared metal catalyst particles can be kept small and uniform.
The complexing agent is selected from one or more of ammonia water, methylamine, pyridine, oxalate, phenanthroline, ethylenediamine, ethylene diamine tetraacetic acid or salt thereof, sodium tripolyphosphate, triethanolamine and sodium pyrophosphate, preferably selected from one or more of oxalate, ethylene diamine tetraacetic acid or salt thereof and sodium tripolyphosphate, and more preferably is ethylene diamine tetraacetic acid or ethylene diamine tetraacetic acid sodium salt.
The addition amount of the complexing agent is 1-15 times, preferably 2-10 times, and more preferably 4-7 times of the molar weight of the compound containing the element A.
The compound containing the element A and the catalyst carrier are preferably mixed under stirring, and the stirring time is preferably 5-20 min, and more preferably 10 min.
And heating and boiling after stirring, wherein the boiling time is preferably 20-45 min, and more preferably 30 min. And cooling and then carrying out post-treatment, wherein the post-treatment comprises suction filtration, washing and drying.
The detergent is preferably water and ethanol, and is washed for multiple times, preferably water and ethanol are washed for 1-3 times respectively, and preferably water and ethanol are washed for 2 times respectively.
And drying after washing, wherein the drying temperature is 100-150 ℃, the drying time is 10-15 h, preferably the drying temperature is 110-130 ℃, the drying time is 11-13 h, more preferably the drying temperature is 120 ℃, and the drying time is 12 h.
And 2, preparing the catalyst by burning and reducing.
And (3) sequentially burning and reducing the catalyst precursor prepared in the step (1) to obtain the catalyst. Both the firing and the reduction are carried out in a tube furnace.
The firing is preferably carried out in an air atmosphere, the firing temperature is 400-1200 ℃, the firing temperature is preferably 600-800 ℃, and the firing temperature is more preferably 700 ℃.
The burning time is 1-60 min, preferably 2-10 min, and more preferably 3 min.
And introducing inert gas into the tubular furnace after the firing so as to exhaust air in the tubular furnace, wherein the inert gas is preferably argon, the introducing rate of the inert gas is 100-300 sccm, the preferably introducing rate is 150-250 sccm, and the more preferably introducing rate is 200 sccm.
The introducing time is 2-15 min, preferably 3-10 min, and more preferably 4 min.
The reduction is preferably performed in a mixed atmosphere of an inert gas and hydrogen, the inert gas is preferably argon, and the inert gas is introduced at a rate of 50 to 200sccm, preferably 70 to 150sccm, and more preferably 100 sccm.
The hydrogen gas is introduced at a flow rate of 20 to 100sccm, preferably 40 to 70sccm, and more preferably 50 sccm.
The reduction temperature is 500-1200 ℃, the preferable reduction temperature is 800-1000 ℃, and the more preferable reduction temperature is 900 ℃.
The reduction time is 1-60 min, preferably 2-5 min, and more preferably 3 min.
A third aspect of the present invention provides a use of the catalyst according to the first aspect of the present invention or the catalyst prepared by the preparation method according to the second aspect of the present invention, which can be used for the preparation of small-diameter bulk single-walled carbon nanotubes.
The fourth aspect of the present invention provides a method for preparing a small-diameter single-walled carbon nanotube, comprising the steps of:
step a, adding a catalyst into a tube furnace, and raising the furnace temperature to the growth temperature of the carbon nano tube.
The catalyst is the catalyst according to the first aspect of the present invention or the catalyst prepared by the preparation method according to the second aspect of the present invention, and the prepared catalyst is placed in a tube furnace.
And adjusting the temperature of the tube furnace to the growth temperature of the carbon nano tube, wherein the temperature adjustment process is carried out under the protection of inert gas, preferably under the protection of argon.
The amount of argon gas is preferably from 100 to 300sccm, more preferably from 150 to 250sccm, and still more preferably 200 sccm.
The growth temperature of the carbon nano tube is 600-1000 ℃, the preferred growth temperature is 650-950 ℃, and the more preferred growth temperature is 700-900 ℃.
The growth temperature of the carbon nano tube is lower than 600 ℃ or higher than 1000 ℃, the growth efficiency of the carbon nano tube is obviously reduced, and the average tube diameter of the carbon nano tube is gradually increased along with the gradual rise of the temperature in the range of 600-1000 ℃.
The growth time of the carbon nano tube is 5-30 min, and the preferable growth time is 10-25 min. More preferably, the growth time is 15-20 min.
And b, introducing a carbon source to prepare the carbon nano tube.
In the present invention, the carbon source is selected from one or more of methanol, methane, carbon monoxide, ethanol, ethylene, acetylene, propanol, toluene and xylene, preferably from one or more of methanol, methane, carbon monoxide, ethanol and toluene, more preferably from one or more of methane and ethanol, such as ethanol.
The kind of the carbon source has a great influence on the diameter of the carbon nanotube, and experiments show that the diameter of the carbon nanotube grown by using ethanol as the carbon source is smaller than that of the carbon nanotube grown by other carbon sources under the same conditions.
In the present invention, the carbon nanotubes are grown by adding a mixture of an inert gas, preferably argon, and hydrogen.
The inert gas is introduced at a rate of 100 to 300sccm, preferably at a rate of 150 to 250sccm, and more preferably at a rate of 200 sccm.
The hydrogen gas is introduced at a flow rate of 10 to 50sccm, preferably 20 to 40sccm, and more preferably 30 sccm.
According to the invention, when the carbon source is a gas, the carbon source is introduced into the tube furnace together with an inert gas and hydrogen, and when the carbon source is a liquid, it is preferred that the liquid carbon source is placed in a bubbler, and the inert gas is introduced into the tube furnace after passing through the bubbler, the inert gas serving as a carrier gas for the carbon source.
The ratio of the inert gas carrier gas introduction rate of the liquid carbon source to the hydrogen gas introduction rate is 200: (5 to 100), preferably the ratio of the introduction rates is 200: (10 to 80), and more preferably the ratio of the flow rates is 200: (10-60).
The ratio of the carbon source to the hydrogen introduction rate also has an influence on the tube diameter of the carbon nano tube, the diameter of the carbon nano tube is gradually reduced along with the reduction of the carbon source to hydrogen introduction ratio, when the introduction ratio is too low, namely the hydrogen introduction rate is too high, the growth of the carbon nano tube is inhibited, if the carbon source introduction rate is too high, a grown graphitized carbon layer quickly coats a catalyst to prevent the catalyst from contacting new carbon source molecules, so that the catalyst is inactivated, and therefore, the growth preparation of the small-diameter carbon nano tube is facilitated only by the proper introduction rate ratio.
The diameter of the small-diameter single-walled carbon nanotube is 0.9-1.2 nm. The method is suitable for the fields of near-infrared biological fluorescence imaging, quantum device single photon light sources and the like.
The invention has the following beneficial effects:
(1) the catalyst for the growth of the small-diameter bulk-phase single-walled carbon nanotube uses a complexing agent in the preparation process, and the catalyst can effectively limit the size of catalyst particles, so that the growth of the small-diameter bulk-phase single-walled carbon nanotube is realized;
(2) the method for removing the catalyst carrier in the small-diameter bulk-phase single-walled carbon nanotube growth catalyst is simple, and the catalyst carrier can be removed only by soaking with dilute acid, so that the subsequent application of the carbon nanotube is facilitated;
(3) the carbon nanotube prepared by the preparation method of the carbon nanotube has a smaller diameter of 0.9-1.2nm, and is suitable for being applied to the fields of near-infrared bioluminescence imaging, quantum device single photon light sources and the like.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
EXAMPLE 1 preparation of the catalyst
Separately, 0.83 mmoleCo (SO) was weighed 4 ) 2 ·7H 2 O (purity 99.5%) and (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O (purity 95%) was dissolved in 7.0mL of ultrapure water, and 3.33g (83mmol) of light MgO was weighed out in 33mL of ultrapure water and sonicated for 5min until uniformly dispersed. Successively adding Co (SO) under stirring 4 ) 2 ·7H 2 O solution, (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 And dropwise adding an O solution into the MgO suspension (the concentrations of Fe and Co in the suspension are 0.16mol/L at this time), then adding EDTA (ethylene diamine tetraacetic acid) which is 5 times of the sum of the molar amounts of Fe and Co, stirring the suspension for 10min, boiling for 30min, cooling, carrying out suction filtration, washing twice by using ultrapure water and absolute ethyl alcohol respectively, and then placing in an oven for drying at 120 ℃ for 12h to obtain the FeCo/MgO catalyst precursor added with the complexing agent, wherein the molar ratio of Mg to Fe to Co is 100:1: 1.
Weighing 50mg of the prepared catalyst precursor in a 7 cm-0.5 cm porcelain boat, pushing the porcelain boat into the center of a tubular furnace, heating to 700 ℃ in air atmosphere, igniting for 3min, introducing Ar gas of 200sccm 4min to exhaust the air in the tubular furnace, simultaneously heating to 900 ℃, introducing Ar gas of 100sccm and H after heating to 900 DEG, and introducing the Ar gas of 100sccm and H 2 Keeping the temperature for 3min at 50sccm, and reducing to obtain the catalyst.
Example 2 preparation of carbon nanotubes
The catalyst prepared in example 1 was placed in a tube furnace, the furnace temperature was adjusted to 900 ℃ under the protection of 200sccm Ar gas, 200sccm Ar gas was passed through an ethanol (carbon source) bubbler (ice water bath constant temperature), and then passed through the tube furnace, and H was simultaneously passed through the tube furnace 2 30sccm, holding at 900 deg.C for 15min, and adding Ar gas and H 2 And reducing the temperature to room temperature under the protection of atmosphere to obtain the small-diameter single-walled carbon nanotube.
Comparative example
Comparative example 1
The procedure of example 1 was repeated except that: no ethylenediaminetetraacetic acid was added.
Comparative example 2
The procedure of example 2 was repeated except that: the catalyst prepared in comparative example 1 was used.
Comparative example 3
The procedure of comparative example 2 was repeated except that: the carbon source adopts methane, and CH is simultaneously introduced under the condition of introducing Ar gas of 200sccm 4 325sccm and H 2 The carbon nanotubes were prepared at 30 sccm.
Comparative example 4
The procedure of comparative example 2 was repeated except that: weighing 0.83 mmoleCo (NO) 3 ) 2 ·6H 2 O (purity 98.5%) and Fe (NO) 3 ) 3 ·9H 2 O (purity 98.5%) was dissolved in 7.0mL of ultrapure water.
Comparative example 5
The procedure of comparative example 2 was repeated except that: weighing 0.83 mmoleCo (CH) 3 COO) 2 ·4H 2 O (purity 95%) and (NH) 4 ) 2 Fe(SO 4 ) 2 ·6H 2 O (purity 99.5%) was dissolved in 7.0mL of ultrapure water.
Comparative example 6
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 80sccm。
Comparative example 7
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 60sccm。
Comparative example 8
Repeating pairThe preparation process of ratio 2, differing only in that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 50sccm。
Comparative example 9
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 40sccm。
Comparative example 10
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 20sccm。
Comparative example 11
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tube furnace while introducing H 2 10sccm。
Comparative example 12
The procedure of comparative example 2 was repeated except that: ar gas of 200sccm was passed through an ethanol (carbon source) bubbler (ice-water bath constant temperature) and introduced into a tubular furnace without introducing hydrogen gas.
Comparative example 13
The procedure of comparative example 2 was repeated except that: the temperature for growing the carbon nanotubes is 1000 ℃.
Comparative example 14
The procedure of comparative example 2 was repeated except that: the temperature for growing the carbon nanotubes is 900 ℃.
Comparative example 15
The procedure of comparative example 2 was repeated except that: the temperature for growing the carbon nano tube is 800 ℃.
Comparative example 16
The procedure of comparative example 2 was repeated except that: the temperature for growing the carbon nano tube is 600 ℃.
Examples of the experiments
Experimental example 1 Raman test
The carbon nanotubes prepared in comparative example 2 and comparative example 3 were subjected to raman measurement at laser wavelengths of 532nm and 633nm, respectively, using a raman spectrometer of the LabRAM armamis type from Horiba Jobin-Yvon corporation, and the measurement spectrum at the laser wavelength of 532nm is shown in fig. 1, and the measurement spectrum at the laser wavelength of 633nm is shown in fig. 2.
As can be seen from fig. 1 and 2, the RBM peak position of the carbon nanotubes grown by using ethanol is significantly higher than that of the carbon nanotubes grown by using methane, which indicates that the diameter of the carbon nanotubes grown by using methane is larger than that of the carbon nanotubes grown by using ethanol.
The carbon nanotubes prepared in comparative example 2, comparative example 4 and comparative example 5 were subjected to raman measurement at laser wavelengths of 532nm and 633nm, respectively, using a raman spectrometer of the LabRAM armamis model from Horiba Jobin-Yvon corporation, and the measurement spectra at the laser wavelengths of 532nm are shown in fig. 3 and 633nm, respectively.
As can be seen from fig. 3 and 4, the RBM peak of the carbon nanotube grown using the sulfate precursor (prepared in example 1) occurs at a higher wave number, that is, the tube diameter of the carbon nanotube is smaller, the acetate grows next to, and the tube diameter of the carbon nanotube grown using the nitrate is the largest.
The carbon nanotubes prepared in comparative example 2, comparative example 6, comparative example 7, comparative example 8, comparative example 9, comparative example 10, comparative example 11 and comparative example 12 were subjected to raman test using a LabRAM ARAMIS type raman spectrometer of Horiba Jobin-Yvon corporation at laser wavelengths of 532nm and 633nm, respectively, as shown in fig. 5 for a test spectrum at a laser wavelength of 532nm and 633nm for a test spectrum at a laser wavelength of 633nm, as shown in fig. 6.
As can be seen from FIGS. 5 and 6, the Raman spectrum shows 100-180 cm as the hydrogen flow rate gradually increases from 0 -1 The RBM peak gradually weakens or disappears (corresponding to the single-walled carbon nanotube with the diameter of 2.4-1.3 nm), and 200cm -1 The RBM peak above gradually increased (corresponding to single-walled carbon nanotubes with diameters less than 1.2nm), indicating that the diameter of the grown carbon nanotubes gradually decreased with decreasing carbon to hydrogen ratio in the CVD atmosphere. When the carbon-hydrogen ratio is too low, namely the hydrogen flow is too high, an RBM peak does not appear in a Raman spectrogram any more, and the growth of the carbon nano tube is inhibited.
The carbon nanotubes prepared in comparative example 2, comparative example 13, comparative example 14, comparative example 15 and comparative example 16 were subjected to raman measurement at laser wavelengths of 532nm and 633nm, respectively, using a raman spectrometer of the LabRAM armamis type from Horiba Jobin-Yvon corporation, and the measurement spectrum at the laser wavelength of 532nm is shown in fig. 7 and the measurement spectrum at the laser wavelength of 633nm is shown in fig. 8.
In fig. 7 and 8, as the growth temperature of the carbon nanotube increases from 700 ℃ to 900 ℃, the intensity of the RBM peak with a lower wave number in the raman spectrogram gradually increases, which means that the tube diameter of the carbon nanotube gradually increases with the increase of the temperature, and when the growth temperature is 600 ℃ and 1000 ℃, the growth efficiency of the carbon nanotube is obviously reduced, and the RBM peak does not appear in the raman spectrogram.
The carbon nanotubes prepared in comparative example 2 and example 2 were subjected to raman measurement at laser wavelengths of 532nm and 633nm respectively using a LabRAM ARAMIS type raman spectrometer of Horiba Jobin-Yvon corporation, and the measurement spectrum at the laser wavelength of 532nm is shown in fig. 9 and the measurement spectrum at the laser wavelength of 633nm is shown in fig. 10.
As can be seen from FIGS. 9 and 10, the RBM peak in the Raman spectrum of the carbon nanotube obtained after EDTA addition exhibits a blue shift, indicating that the diameter of the carbon nanotube after EDTA addition is reduced, as calculated from the RBM peak position (obtained from Zhang, D.; Yang, J.; Li, Y.Small,2013,9,1284-1304.doi: 10.1002/smll.201202986), and the diameter of the carbon nanotube grown after EDTA addition is in the range of 0.9-1.2 nm.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The catalyst for the growth of the small-diameter bulk-phase single-walled carbon nanotube is characterized by being prepared from a compound containing an element A, a catalyst carrier and a complexing agent, wherein the element A is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium.
2. The catalyst according to claim 1, wherein the complexing agent is selected from one or more of ammonia, methylamine, pyridine, oxalate, phenanthroline, ethylenediamine tetraacetic acid or a salt thereof, sodium tripolyphosphate, triethanolamine and sodium pyrophosphate.
3. The preparation method of the catalyst for the growth of the small-diameter bulk single-walled carbon nanotube is characterized by comprising the following steps of:
step 1, preparing a catalyst precursor by adopting a compound containing an element A, a catalyst carrier and a complexing agent;
and 2, preparing the catalyst by burning and reducing.
4. The production method according to claim 3, wherein, in step 1,
the element A is selected from one or more of iron, cobalt, nickel, molybdenum, chromium, copper, tungsten, manganese, silver, gold, palladium, platinum, ruthenium, iridium, rhodium and rhenium;
the compound containing the element A is selected from one or more of water-soluble salts containing the element A;
the catalyst carrier is selected from one or more of magnesia, alumina, silica, calcium oxide, magnesium carbonate, aluminum carbonate, silicon carbonate, calcium carbonate, zeolite and boron nitride.
5. The production method according to claim 4, wherein, in step 1,
the molar ratio of the catalyst carrier to the compound containing the element A is (30-70): 1.
6. The production method according to claim 3, wherein, in step 1,
the complexing agent is selected from one or more of ammonia water, methylamine, pyridine, oxalate, phenanthroline, ethylenediamine, ethylene diamine tetraacetic acid or salts thereof, sodium tripolyphosphate, triethanolamine and sodium pyrophosphate;
the addition amount of the complexing agent is 1-15 times of the molar weight of the compound containing the element A.
7. The production method according to claim 3, wherein, in the step 2,
the firing temperature is 400-1200 ℃, the firing atmosphere is air, and the firing time is 1-60 min;
the reduction temperature is 500-1200 ℃, the reduction atmosphere is a mixed gas of hydrogen and inert gas, and the reduction time is 1-60 min.
8. Use of a catalyst according to any one of claims 1 to 2 or a catalyst prepared according to the method of any one of claims 3 to 7 for the preparation of small diameter bulk single-walled carbon nanotubes.
9. A method of making small diameter bulk single-walled carbon nanotubes, the method comprising the steps of:
step a, adding a catalyst into a tubular furnace, and raising the furnace temperature to the growth temperature of the carbon nano tube;
and b, introducing a carbon source to prepare the carbon nano tube.
10. The production method according to claim 9,
in step a, the catalyst is the catalyst for the growth of the small-diameter bulk single-walled carbon nanotube according to claim 1 or 2;
the growth temperature of the carbon nano tube is 600-1000 ℃, and the growth time is 5-30 min;
in the step b, the carbon source is selected from one or more of methanol, methane, carbon monoxide, ethanol, ethylene, acetylene, propanol, toluene and xylene.
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| CN115672335A (en) * | 2022-11-10 | 2023-02-03 | 无锡碳谷科技有限公司 | Preparation method of iron-nickel-aluminum ternary nano catalyst |
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