CN109248684A - A kind of MWCNT@Cu composite catalyst and its preparation method and application - Google Patents
A kind of MWCNT@Cu composite catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109248684A CN109248684A CN201810931235.0A CN201810931235A CN109248684A CN 109248684 A CN109248684 A CN 109248684A CN 201810931235 A CN201810931235 A CN 201810931235A CN 109248684 A CN109248684 A CN 109248684A
- Authority
- CN
- China
- Prior art keywords
- mwcnt
- walled carbon
- array
- carbon nanotube
- composite catalyst
- 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.)
- Withdrawn
Links
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 7
- 238000004544 sputter deposition Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000005477 sputtering target Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000011257 shell material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- -1 hydrogen alkane Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of MWCNT@Cu composite catalysts and its preparation method and application.The MWCNT Cu composite catalyst includes multi-walled carbon nanotube that is independent, being vertically arranged being grown on vitreous carbon and magnetron sputtering deposits on the multi-walled carbon nanotube polycrystalline copper；The diameter of the multi-walled carbon nanotube is 10~300nm, and length is 100~5000nm, and the distance between pipe is 50nm or more in array of multi-walled carbon nanotubes.The present invention is using the carbon electrode with nano-scale dimension, bigger serface as carrier, the multi-walled carbon nanotube that directly growth is independent i.e. on vitreous carbon, is arranged vertically, and one layer of thin polycrystalline copper is deposited on it as shell, the final MWCNT@Cu array for obtaining vertical arrangement.MWCNT@Cu composite catalyst provided by the invention can be used for being catalyzed reduction carbon dioxide, have preferable catalytic activity and hydrocarbon selectivity.
Description
Technical field
The invention belongs to electrochemical applications technical fields, and in particular to a kind of MWCNT@Cu composite catalyst and its preparation side
Method and application.
Background technique
It is that acquisition hydrocarbon products one is important and environmentally friendly by electrochemically reducing carbon dioxide on copper electrode
Method.It is interesting that copper be it is currently the only known, can be used as catalyst and these products played with the gold of catalytic action
Belong to, other metals cannot be used for identical reaction process.The activity and selectivity of this reaction is highly dependent on such as surface
Active site, the factors such as mass transfer related with copper electrode size, form, porosity.By to monocrystalline crystal and nanometer material
Potential reaction mechanism may be better understood in the system research of material.However, the optimization of selectivity of product is still one severe
Challenge.
In reduction CO2During, the reactivity and selectivity of copper electrode are strongly depend on crystal orientation, wherein Cu
(111) be conducive to CO2It is reduced into CH4, Cu(100) be conducive to CO2It is reduced into C2H4.It is different with bulk phase catalyst, it receives
Meter level catalyst has biggish specific surface area, higher low the advantages that matching bit density and higher catalytic activity.For having
The Cu of nano shape, it has been found that size is lower than the nano particle (NP) of 5nm, for the catalytic electrolysis reduction activation of carbon dioxide
It greatly increases, however due to increasing H using hydrocarbon selective depression as cost2Precipitation and CO formation.And size
Biggish nano particle then observes that the selectivity of hydrocarbon is considerably higher.In the linear copper oxide catalyst of nanometer,
Due to the influence of shape effect and pH value, to CH4Strong inhibition selectivity is shown, to C2H4And C2H6Selectivity increased
Add.Cu(100) the Cu medium crystalline substance blocked is conducive to C2H4Generation.In polycrystalline copper film electroreduction carbon dioxide process, ethane
Also it is accredited as secondary product.Result of study shows that the Cu nanometer foam with nanoscale hole, catalysis primary product have
HCOOH, H2And CO, in addition there are minimal amount of (< 2%) C3H6, CH4, C2H4And C2H6, this is also attributable to active material selectivity
Limitation.In fact, the reactant diffusion of intermediate materials and again absorption are moderate phenomenon, in research nanometer ruler
It is needed when very little electrode system by research multistep reaction, with the selectivity of the different products of determination.In the reduction of carbon dioxide
Cheng Zhong leads to CH due to increasing a possibility that adsorbing again among CO when copper ion spacing reduces4And C2H4The selectivity of test
It increased.When studying nano-scale composite catalyzing system, it is necessary to fully consider above-mentioned factor.To have bigger serface,
CO2Electroreduction activity Cu material will be a kind of very potential developing direction in conjunction with conductive carbon electrode supporter.
Therefore, there is research to coat Cu on Vulcan carbon, graphene oxide and unjustified multi-walled carbon nanotube (MWCNT) respectively to receive
Rice grain (NPs), to study its catalytic performance.In these researchs, largely, due to Cu nano particle (NPs) ruler
Very little and preparation means differences, so as to cause the difference of the selectivity of catalysate.
It therefore, can send out a kind of when being catalyzed carbon dioxide reduction with preferable hydrocarbon selectivity and catalytic activity
Copper catalyst has important research significance and application value.
Summary of the invention
It is an object of the invention to overcome in the prior art carbon dioxide reduction catalyst catalytic activity it is bad, nytron
The defect and deficiency of object poor selectivity provide a kind of MWCNT@Cu composite catalyst and its preparation method and application.Benefit of the invention
Use with nano-scale dimension, bigger serface carbon electrode as carrier, i.e., directly growth is independent on vitreous carbon, vertical arrangement
Multi-walled carbon nanotube, and deposit one layer of thin polycrystalline copper on it and be used as shell, it is final to obtain the MWCNT@being arranged vertically
Cu array.MWCNT@Cu composite catalyst provided by the invention can be used for being catalyzed reduction carbon dioxide, and there is preferable catalysis to live
Property and hydrocarbon selectivity.
Another object of the present invention is to provide the preparation methods of above-mentioned MWCNT@Cu composite catalyst.
Another object of the present invention is to provide above-mentioned MWCNT@Cu composite catalysts in catalysis CO2Application in reduction.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of MWCNT Cu composite catalyst, including grown on vitreous carbon multi-walled carbon nanotube that is independent, being vertically arranged and
The polycrystalline copper that magnetron sputtering deposits on the multi-walled carbon nanotube；The diameter of the multi-walled carbon nanotube is 10~300nm, length
For 100~5000nm, the distance between managing in array of multi-walled carbon nanotubes is 50nm or more.
Vitreous carbon and carbon nanotube are the carbon materials in terms of being widely used in electrochemical applications.Wherein vitreous carbon is a kind of heavy
It wants and efficient inert electrode material, is used usually as catalyst carrier.Carbon nanotube is a kind of nanoscale carbon material, tool
There are unique electronic property and excellent thermal stability, mechanical stability and chemical stability.By vitreous carbon and carbon nanotube
Combine, i.e., directly grow the multi-walled carbon nanotube of independent vertical arrangement on vitreous carbon, multi-wall carbon nano-tube can be obtained
The full carbon electrode of pipe/glass carbon structure, this electrode can be used as further electrochemical applications.The present invention passes through on vitreous carbon
The multi-walled carbon nanotube for growing independent vertical arrangement ensure that the well-ordered of multi-walled carbon nanotube, it is ensured that charge transfer
Homogeneity；Meanwhile multi-walled carbon nanotube conductivity also with higher and chemical stability.The present invention is also by multi wall carbon
One layer of thin polycrystalline copper of nanotube surface sputtering sedimentation is used as shell, the final MWCNT@Cu array for obtaining vertical arrangement
In CO2Electric reduction catalyst.
Specifically, we can obtain higher current density and CH compared with plate copper catalyst4Selectivity.This
Outside, the interval that is directly grown on glass carbon by Direct current plasma enhanced chemical vapour deposition DC-PECVD, vertical arrangement
Carbon nanotube, it is ensured that its excellent conductivity, and as other carbon-carbon/carbon-copper composite materials, do not need adhesive.Separately
One crucial benefit is vertical arrangement, it has the peak structure for increasing electric field, to surpass needed for reducing drive response
Potential.Finally, after CO extraction, the composition very close ideal " hydrogen alkane " composition, this be a kind of cleaning burning hydrogen/
Natural gas mixture has the advantage for improving engine efficiency and reduced NOx emission.It means that our catalyst can
For electroreduction CO2To prepare hydrogen alkane.
The length of multi-walled carbon nanotube can be from 100nm to 5 μm.Shorter MWCNT is embedded in copper, and longer multi wall carbon is received
The coating of mitron the obstruction lower part MWCNT and glass carbon carrier.Void space between individual multi-walled carbon nanotube is 50nm or more
(open end) greatly, advantageously forms sheet material.
In the present invention, the shell thickness of polycrystalline copper can be adjusted by the parameter of sputtering, and shell thickness is simultaneously
Density and length depending on multi-walled carbon nanotube.
Preferably, the diameter of the multi-walled carbon nanotube is 50~200nm, and length is 100~500nm, multi-wall carbon nano-tube
The distance between pipe is 50~200nm in pipe array.
The preparation method of above-mentioned MWCNT@Cu composite catalyst, includes the following steps:
S1: by the method for Direct current plasma enhanced chemical vapour deposition, the orderly multi wall carbon of growth of vertical on vitreous carbon
Nano-tube array；
S2: copper sputtering sedimentation array of multi-walled carbon nanotubes surface described in S1 obtained using magnetron sputtering technique described
MWCNT@Cu composite catalyst.
In the present invention, the carbon of diameter a certain uniform diameters in 10~300nm can be used in array of multi-walled carbon nanotubes
The carbon nanotube of random size in the range also can be used in nanotube.Enhance chemical vapor deposition by direct-current plasma
Long-pending method is difficult to prepare smaller or bigger multi-walled carbon nanotube.The length of carbon nanotube passes through control growth time control
Between 100~5000nm.Length of carbon nanotube is too short to be completely covered by polycrystalline copper, too long, be difficult in carbon nanotube lower part
Divide uniformly coating Shell Materials.The distance between every carbon nanotube is maintained at 50nm or bigger, to ensure that one can be formed
A grid.
Preferably, the array of multi-walled carbon nanotubes is placed in the position perpendicular to sputtering target in S2.
Sample is relative to sputtering target vertical alignment to eliminate shadow effect.
Preferably, make copper deposition by the way of direct current, exchange or radio-frequency sputtering in S2.
Preferably, the condition sputtered in S2 are as follows: sputtering pressure is 0.1 ~ 10Pa, and the gas of sputtering is inert gas argon.
Above-mentioned MWCNT@Cu composite catalyst is in catalysis CO2Application in reduction is also within the scope of the present invention.
Preferably, the CO2The product of reduction is hydrocarbon.
It is further preferable that the CO2The product of reduction is CO, CH4Or C2H6One or more of.With prior art phase
Than, the invention has the following beneficial effects:
The present invention ensure that multi-walled carbon nanotube by growing the multi-walled carbon nanotube of independent vertical arrangement on vitreous carbon
It is well-ordered, it is ensured that the homogeneity of charge transfer；Meanwhile multi-walled carbon nanotube conductivity also with higher and chemical stabilization
Property.The present invention is also by the way that in one layer of thin polycrystalline copper of multi-wall carbon nano-tube pipe surface sputtering sedimentation, as shell, final acquisition is vertical
The MWCNT@Cu array of arrangement.MWCNT@Cu composite catalyst provided by the invention can be used for being catalyzed reduction carbon dioxide, tool
There are preferable catalytic activity and hydrocarbon selectivity.
Detailed description of the invention
Fig. 1 is Cu gusts of MWCNT@after (A) MWCNT and (B) sputtering sedimentation that the individual vertical that embodiment 1 provides arranges
The scanning electron microscope (SEM) photograph of column；
Fig. 2 is to utilize DC-PECVD, the schematic diagram for the multi-walled carbon nanotube process that growth of vertical arranges on vitreous carbon；
Fig. 3 is to sputter Cu on the array of multi-walled carbon nanotubes surface of individual vertical arrangement on vitreous carbon, and deposition forms MWCNT@
The schematic diagram of Cu composite catalyst；
Fig. 4 is the flow chart that MWCNT Cu elctro-catalyst is prepared by MWCNT array；
Fig. 5 be different materials linear polarisation curves (sweep speed be 2 mV/s-1)；
Fig. 6 be different materials current efficiency, wherein a) be MWCNT@Cu array of the vitreous carbon as carrier, MWCNT array,
The current density of polycrystalline Cu film and original glass carbon (GC)；B) MWCNT array；It c) is copper film；D) it is produced for MWCNT@Cu array
Object.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a kind of MWCNT Cu composite catalysts, including growing multi wall that is independent, being vertically arranged on vitreous carbon
Carbon nanotube and the polycrystalline copper that magnetron sputtering deposits on the multi-walled carbon nanotube.
The MWCNT@Cu composite catalyst is prepared via a method which to obtain (such as Fig. 2 ~ 4).
S1: by the method for Direct current plasma enhanced chemical vapour deposition, orderly more of growth of vertical on vitreous carbon
Carbon nanotube array (growth schematic diagram such as Fig. 2)；The electron microscope of the multi-walled carbon nanotube battle array such as Figure 1A；
S2: copper sputtering sedimentation described in S1 array of multi-walled carbon nanotubes surface (such as Fig. 3) is obtained using magnetron sputtering technique
The MWCNT@Cu composite catalyst.Electron microscope such as Figure 1B of the MWCNT@Cu composite catalyst.
Specifically, the diameter control of multi-walled carbon nanotube is in the range of 10 ~ 300nm in S1, by controlling growth time,
The multi-walled carbon nanotube that length is 500nm is obtained, meanwhile, the control of the distance between pipe is in 50nm or more.
In S2, such as Fig. 4, array of multi-walled carbon nanotubes is placed in the position of vertical copper target, avoids that yin occurs in sputtering process
Shadow effect.Argon gas is passed through as protective gas, the length by controlling sputtering time controls the thickness of layers of copper, and sputtering terminates, obtains
To MWCNT@Cu composite catalyst.
The performance of MWCNT@Cu composite catalyst provided in this embodiment is tested.
Such as Fig. 5, (sputtered on the MWCNTs@Cu composite catalyst, vitreous carbon on vitreous carbon identical negative for different materials
The Cu film of load, the MWCNTs and glass carbon source materials that equal length, vertical arrangement are grown on vitreous carbon) linear polarization it is bent
Line.Each dotted line is the take-off potential obtained by linear extrapolation.In Fig. 5 it is found that current potential needed for MWCNT@Cu is minimum.This
It is that its electric field expection can increase than plate material due to the one-dimensional material with sharp spike, for driving phase same electric field
Reaction needs less application potential.
Such as Fig. 6, the current efficiency of different materials.As can be known from Fig. 6, compared with the Cu film of plane sputtering, MWCNTs@Cu
Overall current density increase above 100%(Fig. 6 a), CH4The significant increase of selectivity, and the H from water electrolysis2By-product is reduced
(Fig. 6 c and 6d).As reference, Fig. 6 b is the selectivity of original MWCNT product, it can be seen that no any hydrocarbon products generate.
In addition, can get 66 % CH when separating CO from the catalysate of MWCNT@Cu4With 34 % H2
Gaseous mixture.For the composition very close to the ideal composition of " hydrogen alkane ", " hydrogen alkane " is a kind of hydrogen/natural gas mixture
Cleaning burning, have very high engine efficiency and extremely low NOx emission.Therefore, when isolating CO from our product
Afterwards, it can be used as " hydrogen alkane " use.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of MWCNT Cu composite catalyst, which is characterized in that including growing multi wall that is independent, being vertically arranged on vitreous carbon
Carbon nanotube and the polycrystalline copper that magnetron sputtering deposits on the multi-walled carbon nanotube；The diameter of the multi-walled carbon nanotube is 10
~300nm, length are 100~5000nm, and the distance between pipe is 50nm or more in array of multi-walled carbon nanotubes.
2. MWCNT@Cu array composite catalyst according to claim 1, which is characterized in that the multi-walled carbon nanotube it is straight
Diameter is 50~200nm, and length is 100~500nm, and the distance between pipe is 50~200nm in array of multi-walled carbon nanotubes.
3. the preparation method of any MWCNT@Cu composite catalyst of claim 1 ~ 2, which is characterized in that including walking as follows
It is rapid:
S1: by the method for Direct current plasma enhanced chemical vapour deposition, the orderly multi wall carbon of growth of vertical on vitreous carbon
Nano-tube array；
S2: copper sputtering sedimentation array of multi-walled carbon nanotubes surface described in S1 obtained using magnetron sputtering technique described
MWCNT@Cu composite catalyst.
4. preparation method according to claim 3, which is characterized in that be placed in the array of multi-walled carbon nanotubes vertically in S2
In the position of sputtering target.
5. preparation method according to claim 3, which is characterized in that in S2 by the way of direct current, exchange or radio-frequency sputtering
Make copper deposition.
6. preparation method according to claim 3, which is characterized in that the condition sputtered in S2 are as follows: sputtering pressure be 0.1 ~
10Pa, the gas of sputtering are inert gas argon.
7. any MWCNT@Cu composite catalyst of claim 1 ~ 2 is in catalysis CO2Application in reduction.
8. applying according to claim 7, which is characterized in that the CO2The product of reduction is hydrocarbon.
9. applying according to claim 8, which is characterized in that the CO2The product of reduction is CO, CH4Or C2H6One of
Or it is several.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810931235.0A CN109248684A (en) | 2018-08-15 | 2018-08-15 | A kind of MWCNT@Cu composite catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810931235.0A CN109248684A (en) | 2018-08-15 | 2018-08-15 | A kind of MWCNT@Cu composite catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109248684A true CN109248684A (en) | 2019-01-22 |
Family
ID=65049868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810931235.0A Withdrawn CN109248684A (en) | 2018-08-15 | 2018-08-15 | A kind of MWCNT@Cu composite catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109248684A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733522A (en) * | 2022-04-21 | 2022-07-12 | 广西大学 | Copper-carbon composite catalyst and preparation method thereof |
| CN114965635A (en) * | 2022-04-15 | 2022-08-30 | 齐鲁工业大学 | Nano gene sensor and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820066A (en) * | 2010-03-26 | 2010-09-01 | 北京化工大学 | Single metal/multi-wall carbon nano tube type composite material, preparation method and application thereof |
| CN103566934A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
| CN105772091A (en) * | 2014-12-18 | 2016-07-20 | 中国科学院大连化学物理研究所 | CO2 reduction catalyst and application thereof |
| CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
-
2018
- 2018-08-15 CN CN201810931235.0A patent/CN109248684A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820066A (en) * | 2010-03-26 | 2010-09-01 | 北京化工大学 | Single metal/multi-wall carbon nano tube type composite material, preparation method and application thereof |
| CN103566934A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof |
| CN105772091A (en) * | 2014-12-18 | 2016-07-20 | 中国科学院大连化学物理研究所 | CO2 reduction catalyst and application thereof |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
| CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 刘孟岩等: "铜基电催化剂还原CO2", 《化学进展》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114965635A (en) * | 2022-04-15 | 2022-08-30 | 齐鲁工业大学 | Nano gene sensor and preparation method and application thereof |
| CN114733522A (en) * | 2022-04-21 | 2022-07-12 | 广西大学 | Copper-carbon composite catalyst and preparation method thereof |
| CN114733522B (en) * | 2022-04-21 | 2023-07-28 | 广西大学 | Copper-carbon composite catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Douglas et al. | Toward small-diameter carbon nanotubes synthesized from captured carbon dioxide: critical role of catalyst coarsening | |
| Hiramatsu et al. | Fabrication of carbon nanowalls using novel plasma processing | |
| Hiramatsu et al. | Fabrication of vertically aligned carbon nanowalls using capacitively coupled plasma-enhanced chemical vapor deposition assisted by hydrogen radical injection | |
| CN102482076B (en) | Carbonaceous Nanocomposite having novel structure and fabrication method thereof | |
| CN109518222A (en) | For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid | |
| Hiramatsu et al. | Graphene nanowalls | |
| Zhai et al. | Rational construction of 3D‐networked carbon nanowalls/diamond supporting CuO architecture for high‐performance electrochemical biosensors | |
| Zhu et al. | One-pot synthesis of a nitrogen and phosphorus-dual-doped carbon nanotube array as a highly effective electrocatalyst for the oxygen reduction reaction | |
| CN1978315A (en) | Method for preparing carbon nano tube array | |
| CN103193217B (en) | Method for preparing boron-doped diamond and carbon nanotube composite nanocone | |
| Fan et al. | Carbon‐Based Composite as an Efficient and Stable Metal‐Free Electrocatalyst | |
| CN1223514C (en) | Flaky carbon nano tube, preparation method and special equipment | |
| CN109248684A (en) | A kind of MWCNT@Cu composite catalyst and its preparation method and application | |
| CN102092670A (en) | Carbon nano-tube composite structure and preparation method thereof | |
| Zhou et al. | Multi-directional growth of aligned carbon nanotubes over catalyst film prepared by atomic layer deposition | |
| Xu et al. | Structure transition mechanism of single-crystalline silicon, g-C3N4, and diamond nanocone arrays synthesized by plasma sputtering reaction deposition | |
| Wang et al. | Structure and photoluminescence properties of carbon nanotip-vertical graphene nanohybrids | |
| Chaitoglou et al. | Hybrid nanostructured compounds of Mo2C on vertical graphene nanoflakes for a highly efficient hydrogen evolution reaction | |
| Yuan et al. | Direct growth of vertically well-aligned carbon nanotube arrays on atomic layer deposition of ZnO films | |
| CN104588058A (en) | Graphene nanobelt vertical array-molybdenum carbide nanometer crystal composite material and its preparation method and use | |
| CN102024637A (en) | Method for preparing zinc oxide nano column array field emission component | |
| US10697073B2 (en) | Method for manufacturing electrode for hydrogen production using tungsten carbide nanoflake and electrode for hydrogen production manufactured thereby | |
| Ji et al. | Hydrogen-modulated Ar/CH4 HWP-CVD for fast preparation of multi-wall carbon nanotube arrays with high specific capacitance | |
| Han et al. | 3-Orders-of-magnitude density control of single-walled carbon nanotube networks by maximizing catalyst activation and dosing carbon supply | |
| Rius | Technologies of carbon materials. syntheses and preparations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190122 |