CN107829107B - A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application - Google Patents
A kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application Download PDFInfo
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- CN107829107B CN107829107B CN201710875006.7A CN201710875006A CN107829107B CN 107829107 B CN107829107 B CN 107829107B CN 201710875006 A CN201710875006 A CN 201710875006A CN 107829107 B CN107829107 B CN 107829107B
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- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
The invention discloses a kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and its preparation method and application.The catalyst is supported on on/within graphene and carbon nanotube by single dispersion metal atom and is constituted；Wherein single dispersion metal atom content is the wt% of 0.001 wt%~5.0, and the content of metal nanometre cluster is the wt% of 1 wt%~30.0, and the content of graphene/carbon nano-tube is 45 wt%~97.999%wt%, and Heteroatom doping content is the wt% of 1 wt%~20.The present invention has obtained graphene/carbon nano-tube by electrochemistry and high-temperature heat treatment two-stage process and has loaded single dispersion metal atomic composite catalyst, and technique is green, high-efficient.The catalyst restores CO for electro-catalysis2, its electro-catalysis reduction CO can be improved2Faradic efficiency, selectivity of product is high, stability of material is good, can effectively reduce electro-catalysis reduction CO2Required overpotential.
Description
Technical field
The present invention relates to a kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst and preparation method thereof
And application, belong to electrochemical technology field.
Background technique
CO in atmosphere2Gradually increasing for concentration has become the raised arch-criminal of global mean temperature, therefore results in
Desertification, Ocean acidification and the deterioration of species extinction.In recent years, develop highly effective CO2Method for transformation has obtained
Many concerns.Wherein, CO is restored using electric energy2It is the important transformation routes with very high application prospect, CO2Electro-catalysis
Reduction be counted as it is a kind of method is facilitated with chemical species storage of renewable energy because it have very high environment it is compatible
Property, it can be combined well with renewable energy such as solar energy, wind energy and tide energies.The success of this technology, by CO in atmosphere2It is high
The small organic molecules such as CO, formic acid, methanol, methane are converted to energy density, the CO accumulated in atmosphere is not only reduced2, also real
The preparation dream for having showed neutral carbon fuel and useful industrial products, reduces our dependences to conventional fossil resource.
However, up to the present, the catalyst of report, which rarely has, is able to satisfy practical application request, and many main science are chosen
War still has, such as: 1) form CO2 ·-Intermediary needs very big overvoltage there are high energy barrier, it means that also
The low energy efficiency of former process；2) it is hampered by CO2Restore sluggish dynamics and limited CO2The quality being transferred on elctro-catalyst
Transmission capacity, reaction rate are at a fairly low；3) pass through CO2Reduction, obtains various gases and liquid mix products, this
In the case of, product separation costs are higher；4) in reduction process, the active site of elctro-catalyst can be by electrolyte
Reaction intermediates, by-product or impurity blocking poison, and lead to serious inactivation.Generally, the elctro-catalyst reported at present
Service life is lower than 100 h；Since 5) CO2Reduction is completed in aqueous solution, it is contemplated that emulative evolving hydrogen reaction (HER).As
One great side reaction, HER reaction occur at lower voltages, and HER largely affects CO2The farad of electro-catalysis
Efficiency and selectivity；6) it is compared with HER, OER with hydrogen reduction (ORR), CO2Restore it is more complicated because it there may be very
The electronics and proton step of voluminous object and multiple coupling.Therefore, CO is disclosed2It the basic principle of reduction and accurately reacted
Journey is more difficult.Generally speaking, promising CO2Reduction elctro-catalyst should have the feature that low overvoltage, high electricity
Current density, good stability, at the same time, in order to which the ideal product of output, HER should consumingly be pressed down with high selectivity
System.
Therefore, high catalytic activity, while the new catalyst of selectivity with higher and stability are obtained, is CO2 electricity
The key of catalytic reduction technique development.
It is recent years, various to have electrochemistry living due to the huge advance of advanced nanotechnology and calculation method
The novel inorganic polyphase electrocatalytic agent of property has appeared in the newspapers.Importantly, the appearance of these novel inorganic polyphase electrocatalytic agent
Bring CO2The mechanism study of electroreduction.Noble metal Au and Ag etc. can be efficiently by CO2It is converted into CO, but between its cost
It is high, regeneration is difficult, easily poisons etc., and characteristics cause its large-scale practical application to be hindered.Therefore, it is abundant to find earth resource
Element electro-catalysis restore CO2It is inevitable.Such as: alkali metal, metal oxide.But even if they have centainly
CO2Electrochemical reduction activity, the active site of these heterogeneous catalysts are seldom distributed in surface or edge.And in catalytic activity
The heart is only limitted to the part of atoms of its surface exposure, so a large amount of body phase atom can not participate in reacting, lives to cause catalysis
Property not high and active site waste.In order to increase active site, activated centre is made to be uniformly dispersed as far as possible, it is usually that these are more
Phase catalyst is made form of nanoparticles or stablizes improves catalysis reaction efficiency in certain specific substrates up.
Graphene and carbon nanotube have very high specific surface area, at low cost, good conductivity, stability good, are easy to adulterate
Hetero atom (such as: N, S, P, B) into graphite-structure, nanoparticle is distributed to the graphene and carbon nanotube of Heteroatom doping
And apply it to CO2Electro-catalysis reduction, which has been obtained, to be widely applied.However, continuing to increase the graphene of hetero atom modification
Huge challenge is still had with the active site of carbon nanotube, unless reaching single atomic dispersion.Monatomic catalysis is more
The new concept of phase catalytic field, the uniform active sites of atom dispersion can make metallic atom utilization rate reach maximum, and
Someone's report, the monoatomic catalytic activity of metal are higher than metal nanometre cluster or certain nanoparticles.It has recently been demonstrated that
Synthesizing monoatomic method includes: atomic layer deposition, photochemical syntheses, ball milling etc..Although having there is many researchs to report list
Application of the catalyst atom in the electrochemical reactions such as hydrogen reduction, electrolysis water, but monatomic catalyst is in CO2Electro-catalysis reduction
In application seldom report.
Carbon material provides modified binding site by the doping of different elements for reactant and intermediary.Recently, it studies
Show that inert material can be changed into CO by doping2The active material of reduction.Pure graphene and carbon nanotube all have very small
Electro-catalysis CO2Reducing property, because neutral carbon atom activates CO2Molecule or CO absorption2 -·The ability of intermediary is insignificant.
Fortunately, by introducing hetero atom (B, N, S, P etc.) in synthesis or preprocessing process, easily and efficiently change graphene
Therefore change with the structure and chemical state of carbon nanotube and be used as CO2The charge of the carbon atom in reduction activation site and spin are close
Degree, to make graphene and carbon nanotube that there is certain activity.
Graphene is monoatomic layer thickness graphite, is by carbon atom with sp2Hydridization is tightly packed at hexagonal cell lattice
Opening plane two dimensional crystal, be most thin in known materials and truly two-dimensional material；Compare table with very high
Area, excellent mechanical stability and flexibility, good electric conductivity, good chemical stability, it is cheap, environmental-friendly,
Abundance.Graphene is the basic Component units of other carbonaceous materials, receives the extensive concern of all circles scholar.By monodisperse
Metallic atom is distributed on the skeleton of graphene/in, the dispersion degree in activated centre can be significantly improved, activity on unit area is improved
The quantity at center.
Summary of the invention
The present invention is intended to provide a kind of graphene/carbon nano-tube loads single dispersion metal atomic composite catalyst, the present invention
The preparation method of the catalyst is additionally provided, this method operating procedure is simple, at low cost, high-quality, high-efficient, can satisfy work
The demand of industry production application, the present invention also provides the catalyst in electro-catalysis CO2Application in reduction.
The present invention provides a kind of graphene/carbon nano-tubes to load single dispersion metal atomic composite catalyst, the catalyst
It is supported on on/within graphene/carbon nano-tube and is constituted by single dispersion metal atom.
Graphene/carbon nano-tube as described above loads single dispersion metal atomic composite catalyst, composition are as follows: monodisperse gold
Category atom content is the wt% of 0.001 wt%~5.0, and the content of graphene/carbon nano-tube is 45 wt%~97.999wt%；Metal
The content of nano-cluster is the wt% of 1 wt%~30.0, and Heteroatom doping content is the wt% of 1wt%~20.
Single dispersion metal atom as described above including but not limited to one or both of Fe, Co, Ni, Cu, Zn with
On.
Heteroatom doping graphene/carbon nano-tube as described above is including but not limited to nitrogen-doped graphene/carbon nanometer
Pipe, sulfur doping graphene/carbon nano-tube, phosphorus doping graphene/carbon nano-tube, boron doping graphene/carbon nano-tube, nitrogen sulphur are co-doped with
Miscellaneous graphene/carbon nano-tube, nitrogen-phosphor codoping graphene/carbon nano-tube, nitrogen boron codope graphene/carbon nano-tube, sulphur phosphorus are total
Doped graphene/carbon nanotube, sulphur boron codope graphene/carbon nano-tube, phosphorus boron codope graphene/carbon nano-tube, nitrogen sulphur
Phosphor codoping graphene/carbon nano-tube, nitrogen sulphur boron codope graphene/carbon nano-tube, sulphur phosphorus boron codope graphene/carbon nanometer
One of pipe, nitrogen sulphur phosphorus boron codope graphene/carbon nano-tube.
The present invention also provides a kind of methods by electrochemical deposition and high-temperature heat treatment, efficiently prepare metallic atom
The new method of the controllable graphene/carbon nano-tube load single dispersion metal atomic composite catalyst of type and quantity.In the material,
For metal with monoatomic formal distribution within/on graphene/carbon nano-tube, metallic atom type and component can be according to actual needs
Modulation is carried out, one pack system, bi-component can be divided into.The material has potential application prospect in fields such as energy storage, electro-catalysis.
The preparation method packet of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst provided by the invention
It includes:
The specific technical solution of this method the following steps are included:
(1) the graphene slurry of electrochemical stripping is coated in conductive support and is put into porous insulation polymer pouches
It is used as anode, cathode is pure conductive support；
(2) step (1) made electrode is electrolysed in the electrolytic cell containing source metal, solid is isolated after electrolysis, and
Washes clean recycles to get the graphene for having single dispersion metal atom to load, electrolyte；
(3) single dispersion metal atom/graphene solid obtained by step (2) is mixed with hetero atom raw material and source metal
It is even, then the mixture is placed in high temperature inert atmosphere and is heat-treated；
(4) single dispersion metal atomic composite material is loaded with the graphene/carbon nano-tube that acid elution falls after step (3) heat treatment
The unstable metallic particles in material surface to get to single dispersion metal atom, hetero atom codope graphene/carbon nano-tube is compound urges
Agent.
Technical process is specifically described below:
Step (1) concrete technology includes the following:
Graphene raw material is compressed on two surface of conductive support, and is fitted into porous insulation polymer pouches, as anode
It uses, cathode is then pure conductive support.The two kinds of electrode of anode and cathode forms array, and the spacing of two electrodes is in 5 mm
~30 mm.The conductive support is including but not limited to one of titanium alloy, nickel foil, titanium foil.The average hole of polymer pouches
Diameter is at 0.1 μm ~ 25 μm.
Step (2) concrete technology includes the following:
Electrolytic cell as described above includes but is not limited to the electrod-array of multiple electrodes composition, and multiple electrolytic cells re-form
Cell array.Each electrolytic cell can also be together in parallel independently by single power supply power supply by single power supply power supply.It is more
A electrolytic cell may need multiple power supply power supplies, and power supply can be the AC power source that DC power supply is also possible to frequency conversion, Duo Ge electricity
Xie Chi is easy to construct, convenient for upgrading expanding production.
The source metal is including but not limited to one or more of Fe, Co, Ni, Cu, Zn.
In this method as described above, the DC voltage control between cathode and anode is in the V of 4 V ~ 8.Each electrolysis time exists
Then the h of 2 h ~ 72 exchanges voltage direction 30 s ~ 6 h.Electrolyte can use aqueous electrolyte and organic system electrolyte.
In method as described above, the temperature of electrolysis system is controlled at 25 DEG C ~ 70 DEG C, and the safety of electrolysis and validity obtain
To further strengthening.Polarized electrolyte molecule and electrically charged ion enter the atomic layer of electrode under current or voltage driving
Between, but charge changes, and chemical reaction occurs and is trapped in electrode atom interlayer, while generating gas, forms air pressure and hole
Road, convenient for liquid flowing and intercalator be further inserted into and electrode it is sufficiently delaminated.
The aqueous electrolyte is including but not limited to soluble metal chloride and mixed in hydrochloric acid aqueous solution, soluble gold
Belong to sulfate and sulfuric acid mixed aqueous solution, one of soluble metal nitrate and nitric acid mixed aqueous solution.
The organic system electrolyte is the mixed of metalliferous glyoxaline ion liquid and metal salt and glyoxaline ion liquid
Object is closed, the metal in the metalliferous glyoxaline ion liquid includes: one or more of Fe, Co, Ni, Cu, Zn；
Glyoxaline ion liquid includes: 1- butyl 3- methylimidazole villaumite or 1- vinyl 3- methylimidazole villaumite.
Step (3) concrete technology includes the following:
In method as described above, hetero atom includes one of nitrogen phosphate and sulfur, boron or a variety of.
The nitrogen source include melamine, amino acid, dicyandiamide, urea, polyethyleneimine, in aliphatic unsaturated amine
It is one or more；The sulphur source includes one of thiocarbamide, ammonium thiocyanate, benzyl disulfide or a variety of；Phosphorus source includes planting
One or both of acid, phosphoric acid；The boron source includes one or both of boric acid, amino phenyl boric acid Hemisulphate.
The mass ratio of the single dispersion metal atom/graphene solid and hetero atom raw material is 1:1 ~ 1:100.
The hybrid mode of single dispersion metal atom/graphene and hetero atom raw material as described above is including but not limited to liquid phase
One of ultrasonic disperse mixing, ball milling mixing.
The liquid phase supersonic frequency is the KHz of 5 KHz ~ 35, and power is the W of 100 W ~ 500, and the time is the h of 2 h ~ 6, and temperature is
15 ℃~40 ℃。
The ball milling is one of stainless steel, zirconium oxide and agate pot ball milling, and the diameter of ball milling pearl is 0.5 cm ~ 1.5
Cm, the volume of ball grinder are the ml of 100 ml ~ 250, ratio of grinding media to material 10-100:1；Rotational speed of ball-mill is 200 revs/min ~ 580 revs/min,
Ball-milling Time is the h of 5 h ~ 20；Ball milling is ground using dry bulb and wet ball mill, and the dispersion liquid that wet ball mill uses is water and ethyl alcohol.
Heat treatment temperature as described above is 600 DEG C ~ 1000 DEG C；
The heat treatment time is the h of 1 h ~ 5；
The inert gas is one of argon gas or nitrogen.
Graphene/carbon nano-tube prepared by the present invention loads single dispersion metal atomic composite catalyst, carbon nanometer therein
Also single dispersion metal atom is uniform-distribution on pipe；
A kind of graphene/carbon nano-tube prepared by the present invention loads single dispersion metal atomic composite catalyst, graphene and
There is certain synergistic effect, the presence of graphene can change the type of metallic particles in carbon nanotube between carbon nanotube；
A kind of graphene/carbon nano-tube prepared by the present invention loads single dispersion metal atomic composite catalyst, graphene energy
Enough induce the growth of carbon nanotube；
Preparation method provided by the invention is simple, can be mass produced, and can satisfy actual industrial application.
The present invention also provides the applications of above-mentioned graphene/carbon nano-tube load single dispersion metal atomic composite catalyst.
The present invention also provides a kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst application,
It is applied to electro-catalysis reduction CO2In, there is good catalytic activity.
It is used as working electrode in application, the composite catalyst is coated in gas-diffusion electrode, in the CO of 0.1 M2It is full
The KHCO of sum3It is electrolysed in solution, Pt piece is used to electrode, reference electrode is used saturated calomel electrode, swept using constant potential
It retouches, the gaseous product caused by gas chromatographic detection.
Beneficial effects of the present invention:
(1) electrolyte that present invention process uses can recycle Reusability, reduce cost.
(2) graphene/carbon nano-tube load single dispersion metal atomic composite method for preparing catalyst of the invention it is at low cost,
High-efficient, highly-safe, the good product quality prepared is, it can be achieved that scale industrial production.
(3) graphene/carbon nano-tube prepared by the present invention loads single dispersion metal atomic composite catalyst, by monodisperse gold
Belong to atom, the graphene of Heteroatom doping and the carbon nanotube group of single dispersion metal atom, metal carbides, Heteroatom doping
At single dispersion metal atom, the graphene of hetero atom codope and carbon nanotube all have certain CO2Reduction activation, graphite
There is alkene good electronic conduction ability and heat transfer property to keep away at that same temperature in the preparation process of composite material
The generation of metal simple-substance is exempted from, to inhibit competitive evolving hydrogen reaction, while before the effective evenly dispersed metal of graphene energy
Object is driven, prevents predecessor from assembling, to control the growth of carbon nanotube, the porous structure of carbon nanotube is conducive to mass transfer, graphite
The electric conductivity of alkene is conducive to electron transmission, thus the compound of the two has certain synergistic effect, so that the catalyst has very
High activity and stability.
(4) single dispersion metal atom of the invention by monoatomic metal it is uniform and stable be supported on graphene film and carbon is received
Within/on mitron, physicochemical stability is good.
(5) graphene/carbon nano-tube load single dispersion metal atomic composite catalyst prepared by the present invention is urged applied to electricity
Change CO2When reduction, have very high selectivity of product, stability high.
Detailed description of the invention
In Fig. 1 embodiment 1 single dispersion metal atom hetero atom codope graphene carbon nanotube (M-N-G/CNTs,
Middle M represents monodispersed metallic atom, and N represents hetero atom) STEM of composite material figure.
The XRD diagram of M-N-G/CNTs composite catalyst in Fig. 2 embodiment 1.
The BET phenogram of M-N-G/CNTs composite catalyst in Fig. 3 embodiment 1.
The XPS phenogram of M-N-G/CNTs composite catalyst in Fig. 4 embodiment 1.
0.1 mol/L that M-N-G/CNTs composite catalyst is saturated in argon gas and carbon dioxide in Fig. 5 embodiment 7
KHCO3(a) CV and (b) LSV in solution scheme, and sweep 20 mV/s of speed.
(a) CO faradic efficiency figure of M-N-G/CNTs composite catalyst and (b) CO bias current are close in Fig. 6 embodiment 7
Degree figure.
The cyclical stability figure of M-N-G/CNTs composite catalyst in Fig. 7 embodiment 7.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
(1) graphene of electrochemical stripping is coated on conductive titanium foil, wherein the coating quality of graphene accounts for conductive titanium
The 30% of foil quality, and put it into porous insulation bag, as anode, cathode uses pure titanium foil.(2) 1- butyl -3- first is used
Base imidazoles titanium tetrachloride does electrolyte, applies the DC voltage of 4 V between anode and cathode, is electrolysed 72 h, exchanges one every 2 h
Lower positive and negative anodes.Electrolysis temperature is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carry out ultrasonic suction filtration
Washing, obtains single dispersion metal atom graphene.(4) solid powder obtained in (3) step is mixed with melamine, wherein
The mass ratio of solid powder and melamine is 1:5, by mixture high speed ball milling, using Stainless Steel Vacuum ball grinder ball milling.Ball
Material with 500 revs/min of 20 h of speed ball milling, takes out material, then the heat in 800 DEG C of argon gas than being 50 after ball milling
1 h is handled, graphene/carbon nano-tube load single dispersion metal atomic composite material can be obtained.Through analysis detection, hetero atom nitrogen
Content is 5%, metal Fe3The content of C nano cluster is 25%, and graphene/carbon nano-tube content is 69.65%, and single dispersion metal Fe is former
Son 0.35%.
The STEM characterization of prepared composite material is shown in attached drawing 1, from attached drawing 1a as can be seen that carbon nanotube loaded in stone
Black alkene on piece is coated with Fe in carbon nanotube3C, attached drawing 1b, which can be seen that load in carbon nanotube, has single dispersion metal Fe former
Son can be seen that load has monodisperse Fe atom on graphene from attached drawing 1c, d.The XRD characterization of prepared composite material is shown in
Attached drawing 2, from attached drawing 2 it can be seen that the material only has graphite peaks and Fe3The peak of C.BET and the XPS characterization of the material are shown in attached respectively
Fig. 3 and 4.From attached drawing 3 as can be seen that the material has certain meso-hole structure, from attached drawing 4XPS characterization it can be seen that this is compound
Material contains tetra- kinds of elements of C, N, Fe and O.
Embodiment 2
(1) graphene of electrochemical stripping is coated on electrically conductive graphite paper, wherein the coating quality of graphene accounts for conduction
The 30% of titanium foil quality, and put it into porous insulation bag, as anode, cathode uses pure graphite paper.(2) 1- butyl-is used
Four cobalt chloride of 3- methylimidazole does electrolyte, applies the DC voltage of 6 V between anode and cathode, is electrolysed 72 h, hands over every 2 h
Change positive and negative anodes.Electrolysis temperature is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carry out ultrasound
Filtering and washing obtains single dispersion metal atom graphene.(4) solid powder obtained in (3) step is mixed with melamine,
Wherein the mass ratio of solid powder and melamine is 1:5, by mixture high speed ball milling, using Stainless Steel Vacuum ball grinder ball
Mill.Ratio of grinding media to material is 50, with 500 revs/min of 20 h of speed ball milling, material is taken out after ball milling, then as argon atmosphere
In, graphene/carbon nano-tube load single dispersion metal atomic composite material can be obtained in 800 DEG C of 1 h of heat treatment.It is examined through analysis
It surveys, in the present embodiment, the content of single dispersion metal cobalt atom is 0.2%, and hetero atom nitrogen content is 6%, cobalt metal oxide nano-cluster
Content be 30%, graphene/carbon nano-tube content be 63.8%.
Embodiment 3
(1) graphene of electrochemical stripping is coated on electrically conductive graphite paper, wherein the coating quality of graphene accounts for conduction
The 30% of titanium foil quality, and put it into porous insulation bag, as anode, cathode uses pure graphite paper.(2) by 1- butyl -3-
Methylimidazole and CuCl2According to the molar ratio preparation four chlorination copper ion liquid of 1- butyl -3- methylimidazole of 2:1, and as
Electrolyte applies the DC voltage of 7 V between anode and cathode, is electrolysed 72 h, exchanges positive and negative anodes every 2 h.Electrolysis temperature
Degree is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carried out ultrasonic filtering and washing, obtain monodisperse
Metallic atom graphene.(4) solid powder obtained in (3) step is mixed with melamine, wherein solid powder and trimerization
The mass ratio of cyanamide is 1:5, by mixture high speed ball milling, using Stainless Steel Vacuum ball grinder ball milling.Ratio of grinding media to material is 50, with 500
Rev/min 20 h of speed ball milling, take out material after ball milling, then as in argon atmosphere, 750 DEG C of 1 h of heat treatment,
Graphene/carbon nano-tube load single dispersion metal atomic composite material can be obtained.Through analysis detection, in the present embodiment, single point
The content of dispersed metallic copper atom is 0.1%, and hetero atom nitrogen content is 8%, and the content of metal copper oxide nano-cluster is 15%, graphene/
Content of carbon nanotubes is 76.9%.
Embodiment 4
(1) graphene of electrochemical stripping is coated on conductive titanium foil, wherein the coating quality of graphene accounts for conductive titanium
The 30% of foil quality, and put it into porous insulation bag, as anode, cathode uses pure titanium foil.(2) 1- butyl -3- first is used
Base imidazoles titanium tetrachloride does electrolyte, applies the DC voltage of 7 V between anode and cathode, is electrolysed 72 h, exchanges one every 2 h
Lower positive and negative anodes.Electrolysis temperature is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carry out ultrasonic suction filtration
Washing, obtains single dispersion metal atom graphene.(4) solid powder obtained in (3) step is mixed with melamine, wherein
The mass ratio of solid powder and dicyandiamide is 1:5, by mixture high speed ball milling, using Stainless Steel Vacuum ball grinder ball milling.Ball material
Than being 50, with 500 revs/min of 20 h of speed ball milling, material is taken out after ball milling, then as in argon atmosphere, 800
DEG C heat treatment 1 h, can be obtained graphene/carbon nano-tube load single dispersion metal atomic composite material.Through analysis detection, single point
The content of dispersed metallic iron atom is 0.53%, and hetero atom nitrogen content is 6%, and the content of metallic carbide iron nano-cluster is 18%, graphite
Alkene/content of carbon nanotubes is 75.47%.
Embodiment 5
(1) graphene of electrochemical stripping is coated on conductive titanium foil, wherein the coating quality of graphene accounts for conductive titanium
The 30% of foil quality, and put it into porous insulation bag, as anode, cathode uses pure titanium foil.(2) 1- butyl -3- first is used
Base imidazoles titanium tetrachloride does electrolyte, applies the DC voltage of 4 V between anode and cathode, is electrolysed 72 h, exchanges one every 2 h
Lower positive and negative anodes.Electrolysis temperature is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carry out ultrasonic suction filtration
Washing, obtains single dispersion metal atom graphene.(4) solid powder obtained in (3) step and melamine and boric acid is mixed
It closes, wherein the mass ratio of solid powder and melamine is 1:5, and mixture is dispersed in water, and ultrasonic disperse is uniform, is removed molten
After agent, 12 h are dried in 100 DEG C of vacuum ovens, then as in argon atmosphere, stone is can be obtained in 800 DEG C of 1 h of heat treatment
Black alkene/carbon nanotube loaded single dispersion metal atomic composite material.Through analysis detection, the content of single dispersion metal iron atom is
0.63%, hetero atom nitrogen content is 3%, and hetero atom boron content is 3.5%, and the content of metallic carbide iron nano-cluster is 18%, graphene/
Content of carbon nanotubes is 74.87%.
Embodiment 6
(1) graphene of electrochemical stripping is coated on conductive titanium foil, wherein the coating quality of graphene accounts for conductive titanium
The 30% of foil quality, and put it into porous insulation bag, as anode, cathode uses pure titanium foil.(2) 1- butyl -3- first is used
The mixed liquor of four cobalt chloride of base imidazoles titanium tetrachloride and 1- butyl -3- methylimidazole is cooked electrolyte, and wherein molysite and cobalt salt rub
You apply the DC voltage of 4 V, are electrolysed 72 h, exchange positive and negative anodes every 2 h than being 1:1 between anode and cathode.Electrolysis
Temperature is room temperature.(3) after being electrolysed, graphene in bag is taken out, is dispersed in water, carried out ultrasonic filtering and washing, obtain single point
Dispersed metallic atom graphene.(4) solid powder obtained in (3) step is mixed with melamine and boric acid, wherein solid powder
End and the mass ratio of melamine are 1:5, and mixture is dispersed in water, and ultrasonic disperse is uniform, after removing solvent, at 100 DEG C
12 h are dried in vacuum oven, then as in argon atmosphere, graphene/carbon nano-tube is can be obtained in 800 DEG C of 1 h of heat treatment
Load single dispersion metal atomic composite material.Through analysis detection, the content of single dispersion metal iron atom is 0.34%, monodisperse gold
Belonging to cobalt atom content is 0.45%, and hetero atom nitrogen content is 7%, and the content of metallic carbide iron nano-cluster is 15%, and cobalt metal oxide is received
Rice cluster content is 13%, and graphene/carbon nano-tube content is 64.21%.
Embodiment 7
Electro-catalysis CO2Reduction test, comprising the following steps:
(1) carbon paper passes through following processing: impregnating 12 h of carbon paper according to the amount of volume ratio 1:1 with acetone and ethyl alcohol.
The pretreatment of Nafion117 film: the H of mass fraction 3% is first used2O2In 80 DEG C boil 1 h, then impregnated with deionized water
Half an hour, then 1 h is boiled at 80 DEG C with 5% dilute sulfuric acid (mass ratio), finally half an hour is impregnated with deionized water.
(2) working electrode preparation is as follows: after the grinding uniformly of 10 mg prepared catalysts, being dispersed in 600 uL water+300
In+10 uL Nafion mixed solution of uL isopropanol, ultrasonic disperse is uniform, take 200 uL gradation drop coatings area be 1 cm ×
On carbon paper on 1cm, it is subsequently placed in 12 h in 100 DEG C of vacuum oven.
(3) it using Shanghai Chen Hua 760E electrochemical workstation as test equipment, is tested using dual chamber electrolytic cell.Platinized platinum
For to electrode, saturated calomel electrode is reference electrode.
(4) test result is shown in attached drawing 5-7, can be seen that from CV the and LSV scanning curve of attached drawing 5 in CO2The electricity of saturation
It solves in liquid, current density is obviously bigger than the current density in the electrolyte of argon gas saturation, and it is certain to illustrate that prepared catalyst has
CO2Reduction activation, from attached drawing 6 it can be seen that the faradic efficiency and current density of generated CO.It can from attached drawing 7
Out, which has good cyclical stability.It persistently uses 12 hours, the faradic efficiency of CO is basically unchanged.
Claims (12)
1. a kind of preparation method of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst, it is characterised in that: packet
Include following steps:
(1) the graphene slurry of electrochemical stripping is coated in conductive support and is put into conduct in porous insulation polymer pouches
Anode uses, and cathode is pure conductive support；
(2) step (1) made electrode is electrolysed in the electrolytic cell containing source metal, solid is isolated after electrolysis, and wash
Completely to get the graphene for having single dispersion metal atom to load, electrolyte is recycled；
Source metal includes one or more of Fe, Co, Ni, Cu, Zn；
(3) single dispersion metal atom/graphene solid obtained by step (2) is uniformly mixed with hetero atom raw material and source metal, so
The mixture is placed in high temperature inert atmosphere afterwards and is heat-treated；
The hetero atom raw material includes nitrogen source, phosphorus source, sulphur source, boron source, one in the graphene/carbon nano-tube of Heteroatom doping
Kind is a variety of；The nitrogen source include melamine, amino acid, dicyandiamide, urea, polyethyleneimine, in aliphatic unsaturated amine
It is one or more；The sulphur source includes one of thiocarbamide, ammonium thiocyanate, benzyl disulfide or a variety of；Phosphorus source includes
One or both of phytic acid, phosphoric acid；The boron source includes one or both of boric acid, amino phenyl boric acid Hemisulphate；
The graphene/carbon nano-tube of Heteroatom doping includes nitrogen-doped graphene/carbon nanotube, sulfur doping graphene/carbon nanometer
Pipe, phosphorus doping graphene/carbon nano-tube, boron doping graphene/carbon nano-tube, nitrogen sulphur codope graphene/carbon nano-tube, nitrogen phosphorus
Codope graphene/carbon nano-tube, nitrogen boron codope graphene/carbon nano-tube, sulphur phosphor codoping graphene/carbon nano-tube, sulphur
Boron codope graphene/carbon nano-tube, phosphorus boron codope graphene/carbon nano-tube, nitrogen sulphur phosphor codoping graphene/carbon nanometer
Pipe, nitrogen sulphur boron codope graphene/carbon nano-tube, sulphur phosphorus boron codope graphene/carbon nano-tube, nitrogen sulphur phosphorus boron codope graphite
One of alkene/carbon nanotube；
(4) single dispersion metal atomic composite material table is loaded with the graphene/carbon nano-tube that acid elution falls after step (3) heat treatment
The unstable metallic particles in face loads single dispersion metal atomic composite catalyst to get to graphene/carbon nano-tube.
2. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 1
Method, it is characterised in that: step (1) specifically comprises the processes of: graphene raw material is compressed on two surface of conductive support, and is packed into porous
It in insulating polymer bag, is used as anode, cathode is pure conductive support；The two kinds of electrode of anode and cathode forms battle array
Column, the spacing of two electrodes are the mm of 5 mm ~ 30.
3. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 2
Method, it is characterised in that: the conductive support includes one of titanium alloy, nickel foil, titanium foil；The average pore size of polymer pouches exists
0.1 μm~25 μm。
4. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 1
Method, it is characterised in that: in step (2), the electrolytic cell includes the electrod-array of multiple electrodes composition, multiple electrolytic cells shape again
At cell array；Each electrolytic cell is independently together in parallel by single power supply power supply or multiple electrolytic cells and is supplied by single power supply
Electricity；Power supply is the AC power source of DC power supply or frequency conversion.
5. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 4
Method, it is characterised in that: in the electrode, the DC voltage control between cathode and anode is in the V of 4 V ~ 8；Each electrolysis time
In the h of 2 h ~ 72, voltage direction 30 s ~ 6 h is then exchanged；Electrolyte is aqueous electrolyte or organic system electrolyte；Electrolysis system
Temperature control at 25 DEG C ~ 70 DEG C.
6. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 5
Method, it is characterised in that: the aqueous electrolyte includes soluble metal chloride and mixed in hydrochloric acid aqueous solution, soluble metal sulphur
One of hydrochlorate and sulfuric acid mixed aqueous solution, soluble metal nitrate and nitric acid mixed aqueous solution；
The organic system electrolyte is the mixture of metalliferous glyoxaline ion liquid and metal salt and glyoxaline ion liquid；
Metal in the metalliferous glyoxaline ion liquid includes: one or more of Fe, Co, Ni, Cu, Zn；Imidazoles
Class ionic liquid includes: 1- butyl 3- methylimidazole villaumite or 1- vinyl 3- methylimidazole villaumite.
7. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 1
Method, it is characterised in that: in step (3), the mass ratio of the single dispersion metal atom/graphene solid and hetero atom raw material is 1:
1~1:100；
Single dispersion metal atom/the graphene is that liquid phase ultrasonic disperse mixes or ball milling is mixed with the hybrid mode of hetero atom raw material
It closes.
8. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 7
Method, it is characterised in that: when liquid phase ultrasonic disperse mixes, liquid phase supersonic frequency is the KHz of 5 KHz ~ 35, and power is 100 W ~ 500
W, time are the h of 2 h ~ 6, and temperature is 15 DEG C ~ 40 DEG C；
When ball milling mixing, ball milling is one of stainless steel, zirconium oxide and agate pot ball milling, the diameter of ball milling pearl be 0.5 cm ~
1.5 cm, the volume of ball grinder are the ml of 100 ml ~ 250, ratio of grinding media to material 10-100:1；Rotational speed of ball-mill be 200 revs/min ~ 580 turns/
Point, Ball-milling Time is the h of 5 h ~ 20；Ball milling is ground using dry bulb or wet ball mill, and the dispersion liquid that wet ball mill uses is water and ethyl alcohol.
9. the preparation side of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst according to claim 1
Method, it is characterised in that: the heat treatment temperature is 600 DEG C ~ 1000 DEG C；Heat treatment time is the h of 1 h ~ 5；Inert gas is
Argon gas or nitrogen.
10. a kind of graphene/carbon nano-tube that the described in any item methods of claim 1 ~ 9 are prepared load single dispersion metal is former
Sub- composite catalyst, it is characterised in that: the catalyst is supported on structure on/within graphene/carbon nano-tube by single dispersion metal atom
At；
The single dispersion metal atom content of load is the wt% of 0.001 wt%~5.0；Heteroatom doping content is 1 wt%~20
wt%。
11. a kind of graphene/carbon nano-tube load single dispersion metal atomic composite catalyst described in any one of claim 10 is in CO2Electricity
Application in catalysis reduction.
12. application according to claim 11, it is characterised in that: the composite catalyst to be coated in gas-diffusion electrode
As working electrode, in the CO of 0.1 M2The KHCO of saturation3It is electrolysed in solution, Pt piece is used to electrode, reference electrode uses
Saturated calomel electrode, using potentiostatic scanning, the gaseous product caused by gas chromatographic detection.
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| CN112774669A (en) * | 2019-11-04 | 2021-05-11 | 北京氦舶科技有限责任公司 | Monoatomic noble metal/graphene catalyst for toluene hydrogenation and preparation method thereof |
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