CN109400656A - A kind of cobalt complex catalyst and carbon nanotube/cobalt complex composite catalyst and application - Google Patents
A kind of cobalt complex catalyst and carbon nanotube/cobalt complex composite catalyst and application Download PDFInfo
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- CN109400656A CN109400656A CN201811478153.1A CN201811478153A CN109400656A CN 109400656 A CN109400656 A CN 109400656A CN 201811478153 A CN201811478153 A CN 201811478153A CN 109400656 A CN109400656 A CN 109400656A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- TWIIVLKQFJBFPW-UHFFFAOYSA-N acetaminosalol Chemical compound C1=CC(NC(=O)C)=CC=C1OC(=O)C1=CC=CC=C1O TWIIVLKQFJBFPW-UHFFFAOYSA-N 0.000 claims abstract description 71
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007210 heterogeneous catalysis Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001548 drop coating Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229920000557 Nafion® Polymers 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 229960004424 carbon dioxide Drugs 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 9
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline condition Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The present invention discloses a kind of cobalt complex catalyst and carbon nanotube/cobalt complex composite catalyst and application.It uses with the molecular level cobalt complex Co (salophen) with rock-steady structure as catalyst, by the way that catalyst is compound with carbon nanotube, constitute carbon nanotube/molecular catalyst (CNTs/Co (salophen)) composite catalyst, the cobalt complex catalyst is in strong acid, corresponding water/hydroxo complex and free ligand are resolved under alkaline condition, CNTs/Co (salophen) composite catalyst is fixed on glass-carbon electrode by nafion, since nafion shows faintly acid, cobalt complex structure will not be changed, the composite cathode that the present invention designs not only substantially increases the catalytic activity of catalyst, and realize the composite cathode of the heterogeneous catalysis electro-catalysis reduction carbon dioxide under applied voltage driving.
Description
Technical field
The invention belongs to electro-catalysis field, in particular to a kind of cobalt complex catalyst and carbon nanotube/cobalt complex are multiple
Close catalyst
Background technique
Now, facing mankind two hang-ups: CO in atmosphere2Content constantly increases and leads to Global Greenhouse Effect；Fuel
Resource is increasingly deficient.Make full use of the CO that nature is rich2It is converted and is fixed, not only contribute to eliminate atmospheric greenhouse effect
Answer, and organic-fuel can be generated, synthesize other Organic Chemicals, intermediate or Organic chemical products, at the same can reduce by
Other industrial chemicals react and bring problem of environmental pollution.So CO2Comprehensive utilization have chemical reaction greenization, product
The significance of pole protection environment.Due to electro-catalysis CO2Reduction reaction can eliminate carbon dioxide using electricity, and its system is simple
Easy control, therefore just becoming an important directions of people's research.
The research of early stage, mainly with Ru, the precious metal simple substances such as Ir and corresponding oxide, complex is Journal of Molecular Catalysis
The reduction of carbon dioxide is realized in agent in homogeneous system.By the research of last decade, carbon dioxide reduction is urged from initial chemistry
Change system gradually develops to a variety of reaction systems such as electro-catalysis system and photoelectrochemical cell.With traditional metal oxide multiphase
Catalyst is compared, and the carbon dioxide reduction catalyst of many molecular levels has obvious in catalytic activity and adjustability of structure
Advantage.Therefore the carbon dioxide reduction catalyst of the molecular level of research heterogeneous catalysis system has practical significance.
Summary of the invention
This invention address that being catalyzed the research of carbon dioxide reduction, designing and constructing carbon nanotube/cobalt complex and is compound
The glass-carbon electrode cathode of catalyst modification has a very important significance building novel electrochemical cells.Electro-catalysis result is aobvious
Show, utilizes mode of loading of the present invention, when applying bias is -1.3V (vs RHE), NEW TYPE OF COMPOSITE photocathode CNTs/Co
(salophen) photoelectric current of electrode is -1.2mA, is approximately 10 times of CNTs electrode, and catalytic activity is much better than the glass of carbon pipe modification
Carbon electrode.
The technical solution adopted by the present invention is that: cobalt complex catalyst, the cobalt complex catalyst are Co
(salophen), there is the structural formula as shown in (I):
The preparation method of above-mentioned cobalt complex catalyst, includes the following steps:
1) preparation of salophen ligand: salicylide and o-phenylenediamine are added in ethyl alcohol, is heated to reflux at 70-80 DEG C
6-7h is reacted, after fully reacting, is evaporated under reduced pressure and filters after solution is cooled to room temperature, is then dried in vacuo 12 hours, obtains
Salophen ligand；Reaction equation is as follows:
2) preparation of cobalt complex catalyst Co (salophen): under nitrogen protection, salophen is added in ethyl alcohol
Ligand and Co (OAc)2·4H2O, the heating reflux reaction 2-3h at 70-80 DEG C, after reaction solution is cooled to room temperature, ethanol washing,
It filters, vacuum drying obtains cobalt complex catalyst Co (salophen), reaction equation is as follows:
Preferably, the preparation method of above-mentioned cobalt complex catalyst, in molar ratio, o-phenylenediamine: salicylide=1:2；
Salophen ligand: Co (OAc)2·4H2O=1:1.2.
A kind of carbon nanotube/cobalt complex composite catalyst is by above-mentioned cobalt complex catalyst Co (salophen)
It is compound with carbon nanotube CNTs, carbon nanotube/cobalt complex composite catalyst CNTs/Co (salophen) of composition.
A kind of above-mentioned carbon nanotube/cobalt complex composite catalyst preparation method, includes the following steps: at room temperature,
Above-mentioned cobalt complex catalyst Co (salophen) is dissolved in deionized water, in ethanol by carbon nanotube CNTs dispersion,
Then the aqueous solution of Co (salophen) and the ethanol solution of CNTs are mixed, is stirred 12-13 hours, is centrifuged, vacuum drying obtains
Carbon nanotube/cobalt complex composite catalyst CNTs/Co (salophen).
Preferably, above-mentioned a kind of carbon nanotube/cobalt complex composite catalyst preparation method, in mass ratio, CNTs:
Co (salophen)=(1-10): 1.
A kind of above-mentioned carbon nanotube/cobalt complex composite catalyst restores dioxy in electro-catalysis as heterogeneous catalysis
Change the application of carbon.Method is as follows:
1) preparation of CNTs/Co (salophen) modified electrode: by above-mentioned carbon nanotube/cobalt complex composite catalyst
Dispersion in ethanol, then in uniform drop coating to the surface glass-carbon electrode GC polished after, glass-carbon electrode GC is done in an oven
It is 3-4 hours dry, obtain CNTs/Co (salophen) modified electrode；
It 2) is to electrode, with Ag/ with platinum filament or platinum guaze using CNTs/Co (salophen) modified electrode as working electrode
AgCl electrode is reference electrode, electro-catalysis carbon dioxide reduction.
The present invention uses the surface of molecular catalyst π-π non-covalent modification carbon nanotube, with the molecule with rock-steady structure
Horizontal cobalt complex Co (salophen) is catalyst, and by the way that catalyst is compound with carbon nanotube, composition carbon nanotube/cobalt is matched
Object (CNTs/Co (salophen)) Hybrid Photocathode catalyst system is closed, because the integrality of complex is maintained there was only limited pH
Range, the cobalt complex catalyst resolve into corresponding water/hydroxo complex and free ligand under strong acid, alkaline condition, lead to
It crosses nafion catalyst is fixed on glass-carbon electrode, because nafion shows faintly acid, cobalt complex structure will not be changed.This hair
Bright composite cathode not only substantially increases the catalytic activity of catalyst, but also the composite cathode for realizing heterogeneous catalysis exists
The lower catalysis reduction carbon dioxide of applied voltage driving.
The present invention has the advantage that
1) present invention design has synthesized cobalt complex catalyst, by the way that cobalt complex catalyst is loaded to the surface CNTs,
It is prepared for the compound cathode of carbon nanotube/molecular catalyst.
2) molecular catalysts such as noble ruthenium, iridium are replaced with a large amount of existing base metal cobalt molecular catalysts；With passing through
Cobalt complex catalyst and CNTs are substituted common acid adhesive nafion, PMAA by non-π-π covalent modification carbon nanotube
Deng, realize catalyst structure stablize, the two is combined, preparation can alkalinity, low potential under the conditions of efficiently, stablize electrolysis also
The composite cathode of former carbon dioxide；Such cathode has not been reported.Tentatively realize molecular catalyst electro-catalysis device, be
The application of carbon dioxide reduction molecular catalyst opens new approach.
3) with Mn, Fe, Cu, it is direct benefit that the earth such as Ni, Co, which are rich in the isomerization water oxidation catalyst of a large amount of transition metal,
With the ideal chose of the sustainable energy technology of decomposing water with solar energy.Compared with homogeneous catalyst, the advantages of heterogeneous catalysis
It is that and is easy to separate from reaction system, from the point of view of engineering viewpoint, simple due to assembling, it is desirable to solid yin
Pole.The present invention is by by the surface of the non-π-π covalent modification carbon nanotube of molecular catalyst, to change the superficiality of carbon nanotube
Matter constructs NEW TYPE OF COMPOSITE cathode.Application for transition metal compound catalizer and carbon nano tube compound material provides more
Possibility.
4) present invention uses the surface of molecular catalyst π-π non-covalent modification carbon nanotube, with the molecule with rock-steady structure
Horizontal cobalt complex Co (salophen) is catalyst, and by the way that catalyst is compound with carbon nanotube, composition carbon nanotube/cobalt is matched
Object (CNTs/Co (salophen)) Hybrid Photocathode catalyst system is closed, in environmental protection, is tapped a new source of energy, solar energy and fuel
There is boundless application prospect in the fields such as battery.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram (SEM figure) of carbon nanotube CNTs.
Fig. 2 is the projection electron microscope figure (TEM figure) of carbon nanotube CNTs.
The Co that Fig. 3 is embodiment 3CNTs, independent Co (salophen) and CNTs and Co (salophen) mass ratio are 2:1
(salophen) containing the CV in 0.1M sodium bicarbonate solution.
Fig. 4 is the CV of the CNTs and Co (salophen) of 3 different proportion of embodiment in sodium bicarbonate solution.
Fig. 5 is the it under 3 different voltages of embodiment in the sodium bicarbonate solution of carbon pipe and Co (salophen).
Specific embodiment
Technical solution for a better understanding of the present invention is special further detailed with a series of test and comparative experiments work
Explanation.
1 cobalt complex catalyst Co (salophen) of embodiment
(1) the preparation method is as follows:
(1) preparation of salophen ligand
The salicylide of 0.54g (0.005mol) and the o-phenylenediamine of 1.22g (0.010mol) are added into 100ml ethyl alcohol,
Heating reflux reaction 6h under the conditions of 75 DEG C, after fully reacting, solution is cooled to room temperature, and is evaporated under reduced pressure and is filtered, then very
Sky is 12 hours dry, obtains the salophen ligand of brown.
(2) preparation of cobalt complex catalyst Co (salophen)
Under the conditions of nitrogen protection, into 10ml ethyl alcohol be added 1.65g (0.01mol) salophen ligand and
The Co (OAc) of 2.98g (0.012mol)2·4H2O, heating reflux reaction 2h under the conditions of 75 DEG C, after reaction, to reaction solution
It after being cooled to room temperature, filters (with cold ethanol washing filter cake at least 3 times), then vacuum drying 24 hours, obtain brown solid i.e.
For cobalt complex catalyst Co (salophen).
A kind of carbon nanotube of embodiment 2/cobalt complex composite catalyst
(1) CNTs/Co's (salophen) the preparation method is as follows:
At room temperature, Co (salophen) prepared by 4mg embodiment 1 is dissolved in the deionized water of 20mL, obtains Co
(salophen) aqueous solution.It takes carbon nanotube CNTs to be dispersed in the ethyl alcohol of 10mL by table 1, obtains different quality carbon nanotube
The ethanol solution of CNTs.The aqueous solution of Co (salophen) and the ethanol solution of different quality carbon nanotube CNTs are mixed equal
It is even, it stirs 12 hours, centrifugation after vacuum drying, respectively obtains different quality than carbon nanotube/cobalt complex composite catalyst
CNTs/Co(salophen)。
Table 1
| Carbon nanotube CNTs mass | Mass ratio, CNTs:Co (salophen) | Product |
| 4mg | 1:1 | CNTs/Co(salophen)-1 |
| 8mg | 2:1 | CNTs/Co(salophen)-2 |
| 20mg | 5:1 | CNTs/Co(salophen)-3 |
| 40mg | 10:1 | CNTs/Co(salophen)-4 |
(2) it detects
As shown in Figure 1, testing the scanning electron microscope (SEM) photograph of business CNTs.The surface CNTs is it can be seen from (a) in Fig. 1
Unordered tubulose is overlapped mutually, and has very big specific surface area, provides guarantee for Catalyst Adsorption amount.(b) can be in Fig. 1
Find out, from pattern, (a) is compared in Fig. 1, can more be clearly seen that the tubular structure of carbon pipe.
As shown in Fig. 2, testing the projection electron microscope of business CNTs, the structure of CNTs can be clearly seen that.
3 carbon nanotubes of embodiment/cobalt complex composite catalyst as heterogeneous catalysis electro-catalysis carbon dioxide also
The preparation of application (one) CNTs/Co (salophen) modified electrode in original
1, glass-carbon electrode GC is pre-processed: with 2.0 μm of alumina powders to GC (0.07cm2) electrode polished, then spent
Ionized water and acetone carry out ultrasonic cleaning, and dry in air.
2, the different quality for preparing 4mg embodiment 2 is than carbon nanotube/cobalt complex composite catalyst CNTs/Co
(salophen) it is dispersed in the ethyl alcohol of 10mL, takes in 10 μ L solution drop coatings to the surface of pretreated glass-carbon electrode GC, it
It is afterwards that GC is 3 hours dry at 40 DEG C in an oven, CNTs/Co (salophen) modified electrode of different quality ratio is made.
(2) research of photoelectrochemical behaviour
All tests of this experiment are all made of the CHI660E electrochemical workstation of Shanghai Chen Hua company, are done with platinum filament or platinum guaze
To electrode, reference electrode is done with Ag/AgCl electrode (2.5M saturated potassium chloride solution).
Cyclic voltammetric (CV) test of catalyst carries out in sodium bicarbonate solution.Using three-electrode system, with CNTs/Co
(salophen) modified electrode is working electrode, and Ag/AgCl electrode is as reference electrode, and platinum guaze is used as to electrode, to be full of two
The sodium bicarbonate solution of the 0.1M of carbonoxide carries out electro-chemical test as electrolyte solution.Electrochemical results such as Fig. 3,
Fig. 4 and Fig. 5.
From figure 3, it can be seen that carbon nanotube CNTs, cobalt complex catalyst Co (salophen) voltage be-
Electric current when 1.3VvsAg/AgCl is the CNTs/Co that -0.12mA, carbon pipe and catalyst are obtained with the ratio compound tense of 2:1
(salophen) -2, the electric current when voltage is in -1.3Vvs Ag/AgCl is -1.2mA, is CNTs, independent Co (salophen)
10 times of electric current, it is possible to show that Co (salophen) and carbon pipe recombination energy access good catalytic activity.
From fig. 4, it can be seen that when CNTs and Co (salophen) mass ratio are respectively 1:1,2:1,5:1,10:1, start with
The increase electric current of ratio be continuously increased, after mass ratio reaches 2:1, as the increase electric current of ratio reduces, work as CNTs:Co
(salophen)=2:1 when, CNTs/Co (salophen) -2 obtained, voltage be -1.3Vvs Ag/AgCl when electric current
It is several times of other ratios for -1.2mA.It can thus be seen that when the compositely proportional of CNTs and Co (salophen) are in 2:1,
Catalyst possesses best catalytic effect.
Fig. 5 is carbon pipe and the it of Co (salophen) in sodium bicarbonate solution under different voltages, can from Fig. 5
Out, under different voltage, with the continuous extension of time, the effect of catalyst does not have larger decline, it will thus be seen that this
CNTs/Co (salophen) composite catalyst of invention possesses preferable stability, convenient for application.
Claims (8)
1. cobalt complex catalyst, which is characterized in that the cobalt complex catalyst is Co (salophen), has such as (I)
Shown in structural formula:
2. the preparation method of cobalt complex catalyst described in claim 1, which comprises the steps of:
1) salicylide and o-phenylenediamine, the heating reflux reaction at 70-80 DEG C the preparation of salophen ligand: are added in ethyl alcohol
6-7h after fully reacting, is evaporated under reduced pressure and filters after solution is cooled to room temperature, and is then dried in vacuo 12 hours, obtains
Salophen ligand；
2) preparation of cobalt complex catalyst Co (salophen): under nitrogen protection, salophen ligand is added in ethyl alcohol
With Co (OAc)2·4H2O, the heating reflux reaction 2-3h at 70-80 DEG C, after reaction solution is cooled to room temperature, ethanol washing is filtered,
Vacuum drying, obtains cobalt complex catalyst Co (salophen).
3. the preparation method of cobalt complex catalyst according to claim 2, which is characterized in that in molar ratio, adjacent benzene two
Amine: salicylide=1:2；Salophen ligand: Co (OAc)2·4H2O=1:1.2.
4. a kind of carbon nanotube/cobalt complex composite catalyst, which is characterized in that be by cobalt complex described in claim 1
Catalyst Co (salophen) and carbon nanotube CNTs are compound, carbon nanotube/cobalt complex composite catalyst CNTs/Co of composition
(salophen)。
5. a kind of preparation method of carbon nanotube/cobalt complex composite catalyst as claimed in claim 4, which is characterized in that packet
It includes following steps: at room temperature, cobalt complex catalyst Co (salophen) described in claim 1 being dissolved in deionized water,
In ethanol by carbon nanotube CNTs dispersion, then the aqueous solution of Co (salophen) and the ethanol solution of CNTs are mixed, stirred
It mixes 12-13 hours, is centrifuged, vacuum drying obtains carbon nanotube/cobalt complex composite catalyst CNTs/Co (salophen).
6. a kind of preparation method of carbon nanotube/cobalt complex composite catalyst according to claim 5, feature exist
In, in mass ratio, CNTs:Co (salophen)=(1-10): 1.
7. a kind of carbon nanotube/cobalt complex composite catalyst as claimed in claim 4 is as heterogeneous catalysis in electro-catalysis
Restore the application of carbon dioxide.
8. application according to claim 7, which is characterized in that method is as follows:
1) preparation of CNTs/Co (salophen) modified electrode: carbon nanotube/cobalt complex as claimed in claim 4 is compound
Catalyst disperse in ethanol, then in uniform drop coating to the surface glass-carbon electrode GC polished after, glass-carbon electrode GC is being dried
It is 3-4 hours dry in case, obtain CNTs/Co (salophen) modified electrode；
It 2) is to electrode, with Ag/AgCl electricity with platinum filament or platinum guaze using CNTs/Co (salophen) modified electrode as working electrode
Extremely reference electrode, electro-catalysis restore carbon dioxide.
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| WO2023151336A1 (en) * | 2022-02-14 | 2023-08-17 | 苏州科技大学 | Single-atom cobalt nanozyme material, flexible electrochemical chip sensor, and use thereof |
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| CN110015990A (en) * | 2019-04-12 | 2019-07-16 | 云南师范大学 | A kind of cobalt coordination compound and the preparation method and application thereof |
| CN112473701A (en) * | 2019-08-20 | 2021-03-12 | 天津理工大学 | IrCl6-cobalt hydroxide/carbon nano tube composite electrocatalytic oxygen production material and preparation method and application thereof |
| CN112473701B (en) * | 2019-08-20 | 2022-09-09 | 天津理工大学 | IrCl 6 -cobalt hydroxide/carbon nano tube composite electrocatalytic oxygen production material and preparation method and application thereof |
| WO2023151336A1 (en) * | 2022-02-14 | 2023-08-17 | 苏州科技大学 | Single-atom cobalt nanozyme material, flexible electrochemical chip sensor, and use thereof |
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