CN109400656B - Cobalt complex catalyst, carbon nano tube/cobalt complex composite catalyst and application - Google Patents
Cobalt complex catalyst, carbon nano tube/cobalt complex composite catalyst and application Download PDFInfo
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- 238000000034 method Methods 0.000 claims description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
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Images
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a cobalt complex catalyst, a carbon nano tube/cobalt complex composite catalyst and application. The molecular level cobalt complex Co (salephen) with a stable structure is adopted as a catalyst, the catalyst and the carbon nano tube are compounded to form the carbon nano tube/molecular catalyst (CNTs/Co (salephen)) composite catalyst, the cobalt complex catalyst is decomposed into corresponding water/hydroxyl complex and free ligand under the conditions of strong acid and alkali, the CNTs/Co (salephen) composite catalyst is fixed on a glassy carbon electrode through nafion, and the structure of the cobalt complex cannot be changed because nafion shows weak acid.
Description
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a cobalt complex catalyst and a carbon nano tube/cobalt complex composite catalyst
Background
Today, humans face two major challenges: CO in the atmosphere2The content is continuously increased to cause global greenhouse effect; fuel resources are increasingly scarce. Fully utilizes CO rich in nature2The conversion and fixation are carried out, which is not only beneficial to eliminating the atmospheric greenhouse effect, but also can generate organic fuel, synthesize other organic chemical raw materials, intermediates or organic chemical products, and simultaneously can reduce the environmental pollution problem caused by the reaction of other chemical raw materials. Therefore, CO2The comprehensive utilization of the method has the important significance of greening chemical reaction and actively protecting the environment. Due to electrocatalysis of CO2The reduction reaction can eliminate carbon dioxide by using electricity, and the system is simple and easy to control, so the method is becoming one of the researches of peopleThe direction of importance.
Early researches mainly take noble metal simple substances such as Ru, Ir and the like and corresponding oxides and complexes as molecular catalysts to realize the reduction of carbon dioxide in a homogeneous system. Through research in the last decade, carbon dioxide reduction is gradually developed from an initial chemical catalytic system to various reaction systems such as an electrocatalytic system and a photoelectrochemical cell. Compared with the traditional metal oxide heterogeneous catalyst, the carbon dioxide reduction catalyst at a molecular level has obvious advantages in catalytic activity and structure adjustability. It is therefore of practical interest to investigate molecular-level carbon dioxide reduction catalysts for heterogeneous catalytic systems.
Disclosure of Invention
The invention is dedicated to the research of catalyzing carbon dioxide reduction, designs and constructs the glassy carbon electrode cathode modified by the carbon nano tube/cobalt complex composite catalyst, and has very important significance for constructing a novel electrochemical cell. The electrocatalysis result shows that by utilizing the load mode of the invention, when the external bias voltage is-1.3V (vs RHE), the photocurrent of the novel composite photocathode CNTs/Co (salephen) electrode is-1.2 mA which is about 10 times of that of the CNTs electrode, and the catalytic activity is far superior to that of the carbon tube modified glassy carbon electrode.
The technical scheme adopted by the invention is as follows: a cobalt complex catalyst, wherein the cobalt complex catalyst is Co (salophen), and has a structural formula shown as (I):
the preparation method of the cobalt complex catalyst comprises the following steps:
1) preparation of salophen ligand: adding salicylaldehyde and o-phenylenediamine into ethanol, heating and refluxing at 70-80 ℃ for reaction for 6-7h, cooling the solution to room temperature after complete reaction, carrying out reduced pressure distillation and suction filtration, and then carrying out vacuum drying for 12 hours to obtain a salophen ligand; the reaction formula is as follows:
2) preparation of cobalt complex catalyst Co (salophen): adding salophen ligand and Co (OAc) into ethanol under the protection of nitrogen2·4H2Heating and refluxing the O at 70-80 ℃ for 2-3h, cooling the reaction solution to room temperature, washing with ethanol, filtering, and drying in vacuum to obtain a cobalt complex catalyst Co (salophen), wherein the reaction formula is as follows:
preferably, the above cobalt complex catalyst is prepared by a method comprising, in terms of mole ratio, o-phenylenediamine: salicylaldehyde 1: 2; salophen ligand: co (OAc)2·4H2O＝1:1.2。
The carbon nano tube/cobalt complex composite catalyst is formed by compounding the cobalt complex catalyst Co (salophen) with carbon nano tube CNTs.
The preparation method of the carbon nano tube/cobalt complex composite catalyst comprises the following steps: at room temperature, dissolving the cobalt complex catalyst Co (salophen) in deionized water, dispersing carbon nano tube CNTs in ethanol, then mixing the aqueous solution of Co (salophen) with the ethanol solution of CNTs, stirring for 12-13 hours, centrifuging, and drying in vacuum to obtain the carbon nano tube/cobalt complex composite catalyst CNTs/Co (salophen).
Preferably, in the preparation method of the carbon nanotube/cobalt complex composite catalyst, the mass ratio of CNTs to co (salophen) ═ 1-10: 1 is adopted.
The carbon nano tube/cobalt complex composite catalyst is used as a heterogeneous catalyst for electrocatalytic reduction of carbon dioxide. The method comprises the following steps:
1) preparing a CNTs/Co (salophen) modified electrode: dispersing the carbon nano tube/cobalt complex composite catalyst in ethanol, uniformly dripping the catalyst on the surface of a polished glassy carbon electrode GC, and drying the glassy carbon electrode GC in an oven for 3-4 hours to obtain a CNTs/Co (salophen) modified electrode;
2) and (2) taking a CNTs/Co (salophen) modified electrode as a working electrode, a platinum wire or a platinum net as a counter electrode and an Ag/AgCl electrode as a reference electrode to electro-catalyze the reduction of carbon dioxide.
The invention adopts a molecular catalyst pi-pi to non-covalently modify the surface of a carbon nano tube, takes a molecular level cobalt complex Co (salophen) with a stable structure as a catalyst, and compounds the catalyst and the carbon nano tube to form a carbon nano tube/cobalt complex (CNTs/Co (salophen)) composite photocathode catalytic system. The composite cathode of the invention not only greatly improves the catalytic activity of the catalyst, but also realizes the catalytic reduction of carbon dioxide under the driving of an external voltage by the composite cathode of a heterogeneous catalyst.
The invention has the following advantages:
1) the invention designs and synthesizes a cobalt complex catalyst, and the carbon nano tube/molecular catalyst composite cathode is prepared by loading the cobalt complex catalyst on the surface of CNTs.
2) A large amount of non-noble metal cobalt molecular catalyst is used for replacing noble metal ruthenium, iridium and other molecular catalysts; the carbon nano tube is modified by non-pi covalent, the cobalt complex catalyst and CNTs are used for replacing common acid adhesives nafion, PMAA and the like, the structure of the catalyst is stable, the cobalt complex catalyst and the CNTs are combined, and the composite cathode capable of efficiently and stably electrolyzing and reducing carbon dioxide under the alkaline and low-potential conditions is prepared; such cathodes have not been reported. The device of electrocatalysis of the molecular catalyst is realized preliminarily, and a new way for the application of the carbon dioxide reduction molecular catalyst is opened up.
3) The isomerization water oxidation catalyst which is rich in a large amount of transition metals such as Mn, Fe, Cu, Ni, Co and the like is an ideal choice for sustainable energy technology for decomposing water by directly utilizing solar energy. Heterogeneous catalysts have the advantage of being easily separated from the reaction system compared to homogeneous catalysts, and solid cathodes are desirable from an engineering point of view due to the simple assembly. The invention modifies the surface of the carbon nano tube by the non-pi covalent modification of the molecular catalyst, thereby changing the surface property of the carbon nano tube and constructing the novel composite cathode. Provides more possibility for the application of the transition metal complex catalyst and the carbon nano tube composite material.
4) The invention uses a molecular catalyst pi-pi to non-covalently modify the surface of a carbon nano tube, uses a molecular level cobalt complex Co (salophen) with a stable structure as a catalyst, and compounds the catalyst and the carbon nano tube to form a carbon nano tube/cobalt complex (CNTs/Co (salophen)) composite photocathode catalytic system, and has very wide application prospect in the fields of environmental protection, new energy development, solar energy, fuel cells and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of carbon nanotube CNTs.
FIG. 2 is a projection electron microscope (TEM image) of carbon nanotube CNTs.
FIG. 3 shows CV for example 3CNTs, Co (salophen) alone, and Co (salophen) in a CNTs to Co (salophen) mass ratio of 2:1 in a solution containing 0.1M sodium bicarbonate.
FIG. 4 shows CV values of CNTs and Co (salophen) in sodium bicarbonate solution at different ratios in example 3.
FIG. 5 shows it in sodium bicarbonate solution of carbon tubes and Co (salophen) in example 3 under different voltages.
Detailed Description
In order to better understand the technical scheme of the invention, a series of tests and comparative experiments are specifically described in further detail.
Example 1 cobalt Complex catalyst Co (salophen)
The preparation method comprises the following steps:
(1) preparation of salophen ligands
0.54g (0.005mol) of salicylaldehyde and 1.22g (0.010mol) of o-phenylenediamine are added into 100ml of ethanol, the mixture is heated and refluxed for 6 hours at the temperature of 75 ℃, after the reaction is completed, the solution is cooled to room temperature, reduced pressure distillation and suction filtration are carried out, and then vacuum drying is carried out for 12 hours, so as to obtain brown salophen ligand.
(2) Preparation of cobalt complex catalyst Co (salophen)
1.65g (0.01mol) of salophen ligand and 2.98g (0.012mol) of Co (OAc) were added to 10ml of ethanol under nitrogen protection2·4H2And O, heating and refluxing for reaction for 2h at the temperature of 75 ℃, after the reaction is finished, performing suction filtration (washing a filter cake for at least 3 times by using cold ethanol) after the reaction liquid is cooled to room temperature, and then performing vacuum drying for 24 hours to obtain brown solid, namely the cobalt complex catalyst Co (salophen).
Example 2A carbon nanotube/cobalt Complex composite catalyst
The preparation method of the (mono) CNTs/Co (salophen) comprises the following steps:
4mg of Co (salophen) prepared in example 1 was dissolved in 20mL of deionized water at room temperature to obtain an aqueous solution of Co (salophen). According to the table 1, the carbon nano tube CNTs are taken and dispersed in 10mL of ethanol to obtain ethanol solutions of the carbon nano tube CNTs with different qualities. Uniformly mixing the aqueous solution of Co (salophen) and ethanol solutions of CNTs (carbon nanotubes) with different mass ratios, stirring for 12 hours, centrifuging, and drying in vacuum to respectively obtain the CNTs/Co (salophen) composite catalyst with different mass ratios.
TABLE 1
| Mass of carbon nanotube CNTs | CNTs Co (salophen) | Product of |
| 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 |
(II) detection
As shown in FIG. 1, scanning electron micrographs of commercial CNTs were tested. As can be seen from (a) in FIG. 1, CNTs have disordered tubular surfaces which are mutually overlapped, and have large specific surface area, thereby providing guarantee for the adsorption capacity of the catalyst. As can be seen from fig. 1 (b), the tubular structure of the carbon tube can be seen more clearly from the morphology in comparison with fig. 1 (a).
As shown in FIG. 2, the structure of commercial CNTs can be clearly seen by examining the SEM images of the CNTs.
Example 3 application of carbon nanotube/cobalt complex composite catalyst as heterogeneous catalyst in electrocatalytic carbon dioxide reduction (CNTs/Co (salephen)) modified electrode preparation
1. GC pretreatment of a glassy carbon electrode: using 2.0 μm alumina powder to GC (0.07 cm)2) The electrode was polished, then ultrasonically cleaned with deionized water and acetone, and dried in air.
2. Dispersing 4mg of the carbon nanotube/cobalt complex composite catalyst CNTs/Co (salophen) with different mass ratios prepared in the example 2 into 10mL of ethanol, dripping 10 mu L of solution onto the surface of the pretreated glassy carbon electrode GC, and drying the GC in an oven at 40 ℃ for 3 hours to prepare the CNTs/Co (salophen) modified electrodes with different mass ratios.
(II) study of photoelectrochemical Properties
All tests in this experiment were carried out using CHI660E electrochemical workstation from Shanghai Chenghua, Inc., with platinum wire or mesh as counter electrode and Ag/AgCl electrode (2.5M saturated potassium chloride solution) as reference electrode.
Cyclic Voltammetry (CV) testing of the catalyst was performed in sodium bicarbonate solution. A three-electrode system is adopted, a CNTs/Co (salephen) modified electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum net is used as a counter electrode, and 0.1M sodium bicarbonate solution filled with carbon dioxide is used as an electrolyte solution to carry out electrochemical test. The electrochemical test results are shown in fig. 3, fig. 4 and fig. 5.
As can be seen from FIG. 3, the current of CNTs and Co complex catalyst Co (salophen) is-0.12 mA at a voltage of-1.3 Vvsag/AgCl, CNTs/Co (salophen) -2 obtained by compounding carbon tubes and catalyst in a ratio of 2:1, and the current of CNTs and Co (salophen) alone is 10 times that of CNTs and Co (salophen) at a voltage of-1.3 Vvs Ag/AgCl, so that the good catalytic activity can be obtained by compounding Co (salophen) and carbon tubes.
As can be seen from fig. 4, the current increases with the increasing proportion when the mass ratio of CNTs and co (salophen) is 1:1, 2:1, 5:1, and 10:1, respectively, and decreases with the increasing proportion when the mass ratio reaches 2:1, and CNTs/co (salophen) -2 obtained when CNTs: co (salophen) is 2:1, the current at a voltage of-1.3 Vvs Ag/AgCl is-1.2 mA, which is several times the other ratios. It can be seen that the catalyst has the best catalytic effect when the composite ratio of CNTs and Co (salophen) is 2: 1.
Fig. 5 shows it of carbon tubes and co (salophen) in sodium bicarbonate solution under different voltages, and it can be seen from fig. 5 that the effect of the catalyst is not greatly reduced with the continuous extension of time under different voltages, so that it can be seen that the CNTs/co (salophen) composite catalyst of the present invention has good stability and is convenient for application.
Claims (1)
1. The application of the carbon nano tube/cobalt complex composite catalyst as a heterogeneous catalyst in electrocatalytic reduction of carbon dioxide is characterized in that the method comprises the following steps:
1) preparing a CNTs/Co (salophen) modified electrode: dispersing a carbon nano tube/cobalt complex composite catalyst in ethanol, uniformly dripping the catalyst on the surface of a polished glassy carbon electrode GC, and drying the glassy carbon electrode GC in an oven for 3-4 hours to obtain a CNTs/Co (salophen) modified electrode;
2) using a CNTs/Co (salophen) modified electrode as a working electrode, a platinum wire or a platinum net as a counter electrode and an Ag/AgCl electrode as a reference electrode to carry out electrocatalytic reduction on carbon dioxide;
the preparation method of the carbon nano tube/cobalt complex composite catalyst comprises the following steps:
1) preparation of salophen ligand: adding 0.005mol of salicylaldehyde and 0.010mol of o-phenylenediamine into 100ml of ethanol, heating and refluxing for 6h at 75 ℃, cooling the solution to room temperature after the reaction is completed, distilling under reduced pressure and filtering, and then drying in vacuum for 12 h to obtain brown salophen ligand
2) Preparation of cobalt complex catalyst Co (salophen): 0.01mol of salophen ligand and 0.012mol of Co (OAc) were added to 10ml of ethanol under nitrogen protection2·4H2Heating and refluxing the mixture at 75 ℃ for reaction for 2h, after the reaction is finished, cooling the reaction solution to room temperature, performing suction filtration, and then performing vacuum drying for 24 h to obtain brown solid, namely the cobalt complex catalyst Co (salophen);
3) preparing CNTs (carbon nanotubes)/Co (salophen) = 2:1, dissolving a cobalt complex catalyst Co (salophen) in deionized water at room temperature, dispersing carbon nanotube CNTs in ethanol, mixing an aqueous solution of Co (salophen) and an ethanol solution of CNTs, stirring for 12-13 hours, centrifuging, and drying in vacuum to obtain the carbon nanotube/cobalt complex composite catalyst CNTs/Co (salophen).
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| CN201811478153.1A CN109400656B (en) | 2018-12-05 | 2018-12-05 | Cobalt complex catalyst, carbon nano tube/cobalt complex composite catalyst and application |
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| CN109400656B true CN109400656B (en) | 2022-02-18 |
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| Electrochemical reduction of carbon dioxide catalyzed by transition metal complexes;Gennaro, Amando et al.;《NATO ASI Series, Series C: Mathematical and Physical Sciences》;19931231;314-315页 * |
| Molecular cobalt-salen complexes as novel cocatalysts for highly efficient photocatalytic hydrogen production over a CdS nanorod photosensitizer under visible light;Haiyan Chen et al.;《J. Mater. Chem. A》;20150624;第3卷;Scheme 1、2.2节 * |
| Supported Cobalt Polyphthalocyanine for High-Performance Electrocatalytic CO2 Reduction;Na Han et al.;《Chem》;20171005;第3卷(第4期);标题，摘要，653页第2段，图3，656页最后一段，657页第一段、653页，图1,656页第一段、661页第三段 * |
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