Preparation method of organic carbonyl cobalt compound

Abstract

The invention provides a preparation method of an organic carbonyl cobalt compound, which comprises the following steps: preparing an acetonitrile solution taking 1-butyl-3-methylimidazolium hexafluorophosphate as a supporting electrolyte at a cathode of a double-cell electrolytic tank, and adding cobalt salt, metal nickel powder and 3, 3-dimethyl-1-butyne into the cathode; preparing dilute sulphuric acid for an anode; taking a carbon electrode of a copper-zinc catalyst as a working electrode for reduction reaction, a silver wire as a reference electrode and a platinum net as a counter electrode, connecting with an electrochemical workstation, introducing carbon dioxide into a cathode, controlling the flow rate to be 3-5mL / min, and applying constant potential for reaction; filtering after the reaction is finished, and performing post-treatment on the obtained filtrate to obtain a crude product; carbon dioxide is used as an alternative source of carbon monoxide, an electrochemical reduction method is used for replacing a reducing agent, the organic carbonyl cobalt compound is synthesized by a one-pot method under the action of the metal catalyst, the process is novel and simple, the condition is mild, and the synthesis efficiency is high.

Description

Technical Field

[0001] The present invention relates to the technical field of compound preparation, in particular to a method for preparing an organic carbonyl cobalt compound. Background Art

[0002] (3,3-Dimethyl-1-butyne) dicobalt hexacarbonyl, or cobalt cyclopentadienyl dicarbonyl, is an important cobalt-containing precursor material for chemical vapor deposition (CVD) and atomic layer deposition (ALD), primarily used for depositing various functional layers in chip manufacturing. It can be used to prepare functional materials such as high-purity cobalt metal, cobalt nitride, and cobalt silicide, exhibiting particularly excellent performance in cobalt barrier layers, liners, co-coating layers, and eutectic seed layers. Furthermore, CCTBA exhibits high vapor pressure and excellent thermal stability, enabling efficient deposition at low temperatures, reducing impurity interference, and improving film quality and deposition efficiency, making it an indispensable key material in modern semiconductor manufacturing.

[0003] CN117126208A discloses a method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl, comprising the following steps: uniformly mixing dicobalt octacarbonyl and a solvent in a protective gas atmosphere to obtain an intermediate product; dropwise adding 3,3-dimethyl-1-butyne to the intermediate product to obtain a pre-product after reaction; and separating the pre-product to obtain (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl. Although the preparation method has simple steps and is time-consuming, dicobalt octacarbonyl is expensive, has high synthesis costs, and is sensitive to air and difficult to store.

[0004] CN118108773A discloses a method for preparing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl and its application. The method comprises the following steps: continuously pumping tert-butyl acetylene into a tubular reactor containing dicobalt octacarbonyl at 10-30°C, atmospheric pressure, and nitrogen protection to react; during the continuous pumping process, first collecting the reaction product CCTBA at 40-80°C; then collecting the unreacted tert-butyl acetylene at -20-36°C and pumping it into the reactor to continue the reaction; and finally tert-butyl acetylene is collected at -20-36°C and pumped into the reactor until the dicobalt octacarbonyl is completely reacted. This invention does not involve solvent and effectively utilizes resources, but requires a corresponding reaction apparatus, which has certain limitations.

[0005] CN 119143814A discloses a method for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl using cobalt salt as a raw material. The method comprises the following steps: adding activated carbon, gold chloride, cobalt salt, and water to a reactor, stirring, and controlling the temperature at 10-15°C; adding a 40% aqueous hydrazine hydrate solution dropwise; and slowly heating to 50-55°C after the addition is complete; adding a 30% aqueous sodium hydroxide solution dropwise to the reactor to maintain the pH of the reaction solution between 7.5 and 8, controlling the temperature and stirring to react for 5-6 hours, filtering the reaction solution, drying the filtered solid, and returning it to a reactor; adding dichloromethane and tert-butylacetylene; controlling the temperature at 25-30°C; introducing carbon monoxide gas to a vapor pressure of 0.3-0.4 MPa; and distilling until the reaction is complete to obtain a pure product. This method uses cobalt salt, which is widely available and inexpensive, as a raw material, which reduces costs to a certain extent. However, the use of a precious metal catalyst increases costs, and the reaction conditions are strict and the operation is complex.

[0006] CN117126210A discloses a method for synthesizing cyclopentadienyl cobalt dicarbonyl, comprising the following steps: adding raw materials, octacarbonyl dicobalt and tetrahydrofuran solvent, to a reaction flask under the protection of an inert gas, setting up an atmospheric reflux apparatus, and starting stirring; adding a tetrahydrofuran solution of cyclopentadienyl sodium dropwise to the reaction flask, and after completion of the addition, maintaining a stirring reaction at 70-80°C for 6-10 hours; after the stirring and reflux, first distilling the solvent tetrahydrofuran under atmospheric pressure to remove it; then setting up a vacuum distillation apparatus, and performing vacuum distillation to obtain a crude cyclopentadienyl cobalt dicarbonyl product; and subjecting the obtained crude cyclopentadienyl cobalt dicarbonyl product to vacuum distillation to obtain a finished cyclopentadienyl cobalt dicarbonyl product. Although the preparation method has a streamlined operating procedure and is time-consuming, octacarbonyl dicobalt is expensive, has a high synthesis cost, and is sensitive to air and difficult to store.

[0007] Existing technologies for synthesizing (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl or cyclopentadienylcobalt dicarbonyl primarily use dicobalt octacarbonyl as the cobalt source. While simple to operate and time-efficient, dicobalt octacarbonyl is expensive, sensitive, and difficult to store, resulting in high synthesis costs. Dicobalt octacarbonyl is primarily prepared by reacting cobalt salts with synthesis gas (CO, H2) in an inert solvent under high temperature and high pressure conditions, which presents challenges such as high operating conditions, complex production processes, and safety risks.

[0008] In view of this, it is necessary to develop a method for preparing organic carbonyl cobalt compounds using cheap and readily available cobalt salts as a cobalt source, with a simple operation, low safety risk and low synthesis cost. Summary of the Invention

[0009] The present invention provides a method for preparing an organic carbonyl cobalt compound, which solves the problems of high synthesis cost, complex operation, or high safety risk in the prior art.

[0010] The technical solution of the present invention is achieved as follows: A method for preparing an organic carbonyl cobalt compound comprises: The cathode of the dual-cell electrolytic cell is equipped with an acetonitrile solution containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte, and cobalt salt, metallic nickel powder and 3,3-dimethyl-1-butyne are added to the cathode; the anode is equipped with dilute sulfuric acid; A carbon electrode with a copper-zinc catalyst was used as the working electrode for the reduction reaction, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The electrodes were connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a flow rate of 3-5 mL / min. A constant potential reaction was applied. After the reaction was completed, the reaction was filtered, and the resulting filtrate was post-treated to obtain a crude product of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.

[0011] In some embodiments, the concentration of 1-butyl-3-methylimidazolium hexafluorophosphate is 0.1M-2.0M, preferably 0.5M.

[0012] In some embodiments, the applied constant potential is -1.0V to -6.0V, preferably -1.0V or -2.0V.

[0013] In some embodiments, the cobalt salt is one of cobalt iodide, cobalt sulfide, cobalt chloride, cobalt sulfate, and cobalt acetate, preferably cobalt iodide.

[0014] In some embodiments, the molar ratio of the cobalt salt to 3,3-dimethyl-1-butyne is 1:0.5-1.2, and the preferred molar ratio is 1:0.6-0.8.

[0015] In some embodiments, the 3,3-dimethyl-1-butyne is replaced by cyclopentadiene, and the obtained product is a crude cobalt dicarbonylcyclopentadiene.

[0016] In some embodiments, the molar ratio of the cobalt salt to cyclopentadiene is 1:2.5-4.0, preferably 1:2.6-2.8.

[0017] In some embodiments, the molar ratio of the cobalt salt to the metallic nickel powder is 1:0.05-0.3, preferably 1:0.08-0.12.

[0018] In some embodiments, the preparation method of the carbon electrode of the copper-zinc catalyst includes: a copper / zinc electrode is deposited on carbon paper; the battery is a single-chamber battery equipped with a platinum sheet as a counter electrode; the electrolyte is composed of a mixed solution of 50mL H2SO4 (20mM), CuSO4 (50mM), ZnSO4 (50mM) and (NH4)2SO4 (1.5M), and is deposited using a DC power supply at a current density of -1.0A; the prepared electrode is washed with water multiple times and dried in a vacuum oven at room temperature.

[0019] In some embodiments, the reaction temperature is 20-80°C, preferably 40°C or 60°C.

[0020] In some embodiments, the carbon dioxide flow rate is 3-5 mL / min, preferably 3 mL / min.

[0021] In some embodiments, the filtration process uses a sand core filtration device.

[0022] In some embodiments, the post-treatment is performed by distillation under reduced pressure.

[0023] In some embodiments, the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product is distilled to obtain pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product.

[0024] In some embodiments, the crude cyclopentadienylcobalt dicarbonyl product is distilled to obtain pure cyclopentadienylcobalt dicarbonyl product.

[0025] In some embodiments, the potentiostatic reaction is applied for 6-8 hours.

[0026] In some embodiments, the cobalt salt is cobalt iodide, and the amount used is 1.56 grams; the catalyst metal nickel powder, and the amount used is 0.03 grams.

[0027] In some embodiments, the cobalt salt is cobalt iodide, and the amount used is 3.12 grams; the catalyst metal nickel powder is used in an amount of 0.05 grams.

[0028] Compared with the prior art, the present invention has the following beneficial effects: The present invention uses carbon dioxide as a substitute source for carbon monoxide, which can solve the problems of toxicity, high pressure and difficulty in operation when using traditional gaseous CO carbonyl sources.

[0029] (2) The present invention uses an electrochemical reduction method to replace the reducing agent, reducing divalent cobalt salt and carbon dioxide to cobalt and carbon monoxide respectively, and synthesizing organic carbonyl cobalt compounds in a one-pot method under the action of a metal catalyst. The process is novel and simple, the conditions are mild, and the synthesis efficiency is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0031] Figure 1This is the H NMR spectrum of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in Example 1.

[0032] Figure 2 This is the C NMR spectrum of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in Example 1.

[0033] Figure 3 This is the TG-DSC curve of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl prepared in Example 1.

[0034] Figure 4 This is the H NMR spectrum of dicarbonylcyclopentadienylcobalt prepared in Example 7.

[0035] Figure 5 This is the C NMR spectrum of dicarbonylcyclopentadienylcobalt prepared in Example 7. DETAILED DESCRIPTION

[0036] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0037] The reagents and equipment used in the following examples are all commercially available.

[0038] Example 1 Preparation method of carbon electrode of copper-zinc catalyst: copper / zinc electrode is deposited on 1cm 2 The electrodes were deposited on carbon paper. Before deposition, the carbon paper was ultrasonically cleaned with acetone, ethanol, and deionized water. The cell was a single-chamber cell equipped with a platinum sheet as the counter electrode. The electrolyte consisted of a mixed solution of 50 mL of H2SO4 (20 mM), CuSO4 (50 mM), ZnSO4 (50 mM), and (NH4)2SO4 (1.5 M). Deposition was performed at a current density of -1.0 A for 30 seconds using a DC power supply (Hangzhou Huayi Electronic Industry Co., Ltd.). The prepared electrodes were rinsed several times with water and dried in a vacuum oven at room temperature before use.

[0039] A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 1.56 g of cobalt iodide, 0.03 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode, and dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 20°C for 6 h. After the reaction, the reaction was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0040] The reaction formula of the above process is as follows: ;

[0041] The filtration process uses a sand core filtration device.

[0042] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 82%.

[0043] Example 2 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was equipped with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 0.46 g of cobalt sulfide, 0.03 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode. Dilute sulfuric acid (0.5 M) was added to the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 20°C for 6 h. After the reaction, the reaction was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0044] The reaction formula of the above process is as follows: ;

[0045] The filtration process uses a sand core filtration device.

[0046] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 76%.

[0047] Example 3 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 0.89 g of cobalt acetate, 0.03 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode, and dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 20°C for 6 h. After the reaction, the reaction was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0048] The reaction formula of the above process is as follows: ;

[0049] The filtration process uses a sand core filtration device.

[0050] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 75%.

[0051] Example 4 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 1.56 g of cobalt iodide, 0.03 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode, and dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 40°C for 6 h. After the reaction, the reaction was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0052] The reaction formula of the above process is as follows:

[0053] The filtration process uses a sand core filtration device.

[0054] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 90%.

[0055] Example 5 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 1.56 g of cobalt iodide, 0.03 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 80°C for 6 h. After the reaction, the reaction was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0056] The reaction formula of the above process is as follows: ;

[0057] The filtration process uses a sand core filtration device.

[0058] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 82%.

[0059] Example 6 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 1.56 g of cobalt iodide, 0.06 g of 200-mesh nickel powder, and 0.25 g of 3,3-dimethyl-1-butyne were added to the cathode, and dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc-catalyzed carbon electrode served as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire as the reference electrode, and a platinum mesh as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -1.0 V was applied at 40°C for 6 h. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain the crude (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product. The pure (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl product was then obtained by rectification.

[0060] The reaction formula of the above process is as follows: ;

[0061] The filtration process uses a sand core filtration device.

[0062] The yield of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl synthesized in this example is 85%.

[0063] The comparison components are detailed in the following table: ; In summary, when 1.56 g of cobalt iodide, 0.03 g of 200 mesh nickel powder, and 0.25 g of tert-butylacetylene were used at 40 °C, the yield reached 90%, which was the optimal ratio.

[0064] Example 7 A dual-cell electrolytic cell was used as an electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) with 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 3.12 g of cobalt iodide, 0.05 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for carbon dioxide reduction, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 40°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain a crude dicarbonyl cyclopentadienyl cobalt product. The dicarbonyl cyclopentadienyl cobalt product was then obtained by distillation.

[0065] The reaction formula of the above process is as follows: ;

[0066] The filtration process uses a sand core filtration device.

[0067] The yield of dicarbonylcyclopentadienylcobalt synthesized in this example is 84%.

[0068] Example 2 A dual-cell electrolytic cell was used as an electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) with 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 0.91 g of cobalt sulfide, 0.05 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 40°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain a crude dicarbonyl cyclopentadienyl cobalt product. The dicarbonyl cyclopentadienyl cobalt product was then obtained by distillation.

[0069] The reaction formula of the above process is as follows: ;

[0070] The filtration process uses a sand core filtration device.

[0071] The yield of dicarbonylcyclopentadienylcobalt synthesized in this embodiment is 79%.

[0072] Example 3 A dual-cell electrolytic cell was used as an electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) with 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 1.77 g of cobalt acetate, 0.05 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 40°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain a crude dicarbonyl cyclopentadienyl cobalt product. The dicarbonyl cyclopentadienyl cobalt product was then obtained by distillation.

[0073] The reaction formula of the above process is as follows: ;

[0074] The filtration process uses a sand core filtration device.

[0075] The yield of dicarbonylcyclopentadienylcobalt synthesized in this embodiment is 72%.

[0076] Example 4 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 3.12 g of cobalt iodide, 0.05 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 60°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain the crude product of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl. The pure product of dicarbonylcyclopentadienyl cobalt was then obtained by distillation.

[0077] The reaction formula of the above process is as follows: ;

[0078] The filtration process uses a sand core filtration device.

[0079] The yield of dicarbonylcyclopentadienylcobalt synthesized in this example is 91%.

[0080] Example 5 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 3.12 g of cobalt iodide, 0.05 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 80°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain the crude product of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl. The pure product of dicarbonylcyclopentadienyl cobalt was then obtained by distillation.

[0081] The reaction formula of the above process is as follows: ;

[0082] The filtration process uses a sand core filtration device.

[0083] The yield of dicarbonylcyclopentadienylcobalt synthesized in this embodiment is 85%.

[0084] Example 6 A dual-cell electrolytic cell was used as the electroreduction device. The cathode was configured with an acetonitrile solution (0.5 M) containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte. 3.12 g of cobalt iodide, 0.12 g of 200-mesh nickel powder, and 0.40 g of cyclopentadiene were added to the cathode. Dilute sulfuric acid (0.5 M) was configured as the anode. A copper-zinc catalyst carbon electrode was used as the working electrode for the reduction of cobalt salt and carbon dioxide, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The cell was connected to an electrochemical workstation. Carbon dioxide was introduced into the cathode at a controlled carbon dioxide flow rate of 3 mL / min. A constant potential of -2.0 V was applied at 60°C for 48 hours. After the reaction, the cell was filtered and the filtrate was distilled under reduced pressure to obtain the crude product of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl. The pure product of dicarbonylcyclopentadienyl cobalt was then obtained by distillation.

[0085] The reaction formula of the above process is as follows: ;

[0086] The filtration process uses a sand core filtration device.

[0087] The yield of dicarbonylcyclopentadienylcobalt synthesized in this embodiment is 88%.

[0088] The comparison components are detailed in the following table: ;

[0089] In summary, when 3.12 g of cobalt iodide, 0.05 g of 200 mesh nickel powder, and 0.40 g of tert-butylacetylene were used at 60 °C, the yield reached 91%, which was the optimal ratio.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an organic carbonyl cobalt compound, characterized in that: include: The cathode of the dual-cell electrolytic cell is equipped with an acetonitrile solution containing 1-butyl-3-methylimidazolium hexafluorophosphate as the supporting electrolyte, and cobalt salt, metallic nickel powder and 3,3-dimethyl-1-butyne are added to the cathode; the anode is equipped with dilute sulfuric acid; A carbon electrode with a copper-zinc catalyst was used as the working electrode for the reduction reaction, a silver wire was used as the reference electrode, and a platinum mesh was used as the counter electrode. The electrodes were connected to an electrochemical workstation, and carbon dioxide was introduced into the cathode at a flow rate of 3-5 mL / min. A constant potential reaction was applied. After the reaction was completed, the reaction was filtered, and the resulting filtrate was post-treated to obtain a crude product of (3,3-dimethyl-1-butyne) dicobalt hexacarbonyl.

2. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The concentration of the 1-butyl-3-methylimidazolium hexafluorophosphate is 0.1M-2.0M.

3. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The applied constant potential is -1.0V--6.0V.

4. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The cobalt salt is one of cobalt iodide, cobalt sulfide, cobalt chloride, cobalt sulfate and cobalt acetate.

5. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The molar ratio of the cobalt salt to 3,3-dimethyl-1-butyne is 1:0.5-1.

2.

6. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The 3,3-dimethyl-1-butyne is replaced by cyclopentadiene, and the obtained product is a crude dicarbonyl cyclopentadienyl cobalt product.

7. The method for preparing an organic carbonyl cobalt compound according to claim 6, characterized in that: The molar ratio of the cobalt salt to cyclopentadiene is 1:2.5-4.

0.

8. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The molar ratio of the cobalt salt to the metallic nickel powder is 1:0.05-0.

3.

9. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The method for preparing the carbon electrode of the copper-zinc catalyst includes: depositing a copper / zinc electrode on carbon paper; the battery is a single-chamber battery equipped with a platinum sheet as a counter electrode; the electrolyte is composed of 50mL of a mixed solution of H2SO4 (20mM), CuSO4 (50mM), ZnSO4 (50mM) and (NH4)2SO4 (1.5M), and deposition is performed using a DC power supply at a current density of -1.0A; the prepared electrode is washed with water multiple times and dried in a vacuum oven at room temperature.

10. The method for preparing an organic carbonyl cobalt compound according to claim 1, characterized in that: The reaction temperature is 20-80° C.; the carbon dioxide flow rate is 3-5 mL / min.

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