CN119977974A - A benzimidazole-modified nickel phthalocyanine catalyst and its preparation method and application - Google Patents
A benzimidazole-modified nickel phthalocyanine catalyst and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种苯并咪唑改性酞菁镍催化剂及其制备方法和应用，苯并咪唑改性酞菁镍催化剂的制备方法包括以下步骤：将苯并咪唑改性酞菁镍溶解在第二溶剂中，得到酞菁镍溶液，碳纳米管分散在第三溶剂中，得到碳纳米管溶液，将酞菁镍溶液和碳纳米管溶液混合，超声，搅拌，抽滤，洗涤，冷冻干燥，得到苯并咪唑改性酞菁镍催化剂，该苯并咪唑改性酞菁镍催化剂的一氧化碳法拉第效率高达94％以上，最高能达到98％，在酸性条件下，可有效的抑制体系中产生的析氢反应的发生，在较宽的电压范围内，其氢气法拉第效率控制在7％以下，具有出色的产物选择性。The invention discloses a benzimidazole-modified nickel phthalocyanine catalyst and a preparation method and application thereof. The preparation method of the benzimidazole-modified nickel phthalocyanine catalyst comprises the following steps: dissolving the benzimidazole-modified nickel phthalocyanine in a second solvent to obtain a nickel phthalocyanine solution, dispersing carbon nanotubes in a third solvent to obtain a carbon nanotube solution, mixing the nickel phthalocyanine solution and the carbon nanotube solution, ultrasonicating, stirring, filtering, washing, freeze-drying, and obtaining the benzimidazole-modified nickel phthalocyanine catalyst. The carbon monoxide Faraday efficiency of the benzimidazole-modified nickel phthalocyanine catalyst is as high as more than 94%, and can reach 98% at the highest. Under acidic conditions, the occurrence of hydrogen evolution reaction generated in the system can be effectively suppressed. In a wider voltage range, the hydrogen Faraday efficiency is controlled to be less than 7%, and the product selectivity is excellent.
Description
Technical Field
The invention belongs to the technical fields of environmental functional materials and electrochemistry, and particularly relates to a benzimidazole modified nickel phthalocyanine catalyst, and a preparation method and application thereof.
Background
Since the 19 th industrial revolution, the overuse of fossil fuels (e.g., petroleum, coal, and natural gas) has created a series of problems. On the one hand, due to the growing population and the rapid development of science and technology, the demand of human beings for fossil fuels is increasing, however fossil fuels are non-renewable energy sources and have limited reserves, which also results in an aggravation of energy crisis. On the other hand, due to the continuous use of fossil fuels, a large amount of CO 2 is discharged into the atmosphere, and at the same time, the global warming is increased. The electroreduction of CO 2 to sustainable fuels or high value-added chemicals (e.g., carbon monoxide, methane, ethanol, ethylene, etc.) is a promising strategy, and among the chemicals produced by electrocatalytic reduction of CO 2, CO is a promising industrial feedstock, playing a key role in many industrial processes.
The nickel phthalocyanine catalyst formed by loading the metal phthalocyanine on the surface of the carbon nano tube is commonly used for electrocatalytic reduction of CO 2, has excellent performance, and particularly, the nickel phthalocyanine catalyst has excellent product selectivity and current density in the catalytic process. However, nickel phthalocyanine is generally used in the electrocatalytic reduction of CO 2 under neutral or weakly alkaline conditions, and refractory carbonate is formed during the reaction, which results in coverage of active sites on the surface of the nickel phthalocyanine catalyst, thereby affecting the stability and catalytic efficiency of the nickel phthalocyanine catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide benzimidazole modified nickel phthalocyanine.
Another object of the present invention is to provide a method for preparing benzimidazole modified nickel phthalocyanine, which modifies common nickel phthalocyanine with imidazole group containing basic functional group to obtain benzimidazole modified nickel phthalocyanine.
The invention also aims to provide a preparation method of the benzimidazole modified nickel phthalocyanine catalyst.
The invention further aims to provide an application of the benzimidazole modified nickel phthalocyanine catalyst in electrocatalytic CO 2, the benzimidazole modified nickel phthalocyanine catalyst can inhibit hydrogen evolution reaction in electrocatalytic CO 2 under an acidic condition, and can optimize the current density of central active metal, promote electron overflow and transfer and further improve the catalytic conversion rate of CO 2.
The aim of the invention is achieved by the following technical scheme.
A benzimidazole modified nickel phthalocyanine has the following structural formula:
a preparation method of benzimidazole modified nickel phthalocyanine comprises the following steps:
Step 1, dissolving 4-nitrophthalonitrile in anhydrous DMF, adding 2-mercaptobenzimidazole in nitrogen atmosphere, stirring for 20-30 minutes at 50-60 ℃, adding anhydrous potassium carbonate for multiple times, reacting for 72-84 hours at 50-55 ℃ under stirring, obtaining a mixture after the reaction is finished, pouring the mixture into ice water, stirring, standing for at least 12 hours, filtering, cleaning, and freeze-drying to obtain 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, wherein the ratio of 4-nitrophthalonitrile to 2-mercaptobenzimidazole is (1-2) in parts by weight;
In the step 1, the ratio of the mass parts of the 4-nitrophthalonitrile, the anhydrous potassium carbonate and the anhydrous DMF is (1-2): 4-8): 35-40, wherein the unit of the mass parts is g, and the unit of the volume parts is mL.
In the step 1, the operation of adding the anhydrous potassium carbonate for multiple times comprises adding the anhydrous potassium carbonate for 6-8 times within 2-3 hours.
In the step 1, the mixture is poured into ice water and stirred for 1-2 hours.
In the step 1, the standing time is 12-16 hours.
In the step 1, the cleaning operation comprises the steps of flushing the solid obtained by filtering with water until the filtrate is neutral, and then washing with methanol for 3-5 times.
And 2, dispersing 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, anhydrous NiCl 2 and 1.8 diazabicyclo [5.4.0] undec-7-ene (DBU) in ultra-dry n-amyl alcohol under the atmosphere of nitrogen, refluxing at 70-90 ℃ for 20-24 hours under stirring, obtaining a reaction solution after the reaction is finished, cooling to room temperature, diluting with a first solvent to enable solid precipitates to appear, filtering, washing and freeze-drying to obtain benzimidazole modified nickel phthalocyanine, wherein the volume part ratio of the mass part of 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, anhydrous NiCl 2 and 1.8 diazabicyclo [5.4.0] undec-7-ene is (0.2:0.2) - (0.5-0.6), and the volume part ratio is (0.2:0.1-0.2:0.6), and the volume part is g.
In the step 2, the first solvent is methanol.
In the step 2, the ratio of the mass parts of anhydrous NiCl 2 to the volume parts of ultra-dry n-amyl alcohol to the volume parts of the first solvent is (0.1-0.2): (20-30): (100-150), the mass parts are in g, and the volume parts are in mL.
In the step 2, washing comprises the steps of washing with normal hexane, methanol, ethanol and water for 1-2 times.
In the step 1 and the step 2, the freeze drying temperature is-80 to-50 ℃, and the freeze drying time is 36-48 hours.
A preparation method of benzimidazole modified nickel phthalocyanine catalyst comprises the following steps:
Dissolving the benzimidazole modified nickel phthalocyanine in a second solvent to obtain a nickel phthalocyanine solution, dispersing carbon nanotubes in a third solvent by ultrasonic treatment to obtain a carbon nanotube solution, mixing the nickel phthalocyanine solution and the carbon nanotube solution, carrying out ultrasonic treatment, stirring for 12-24 hours, carrying out suction filtration, washing and freeze drying to obtain the benzimidazole modified nickel phthalocyanine catalyst, wherein the ratio of the benzimidazole modified nickel phthalocyanine to the carbon nanotubes is (0.003-0.004) (0.03-0.04) in parts by weight.
In the above technical scheme, the second solvent is DMF, and the third solvent is DMF.
In the technical scheme, the mass parts of the benzimidazole modified nickel phthalocyanine, the volume parts of the second solvent and the volume parts of the third solvent are (0.003-0.004): (30-40): (20-30), the mass parts are in g, and the volume parts are in mL.
In the technical scheme, the frequency of the ultrasonic wave is 80-100 Hz, and the time of the ultrasonic wave is 1-2 hours.
In the preparation method of the benzimidazole modified nickel phthalocyanine catalyst, washing comprises the steps of sequentially washing with DMF, ethanol and water for 1-2 times.
In the technical scheme, the freeze-drying temperature is-80 to-50 ℃, and the freeze-drying time is 36-48 hours.
The benzimidazole modified nickel phthalocyanine catalyst is applied to electrocatalytic CO 2.
In the above technical solution, the electrocatalytic electrolyte has a pH of less than 8, preferably less than 7.2, and more preferably acidic.
Compared with the prior art, the invention has the following beneficial effects:
(1) The benzimidazole modified nickel phthalocyanine catalyst has high current density and high binding energy, is favorable for electron transmission, and has better catalytic activity.
(2) The benzimidazole modified nickel phthalocyanine catalyst provided by the invention has the advantages that the Faraday efficiency of carbon monoxide reaches more than 94% and the highest Faraday efficiency reaches 98% under the voltage of-1.20 to-1.00V (vs. RHE) and the pH=1.85 of the electrolyte, the hydrogen evolution reaction generated in the system can be effectively inhibited under the acidic condition, the Faraday efficiency of the hydrogen is controlled below 7% in a wider voltage range, the product selectivity is excellent, and a new knowledge is provided for carrying out electrocatalytic CO 2 reduction in an actual acidic environment.
Drawings
FIG. 1 is a Co2p graph of the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 2 shows a Transmission Electron Microscope (TEM) image and (b-e) energy dispersive X-ray scanning spectra of the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2, wherein (b) is C element, (C) is N element, (d) is Ni element, and (e) is S element;
FIG. 3 shows TEM images and energy-dispersive X-ray scanning spectra of (b) C, (C) N, and (d) Ni of the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 4 is a linear voltammogram of an H-type electrolytic cell employing the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 5 is a cyclic voltammogram of an H-type electrolytic cell employing the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 6 is an impedance diagram (EIS) of an H-type electrolytic cell using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
Fig. 7 is a graph of (a) carbon monoxide faradaic efficiency (FE CO) and (b) hydrogen faradaic efficiency (FE H2) at electrolyte ph=1.85 for an H-type cell employing the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 8 is a graph of current density and carbon monoxide Faraday efficiency (FE CO) of an H-cell electrocatalytic 20 hours at electrolyte pH=1.85 using the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2;
FIG. 9 is a graph of (a) carbon monoxide Faraday efficiency (FE CO) and (b) hydrogen Faraday efficiency (FE H2) for H-type cells using the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2, under different electrolytes;
Fig. 10 is a graph of (a) carbon monoxide faradaic efficiency (FE CO) and (b) hydrogen faradaic efficiency (FE H2) at electrolyte ph=7.2 for an H-type cell employing the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1;
FIG. 11 is a Fourier transform infrared (FT-IR) spectrum of benzimidazole modified nickel phthalocyanine prepared in example 1 and nickel phthalocyanine in comparative example 1.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and examples.
The following drugs were purchased from the following sources:
4-nitrophthalonitrile, 2-mercaptobenzimidazole and 1.8 diazabicyclo [5.4.0] undec-7-ene were all available from Shanghai Michlin Biochemical technologies Co.
In the examples below, XPS spectra were measured using an X-ray photoelectron spectrometer (manufacturer: thermo FISHER SCIENTIFIC K-Alpha). The testing condition of the X-ray photoelectron spectrometer is that the vacuum degree of an analysis chamber is 5×l0 -10 Pa, the excitation source is Al-ka rays (hv= 1486.68 eV), the working voltage is 15kV, the filament current is 10mA, and 5-10 times of signal accumulation are carried out. The test passes the energy of 50eV, the step size of 0.05eV, and the charge correction takes the binding energy of c1s= 284.80eV as an energy standard.
In the following examples, a transmission electron microscope (TEM, model: FEI-Tecnai G2F 20S-Tain) was used to analyze microscopic morphology at an acceleration voltage of 200kV to obtain a Transmission Electron Microscope (TEM) image.
In the examples below, nafion membrane solution (model: D520) was purchased from DuPont DuPontont.
In the following examples, a method for preparing a working electrode, comprising placing 2mg of a catalyst, 1990uL of ethanol and 10uL of nafion membrane solution in a 2mL centrifuge tube, carrying out ultrasonic treatment for 1 hour to obtain an ink-shaped mixed solution, uniformly dripping 300uL of the mixed solution on two sides of 1cm 2 carbon cloth, drying in a 60 ℃ oven for 5 minutes, and fixing the carbon cloth with the mixed solution dripped on the two sides by using a platinum electrode clamp to obtain the working electrode, wherein the catalyst is the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 or the nickel phthalocyanine catalyst prepared in comparative example 1.
In the following examples, the H-type electrolytic cell comprises a working electrode, a reference electrode and a counter electrode, wherein the electrolyte is one of KCl-HCl mixed solution (pH=1.85), K 2SO4-H2SO4 mixed solution (pH=2.19) and KHCO 3 aqueous solution (pH=7.2), the KCl-HCl mixed solution is a mixture of KCl, HCl and water, the KCl concentration in the KCl-HCl mixed solution is 0.5M, the HCl concentration in the KCl-HCl mixed solution is 0.01M, the K 2SO4-H2SO4 mixed solution is a mixture of K 2SO4、H2SO4 and water, the K 2SO4 concentration in the K 2SO4-H2SO4 mixed solution is 0.5M, the H 2SO4 concentration in the K 2SO4-H2SO4 mixed solution is 0.01M, the KHCO 3 aqueous solution is a mixture of KHCO 3 and water, the KHCO 3 concentration in the KHCO 3 aqueous solution is 0.5M, the catalyst in the working electrode is the benzimidazole modified nickel catalyst prepared in example 2 or the benzimidazole nickel phthalocyanine prepared in comparative example 1, and the reference electrode is saturated with mercury electrode.
Example 1
A preparation method of benzimidazole modified nickel phthalocyanine comprises the following steps:
Step 1, 4-nitrophthalonitrile (1.73 g,0.01 mol) is dissolved in anhydrous DMF (35 mL), 2-mercaptobenzimidazole (1.50 g,0.01 mol) is added under nitrogen atmosphere, stirring is carried out for 20 minutes at 50 ℃, anhydrous potassium carbonate (4.14 g,0.03 mol) is added for 8 times in 2 hours, under stirring, reaction is carried out for 72 hours at 50 ℃, a mixture is obtained after the reaction is finished, the mixture is poured into ice water and stirred for 2 hours, standing is carried out for 12 hours, the gray solid is collected by filtration, the filtrate is washed with water until the gray solid is neutral, then 3 times with methanol, and freeze drying is carried out at-80 ℃ for 48 hours, thus obtaining 4- { [ 1H-benzo (d) imidazol-2-yl ] mercaptan } phthalonitrile;
Step 2,4- { [ 1H-benzo (d) imidazol-2-yl ] thiol } phthalonitrile (0.221 g,0.8 mmol), anhydrous NiCl 2 (0.104 g,0.8 mmol) and 1.8 diazabicyclo [5.4.0] undec-7-ene (0.5 mL) were dispersed in ultra-dry n-pentanol (20 mL) under nitrogen atmosphere, and after the reaction was completed under stirring, a dark green reaction solution was obtained, cooled to room temperature, diluted with methanol (100 mL) to give a solid precipitate in the reaction solution, filtered, and the solid precipitate was washed 2 times with n-hexane, methanol, ethanol and water, respectively, and freeze-dried at-80℃for 48 hours to give benzimidazole-modified nickel phthalocyanine (No. im-Nipc).
Example 2
A preparation method of benzimidazole modified nickel phthalocyanine catalyst comprises the following steps:
the benzimidazole modified nickel phthalocyanine (0.003 g) prepared in example 1 was dissolved in DMF (30 mL, second solvent) to obtain a nickel phthalocyanine solution;
Carbon nanotubes (0.03 g) were dispersed in another portion of DMF (30 mL, third solvent) by sonication at 100Hz frequency for 1 hour to give a carbon nanotube solution.
The nickel phthalocyanine solution and the carbon nanotube solution are mixed and are subjected to ultrasonic treatment at a frequency of 100Hz for 1 hour, the mixture is stirred for 12 hours after ultrasonic treatment, suction filtration is carried out, the mixture is sequentially washed with DMF, ethanol and water for 2 times, and freeze drying is carried out at-80 ℃ for 48 hours, thus obtaining the benzimidazole modified nickel phthalocyanine catalyst (No. im-Nipc/CNT).
Comparative example 1
A preparation method of a nickel phthalocyanine catalyst (number: nipc/CNT) comprises the following steps:
Step 1, phthalonitrile (0.102 g,0.8 mmol), anhydrous NiCl 2 (0.104 g,0.8 mmol) and 1.8 diazabicyclo [5.4.0] undec-7-ene (0.5 mL) were dispersed in ultra-dry n-pentanol (20 mL) under nitrogen atmosphere, and after the reaction was completed, a dark green reaction solution was obtained by refluxing at 80℃for 24 hours, cooled to room temperature, diluted with methanol (100 mL) to make solid precipitate appear in the reaction solution, filtered, and the solid precipitate was washed 2 times with n-hexane, methanol, ethanol and water in this order, and dried at-80℃for 48 hours to obtain nickel phthalocyanine (No. Nipc).
Step 2, nickel phthalocyanine (0.003 g) was dissolved in DMF (30 mL) to obtain a nickel phthalocyanine solution. Carbon nanotubes (0.03 g) were dispersed in another portion of DMF (30 mL) by sonication at 100Hz for 1 hour to give a carbon nanotube solution. The nickel phthalocyanine solution and the carbon nanotube solution were mixed and sonicated at a frequency of 100Hz for 1 hour, stirred for 12 hours after sonication, suction filtered, washed 2 times with DMF, ethanol and water, and freeze-dried at-80℃for 48 hours to give a nickel phthalocyanine catalyst (number: nipc/CNT).
The benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1 were tested by an X-ray photoelectron spectrometer to obtain XPS spectra (i.e., co2p diagram) of the Ni site electronic structure, and as shown in fig. 1, as can be seen from fig. 1, the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 has a Ni2p 3/2 -fitted peak at 856eV, a Ni2p 1/2 -fitted peak at 873.89eV, and the nickel phthalocyanine catalyst prepared in comparative example 1 has a Ni2p 3/2 -fitted peak at 855.05eV, and a Ni2p 1/2 -fitted peak at 872.63eV, it can be seen that the benzimidazole-modified nickel phthalocyanine prepared in example 2 has higher binding energy and is more advantageous for charge transfer between central metal Ni and a conductive substrate (carbon nanotube) than the nickel phthalocyanine catalyst prepared in comparative example 1.
The benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the nickel phthalocyanine catalyst prepared in comparative example 1 were subjected to energy dispersive X-ray scanning (TEM-EDS) test by a transmission electron microscope, and the test results are shown in fig. 2 and 3, and as can be seen from fig. 2 (a), the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 has a carbon nanotube structure, and as can be seen from fig. 2 (b-e), since the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 contains a mercaptobenzimidazole structure, and thus contains S element, the S element is clearly distributed, and at the same time, the C element, the N element and the Ni element are uniformly distributed on the carbon nanotube, which proves that the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 is successfully prepared and uniformly supported on the surface of the carbon nanotube, and as can be seen from fig. 3, the elements in the nickel phthalocyanine catalyst prepared in comparative example 1 are uniformly distributed, and the preparation is successful.
Example 3
The current density of the H-type electrolytic cell using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the phthalocyanine nickel catalyst prepared in comparative example 1 as the catalyst (the electrolyte is KCl-HCl mixed solution) was linearly volt-ampered under the reversible hydrogen voltage range of-1.45 to-0.25V to obtain the current density of each catalyst under different voltages, and as shown in FIG. 4, the current density of the H-type electrolytic cell using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 can reach 49.6mA cm -2 under the reversible hydrogen voltage range of-1.45V, whereas the current density of the H-type electrolytic cell using the phthalocyanine nickel catalyst prepared in comparative example 1 only reaches 27.3mA cm -2, the activity of central metal Ni is optimized in example 2, and the electron transfer capability is enhanced, which enables the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 to have high catalytic activity.
Example 4
In the reversible hydrogen voltage range of-1.35V to 1.6V, the H-type electrolytic cell (electrolyte is KCl-HCl mixed solution) which respectively adopts the benzimidazole modified nickel phthalocyanine catalyst prepared in the example 2 and the phthalocyanine nickel catalyst prepared in the comparative example 1 as a catalyst is subjected to cyclic voltammetry scanning at the rate of 0.05V/s, the test result is shown in figure 5, as shown in figure 5, the reduction peak of the H-type electrolytic cell adopting the benzimidazole modified nickel phthalocyanine catalyst prepared in the example 2 appears at 1.16V (vs. RHE), the reduction peak of the H-type electrolytic cell adopting the phthalocyanine nickel phthalocyanine catalyst prepared in the comparative example 1 appears at 1.22V (vs. RHE), after the benzimidazole modified nickel phthalocyanine catalyst prepared in the example 2 is modified by benzimidazole groups, the benzimidazole modified nickel phthalocyanine electronic structure is changed, the reduction peak moves forward by 60mV, and as the electrolyte in the H-type electrolytic cell is acidic, protons (H +) in the electrolyte are combined with N atoms at the 1-position in the nickel groups to form organic cations, so that the reduction peak of the benzimidazole modified phthalocyanine nickel phthalocyanine catalyst prepared in the example 2 is better in the catalytic reduction condition of the embodiment of the acid cobalt phthalocyanine nickel phthalocyanine catalyst, and the reduction condition of the catalyst prepared in the embodiment 2 is better in the catalytic reduction condition of the reduction of the phthalocyanine electronic phthalocyanine catalyst is better than the catalyst prepared in the embodiment of the acid catalyst under the condition of the reduction condition of the CO is better reduced in the reduction condition of the catalyst is prepared in the catalyst.
Example 5
The resistance test of the H-type electrolytic cell (the electrolyte is KCl-HCl mixed solution) using the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 and the phthalocyanine nickel catalyst prepared in comparative example 1 as the catalyst respectively under the reversible hydrogen voltage of-1.00V shows that the H-type electrolytic cell using the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 has smaller semicircular radius than the H-type electrolytic cell using the phthalocyanine nickel catalyst prepared in comparative example 1, which shows that the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 has smaller resistance compared with the phthalocyanine nickel catalyst prepared in comparative example 1, the resistance of the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 is 50.8 omega, the resistance of the phthalocyanine nickel catalyst prepared in comparative example 1 is 460 omega, and further shows that in the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2, the transmission reaction speed of electrons between the benzimidazole modified nickel phthalocyanine and carbon nanotubes is faster and the surface reaction activity is higher.
Example 6
The electrochemical CO 2 reduction test was performed by a constant voltage amperometric method under different reversible hydrogen voltages G using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the phthalocyanine nickel catalyst prepared in comparative example 1 as "catalysts", respectively, in which the generated gas (carbon monoxide and hydrogen) was detected by gas chromatography for components and concentrations, and the carbon monoxide faradic efficiency (FE CO) and the hydrogen faradic efficiency (FE H2),FECO test results and G are shown in table 1 and fig. 7 (a) and the FE H2 test results and G are shown in table 2 and fig. 7 (b)) were obtained by using the faraday efficiency calculation formulas in literature (Zhu Jiajia, ruzui, dan Wenwen, et al, construction of nickel/nitrogen CO-doped self-supporting foam carbon electrode and the electrochemical CO 2 reduction performance [ J ]. University chemistry report, 2024,45 (10): 20-28).
TABLE 1
| G | Example 2 | Comparative example 1 |
| -0.95V(vs.RHE) | 81% | 21% |
| -1.00V(vs.RHE) | 91% | 26% |
| -1.05V(vs.RHE) | 98% | 26% |
| -1.10V(vs.RHE) | 98% | 34% |
| -1.15V(vs.RHE) | 95% | 47% |
| -1.20V(vs.RHE) | 94% | 47% |
| -1.25V(vs.RHE) | 73% | 39% |
As can be seen from Table 1 and FIG. 7 (a), the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 has higher carbon monoxide Faraday efficiency FE CO, with a reversible hydrogen voltage of-1.05V, FE CO reaches 98% which is much higher than FE CO (26%) of the phthalocyanine nickel catalyst prepared in comparative example 1, and with a different reversible hydrogen voltage range, FE CO of the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 is much higher than that of the phthalocyanine nickel catalyst prepared in comparative example 1 by up to 2-3 times, which proves that the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 has excellent CO 2 reduction performance.
TABLE 2
Under different reversible hydrogen voltages, the FE H2 of the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 is less than 6%, while the FE H2 of the phthalocyanine nickel catalyst prepared in comparative example 1 is as low as 22%, which is just because the benzimidazole group is modified, so that the benzimidazole modified nickel phthalocyanine catalyst prepared in example 2 can effectively inhibit hydrogen evolution reaction under an acidic condition. Thus, the benzimidazole modified nickel phthalocyanine catalyst of the present invention has more excellent product selectivity under an acidic electrolyte.
Example 7
The stability test was performed on the H-type electrolytic cell (KCl-HCl mixed solution as electrolyte) using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 as a "catalyst" by a constant voltage amperometric method at a reversible hydrogen voltage of-1.00V, and the test results are shown in FIG. 8, and it is understood from FIG. 8 that the current density was stably fluctuated around 75mA cm -2 and the carbon monoxide Faraday efficiency was always uniformly stabilized at 91% during the test for 20 hours.
Example 8
The electrocatalytic CO 2 reduction test was performed on an H-type electrolytic cell (electrolyte is a K 2SO4-H2SO4 mixed solution) using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 as a "catalyst" under different reversible hydrogen voltages G by a constant voltage amperometric method to obtain a carbon monoxide faradic efficiency (FE CO(H2SO4 in fig. 9) and a hydrogen faradic efficiency (FE H2(H2SO4 in fig. 3) as shown in table 3), and the results were counted with FE CO (FE CO (HCl) and FE H2 (FE H2 (HCl) in fig. 9) of the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 in example 6 to analyze the electrocatalytic conditions under different electrolyte pH, and as can be seen from table 3 and fig. 9, the carbon monoxide faradic efficiency is 90% or more and the hydrogen faradic efficiency is controlled to be 7% or less in the reversible hydrogen voltage range of-1.15V to-1.00V.
TABLE 3 Table 3
Example 9
The electrochemical CO 2 reduction test was performed by a constant voltage amperometric method under different reversible hydrogen voltages G using the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 and the phthalocyanine nickel catalyst prepared in comparative example 1 as "catalysts" in an H-type electrolytic cell (the electrolyte is KHCO 3 aqueous solution) to obtain carbon monoxide faradaic efficiency (FE CO) and hydrogen faradaic efficiency (FE H2),FECO test result and G are shown in table 4 and fig. 10 (a)), and FE H2 test result and G are shown in table 4 and fig. 10 (b), respectively, and it is understood from table 4 and fig. 10 that the benzimidazole-modified nickel phthalocyanine catalyst prepared in example 2 still has better carbon monoxide faradaic efficiency than the phthalocyanine nickel catalyst prepared in comparative example 1 under neutral conditions.
TABLE 4 Table 4
The benzimidazole-modified nickel phthalocyanine prepared in example 1 and the nickel phthalocyanine in comparative example 1 were respectively subjected to FT-IR analysis at a resolution of 4cm -1 using Thermo Scientific Nicolet iS spectrometer, and the test results, as can be seen from fig. 11, show that in the fourier transform infrared spectrum of nickel phthalocyanine, the absorption peak at 2914cm -1 is attributed to C-H stretching vibration, the absorption peak at 1603cm -1 is attributed to internal stretching vibration of the benzene ring, the absorption peak at 1524cm -1 is attributed to plane deformation vibration of the benzene ring, the absorption peak at 1392cm -1 is attributed to C-C stretching vibration, the absorption peak at 1093cm -1 is attributed to N-N stretching vibration and the absorption peak at 716cm -1 is attributed to C-N vibration on the phthalocyanine conjugated ring. In the Fourier transform infrared spectrum of the benzimidazole modified nickel phthalocyanine prepared in example 1, vibration peaks similar to nickel phthalocyanine were also found at 2959cm -1、1604cm-1、1531cm-1、1406cm-1、1102cm-1 and 725cm -1, respectively, and these peaks showed a slight blue shift compared to nickel phthalocyanine, possibly due to the electronic structural change caused by the introduction of benzimidazole groups, which can better lower the reaction barrier of the benzimidazole modified nickel phthalocyanine. In addition, C-H stretching vibration peaks and C-H bending vibration peaks in benzimidazole groups were also found at 3062cm -1 and 934cm -1, respectively. This demonstrates the successful synthesis of the benzimidazole modified nickel phthalocyanine prepared in example 1.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. The benzimidazole modified nickel phthalocyanine is characterized by having the following structural formula:
2. The preparation method of the benzimidazole modified nickel phthalocyanine is characterized by comprising the following steps of:
Step 1, dissolving 4-nitrophthalonitrile in anhydrous DMF, adding 2-mercaptobenzimidazole in nitrogen atmosphere, stirring for 20-30 minutes at 50-60 ℃, adding anhydrous potassium carbonate for multiple times, reacting for 72-84 hours at 50-55 ℃ under stirring, obtaining a mixture after the reaction is finished, pouring the mixture into ice water, stirring, standing for at least 12 hours, filtering, cleaning, and freeze-drying to obtain 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, wherein the ratio of 4-nitrophthalonitrile to 2-mercaptobenzimidazole is (1-2) in parts by weight;
And 2, dispersing 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, anhydrous NiCl 2 and 1.8 diazabicyclo [5.4.0] undec-7-ene in ultra-dry n-amyl alcohol under a nitrogen atmosphere, refluxing at 70-90 ℃ for 20-24 hours under stirring, obtaining a reaction solution after the reaction is finished, cooling to room temperature, diluting with a first solvent to enable solid precipitates to appear, filtering, washing and freeze-drying to obtain benzimidazole modified nickel phthalocyanine, wherein the volume parts ratio of the 4- { [ 1H-benzo (d) imidazole-2-yl ] mercaptan } phthalonitrile, the anhydrous NiCl 2 and the 1.8 diazabicyclo [5.4.0] undec-7-ene is (0.2-0.3): (0.5-0.6), and the volume parts are expressed in terms of g.
3. The preparation method of claim 2, wherein the ratio of the mass parts of 4-nitrophthalonitrile, the mass parts of anhydrous potassium carbonate and the volume parts of anhydrous DMF is (1-2): (4-8): (35-40), the unit of the mass parts is g, and the unit of the volume parts is mL.
4. The method according to claim 2, wherein the step of adding the anhydrous potassium carbonate in multiple portions comprises adding the anhydrous potassium carbonate 6 to 8 times within 2 to 3 hours.
5. The preparation method according to claim 2, wherein the first solvent is methanol, and the mixture is poured into ice water and stirred for 1 to 2 hours.
6. The preparation method according to claim 2, wherein the ratio of the parts by mass of anhydrous NiCl 2 to the parts by volume of ultra-dry n-amyl alcohol to the parts by volume of the first solvent is (0.1-0.2): (20-30): (100-150), the parts by mass are in g, and the parts by volume are in mL.
7. The preparation method of the benzimidazole modified nickel phthalocyanine catalyst is characterized by comprising the following steps of:
Dissolving one of the benzimidazole modified nickel phthalocyanine in claim 1 and the benzimidazole modified nickel phthalocyanine obtained by the preparation method in claims 2-6 in a second solvent to obtain a nickel phthalocyanine solution, dispersing carbon nanotubes in a third solvent by ultrasonic waves to obtain a carbon nanotube solution, mixing the nickel phthalocyanine solution and the carbon nanotube solution, carrying out ultrasonic waves, stirring for 12-24 hours, carrying out suction filtration, washing and freeze-drying to obtain the benzimidazole modified nickel phthalocyanine catalyst, wherein the ratio of the benzimidazole modified nickel phthalocyanine to the carbon nanotubes is (0.003-0.004) (0.03-0.04) in parts by weight.
8. The preparation method of claim 7, wherein the mass fraction of the benzimidazole modified nickel phthalocyanine, the volume fraction of the second solvent and the volume fraction of the third solvent are (0.003-0.004): (30-40): (20-30), the mass fraction is g, the volume fraction is mL, the second solvent is DMF, and the third solvent is DMF.
9. The benzimidazole modified nickel phthalocyanine catalyst obtained by the production process according to claim 7.
10. Use of the benzimidazole modified nickel phthalocyanine catalyst of claim 9 in electrocatalytic CO 2.
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