Copper-based nanowire array material based on metal phthalocyanine load and preparation method

Abstract

The invention discloses a copper-based nanowire array material based on metal phthalocyanine load and a preparation method. A substrate of the material is of a copper-based nanowire array structure annealed and reduced by a tube furnace, and the surface of the material is linked with a molecular catalyst metal phthalocyanine through a linker; the size of the copper-based nanowire array is 500 nm to 4 [mu] m; the thickness of the metal phthalocyanine layer on the surface of the metal phthalocyanine loaded copper-based nanowire array is 3 nm to 4 nm. According to the material, directional extension and expansion of active sites are achieved, a molecular catalyst is stably linked to the surface of the material through chemical bonds, when the material serves as an electro-catalytic material, the material shows low overpotential and good cycling stability, meanwhile, the material is simple in synthesis method, large-scale production can be achieved, and the material is suitable for industrial production. And the method has a wide commercial application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalytic cathode materials, and particularly relates to a copper-based nanowire array material based on metal phthalocyanine loading and a preparation method. BACKGROUND

[0002] With the increasingly serious global climate change problem, the greenhouse effect caused by CO2 emission has become a major challenge to the sustainable development of human society. At the same time, under the dual pressure of energy crisis and environmental pollution, and in the realistic background that fossil energy cannot be completely abandoned in the short term, the importance of carbon capture, utilization and storage (CCUS) technology as a key technology combination to achieve the goal of "carbon neutralization" is increasingly prominent.

[0003] At present, capturing CO2 from industrial point sources or directly from the environment air and storing or converting it for use has been widely recognized as a core strategy to alleviate global warming. However, the existing CCUS technology generally has problems such as large equipment size and high energy consumption, which limits its large-scale application. Under this background, it is of important practical significance and strategic value to develop green and efficient CO2 conversion and utilization technology.

[0004] Electrocatalytic CO2 reduction reaction (CO2RR) provides a sustainable new way to convert CO2 into high-value-added multi-carbon compounds, but it faces two major challenges: first, the stable structure of CO2 molecules requires overcoming a high thermodynamic energy barrier in the activation process, thereby generating a large overpotential and increasing energy consumption; second, the reaction products are complex, and the selectivity of the target product is poor, making it difficult to achieve efficient and directional conversion. Therefore, designing electrode materials that can reduce the overpotential of electrocatalytic CO2RR and improve the selectivity of products has become a research hotspot and difficulty in this field.

[0005] Traditional bulk electrode materials are difficult to meet the needs of efficient and high-selectivity reactions in electrocatalytic reactions (such as CO2 reduction, hydrogen evolution, etc.) due to their inherent limitations in structure and performance. The core shortcomings can be summarized into three categories: insufficient active sites, low mass transfer efficiency, and single function, which directly restrict the improvement of catalytic performance. In addition, the main shortcomings of the synthesis method of traditional electrode materials can be summarized as low structure control precision, insufficient product purity and stability, cost and efficiency imbalance, and limited functional expansion. These limitations make it difficult for electrode materials prepared by traditional methods to meet the requirements of high activity, high selectivity, and high stability for modern electrocatalytic reactions (such as efficient CO2RR).

[0006] Therefore, it is urgent to develop a new material and method to realize a more efficient and stable electrochemical reaction system. SUMMARY

[0007] The present application aims to solve the problem that more active sites cannot be exposed on the current block electrode material, the preparation method is complex in operation process, large-scale instruments and equipment are needed, and the preparation process is uncontrollable, and provides a copper-based nanowire array material loaded based on metal phthalocyanine and a preparation method.

[0008] In order to achieve the above technical purpose, the technical scheme provided by the present application is: A copper-based nanowire array material loaded based on metal phthalocyanine, the material substrate composition is an annealed and reduced copper-based nanowire array structure, and the surface is coated with a linking agent molecular catalyst metal phthalocyanine; The size of the copper-based nanowire array loaded with metal phthalocyanine is 500 nm-4 μm; The thickness of the metal phthalocyanine layer on the surface of the copper-based nanowire array loaded with metal phthalocyanine is 3 nm-4 nm.

[0009] In a specific embodiment, the annealing reduction is carried out in a tube furnace, and the tube furnace annealing reduction is safer and more feasible, and the copper nanowire in situ growth with a size of 500 nm-4 μm can greatly increase the reaction active sites.

[0010] Further, the linking agent is one of 3-mercaptopropionic acid, 3-mercaptopropionic anhydride, 2-mercaptoacetic acid, 3-mercaptopropionic acid methyl ester and 3-mercaptopropionic acid ethyl ester.

[0011] The linking agent mercapto end is linked to the copper nanowire through a chemical bond, and the copper nanowire is wrapped with a layer of linking agent, the hydroxyl end is linked to the metal phthalocyanine through a chemical bond, and finally the copper nanowire is linked to the molecular catalyst metal phthalocyanine through the linking agent.

[0012] The present application also provides a preparation method of a copper-based nanowire array material loaded based on metal phthalocyanine, comprising the following steps: Step 1: preparing a copper-based nanowire array precursor; Step 2: placing and soaking the copper-based nanowire array precursor of step 1 in a linking agent solution for a certain time, and then washing and drying; Step 3: placing and soaking the dried product of step 2 in a metal phthalocyanine organic solvent solution for a certain time, and then washing and drying to obtain a copper-based nanowire array material loaded based on metal phthalocyanine.

[0013] Further, in step 1, the step of preparing the copper-based nanowire array precursor comprises soaking the foamed copper material in a mixed solution of high ammonium sulfate and sodium hydroxide, then taking out and drying to obtain Cu(OH)2 / foamed copper; then heating the Cu(OH)2 / foamed copper for a certain time and cooling.

[0014] Further, the drying temperature is 30 ℃-60 ℃.

[0015] In a specific embodiment, drying can be performed in a forced air drying oven.

[0016] Further, the heating atmosphere is a mixed atmosphere of H2 and Ar, the ratio of the mixed atmosphere of H2 and Ar is 15:85, the heating rate is 1℃ / min, the heating temperature is 300℃, and the heating time is 2-6 h.

[0017] Further, in step 2, the standing soaking condition is at room temperature, and the linker concentration is 1 mM-10 mM, which can be any one of 1 mM, 5 mM, 7 mM, and 10 mM.

[0018] In a specific embodiment, in step 2, the washing method can be washing three times with ionized water and anhydrous ethanol.

[0019] In a specific embodiment, in step 2, the washing method can be washing three times with deionized water and methanol, and the drying temperature is 30℃-60℃, and drying is performed in a vacuum drying oven.

[0020] Further, in step 3, the metal phthalocyanine is any one of cobalt phthalocyanine CoPc, iron phthalocyanine FePc, copper phthalocyanine CuPc, zinc phthalocyanine ZnPc, and manganese phthalocyanine MnPc.

[0021] Further, in step 3, the standing soaking condition is at room temperature, and the soaking time can be 30-120 min, which can be any one of 30 min, 60 min, 90 min, and 120 min.

[0022] In a specific embodiment, in step 3, the organic solvent is any one of methanol and DMF; preferably, methanol, because the solubility of the metal phthalocyanine in methanol is good, and the metal phthalocyanine can also be well dissolved in DMF, but DMF has a higher boiling point than methanol, and thus there will be a certain residue, so methanol solution is used as the solvent in the subsequent steps.

[0023] The application also provides an application of a copper-based nanowire array material loaded with metal phthalocyanine in constructing a C-N bond by electrocatalytic CO2 coupling with an amine compound.

[0024] The application has the following beneficial effects: 1. The copper-based nanowire array material loaded with metal phthalocyanine in the application can build a conductive network with the in-situ loaded molecular catalyst sites and the three-dimensional nanowire array structure of the material itself, which is conducive to the effective transmission of electrons, and more active sites are exposed on the material compared to traditional bulk electrode materials, which is conducive to the infiltration of electrolyte, thereby ensuring the effective performance of the electrochemical process.

[0025] 2、 Compared with the traditional electrode material synthesis method, the copper-based nanowire array is used as a precursor to load molecular catalyst material in the application, the thiol end of the linker is linked with the copper nanowire through a chemical bond, a layer of linker is wrapped on the copper nanowire, the hydroxyl end is linked with the metal phthalocyanine through a chemical bond, and finally the copper nanowire is linked with the molecular catalyst metal phthalocyanine through the linker; the preparation method has the advantages of simple operation process, no need for large-scale instrument equipment, economic feasibility, strong controllability in the preparation process, superior electrochemical synthesis performance, and provides a simple and novel material synthesis concept, and provides a new idea for the design of a new type of complex structure electrode material.

[0026] 3、 The copper-based nanowire array material based on the metal phthalocyanine loading is used as a new type of cathode material applied to electrocatalytic CO2 coupling amines to construct a C-N bond, 100 % selectivity and 82.72 % FE of CO2 to a high value-added methylation reaction are realized NMP , and has certain cycle stability. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a scanning electron microscope image of Cu NWAs, MPA / Cu NWAs and CoPc / Cu NWAs in Example 1, and the scale is 10 μm and 2 μm; Figure 2 is a transmission electron microscope image of CoPc / Cu NWAs in Example 1, and the scale is 50 nm; Figure 3 is an X-ray photoelectron spectrogram of Cu NWAs, MPA / Cu NWAs and CoPc / Cu NWAs in Example 1; Figure 4 is an in-situ Raman spectrogram of different MPc / Cu NWAs in Examples 1-5, wherein a is an in-situ Raman spectrogram of CoPc / Cu NWAs, b is an in-situ Raman spectrogram of CuPc / Cu NWAs, c is an in-situ Raman spectrogram of FePc / Cu NWAs, d is an in-situ Raman spectrogram of MnPc / Cu NWAs, and e is an in-situ Raman spectrogram of ZnPc / Cu NWAs; Figure 5 is an ultraviolet-visible light spectrogram of different MPc / Cu NWAs in Examples 1-5, wherein a is an ultraviolet-visible light spectrogram of CoPc / Cu NWAs, b is an ultraviolet-visible light spectrogram of CuPc / Cu NWAs, c is an ultraviolet-visible light spectrogram of FePc / Cu NWAs, d is an ultraviolet-visible light spectrogram of MnPc / Cu NWAs, and e is an ultraviolet-visible light spectrogram of ZnPc / Cu NWAs; Figure 6 is the electrochemical performance graph of CoPc / Cu NWAs as a cathode material for electrocatalytic CO2 coupling with amine compounds to construct C-N bonds in Example 6; Figure 7 is the cycle stability graph of CoPc / Cu NWAs as a cathode material for electrocatalytic CO2 coupling with amine compounds to construct C-N bonds in Example 7; DETAILED DESCRIPTION

[0028] The technical solutions of the present application will be described clearly and completely below with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0029] In addition, the technical features involved in different embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0030] Abbreviation meaning NWAs: nanowire arrays Example 1 A preparation method of a copper-based nanowire array material based on metal phthalocyanine loading, comprising the following steps: Step 1: synthesis of copper-based nanowire array precursor: immerse the foam copper material after pre-washing treatment in 30 ml of an alkaline solution in which 0.68 g of ammonium persulfate and 3 g of sodium hydroxide are dissolved, and Cu(OH)2nanowire array material grows on the surface of the foam copper. Put the Cu(OH)2 / foam copper in a porcelain boat in a tube furnace and heat at 300 ℃ under H2 / Ar (15:85) atmosphere at a heating rate of 1 ℃ / min for 4 h. Cool the final product to ambient temperature under H2 / Ar atmosphere to obtain Cu NWAs precursor.

[0031] Step 2: immerse the cut Cu NWAs in a 5 mM 3-mercaptopropionic acid (3-MPA) solution for 10 min, and then wash with deionized water and anhydrous ethanol three times respectively, and dry with cold air.

[0032] The thiol end of 3-mercaptopropionic acid is linked to the copper nanowire through a chemical bond, and a layer of linker is wrapped around the copper nanowire. The sample is denoted as MPA / Cu NWAs.

[0033] Step 3: MPA / Cu NWAs were immersed in 1 mM of cobalt phthalocyanine methanol solution for 90 min. After taking out, they were washed by deionized water and methanol for three times, respectively, and then dried in a vacuum drying oven at 60 °C overnight.

[0034] 3-mercaptopropionic acid was linked to metal phthalocyanine through chemical bonds at the hydroxyl end, and finally the molecular catalyst gold phthalocyanine cobalt was linked to the copper nanowire through the linker 3-mercaptopropionic acid, and the sample was recorded as CoPc / Cu NWAs.

[0035] Example 2 A preparation method of a copper-based nanowire array material loaded based on metal phthalocyanine, comprising the following steps: MPA / Cu NWAs were immersed in 1 mM of copper phthalocyanine methanol solution for 90 min. After taking out, they were washed by deionized water and methanol for three times, respectively, and then dried in a vacuum drying oven at 60 °C overnight.

[0036] Example 3 A preparation method of a copper-based nanowire array material loaded based on metal phthalocyanine, comprising the following steps: MPA / Cu NWAs were immersed in 1 mM of iron phthalocyanine methanol solution for 90 min. After taking out, they were washed by deionized water and methanol for three times, respectively, and then dried in a vacuum drying oven at 60 °C overnight.

[0037] Example 4 A preparation method of a copper-based nanowire array material loaded based on metal phthalocyanine, comprising the following steps: MPA / Cu NWAs were immersed in 1 mM of manganese phthalocyanine methanol solution for 90 min. After taking out, they were washed by deionized water and methanol for three times, respectively, and then dried in a vacuum drying oven at 60 °C overnight.

[0038] Example 5 A preparation method of a copper-based nanowire array material loaded based on metal phthalocyanine, comprising the following steps: MPA / Cu NWAs were immersed in 1 mM of zinc phthalocyanine methanol solution for 90 min. After taking out, they were washed by deionized water and methanol for three times, respectively, and then dried in a vacuum drying oven at 60 °C overnight.

[0039] Example 6 Application in electrocatalytic CO2 coupling amines to construct C-N bonds.

[0040] (1) Preparation of working electrode 1*2 cm2 CoPc / Cu NWAs electrode material, using platinum electrode clamps to fix 1*1 cm 2 area as the working electrode, and the metal cobalt loading on the working electrode was 0.3180 wt% of the total mass. A 2*2 cm 2 nickel foam as the counter electrode, an Ag / AgCl electrode filled with saturated KCl solution as the reference electrode, a Nafion 117 membrane as the separator, and a 0.1 M KHCO3 aqueous solution as the electrolyte. An H-type absolute sealed electrolytic cell was assembled at room temperature for electrochemical performance testing.

[0041] (2) Electrochemical experiment test All electrochemical experiments were completed on an electrochemical workstation (CS350MA, Wuhan Corrtest Electrochemical Workstation). The electrolysis experiment was performed at 25°C, and the electrolytic cell device used was a three-electrode H-type electrolytic cell system, which included the working electrode described above, a nickel foam counter electrode, and an Ag / AgCl reference electrode, with saturated KCl aqueous solution added. Before the experiment, the reference electrode was calibrated according to the method in the literature. In the experiment, a Nafion 117 membrane was used as a proton exchange membrane to separate the cathode and anode. The cathode used 400 mM amine compounds and 0.1 M KHCO3 as the electrolyte, and the anode used 0.1 M KHCO3 aqueous solution as the electrolyte. The amount of electrolyte used in each experiment was 20 ml, the CO2 flow rate was 20 sccm, the reaction time was 1 h, and the electrolysis was performed. The gas products were collected using a gas bag, analyzed using a gas chromatograph (GC, 7890A, Agilent), and the liquid products were analyzed using nuclear magnetic resonance (1H NMR, Bruker Avance III 400M).

[0042] Example 7 The cyclic stability of the CoPc / Cu NWAs was evaluated under the conditions of 25°C, a working potential of -0.6 V vs. Ag / AgCl, and a reaction time of 1 h, with the reaction repeated 27 times.

[0043] As shown in Figure 1 The scanning electron microscope images of the Cu NWAs, MPA / Cu NWAs, and CoPc / Cu NWAs prepared in Example 1 are shown. As shown in the scanning electron microscope images, the precursor Cu NWAs have a three-dimensional nanowire array structure, with uniform morphology and size, and the nanowire length is about 500 nm-4 μm.

[0044] As shown in Figure 2The image shown is a transmission electron microscope (TEM) image of the CoPc / Cu NWAs prepared in Example 1. As can be seen from the image, a 3.2 nm thick molecular catalyst layer is coated on the surface of the copper-based nanowire array.

[0045] like Figure 3 The figure shows the X-ray photoelectron spectra of Cu NWAs, MPA / Cu NWAs, and CoPc / Cu NWAs in Example 1. As shown in the figure, the Cu 2P of MPA / Cu NWAs and CoPc / Cu NWAs compared to Cu NWAs is... 3 / 2 The shift towards a lower binding energy direction proves that 3-MPA is linked to Cu nanowires via Cu-S.

[0046] like Figure 4 The figures shown are in-situ Raman spectra of different MPc / Cu NWAs prepared in Examples 1-5. Figure 4 As shown, this demonstrates the successful loading of materials with different MPc values.

[0047] like Figure 5 The figures show the UV-Vis spectra of different MPc / Cu NWAs prepared in Examples 1-5. As shown, peak shifts occur with different MPc loadings, proving the successful loading of different MPcs into the material.

[0048] like Figure 6 The figure shows the electrochemical performance of CoPc / Cu NWAs as a CN-bonded cathode material for electrocatalytic CO2 coupling with amine compounds in Example 6. As shown, CoPc / Cu NWAs exhibits excellent electrochemical performance, achieving a Faradaic efficiency of 82.72% and a selectivity of 100% for N-methylpiperidine at an ultra-low potential of 0.06 V vs. RHE.

[0049] like Figure 7 The figure shows the cycling stability of CoPc / Cu NWAs as a CN-bonded cathode material for electrocatalytic CO2 coupling with amine compounds in Example 7. As shown, CoPc / Cu NWAs exhibits long-term cycling stability, maintaining its FE value after 27 cycles at an ultra-low potential of 0.06 V vs. RHE. NMP It remains around 82%.

[0050] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

[0051] The above detailed description of the application is not intended to limit the application to the specific embodiments described, but is intended to cover all alternatives that fall within the scope of the application.

Claims

1. A copper-based nanowire array material supported on a metal phthalocyanine, characterized in that, The material substrate is a copper-based nanowire array structure annealed and reduced by a tube furnace, and the surface is coated with a metal phthalocyanine catalyst by a linker molecule; the size of the metal phthalocyanine-loaded copper-based nanowire array is 500 nm-4 μm; The thickness of the metal phthalocyanine layer on the surface of the metal phthalocyanine-loaded copper-based nanowire array is 3 nm-4 nm.

2. The copper-based nanowire array material supported on metal phthalocyanine according to claim 1, wherein, The linker is one of 3-mercaptopropionic acid, 3-mercaptopropionic anhydride, 2-mercaptoacetic acid, 3-mercaptopropionic acid methyl ester, and 3-mercaptopropionic acid ethyl ester.

3. A method of preparing a metallophthalocyanine-based supported copper-based nanowire array material as claimed in claim 1, characterized by, The method comprises the following steps: Step 1: preparing a copper-based nanowire array precursor; Step 2: placing the copper-based nanowire array precursor of step 1 in a linker solution for a certain period of time, then washing and drying; Step 3: placing the dried product of step 2 in a metal phthalocyanine organic solution for a certain period of time, then washing and drying to obtain a metal phthalocyanine-loaded copper-based nanowire array material.

4. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 3, characterized in that, In step 1, the step of preparing the copper-based nanowire array precursor comprises soaking a foamed copper material in a mixed solution of high ammonium sulfate and sodium hydroxide, then taking it out and drying to obtain Cu(OH)2 / foamed copper; then heating the Cu(OH)2 / foamed copper for a certain period of time and cooling it.

5. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 4, characterized in that, The drying temperature is 30-60°C.

6. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 4, characterized in that, The heating atmosphere is a mixed atmosphere containing H2 and Ar, the ratio of the mixed atmosphere of H2 and Ar is 15:85, the heating rate is 1°C / min, the heating temperature is 300°C, and the heating time is 2-6 h.

7. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 3, characterized in that, In step 2, the soaking condition is at room temperature, and the concentration of the linker is 1-10 mM.

8. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 3, characterized in that, In step 3, the metal phthalocyanine is any one of cobalt phthalocyanine, iron phthalocyanine, copper phthalocyanine, zinc phthalocyanine, and manganese phthalocyanine.

9. The method for preparing a copper-based nanowire array material supported on metal phthalocyanine according to claim 3, characterized in that, In step 3, the soaking condition is at room temperature, and the soaking time can be 30-120 min.

10. Use of the metal phthalocyanine-loaded copper-based nanowire array material according to claim 1 in electrocatalytic CO2 coupling amines to construct C-N bonds.

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