Carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, its preparation method and use

Abstract

The present invention relates to a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, which comprises a carbon nanotube support and a polymer supported on the support, and the polymer is a polymer formed by copolymerizing tetraaminometal phthalocyanine and a ligand containing an anhydride. In the polymer catalyst, metal atoms with catalytic activity are stably and uniformly dispersed on the surface of the imide polymer, not only retaining the ultra-high specific surface area and catalytic effect of the single-atom catalyst, but also preventing the atoms from agglomerating due to the stabilizing and dispersing effect of the polymer on the catalytically active atoms, effectively improving the stability of the catalyst. The carbon nanotubes provide conductivity for the polymer, enabling the polymer catalyst to have good application performance in electrocatalysis. The uses of the polymer catalyst include catalyzing water decomposition, CO2 cycloaddition, epoxide cycloaddition, oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), etc.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly to a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, its preparation method and uses. Background Art

[0002] Nanomaterials have an ultra-high specific surface area and obvious size effects, which can provide sufficient surface reaction active sites for catalytic reactions. At the same time, they are conducive to the adsorption of reactants and the desorption of intermediate and final products during the reaction process. Therefore, they are widely used in catalytic fields such as thermal catalysis, electrocatalysis, photocatalysis, and photoelectrocatalysis.

[0003] Single-atom catalysts have become a new focus of research in the catalytic field in recent years due to their 100% atomic utilization rate, unique catalytic effects, uniform active site structures, and ultra-high catalytic activities caused by low coordination numbers. However, thermodynamically, single atoms have high surface energy, which easily leads to atomic agglomeration and catalyst instability. In addition, some catalysts have poor conductivity, which limits their application in electrocatalysis. How to prepare catalysts with high activity, good conductivity, well-defined structures, and high stability has become a major problem in the current field of single-atom catalysis research. Summary of the Invention

[0004] (I) Technical Problems to be Solved

[0005] In view of the above-mentioned disadvantages and deficiencies of the prior art, the present invention provides a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst and its preparation method. This catalyst uses tetraaminometal phthalocyanine and a ligand containing an anhydride to copolymerize to obtain a polymer catalyst, so that the catalytically active metal atoms are stably and uniformly dispersed on the polymer surface. It not only retains the ultra-high specific surface area and catalytic effects of single-atom catalysts, but also, due to the stabilizing and dispersing effect of the polymer on the catalytically active atoms, can prevent atomic agglomeration and effectively improve the stability of the catalyst. The carbon nanotubes provide conductivity for the polymer, enabling the polymer catalyst to have good application performance in electrocatalysis.

[0006] (II) Technical Solutions

[0007] In a first aspect, the present invention provides a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, which includes a carbon nanotube support and an imide polymer supported on the support. The imide polymer is a polymer formed by copolymerizing tetraaminometal phthalocyanine and a ligand containing an anhydride.

[0008] According to a preferred embodiment of the present invention, the metal in the tetraaminometal phthalocyanine is a non-precious metal atom such as Fe, Co, Ni, Cu, or Zn, and the structure is as follows:

[0009]

[0010] According to a preferred embodiment of the present invention, the ligand containing anhydride is at least one of phthalic anhydride, pyromellitic dianhydride PMDA, 3,4,9,10-perylene tetracarboxylic dianhydride PTDA, diethylenetriaminepentaacetic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, hexafluorodiacid dianhydride, 4,4'-oxybisphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride NTDA, 3,4,9,10-tetracarboxylic dianhydride PTCDA.

[0011] According to a preferred embodiment of the present invention, the ligand containing anhydride is a polyanhydride, and there is a molecular chain, a carbocyclic ring or a heterocyclic ring between at least two anhydrides.

[0012] According to a preferred embodiment of the present invention, the ligand containing anhydride is 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), 3,4,9,10-perylene tetracarboxylic dianhydride (PTDA), pyromellitic dianhydride (PMDA), 3,4,9,10-tetracarboxylic dianhydride (PTCDA), diethylenetriaminepentaacetic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, hexafluorodiacid dianhydride (6FDA), 4,4'-oxybisphthalic anhydride or 3,3',4,4'-benzophenone tetracarboxylic dianhydride.

[0013] According to a preferred embodiment of the present invention, the carbon nanotubes include single-walled carbon nanotubes, multi-walled carbon nanotubes, short multi-walled carbon nanotubes, carboxyl carbon nanotubes, amino carbon nanotubes or hydroxyl carbon nanotubes.

[0014] According to a preferred embodiment of the present invention, the inner diameter of the carbon nanotubes is 3 - 5 nm, the outer diameter is 8 - 15 nm, and the length is 15 - 50 μm.

[0015] In a second aspect, the present invention also provides a method for preparing a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, which includes:

[0016] Disperse tetraaminometal phthalocyanine, a ligand containing anhydride, and carbon nanotubes in a mixed organic solvent, apply ultrasonic-assisted dispersion, freeze with liquid nitrogen and then evacuate to vacuum, and react at 180 - 210 o °C for 3 - 7 days, centrifuge, wash and dry in vacuum to obtain a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst MPc-Y @CNT with uniformly distributed metal; Y represents the ligand of the anhydride, and M represents the metal element in the tetraaminometal phthalocyanine.

[0017] According to a preferred embodiment of the present invention, ultrasonic treatment for 0.5 - 1 h is used for auxiliary dispersion, and the liquid nitrogen temperature is 77 K.

[0018] According to a preferred embodiment of the present invention, the mixed organic solvent is obtained by mixing N-methylpyrrolidone: m-cresol: isoquinoline in a volume ratio of 9-11:9-11:1; preferably, it is obtained by mixing N-methylpyrrolidone: m-cresol: isoquinoline in a volume ratio of 10:10:1.

[0019] In a third aspect, the present invention also relates to the use of the above-mentioned carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, and the uses include catalyzing various organic catalytic reactions such as water decomposition, CO2 cycloaddition, epoxide cycloaddition, oxygen reduction reaction (ORR), and carbon dioxide reduction reaction (CO2RR).

[0020] (III) Beneficial effects

[0021] The present invention synthesizes for the first time a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst. By in-situ polymerization of four symmetric terminal amino groups around tetraaminometal phthalocyanine with a ligand containing anhydride, a non-precious metal single-atom polymer catalyst supported by an enamine-based covalent organic framework is formed. The microscopic morphology of the product is a two-dimensional film-like shape, with a large specific surface area. The metal single atoms are stably and uniformly dispersed on the film, avoiding the aggregation of metal atoms and providing multiple active sites. In addition, the polymer itself also has an adsorption effect on reactants. At the same time, in the preparation process, by uniformly dispersing tetraaminometal phthalocyanine, a ligand containing anhydride, and carbon nanotube materials in an organic solvent, the polymer generated by the copolymerization of tetraaminometal phthalocyanine and the ligand is in-situ wrapped on the surface of the dispersed carbon nanotubes, so that the single-atom polymer catalyst is loaded onto the carbon nanotube carrier. Utilizing the characteristics of the ultra-high specific surface area and nano-particle size of carbon nanotubes, the specific surface area of catalysis is further increased, the catalytic activity is improved, and the conductivity of the catalyst is improved, and thus it can be used in electrocatalytic reactions. The preparation method of the present invention is simple, the product is easy to separate, environmentally friendly, and has the prospect of industrial application.

[0022] Verified by experiments, CoPc-PM@CNT prepared in the examples of the present invention exhibits excellent electrocatalytic OER performance. Under the conditions of 1M KOH and room temperature, the overpotential required for the sample to drive a current density of 10 mA·cm -2 is only 268 mV, while maintaining a Faraday efficiency of about 98%. In addition, CoPc-PM@CNT prepared in the examples of the present invention exhibits excellent electrochemical stability. Under the conditions of 1M KOH and room temperature, it can continuously catalyze water decomposition at a large current density of 100 mA·cm -2 for 12 h without obvious decline.

[0023] In summary, the non-precious metal single-atom catalyst supported by the organic framework prepared by the present invention has high potential application value in the field of energy catalysis and can be used in other reactions such as HER, ORR, CO2RR, and various organic catalytic reactions. Description of the drawings

[0024] Figure 1 is the chemical structural formula of tetraaminometal phthalocyanine.

[0025] Figure 2 is the X-ray diffraction pattern of the CoPc-PM@CNT sample prepared in Example 1.

[0026] Figure 3 is the field emission scanning electron microscope image of the CoPc-PM@CNT sample prepared in Example 1.

[0027] Figure 4 is the transmission electron microscope image of the CoPc-PM@CNT sample prepared in Example 1.

[0028] Figure 5 is the EDS-Mapping energy spectrum of the CoPc-PM@CNT sample prepared in Example 1.

[0029] Figure 6 is the Raman spectrum of the CoPc-PM@CNT sample prepared in Example 1.

[0030] Figure 7 is the X-ray photoelectron spectrum of the CoPc-PM@CNT sample prepared in Example 1.

[0031] Figure 8 is the OER polarization curve of the CoPc-PM@CNT sample prepared in Example 1.

[0032] Figure 9 is the current density curve of electrolysis for 12 h using CoPc-PM@CNT of Example 1 at 100 mA·cm -2 under.

[0033] Figure 10 The voltammetric curves of CoPc-PM@CNT(1:1) and CoPc-PM@CNT(2:1) on a glassy carbon electrode obtained at a scan rate of 20 mV / s in Example 3.

[0034] Figure 11 is the voltammetric curve of CoPc-NT@CNT on a glassy carbon electrode obtained at a scan rate of 20 mV / s in Example 4.

[0035] Figure 12 is the mass activity of CoPc-NT@CNT at 1.58 V vs .RHE in Example 4.

[0036] Figure 13 is Co obtained at a scan rate of 20 mV / s 0.5 Ni 0.5Pc-PM@CNT and Fe 0.5 Ni 0.5 The voltammetric curve of Pc-PM@CNT on a glassy carbon electrode. Detailed implementation manners

[0037] For better explaining the present invention for easy understanding, the present invention will be described in detail below in conjunction with the accompanying drawings through specific implementation manners.

[0038] Metal phthalocyanine-based compounds are a kind of natural SACs, having excellent electron transfer and mass transfer capabilities, and having a tunable structure and excellent stability. Among them, the phthalocyanine macrocycle can coordinate with almost all metal elements in the periodic table, having a clear and uniform M-N4 center chemical structure and excellent catalytic activity. However, strong Π-Π interactions easily cause metal phthalocyanines to stack, thereby losing the number of active sites. In addition, the poor conductivity of metal phthalocyanines limits their application in electrocatalysis.

[0039] The present invention uses an acid anhydride as a ligand to polymerize with tetraaminometal phthalocyanine. During the polymerization, the polymerization product is in-situ compounded on carbon nanotubes, which can effectively improve the electrocatalytic performance of metal phthalocyanines and is of great significance for promoting industrial production in the field of energy catalysis.

[0040] The polymer catalyst provided by the present invention has uses that include all catalytic uses of the corresponding metal atoms (such as Fe, Co, Ni, Cu, or Zn, etc.) in tetraaminometal phthalocyanine as single-atom catalysts. By copolymerizing tetraaminometal phthalocyanine with an acid anhydride to form a polymer-form catalyst, in this polymer, the metal atoms are stably distributed and uniformly dispersed on the polymer in the form of single atoms, having a super-high specific surface area and thermal stability, preventing the aggregation of metal atoms while retaining the catalytic activity of metal single atoms, having 100% atomic utilization rate, unique catalytic effects, a uniform active site structure, and low coordination numbers. On the one hand, the phthalocyanine macrocycle has a universal metal element coordination ability, a clear and uniform M-N4 center chemical structure, and excellent catalytic activity. On the other hand, the problem of loss of active sites caused by phthalocyanine stacking is avoided through copolymerization. In addition, by virtue of the loading of carbon nanotubes, the polymer catalyst has conductivity, broadening the application scope of the catalyst, especially applicable to electrocatalytic reactions.

[0041] The following is described in conjunction with specific examples. Example 1

[0042] The polymer catalyst prepared in this example is CoPc-PM@CNT, and the preparation method includes:

[0043] Tetraaminocobalt phthalocyanine, pyromellitic dianhydride, and carbon nanotubes (mass ratio = 21:14:60) were uniformly dispersed in an organic solvent with a certain ratio (N-methylpyrrolidone: m-cresol: isoquinoline were mixed according to a volume ratio of 10:10:1), sonicated for 1 h, and frozen under liquid nitrogen at 77 K. After evacuation, the reaction was carried out at 200 o °C for 5 days, and then centrifuged and washed three times with ethanol, deionized water, and N-methylpyrrolidone respectively. After centrifugation, it was placed in a vacuum drying oven and dried for 24 h to obtain the sample CoPc-PM@CNT.

[0044] The X-ray diffraction pattern of the CoPc-PM@CNT sample is shown in Figure 2 , and the diffraction peaks of a certain intensity indicate that the sample has a certain degree of crystallinity, suggesting the orderliness of the structure; the field emission scanning electron microscope image is shown in Figure 3 , and the product is a curved short fiber rod with a rough surface, indicating that tetraaminocobalt phthalocyanine and pyromellitic dianhydride have been successfully polymerized on the surface of the short fiber rod; the transmission electron microscope image is shown in Figure 4 , and there is a polymer film about 0.34 - 1.3 nm thick on the surface of the short fiber rod; the EDS-Mapping energy spectrum image is shown in Figure 5 , and uniformly dispersed single metal Co atoms in the form of star dots and all elements can be observed to be uniformly dispersed; the Raman spectrum is shown in Figure 6 , and the D and G band signals of carbon nanotubes and the signals of phthalocyanine polymers are shown in the spectrum; the X-ray photoelectron spectrum is shown in Figure 7 , and the typical divalent Co characteristic signal indicates that Co has been successfully loaded onto the catalyst. The above experimental results show that the polymer catalyst CoPc-PM@CNT has been prepared in this example. Example 2

[0045] In this example, the electrocatalytic OER performance of CoPc-PM@CNT was tested. The test method was as follows:

[0046] Electrochemical tests were carried out at room temperature on a CHI760E electrochemical workstation using a classical three-electrode system. The electrolyte was 1.0 M KOH solution. Hg / HgO and Pt sheet were used as the reference electrode and the counter electrode. 3 mg of CoPc-PM@CNT prepared in Example 1 was taken, 120 μL of n-propanol and 30 μL of Nafion were added, sonicated for 2 h, and then dropped onto a glassy carbon electrode as the working electrode.

[0047] Figure 8 The linear sweep voltammetry curve shown was obtained at a scan rate of 20 mV / s. It can be seen from the figure that the overpotential required for CoPc-PM@CNT to drive a current density of 10 mA·cm -2 on the glassy carbon electrode is 268 mV. Figure 9The shown CoPc-PM@CNT at 100 mA·cm -2 After 12 h of electrolysis, the curve is flat, indicating that the performance of the catalyst material does not show any loss with the increase in usage time. Therefore, the experiment proves that CoPc-PM@CNT has good electrochemical stability.

[0048] In the present invention, tetraaminocobalt phthalocyanine, pyromellitic dianhydride and carbon nanotubes are first selected as reaction precursors, and a metal phthalocyanine-based imide polymer catalyst MPc-Y@CNT with extremely thin size and highly uniform metal distribution can be prepared in large quantities by a solvothermal one-pot method; wherein, M can be any non-precious metal such as Fe, Co, Ni, Cu, Zn, etc., and Y can be any anhydride such as PMDA, NTDA, PTDA, etc.; according to different ligands, MPc-PM@CNT, MPc-NT@CNT or MPc-PT@CNT, etc. can be obtained.

[0049] The preparation method of the polymer catalyst of the present invention is simple and has a low cost, suitable for large-scale synthesis, and has high potential industrial application value in the field of energy catalysis. It can be used in electrocatalytic water splitting reaction, oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR) and various organic catalytic reactions. Taking electrocatalytic water splitting as an example, since hydrogen has a high energy density and is clean and environmentally friendly, the technology of electrocatalytic water splitting to produce hydrogen has very broad application prospects. Water splitting includes two half-reactions: hydrogen evolution reaction (HER) on the cathode and oxygen evolution reaction (OER) on the anode, both of which require the introduction of a catalyst to reduce the reaction overpotential in the electrocatalytic reaction and improve the reaction efficiency. Among them, the OER process has slow kinetics due to the need for 4 electron transfer steps, and some precious metals and their oxides are currently recognized as excellent electrolytic water catalysts with good performance. However, due to the scarcity of such catalysts, the materials are expensive and the cost is high, and their commercial applications are greatly limited. CoPc-PM@CNT has excellent OER electrocatalytic performance, with a performance superior to the current commercial catalyst RuO2, and the cost is 0.98 yuan / g, only 1 / 400 of the price of commercial RuO2. Example 3

[0050] In this example, the electrocatalytic OER performance of CoPc-PM@CNT(1:1) and CoPc-PM@CNT(2:1) was tested. The test method is as follows:

[0051] Electrochemical tests were carried out at room temperature on a CHI760E electrochemical workstation using a classical three-electrode system. The electrolyte was 1.0 M KOH solution. Hg / HgO and Pt sheet were used as the reference electrode and the counter electrode, respectively. 3 mg of CoPc-PM@CNT(1:1) or CoPc-PM@CNT(2:1) was taken, 120 μL of n-propanol and 30 μL of Nafion were added, and after ultrasonic treatment for 2 h, the sample was dropped onto a glassy carbon electrode as the working electrode. Among them, 1:1 or 2:1 is the mass ratio of the catalytic active material imide polymer to the carrier CNT.

[0052] Figure 10 The linear sweep voltammetry curve shown was obtained at a scan rate of 20 mV / s. It can be seen from the figure that the overpotentials required for CoPc-PM@CNT(1:1) and CoPc-PM@CNT(2:1) to drive 10 mA·cm -2 Current density were 312 and 326 mV, respectively. Therefore, the experiment proves that CoPc-PM@CNT has good electrochemical performance. Example 4

[0053] In this example, the electrocatalytic OER performance of CoPc-NT@CNT was tested. The test method was as follows:

[0054] Electrochemical tests were carried out at room temperature on a CHI760E electrochemical workstation using a classical three-electrode system. The electrolyte was 1.0 M KOH solution. Hg / HgO and Pt sheet were used as the reference electrode and the counter electrode, respectively. 3 mg of CoPc-NT@CNT was taken, 120 μL of n-propanol and 30 μL of Nafion were added, and after ultrasonic treatment for 2 h, the sample was dropped onto a glassy carbon electrode as the working electrode.

[0055] Among them, the preparation method of CoPc-NT@CNT was the same as that in Example 1, except that pyromellitic dianhydride PMDA was replaced with an equimolar amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride NTDA.

[0056] Figure 11 The linear sweep voltammetry curve shown was obtained at a scan rate of 20 mV / s. It can be seen from the figure that the overpotential required for CoPc-NT@CNT to drive 10 mA·cm -2 Current density was 282 mV. Figure 12 The mass activity of CoPc-NT@CNT shown at 1.58 V vs .RHE was measured, and its mass activity was as high as 121673 A·g -1 . Therefore, the experiment proves that CoPc-NT@CNT has good electrochemical performance. Example 5

[0057] This example tests Co0.5 Ni 0.5 Pc-PM@CNT and Fe 0.5 Ni 0.5 The electrocatalytic OER performance of Pc-PM@CNT was tested by the following method:

[0058] At room temperature, electrochemical tests were carried out on a CHI760E electrochemical workstation using a classical three-electrode system. The electrolyte was 1.0 M KOH solution. Hg / HgO and Pt plate were used as the reference electrode and the counter electrode, respectively. 3 mg of Co tested in this example was taken 0.5 Ni 0.5 Pc-PM@CNT or Fe 0.5 Ni 0.5 Pc-PM@CNT was added with 120 μL of n-propanol and 30 μL of Nafion, and after ultrasonic treatment for 2 h, the sample was dropped onto a glassy carbon electrode as the working electrode.

[0059] Among them, Co 0.5 Ni 0.5 The preparation method of Pc-PM@CNT was the same as that of Example 1, except that cobalt tetraaminophthalocyanine was replaced with an equal amount of a mixture of iron tetraaminophthalocyanine and cobalt tetraaminophthalocyanine in a molar ratio of 1:1.

[0060] Fe 0.5 Ni 0.5 The preparation method of Pc-PM@CNT was the same as that of Example 1, except that cobalt tetraaminophthalocyanine was replaced with an equal amount of a mixture of iron tetraaminophthalocyanine and nickel tetraaminophthalocyanine in a molar ratio of 1:1.

[0061] Figure 13 The linear sweep voltammetry curve shown was obtained at a scan rate of 20 mV / s. It can be seen from the figure that Co 0.5 Ni 0.5 Pc-PM@CNT and Fe 0.5 Ni 0.5 Pc-PM@CNT on the glassy carbon electrode required overpotentials of 312 mV and 337 mV to drive a current density of 10 mA·cm -2 respectively. Therefore, the experiment proved that Co 0.5 Ni 0.5 Pc-PM@CNT and Fe 0.5 Ni 0.5 Pc-PM@CNT has good electrochemical performance.

[0062] 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 foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and 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 carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst, characterized in that It includes a carbon nanotube support and an imide polymer supported on the support, and the imide polymer is a polymer formed by copolymerizing tetraaminometal phthalocyanine and a ligand containing an acid anhydride; The metal in the tetraaminometal phthalocyanine is Fe, Co, Ni, Cu or Zn; The ligand containing an acid anhydride is at least one of phthalic anhydride, pyromellitic dianhydride PMDA, 3,4,9,10-perylene tetracarboxylic dianhydride PTDA, diethylenetriaminepentaacetic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, hexafluorodiacid anhydride, 4,4'-oxybisphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride NTDA, 3,4,9,10-tetracarboxylic dianhydride PTCDA.

2. The carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst according to claim 1, wherein The carbon nanotubes include single-walled carbon nanotubes, multi-walled carbon nanotubes, carboxyl carbon nanotubes, amino carbon nanotubes or hydroxyl carbon nanotubes.

3. The carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst according to claim 2, wherein The inner diameter of the carbon nanotubes is 3-5 nm, the outer diameter is 8-15 nm, and the length is 15-50 μm.

4. A method for preparing a carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst according to any one of claims 1 to 3, characterized in that, It includes: Disperse tetraaminometal phthalocyanine, a ligand containing an acid anhydride, and carbon nanotubes in a mixed organic solvent, apply ultrasonic-assisted dispersion, freeze with liquid nitrogen and then evacuate, react at 180-210 °C for 3-7 days, centrifuge, wash and dry in vacuum to obtain a metal phthalocyanine-based imide polymer catalyst MPc-Y @CNT with uniform distribution of metals loaded on carbon nanotubes; Y represents the ligand of the acid anhydride, and M represents the metal element in the tetraaminometal phthalocyanine.

5. The preparation method according to claim 4, characterized in that, Ultrasonic treatment for 0.5-1 h is used for auxiliary dispersion, and the liquid nitrogen temperature is 77 K.

6. The preparation method according to claim 4, characterized in that, The mixed organic solvent is obtained by mixing N-methylpyrrolidone: m-cresol: isoquinoline in a volume ratio of 9-11: 9-11:

1.

7. Use of the carbon nanotube-supported metal phthalocyanine-based imide polymer catalyst according to any one of claims 1 to 3, characterized in that, The uses include catalyzing water decomposition.

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