Metalloporphyrin polyurethane, synthesis method thereof and application thereof in electrocatalytic oxidation of organic matter

Abstract

The present invention discloses a metalloporphyrin polyurethane, a synthesis method thereof, and its application in the electrocatalytic oxidation of organic matter. This invention belongs to the technical field of metalloporphyrin electrocatalytic oxidation applications. The invention primarily utilizes the Alder solvothermal method to synthesize a metalloporphyrin precursor, which is then bridged with a diisocyanate as a coupling reagent to obtain the metalloporphyrin polyurethane. The synthesized intermediate and product are characterized using instruments such as a Fourier transform infrared analyzer and a nuclear magnetic resonance spectrometer. The catalytic activity and catalytic cycle performance of the polymer in the electrocatalytic oxidation of organic matter are studied, providing new ideas for the application of metalloporphyrin polymers in the electrocatalytic oxidation of organic matter.

Description

Technical Field

[0001] The invention relates to the technical field of metalloporphyrin electrocatalytic oxidation applications, and in particular to a metalloporphyrin polyurethane, a synthesis method thereof and application thereof in electrocatalytic oxidation of organic matter. Background Art

[0002] In organic synthesis, the oxidation of organic compounds is a very important reaction, which is mainly used to prepare organic compounds such as alcohols, ketones, and carboxylic acids. Conventional oxidation of organic compounds has multiple limitations, such as the use of highly toxic reagents, high temperature and high pressure reaction conditions, and the need for hazardous solvents. In addition, commonly used oxidants are often dangerous, which increases the complexity of operation and handling, and makes product post-processing more difficult. These factors make the oxidation process of alcohols face many bottlenecks in industrial applications and laboratory research. In the process of exploring solutions to the above problems, metalloporphyrins have attracted much attention due to their excellent catalytic oxidation activity. However, the direct use of metalloporphyrins as catalysts for conventional oxidation also inevitably requires the use of high temperature and high pressure or highly dangerous solvents, and single metalloporphyrin catalysts also have problems such as difficulty in recycling. Therefore, how to effectively utilize the catalytic properties of metalloporphyrins and overcome their shortcomings has become an important research topic that urgently needs to be solved.

[0003] This application aims to address the above challenges by designing and synthesizing metalloporphyrin polymer catalysts, particularly for the research on electrocatalytic oxidation of organic matter. In addition to the catalyst, the metalloporphyrin electrocatalytic oxidation reaction system only requires a solvent and an electrolyte, without the need for an additional oxidant, thereby avoiding the use of highly toxic and dangerous chemical reagents. In the electrocatalytic system, the role of the anode replaces the traditional oxidant, greatly simplifying the reaction conditions and post-processing process. However, directly using metalloporphyrin as an electrocatalyst also faces the problem of catalyst recovery difficulties. By designing metalloporphyrin polymers, the catalyst can be easily recovered after the reaction, thereby improving the reusability of the catalyst, reducing costs, and enhancing the sustainability of the reaction. In addition, by systematically optimizing the electrocatalytic oxidation reaction conditions of the metalloporphyrin polymer catalyst, the reaction efficiency and selectivity can be further improved. The application research of metalloporphyrin polymers in the electrocatalytic oxidation of organic matter is currently relatively small, and has far-reaching research significance and broad application prospects. This research can not only promote the application of metalloporphyrin catalysts in electrocatalytic oxidation organic synthesis, but also provide new ideas and methods for the development of green chemistry and sustainable chemical processes. Summary of the Invention

[0004] The present invention aims to design and synthesize a metalloporphyrin polymer catalyst, which can make the catalyst easy to recycle after the reaction, thereby improving the reusability of the catalyst, reducing costs, and promoting the sustainability of the reaction. In addition, by systematically optimizing the electrocatalytic oxidation reaction conditions of the metalloporphyrin polymer catalyst, the optimal reaction conditions can be determined, further improving reaction efficiency and selectivity. The application research of metalloporphyrin polymers in the electrocatalytic oxidation of alcohols is currently less, with far-reaching research significance and broad application prospects. This research can not only promote the application of metalloporphyrin catalysts in electrocatalytic oxidation organic synthesis, but also provide new ideas and methods for the development of green chemistry and sustainable chemical processes.

[0005] Based on the above objectives, the present invention adopts the following technical solutions:

[0006] A method for synthesizing metalloporphyrin polyurethane comprises the following steps: dissolving metalloporphyrin and triethylenediamine in an organic solvent A under a protective atmosphere to obtain solution A; dissolving p-phenylene diisocyanate in an organic solvent to obtain solution B; dropping solution B into solution A, stirring for complete reaction; and removing most of the solvent by vacuum distillation after the reaction. The mixture is cooled, water is added, and vacuum filtration is performed. The filter cake is washed with water multiple times and then rinsed with organic solvent B until the filtrate is colorless. The filter cake is collected and dried to obtain the metalloporphyrin, diisocyanate, and triethylenediamine. The molar ratio of the metalloporphyrin, diisocyanate, and triethylenediamine is 1:(2-2.5):(0.1-0.2).

[0007] Furthermore, the metalloporphyrin is meso-tetra(p-hydroxyphenyl)cobaltporphyrin, meso-tetra(p-hydroxyphenyl)nickelporphyrin, meso-tetra(p-hydroxyphenyl)copperporphyrin, meso-tetra(p-hydroxyphenyl)ironporphyrin, meso-tetra(p-hydroxyphenyl)zincporphyrin or meso-tetra(p-hydroxyphenyl)manganeseporphyrin.

[0008] Furthermore, the metalloporphyrin is obtained by the following process: Meso-tetrakis(p-hydroxyphenyl)porphyrin (THPP) and the corresponding metal salt are dissolved in DMF, stirred at 140-160°C until the reaction is complete, heating is stopped, most of the DMF is evaporated, and after cooling to near room temperature, ice water is added and refrigerated. After 5-15 minutes, the filter cake is filtered under reduced pressure, rinsed with water multiple times, transferred to a petri dish, and dried at 80-100°C to obtain the metalloporphyrin. The molar ratio of THPP to metal salt is 1:10. The metal salt is a metal chloride, such as cobalt chloride, nickel chloride, copper chloride, iron chloride, zinc chloride, or manganese chloride, or a metal nitrate or acetate.

[0009] Furthermore, the reaction temperature is 70-180°C.

[0010] Furthermore, the organic solvent A is DMF or NMP, and the organic solvent B is one or a mixture of two or more of ethyl acetate, dichloromethane and petroleum ether in any proportion.

[0011] Furthermore, the drying temperature of the filter cake is 80-100°C.

[0012] The metalloporphyrin polyurethane obtained by the above-mentioned synthesis method.

[0013] The structural formula (I) of metalloporphyrin polyurethane is:

[0014] Structural formula (Ⅰ)

[0015] Another object of the present invention is to provide a use of the above-mentioned metalloporphyrin polyurethane in the electrocatalytic oxidation of organic matter, wherein a platinum sheet electrode is used as a working electrode and a graphite sheet electrode is used as an auxiliary electrode. Organic matter and metalloporphyrin polyurethane are added to a mixed solution consisting of an electrolyte solution and a solvent in a volume ratio of (1-2):(1-1.5), and the reaction is stirred at a constant voltage of 4-12 V for 3-6 hours.

[0016] Preferably, the electrolyte solution is a 0.1-0.5 mol / L tetrabutylammonium trifluoromethanesulfonate solution, a saturated sodium acetate solution, or a 0.1-1 mol / L acetic acid solution, and the solvent is acetonitrile, DMF, or DMAc.

[0017] Preferably, the organic compound is indanol, cyclohexane, 1-phenylethanol, 1,3,5-benzenetriol or benzhydrol.

[0018] Preferably, the amount of the metalloporphyrin polyurethane added is 1-6 mg / mmol based on the molar amount of the organic matter.

[0019] The present invention has the following beneficial effects:

[0020] The present invention aims to design and synthesize a metalloporphyrin polymer catalyst so that the catalyst can be easily recovered after the reaction, thereby improving the reusability of the catalyst, reducing costs, and enhancing the sustainability of the reaction.

[0021] The metalloporphyrin polymer synthesized by the present invention can electrocatalytically oxidize organic substances such as alcohols, alkanes, and cycloalkanes without adding a co-catalyst. The reaction conditions are relatively mild, the catalytic activity is high, the product selectivity is high, the recovery and regeneration process is simple, and the polymer can be reused multiple times.

[0022] The application of the metalloporphyrin catalyst prepared by the present invention in electrocatalytic oxidation organic synthesis provides new ideas and methods for the development of green chemistry and sustainable chemical processes, and has far-reaching research significance and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the possible mechanism of the electrocatalytic oxidation of indanol by metalloporphyrin polyurethane;

[0024] Figure 2 This is the IR spectrum of Meso-tetrakis(p-hydroxyphenyl)porphyrin (THPP);

[0025] Figure 3 This is the H NMR spectrum of Meso-tetrakis(p-hydroxyphenyl)porphyrin (THPP);

[0026] Figure 4 This is the carbon NMR spectrum of Meso-tetrakis(p-hydroxyphenyl)porphyrin (THPP);

[0027] Figure 5 is the IR spectrum of THPP and CoTHPP;

[0028] Figure 6 It is a synthetic route for metalloporphyrin polyurethane;

[0029] Figure 7 is the IR spectrum of THPP, CoTHPP and cobalt porphyrin polyurethane;

[0030] Figure 8 is the IR spectrum of THPP, NiTHPP and nickel porphyrin polyurethane;

[0031] Figure 9 is the IR spectrum of cobalt porphyrin polyurethane and nickel porphyrin polyurethane;

[0032] Figure 10 These are electron microscope images of cobalt porphyrin polyurethane, where the scale bars in a and d are 500 nm, the scale bars in b and e are 1 μm, and the scale bars in c and f are 2 μm.

[0033] Figure 11 The electron microscope image of nickel porphyrin polyurethane (a) and the comparison with the electron microscope image of cobalt porphyrin polyurethane (b) are shown. The scale bars in a and b are 500 nm.

[0034] Figure 12 This is the element distribution diagram of cobalt porphyrin polyurethane (left) and nickel porphyrin polyurethane (right);

[0035] Figure 13 This is the plot analysis diagram of the BET test of cobalt porphyrin polyurethane and nickel porphyrin polyurethane;

[0036] Figure 14 This is the H NMR spectrum of the product generated by the electrocatalytic oxidation of indanol;

[0037] Figure 15 This is the carbon NMR spectrum of the products generated by the electrocatalytic oxidation of indanol. DETAILED DESCRIPTION

[0038] The present invention is further described in detail below by way of examples. However, these examples are for illustration only and should not be construed as limiting the present invention in any way.

[0039] Example 1 Synthesis of Meso-tetrakis(p-hydroxyphenyl)porphyrin (THPP)

[0040] Under nitrogen protection, 5.04 g of p-hydroxybenzaldehyde, 5 mL of DMSO and 98 mL of propionic acid were added to a three-necked flask, and the mixture was heated to reflux in a 140 °C oil bath with magnetic stirring. 3.5 mL of pyrrole was drawn with a syringe and added dropwise within 15 min, and the reaction was continued for 2 h. After the reaction was completed, it was filtered while hot to obtain a blue viscous solid. After washing the blue viscous solid with a small amount of propionic acid, the sample was dried and purified by column chromatography on silica gel. Dichloromethane: methanol (V / V=3:1) was used as the eluent to elute the product. The product was monitored by TCL, and the main color band was collected. After the eluent was concentrated and evaporated using a rotary evaporator, the product was collected and dried in an oven at 80 °C. The final product was a purple powdery solid. Figure 2 The IR spectrum analysis showed that 3496 cm -1 、3400 cm -1 The strong absorption peak at 3022 cm corresponds to the NH stretching vibration of the amino group and the OH stretching vibration of the hydroxyl group. The OH stretching vibration absorption bandwidth is large and overlaps with the NH stretching vibration absorption peak of the amino group; -1 The shoulder peak at 1603 cm corresponds to the CH stretching vibration of the porphyrin ring; -1 、1507 cm -1 The strong absorption peak at 1255 cm corresponds to the stretching vibration of the benzene ring skeleton; -1 The corresponding position is the stretching vibration of CN on the porphyrin ring; 1173 cm -1 The strong absorption peak at 966 cm corresponds to the CO stretching vibration of phenolic hydroxyl groups; -1 The absorption peak at 799 cm is the bending vibration of NH on the porphyrin ring; -1 The absorption peak at corresponds to the bending vibration of CH on the benzene ring. According to the analysis of the above IR spectrum, the successful synthesis of THPP can be preliminarily confirmed. Figure 3The H NMR spectrum of THPP shows that the A group peak δ = 9.97 ppm (s, 4H) is a single peak, and the four hydrogens are the hydrogen proton signals of the four phenolic hydroxyl groups on the four benzene rings; the B group peak δ = 8.87 ppm (s, 8H) is a single peak, and the eight hydrogens are the hydrogen proton signals on the pyrrole ring; the C and D group peaks are coupled and split to form a double peak, the C group peak, δ = 8.00 ppm (d, J = 8.4 Hz, 8H), corresponding to the eight proton signal peaks alternating with the hydroxyl groups on the benzene ring; the D group peak, δ = 7.21 ppm (d, J = 8.4 Hz, 8H), the eight signal peaks correspond to the proton resonances adjacent to the hydroxyl groups on the benzene ring; the E group peak, δ = -2.88 ppm (s, 2H), is a single peak, corresponding to the two hydrogen proton signals of NH on the porphyrin ring; The proton signals at ppm and δ = 2.49 ppm ~ 2.51 ppm correspond to the water peak and the solvent peak of DMSO-d6.

[0041] 1 H NMR (400 MHz, DMSO- d 6 ) δ 9.97 (s, 4H), 8.87 (s, 8H), 8.00 (d, J =8.4 Hz, 8H), 7.21 (d, J = 8.4 Hz, 8H), -2.88 (s, 2H).THPP 13 C NMR spectrum Figure 4 As shown, DMSO-d6 is used as the solvent, and the solvent peak is at δ=40 ppm. The four peaks at δ=157.42 ppm, 135.54 ppm, 131.94 ppm, and 120.02 ppm correspond to the four aromatic carbons of the phenol substituent at the meso position on THPP, and δ=113.94 ppm is the carbon on the porphyrin ring.

[0042] Example 2 Synthesis of Meso-Tetrakis(p-Hydroxyphenyl)Cobalt Porphyrin

[0043] Take 2 g (2.94 mmol) of the above product, 200 mL of DMF, and 3.83 g (29.4 mmol) of anhydrous cobalt chloride with an equimolar mass of 10 times that of Meso-tetra(p-hydroxyphenyl)porphyrin, and add them to a 500 mL round-bottom flask. Use a heat-collecting constant temperature heating magnetic stirrer to heat to reflux at 150°C in an oil bath. Stop heating after 1 hour. After the temperature drops, use a circulating water vacuum pump to distill under reduced pressure to evaporate about four-fifths of the DMF. After cooling to near room temperature, add 150 mL of ice water to the round-bottom flask and place it in the refrigerator. After 5 minutes, filter under reduced pressure. Rinse the filter cake with water several times, transfer it to a Petri dish, and dry it in an oven at 80°C. The final product is a dark purple powdery solid. Figure 5 The IR spectra of THPP and CoTHPP show that when the cobalt ion successfully complexes with the N in the center of THPP, the hydrogen atom of the NH bond will be replaced by the cobalt ion, i.e., 966 cm -1 The bending vibration absorption peak of NH at 1002 cm -1 A new Co-N characteristic strong absorption peak appears at , which indicates that CoTHPP is successfully prepared.

[0044] In the preparation of NiTHPP, nickel chloride hexahydrate is used as the nickel salt, and the other conditions are the same as above.

[0045] Example 3 Synthesis of Metalloporphyrin Polyurethane and Other Metalloporphyrin Polyurethanes

[0046] 0.2487 g of CoTHPP (0.338 mmol), 10 mL of anhydrous DMF, and 5 mg (0.0446 mmol) of triethylenediamine were added to a 150 mL three-necked flask. Under nitrogen, the mixture was preheated at 80°C for 5 min. 0.1135 g (0.709 mmol) of p-phenylenediisocyanate was dissolved in 10 mL of anhydrous DMF and added dropwise to the flask using a syringe. The mixture was stirred in an oil bath at 100°C for 4 h under magnetic stirring. After the reaction, most of the solvent was removed by vacuum distillation. The mixture was cooled to near room temperature, and 50 mL of water was added to the flask. The mixture was filtered under reduced pressure. The filter cake was rinsed with water several times and then washed with ethyl acetate until the filtrate was colorless. The filter cake was collected and dried in an oven at 80°C. The final product was a dark brown to purple powdery solid.

[0047] After the reaction is completed, the product is first washed with a large amount of water, and then ethyl acetate is used to wash away the unpolymerized metal porphyrin. The final product, nickel porphyrin polyurethane, is a dark brown granular solid.

[0048] like Figure 6 The synthesis of other metalloporphyrin polyurethane catalysts is similar to the above method. Under nitrogen protection, a trace amount of triethylenediamine is used to provide a weak alkaline environment for the reaction and catalyze the reaction.

[0049] The hydroxyl groups on Meso-tetra(p-hydroxyphenyl)cobalt porphyrin react with the O=C=N bond on p-phenylene isocyanate to form a new urethane bond (CO-CO-NH), leaving a small amount of uncapped phenolic hydroxyl groups. The hydroxyl peak of the polymer will be significantly weakened, at 3300 cm -1 The NH stretching vibration absorption peak at the position will be significantly enhanced, and since the stretching vibration absorption bandwidth of NH is much smaller than the stretching vibration absorption peak of hydroxyl, the NH stretching vibration absorption peak will be significantly prominent, such as Figure 7 As shown, cobalt porphyrin polyurethane (p-CoTHPP) is located at 3300 cm -1 The NH stretching vibration absorption peak at is the characteristic peak of the urethane bond (-O-CO-NH) in the polymer, which proves the successful synthesis of the polymer.

[0050] like Figure 8 As shown in the IR spectrum of nickel porphyrin polyurethane (poly-NiTHPP) at 3300 cm -1 There is an obvious NH stretching vibration absorption peak at , which proves that nickel porphyrin polyurethane is successfully synthesized.

[0051] like Figure 9 As shown, nickel porphyrin polyurethane is similar to cobalt porphyrin polyurethane, with a wavelength of 3300 cm -1 There is also an obvious peak corresponding to NH stretching vibration, and the overall absorption peak waveforms of nickel porphyrin polyurethane polymer and cobalt porphyrin polyurethane are similar, which also shows that the structures of the two polymers are basically the same.

[0052] Electron microscopy imaging of cobalt porphyrin polyurethane Figure 10 As shown in the figure, the image shows the microstructure of the catalyst in two groups of different areas with magnifications from small to large (500nm, 1 µm and 2 µm), showing a spatial network stacking morphology, similar to the expected polymer structure, with uneven distribution of pore sizes and pore diameters between 70nm and 700nm.

[0053] Figure 11 The electron microscope image of nickel porphyrin polyurethane and the comparison with cobalt porphyrin polyurethane show that the microstructure of nickel porphyrin polyurethane is relatively dense compared with cobalt porphyrin polyurethane, and it is almost impossible to find a microporous network structure similar to cobalt porphyrin polyurethane. Figure 11 In (a), a structure similar to the collapsed compression of the web can be seen.

[0054] Figure 12 The element distribution diagram of cobalt porphyrin polyurethane and nickel porphyrin polyurethane further demonstrates the successful synthesis of metalloporphyrin polyurethane. Figure 12It can be seen that the contents of cobalt and nickel in cobalt porphyrin polyurethane and nickel porphyrin polyurethane are 1.49% and 2.28% respectively.

[0055] Figure 13 This is the plot analysis diagram of the BET test. By looking at the data processing results of the BET test plot analysis diagram and the BET test analysis report, we can know that the specific surface area of ​​cobalt polyurethane is 136.3971 m 2 / g, and the specific surface area of ​​nickel metalloporphyrin polyurethane is 55.0187 m 2 / g, which is consistent with the morphology observed by electron microscopy. Cobalt porphyrin polyurethane has a network porous structure with a larger specific surface area, while the microstructure of nickel porphyrin polyurethane is much denser than that of cobalt porphyrin polyurethane, and its specific surface area is only two-fifths of that of cobalt porphyrin polyurethane.

[0056] Example 4 Application of Metalloporphyrin Polyurethane Electrocatalytic Oxidation of 1-Indanol

[0057] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet as the working electrode and a graphite sheet as the counter electrode, and a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of a 0.2 M tetrabutylammonium trifluoromethanesulfonate solution and 4 mL of acetonitrile. The reactants were 0.5 mmol of 1-indanol and 3 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 4 V. The reaction time was 3 h, and the reaction progress was monitored using a TCL plate. The reaction was terminated when the starting materials disappeared, the solvent was removed, 10 mL of H₂O was added, and the mixture was extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed three times with saturated brine, dried over Na₂SO₄, and concentrated to yield the crude product. The product was purified by column chromatography using a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 50:1 to 10:1 as the eluent. The product was collected with a rotary flask and the eluent was removed using a rotary evaporator to obtain the product 1-indanone with a yield of 78%.

[0058] Combining the classical theory of conventional oxidation of metalloporphyrins and the mechanism of electrooxidation of high-valent metals, the possible mechanism of electrocatalytic oxidation of 1-indanol by cobalt porphyrin polyurethane was taken as an example ( Figure 1 ) to explain the catalytic principle: the water in the anode and electrolyte acts as an oxidant, oxidizing the Co(II) on the catalyst to Co(III) and then coupling with the hydroxyl group of 1-indanol. After oxidative dehydrogenation of 1-indanol, it is reduced to Co(II) to complete the catalytic cycle.

[0059] Example 5 Application of Metalloporphyrin Polyurethane Electrocatalytic Oxidation of 1-Indanol

[0060] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet as the working electrode and a graphite sheet as the counter electrode, equipped with a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of a 0.2 M tetrabutylammonium trifluoromethanesulfonate solution and 4 mL of acetonitrile. The reactants were 0.5 mmol of 1-indanol and 0 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 4 V. The reaction time was 3 h. A TCL monitor was used to monitor the reaction progress, indicating no product formation.

[0061] Example 6 Application of Metalloporphyrin Polyurethane Electrocatalytic Oxidation of 1-Indanol

[0062] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet as the working electrode and a graphite sheet as the counter electrode, and a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of a 0.2 M tetrabutylammonium trifluoromethanesulfonate solution and 4 mL of acetonitrile. The reactants were 0.5 mmol of 1-indanol and 3 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage. The experimental input voltage was 0 V, and the reaction time was 3 h. A TCL monitor was used to monitor the reaction progress, indicating no product formation.

[0063] Example 7 Application of Metalloporphyrin Polyurethane Electrocatalytic Oxidation of 1-Indanol

[0064] This experiment used a two-electrode system, a single-chamber electrolytic cell, a platinum sheet electrode as the working electrode, a graphite sheet electrode as the auxiliary electrode, and a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of saturated sodium acetate solution and 4 mL of acetonitrile. The reactants were 0.5 mmol of 1-indanol and 3 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 4 V. The reaction time was 3 h, and the reaction progress was monitored using a TCL panel. After the reaction was completed, the post-treatment method described in Example 4 was used, and the yield of the product, 1-indanone, was 70%.

[0065] Example 8 Application of Metalloporphyrin Polyurethane Electrocatalytic Oxidation of 1-Indanol

[0066] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet electrode as the working electrode and a graphite sheet electrode as the auxiliary electrode, and a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of saturated sodium acetate solution and 4 mL of DMF. The reactants were 0.5 mmol of 1-indanol and 3 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode (i.e., a regulated input voltage of 4 V). The reaction time was 3 h, and the reaction progress was monitored using a TCL monitor. Upon completion of the reaction, the post-treatment method described in Example 4 was used, resulting in a 70% yield of the product, 1-indanone.

[0067] Example 9 Application of Metalloporphyrin Polyurethane in Electrocatalytic Oxidation of 1-Indanol

[0068] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet electrode as the working electrode and a graphite sheet electrode as the auxiliary electrode, and a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 6 mL of saturated sodium acetate solution and 4 mL of DMF. The reactants were 0.5 mmol of 1-indanol and 3 mg of nickel porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 4 V. The reaction time was 3 h, and the reaction progress was monitored using a TCL monitor. Upon completion of the reaction, the post-treatment method described in Example 4 was used, resulting in a 60% yield of the product, 1-indanone.

[0069] Examples 4 to 9 Electrocatalytic Oxidation of Indanol Product 1-Indanone 1 H NMR and 13 C NMR Figure 14 and 15 As shown by Figure 14 and 15 It can be seen that 1 H NMR (400 MHz, CDCl3): δ 2.60-2.72 (m, 2H), 3.18-3.06 (m, 2H), 7.34 (d, J = 7.4 Hz, 1H), 7.45 (d, J = 7.7 Hz, 1H), 7.62-7.52 (m, 1H), 7.72(d, J = 7.7 Hz, 1H). 13 C NMR (101 MHz, CDCl3): δ 207.13, 155.22, 137.11,127.31, 126.76, 123.72, 36.26, 25.84.

[0070] Example 10 Application of Metalloporphyrin Polyurethane in Electrocatalytic Oxidation of Cyclohexane

[0071] This experiment used a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet electrode as the working electrode and a graphite sheet electrode as the counter electrode, and was equipped with a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 12 mL of saturated sodium acetate solution and 8 mL of DMF. The reactants were 2.5 mmol of cyclohexane and 4.5 mg of cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode (i.e., a regulated input voltage of 10 V). The reaction time was 3 h, and the reaction progress was monitored using a TCL plate. The reaction was terminated when the starting materials disappeared. The solvent was removed, 10 mL of H₂O was added, and the mixture was extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed twice with saturated brine, dried over Na₂SO₄, and concentrated to yield the crude product. The product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1 to 8:1. The product eluted with the eluent and was collected in a rotary flask. The eluent was removed using a rotary evaporator to obtain the product cyclohexanone in an 85% yield. 1 H NMR (400 MHz, CDCl3): δ 2.33 (t, J = 6.4 Hz, 2H), 1.90-1.82(m, 2H), 1.76 – 1.67(m, 1H). 13 C NMR (101 MHz, CDCl3): δ 212.08, 41.96, 27.01,24.98.

[0072] Example 11 Application of Metalloporphyrin Polyurethane to Prepare Adipic Acid by Electrocatalytic Oxidation of Cyclohexane

[0073] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet electrode as the working electrode and a graphite sheet electrode as the counter electrode, equipped with a magnetic stirrer. The electrolyte solution consisted of 6 mL of acetic acid solution (4 mL of acetic acid and 2 mL of water) and 6 mL of DMAc. The reactants were 2.0 mmol of cyclohexane and 6 mg of cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode (i.e., a regulated input voltage of 12 V). The reaction time was 5 h, and the progress of the cyclohexane reaction was monitored by gas chromatography-mass spectrometry. Upon completion of the reaction, the reaction was stopped when the starting materials disappeared. The reaction was acidified by adding 10 mL of distilled water and 2 mL of 12 mol / L hydrochloric acid solution, and extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed twice with saturated brine, dried over Na2SO4, and concentrated to yield the crude product. The product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 to 1:1. The product eluted with the eluent and was collected in a rotary flask. The eluent was removed using a rotary evaporator to obtain a 42% yield of adipic acid.1 H NMR (400 MHz, DMSO-d): δ 1.51(m,4H),2.21 (m, 4H),11.96 (br, 2H); 13 C NMR (101 MHz, DMSO-d): δ 174.28, 33.35, 24.00.

[0074] Example 12 Application of Metalloporphyrin Polyurethane in Electrocatalytic Oxidation of 1-Phenylethanol

[0075] This experiment used a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet electrode as the working electrode and a graphite sheet electrode as the counter electrode, and was equipped with a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 12 mL of saturated sodium acetate solution and 8 mL of DMF. The reactants were 2.5 mmol of 1-phenylethanol and 10 mg of cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 6 V. The reaction time was 3 h, and the reaction progress was monitored using a TCL plate. The reaction was terminated when the starting materials disappeared. The solvent was removed, 10 mL of H₂O was added, and the mixture was extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed three times with saturated brine, dried over Na₂SO₄, and concentrated to yield the crude product. The product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1 to 20:1. The product eluted with the eluent and was collected in a rotary flask. The eluent was removed using a rotary evaporator to obtain the product, acetophenone, in an 89% yield. 1 H NMR (400 MHz, CDCl3): δ 7.97 (d, J = 8.0 Hz, 2H), 7.58 (t,1H), 7.47 (t, 2H), 2.61 (s, 3H). 13 C NMR (101 MHz, CDCl3): δ 198.14, 137.14,133.11, 128.58, 128.31, 26.0.

[0076] Example 13 Application of Metalloporphyrin Polyurethane in Electrocatalytic Oxidation of 1,3,5-Benzenetriol

[0077] This experiment used a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet as the working electrode and a graphite sheet as the counter electrode, and was equipped with a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent volume ratio was 1.5:1, consisting of 12 mL of saturated sodium acetate solution and 8 mL of DMF. The reactants were 2.5 mmol of 1,3,5-benzenetriol and 10 mg of a cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode (i.e., a regulated input voltage of 10 V). The reaction time was 3 h, and the reaction progress was monitored using a TCL plate. The reaction was terminated when the starting materials disappeared. The solvent was removed, 10 mL of H₂O was added, and the mixture was extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed twice with saturated brine, dried over Na₂SO₄, and concentrated to yield the crude product. The product was purified by column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1 to 5:1. The product was collected in a rotary flask and the eluent was removed using a rotary evaporator to obtain cyclohexanone octahydrate in an 85% yield. 13 C NMR (101 MHz, CDCl3): δ 95.00, Ms: 168.06.

[0078] Example 14 Catalytic Cycling Performance of Metalloporphyrin Polyurethane for Electrocatalytic Oxidation of Benzhydrol

[0079] This experiment employed a two-electrode system, a single-chamber electrolytic cell, with a platinum sheet as the working electrode and a graphite sheet as the counter electrode, equipped with a magnetic stirrer. Unless otherwise specified, the electrolyte solution and solvent were used in a 1.5:1 volume ratio, consisting of 6 mL of 0.2 M tetrabutylammonium trifluoromethanesulfonate solution and 4 mL of acetonitrile. The reactants included 0.5 mmol of benzhydrol and 3 mg of cobalt porphyrin polyurethane catalyst. The power supply operated in CV mode, i.e., a regulated input voltage of 4 V. The reaction time was 3 h, and the reaction progress was monitored using a TCL monitor. After the reaction, the reaction was filtered, washed with distilled water, and the catalyst was washed with a mixed solvent of petroleum ether, ethyl acetate, and ethanol in a 10:2:1 volume ratio. After drying, the catalyst was recycled. The filtrate was then evaporated to remove the solvent, 10 mL of H₂O was added, and the mixture was extracted with ethyl acetate (20 mL x 3). The combined organic phases were washed three times with saturated brine, dried over Na₂SO₄, and concentrated to yield the crude product. The column chromatography purification eluent is a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 50:1 to 20:1. The product flows out with the eluent and is collected with a rotary evaporator. The eluent is removed using a rotary evaporator to obtain the product benzophenone. 1H NMR (400 MHz, DMSO): δ 7.78 -7.72 (m, 2H), 7.72-7.64 (m, 1H), 7.61-7.52 (m, 2H); 13 C NMR (101 MHz, DMSO): δ 196.28, 137.48, 133.15, 130.08, 129.04. The yields are as follows:

[0080] Number of times catalyst is used 1 2 3 4 5 Product yield 95% 95% 94% 94% 93%

[0081] The experimental results show that the catalyst can be recycled and the activity of the catalyst remains basically unchanged.

[0082] Although the present invention has been disclosed above in terms of preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. Application of metalloporphyrin polyurethane in electrocatalytic oxidation of organic matter, characterized in that: A platinum sheet electrode is used as a working electrode and a graphite sheet electrode is used as an auxiliary electrode. An organic matter and a metalloporphyrin polyurethane are added to a mixed solution consisting of an electrolyte solution and a solvent in a volume ratio of (1-2):(1-1.5), and the mixture is stirred and reacted at a constant voltage of 4-12 V for 3-6 hours. The metalloporphyrin polyurethane is obtained by the following process: dissolving the metalloporphyrin and triethylenediamine in an organic solvent A under a protective atmosphere to obtain a solution A, dissolving p-phenylene diisocyanate in an organic solvent to obtain a solution B, dropping the solution B into the solution A, stirring until the reaction is complete, and after the reaction is completed, removing most of the solvent by vacuum distillation, cooling, adding water, and vacuum filtering. After the filter cake is washed with water multiple times, it is then rinsed with an organic solvent B until the filtrate is colorless, the filter cake is collected, and dried to obtain the metalloporphyrin, diisocyanate, and triethylenediamine in a molar ratio of 1:(2-2.5):(0.1-0.2).

2. The use according to claim 1, characterized in that The metalloporphyrin is meso-tetrakis(p-hydroxyphenyl)cobaltporphyrin, meso-tetrakis(p-hydroxyphenyl)nickelporphyrin, meso-tetrakis(p-hydroxyphenyl)copperporphyrin, meso-tetrakis(p-hydroxyphenyl)ironporphyrin, meso-tetrakis(p-hydroxyphenyl)zincporphyrin or meso-tetrakis(p-hydroxyphenyl)manganeseporphyrin.

3. The use according to claim 1, characterized in that The reaction temperature is 70~180℃.

4. The use according to claim 1, characterized in that The organic solvent A is DMF or NMP, and the organic solvent B is one or a mixture of two or more of ethyl acetate, dichloromethane and petroleum ether in any proportion.

5. The use according to claim 1, characterized in that The drying temperature of the filter cake is 80~100℃.

6. The use according to claim 1, characterized in that The electrolyte solution is a 0.1-0.5 mol / L tetrabutylammonium trifluoromethanesulfonate solution, a saturated sodium acetate solution, or a 0.1-1 mol / L acetic acid solution, and the solvent is acetonitrile, DMF, or DMAc.

7. The use according to claim 1, characterized in that The organic matter is indanol, cyclohexane, 1-phenylethanol, 1,3,5-benzenetriol or benzhydrol.

8. The use according to claim 1, characterized in that Calculated on the molar amount of the organic matter, the added amount of the metalloporphyrin polyurethane is 1-6 mg / mmol.

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