SYNTHESIS OF METAL ORGANIC PRECURSOR STRUCTURE-BASED MAGNETIC NANOCATALYSTS

Abstract

The invention relates to carbon-supported metal oxide nanocatalysts containing copper oxide and cobalt oxide (CuO / CoO@PC) or nitrogen-doped carbon-supported metal oxide nanocatalysts containing copper oxide, zinc oxide, and cobalt oxide (CuO / ZnO / Co3O4@NPC), the synthesis of these nanocatalysts using metal-organic precursor structures, and the application of the resulting catalysts in CuAAC organic synthesis reactions. Specifically, the invention relates to the magnetic nanocatalyst obtained by controlled carbonization of copper / cobalt or copper / zinc / cobalt-based metal-organic precursors prepared using different ligands (trimestic acid or benzimidazole) and the subsequent controlled oxidation / calcination process.

Description

1 TARIFF METAL ORGANIC PRIMARY STRUCTURE-BASED MAGNETIC SYNTHESIS OF NANOCATALYSTS Technical Area The invention relates to carbon-supported metal oxides containing copper / cobalt or copper / cobalt / zinc. nanocatalysts, these nanocatalysts are created using metal-organic precursor structures. synthesis and the use of the resulting nanocatalysts in organic synthesis reactions The invention relates to the use of copper / cobalt or trimesic acid in preparations using trimesic acid. copper / cobalt / zinc based metal-organic precursors prepared using benzimidazole controlled carbonization followed by a controlled oxidation / calcination process This relates to the magnetic nanocatalyst obtained as a result. State of the Art Catalysts used in organic synthesis reactions allow reactions to occur more quickly and efficiently. This is an important technique because it allows for execution with high efficiency and in a more selective manner. It has a field of study. In particular, azide-alkyne cycloaddition reactions of 1,2,3-triazole derivatives. It is widely used in synthesis, and copper-catalyzed azide-alkyne cycloaddition. Through these reactions, 1,4-disubstituted-1,2,3-triazole compounds are obtained with high regioselectivity. It is possible. In the current state of the art, different sources of copper are used for these reactions. Copper Homogeneous catalysts such as salts and copper complexes can exhibit high catalytic activity. together, they are difficult to separate from the reaction medium, and there are metal residues in the product. They have disadvantages such as being disposable and having limited reusability. Therefore, the development of copper-containing heterogeneous catalysts is particularly important, as it reduces the burden of product purification. This has become important in terms of reducing and increasing the reusability of the catalyst. Among heterogeneous catalysts, carbon-supported metal and metal oxide catalysts are of particular importance. It has porous carbon supports that allow active metal species to adhere to the surface or within the porous structure. It can ensure better dispersion and reduce the agglomeration of metal particles. and can form a more stable catalytic system in the reaction environment. Nitrogen-doped Porous carbon supports, on the other hand, are metallic thanks to the nitrogen atoms incorporated into the carbon structure. It can interact more strongly with different species and contribute to the distribution of catalytic active centers. It can provide. 2 In the current state of the art, metal-organic precursor structures or MOF / ZIF derivative structures Porous carbon or nitrogen-doped porous structures containing metal nanoparticles through carbonization. It is known that carbon-supported materials are obtained. In this context, copper and cobalt-containing materials are used. Carbon-supported structures and nitrogen-doped porous carbon-supported structures containing copper, zinc, and cobalt. These structures have been studied previously. In addition, metal oxides such as CuO, ZnO, CoO, and Co₃O₄ are also studied. There are also studies aimed at preparing different nanocomposites containing these materials. However, known studies have shown that carbon-supported structures containing metallic phases or Description of support-free metal oxide nanocomposites, directly controlled oxide a sufficient solution for obtaining carbon-supported magnetic nanocatalysts with phases It does not offer. Especially controlled applications after carbonization. In the oxidation / calcination step, on the one hand, the targeted metal oxide phases the creation of, on the other hand, porous carbon or nitrogen-doped porous carbon supports Preserving its structure is of technical importance. Therefore, in technology, it can be used in copper-catalyzed azide-alkyne cycloaddition reactions. Reusable and carbon-supported variants that can be easily separated from the reaction medium. There is a need for novel magnetic nanocatalysts containing metal oxide phases of this type. Furthermore... These nanocatalysts enable controlled carbonization via metal-organic precursor structures and Reliable and repeatable through controlled oxidation / calcination steps The need for synthesis methods that enable its preparation continues. Figures: Figure 1. XRD spectrum of CuO / CoO@PC catalyst. Figure 2. XPS spectra of CuO / CoO@PC catalyst. Figure 3. SEM images of the CuO / CoO@PC catalyst. Figure 4. EDX spectrum and mapping images of CuO / CoO@PC material. 5 Figure 5. TEM and TEM-SAED images of the CuO / CoO@PC catalyst. Figure 6. N2 adsorption / desorption isotherms (a) and raman of CuO / CoO@PC material. spectrum (b). Figure 7. XRD spectrum of CuO / ZnO / Co3O4@NPC catalyst. Figure 8 XPS spectra of CuO / ZnO / Co3O4@NPC catalyst. 10 Figure 9. SEM images of the CuO / ZnO / Co3O4@NPC catalyst. Figure 10. EDX spectrum and mapping images of CuO / ZnO / Co3O4@NPC material. Figure 11. TEM and TEM-SAED images of the CuO / ZnO / Co3O4@NPC catalyst. Figure 12. N2 adsorption / desorption isotherms (a) of CuO / ZnO / Co3O4@NPC material, por Scatter plot (b) and Raman spectrum (c). 15 3 Brief Description of the Invention The invention specifically concerns copper oxide on porous carbon or nitrogen-doped porous carbon support. and magnetic nanocatalysts containing additional metal oxide (CoO or ZnO / Co3O4) phases It is related to this. In this context, the invention involves the simultaneous production of CuO and CoO phases on a porous carbon support. The magnetic nanocatalyst containing CuO / CoO@PC and CuO, ZnO and Co₃O₄ phases are on the same surface. CuO / ZnO / Co₃O₄@NPC on a nitrogen-doped porous carbon support. It relates to nanocatalysts. The invention also concerns the use of metal-organic precursors of these nanocatalysts. controlled carbonization of the structures followed by a controlled oxidation / calcination process It relates to the preparation of trimesic acid containing copper and cobalt. In this context, the invention specifically covers trimesic acid 10 containing copper and cobalt. The production of CuO / CoO@PC nanocatalysts from a basic precursor and the use of copper, zinc and cobalt The CuO / ZnO / Co₃O₄@NPC nanocatalyst is obtained from a benzimidazole-based precursor. It is aimed at being done. CuO / CoO@PC magnetic substrate containing CuO and CoO phases on a porous carbon support. The nanocatalyst is developed from a metal-organic precursor based on trimesic acid containing copper and cobalt. Technical requirements for its preparation continue. In this structure, carbonization and carbon formation of a supported intermediate structure and subsequent controlled oxidation / calcination of CuO and The formation of CoO phases requires the catalyst to contain both active metal oxide centers. magnetically separable from the reaction medium, maintaining its heterogeneous catalyst properties. It provides. 20 Similarly, CuO, ZnO, and Co₃O₄ phases can be formed on a nitrogen-doped porous carbon support. In terms of CuO / ZnO / Co₃O₄@NPC nanocatalysts, as well as polymetallic oxide phases Technical requirements for its controlled creation along with a carbon support structure. It is found in. Known ternary metal oxide nanocomposites are nitrogen-doped porous carbon. While not directly offering the structural and catalytic advantages provided by the support, only 25 Nitrogen-doped carbon-supported structures containing metallic Cu / Zn / Co also target the oxide phases. It does not include. Detailed Description of the Invention Copper and cobalt, or copper, cobalt, and zinc metals, simultaneously produce metal oxide derivatives. composite magnetic catalysts containing in the structure (CuO / CoO@PC, CuO / ZnO / Co3O4@NPC; 30 PC: Porous carbon, NPC: N-doped porous carbon), CuAAC reactions are mild. High selectivity in water or solvent mixtures containing water in specific proportions under certain conditions. 4 In addition to high yield, it can synthesize products of high purity. It has magnetic properties. Composite catalysts containing CuO phase are synthesized, thus creating the aforementioned heterogeneous By eliminating a large portion of the disadvantages of catalysts, it has become readily available in the literature. Two or three triazole rings, which are almost never found in other examples, together with different chromophore groups. synthesizing in molecular form with high yield and high chemical purity 5 It can be synthesized. Within the scope of this specification, the term "porous carbon support" refers to a material containing micro, meso and / or which may contain macropores, on and / or within metal or metal oxide phases. It refers to a carbon-based support structure that allows for dispersion. This porous structure... Carbon support can be formed in situ as a result of carbonization of the metal-organic precursor structure. 10 and to reduce the agglomeration of active metal oxide phases within the catalyst, active Increasing the surface area and the distribution of centers exhibiting active catalytic effects, chemical and to increase corrosion resistance, facilitate mass transfer, and It contributes to maintaining the heterogeneous structure of the catalyst. Since magnetic catalysts containing CuO exist in a heterogeneous phase in the reaction medium, this 15 Catalysts are removed from the product or reaction medium at the end of the reaction with the help of a magnet. Its separation is easier compared to homogeneous copper salts or non-magnetic catalysts. Thanks to their magnetic properties, these catalysts are attracted to an external magnet. With the help of this property, it can be easily removed from the reaction environment, i.e., the products. This magnetic property, which is not present in many catalysts in the literature, is found in the structure of the catalyst. This is due to the different cobalt oxide (CoO or Co3O4) phases present. Reassembly of catalysts through magnetic separation, washing with water and ethanol After drying, it becomes possible to reuse it repeatedly. The one we synthesized... Thanks to these properties of catalysts, these catalysts can be reused at least 5 times. Minimizing the cost of using catalysts increases the sustainability and environmental friendliness of the method. It enhances its properties. The catalyst can be easily separated at the end of the reaction, leaving no copper residue in the product. This reduces the possibility of further complications. Furthermore, the stability of the catalyst's structure ensures that the catalyst does not interfere with the reaction. by breaking down or separating metals from the catalyst structure and incorporating them into the structure of precious products. Entry or attachment is prevented. The catalysts we synthesized are either core-shell or yolk-shell 30 The presence of carbon embedded in the structure increases the chemical stability of the catalysts. This makes it difficult for metal atoms to detach from the catalyst structure. These superior properties are particularly important. Product purity required for medical chemistry, pharmaceutical chemistry, and biological activity studies. It is extremely essential from that point of view. One of the main problems in catalysts that catalyze CuAAC reactions is the interaction of different reactants. The problem is the limited variety of products that can be obtained under different reaction conditions. This invention... The catalysts synthesized within this scope include a wide variety of benzyl halides and terminal alkynes 5. It allows the use of derivatives such as biphenyl-nitrile, carboxylic acid, and trifluoromethyl. Aromatic compounds containing functional groups such as trifluoromethoxy, nitro, methoxy, fluorophenyl, and quinoxaline. Mono-, bis-, and tris-triazole derivatives carrying nuclei can be obtained. In conclusion, magnetic fields containing CuO along with CoO or Co3O4 and ZnO phases simultaneously. The use of heterogeneous catalysts makes the CuAAC reaction more practical and selective, with 10 catalysts. It can be used repeatedly, and the resulting triazole products can be produced with high yield and purity and on a wide scale. This has made it more advantageous in terms of diversity. Thanks to this, the invention overcomes the existing homogeneous limitations. Separation difficulties, metal residue risk, and low yields observed in heterogeneous copper catalyst systems. It eliminates technical problems such as recyclability. The metal oxide phases based on CuO, CoO or Co3O4 and ZnO included in the invention are the active catalysts. They form the centers. The CuO phase facilitates electron transfer, leading to catalytic reactions. increasing the rate, while CoO or Co₃O₄ phases influence reaction kinetics through redox activity. It contributes to the development of a porous structure and a more homogeneous active phase. It helps to disperse the surface and increase its polarity. The porous carbon support used in the invention enables the dispersion of active metal species on the surface. This is provided by nitrogen-doped porous carbon supports, which, thanks to nitrogen-containing active sites. It strengthens the interaction between metal types and carbon support, any metal It reduces leakage and increases catalytic activity. Therefore, PC and NPC support their structures ensure that the catalyst has a high surface area, good conductivity, and high stability. It plays an important role. 25 Trimestic acid is used as a ligand and carbon source in the formation of Cu / Co-based metal-organic precursors. Benzimidazole serves as both a ligand and a nitrogen source in the Cu / Zn / Co based system. It is used as and after carbonization, a nitrogen-doped porous carbon structure is formed. It enables its formation. The mere presence of metal oxide active phases is not sufficient for the invention to function; these phases must be 30 Homogeneous on porous carbon (PC) or nitrogen-doped porous carbon (NPC) support. It is important that they are found in this way. The CuO–CoO binary system and the CuO–ZnO–Co3O4 ternary system are single systems. 6 More active centers and better electron configuration compared to systems containing metal oxide phases. The transfer creates a synergistic structure that provides stronger magnetic properties and higher catalytic efficiency. It constitutes. In conclusion, when the elements involved in the invention are considered together, it is understood that there are multiple metal oxides. active phases determine catalytic activity, PC / NPC support structure determines conductivity and surface area, organic 5 Ligands, on the other hand, provide the precursor structure and the carbon / nitrogen source. Carbonization and calcination. By combining these elements through various processes, a highly active surface, good conductivity, and high performance are achieved. It has magnetic properties, strong metal-support interaction, and enhanced catalytic performance. catalysts are obtained. Production Method of CuO / CoO@PC Catalysts 10 In the first stage, 3.6 mmol Cu(NO₃)₂·3H₂O and 1.2 mmol Co(NO₃)₂·6H₂O metal salts are added to 15 mL of pure water. It dissolves in water. In a separate container, 2.0 mmol of trimesic acid is dissolved in 15 mL of ethanol. The prepared trimesic acid solution is mixed into the aqueous solution containing Cu and Co metal salts. It is added underneath. After the resulting mixture is homogenized, it is placed in a Teflon-coated inner chamber. The mixture is transferred to a stainless steel autoclave. The autoclave is closed and the mixture is left at 120 °C for 12 hours. It is heated. After the heat treatment, the autoclave is cooled to room temperature and the resulting solid product is centrifuged. They leave. Washing and Drying: The solid precursor containing Cu / Co, separated by centrifugation, remains unreacted. several times for the purpose of removing salts, ligand residues and solvent residues It is washed with a water / ethanol mixture. After the washing process, the resulting solid product is kept at 80 °C for 24 hours. It is dried in an oven. As a result of this process, a metal-organic precursor material containing Cu / Co is obtained. Preparation of CuO / CoO@PC Catalyst For the production of CuO / CoO@PC catalyst, Cu / Co-containing precursor material undergoes two-stage heat treatment. It is subjected to a process. First, the precursor material is carbonized at 800 °C for 3 hours under an argon atmosphere. This step results in the formation of a carbon-supported Cu / Co-containing structure. Then, the resulting 25 The carbonized product is calcined in an open atmosphere at 500 °C for 2 hours. This calcination... During this stage, Cu and Co species transform into oxide phases, forming CuO and CoO on a carbon support. It forms a catalyst structure containing CuO / CoO@PC. The resulting product is used as a catalyst. It is defined. 7 Production Method of CuO / ZnO / Co₃O₄@NPC Catalysts For the synthesis of Zn / benzimidazole-based metal-organic material, benzimidazole and Zn-based metal-organic precursor structures are prepared using Zn(NO₃)₂·6H₂O. For this purpose... Benzimidazole and Zn(NO₃)₂·6H₂O are dissolved in methanol at a ratio of 1 mmol:4 mmol. The resulting mixture is stirred at room temperature under atmospheric pressure for 3 hours. This 5 The process results in the formation of a metal-organic structure containing Zn and benzimidazole. Preparation of Cu-Containing Intermediate Material 0.5 g of the prepared Zn / benzimidazole-based metal-organic material is taken and 1 M Cu(NO₃)₂·3H₂O is dispersed in methanol solution. The mixture is left at room temperature for 30 minutes. It is mixed for a period of time. During this process, Cu species are incorporated into the Zn / benzimidazole-based structure. 10 After mixing, the solid product is separated by centrifugation. The resulting solid product is mixed with methanol. The material is washed and dried to obtain an intermediate metal-organic material containing Cu / Zn. Preparation of Cu / Zn / Co Containing Metal-Organic Precursor In the next step, the metal-organic material containing 1.0 g Cu / Zn is dispersed in methanol. Benzimidazole and Co(NO₃)₂·6H₂O are added to this mixture in a ratio of 1 mmol : 4 mmol. 15 The mixture is stirred for 2 hours at room temperature under atmospheric pressure. This process... As a result, a metal-organic precursor structure containing Cu, Zn, and Co is obtained. Washing and Drying: The resulting solid product containing Cu / Zn / Co is separated by centrifugation. The product, Removal of unreacted metal salts, excess ligands, and solvent residues. For this purpose, it is washed with methanol and acetone. After the washing process, the solid product is baked in an oven at 60 °C for 20 minutes. It is dried. Thus, a metal-organic precursor containing Cu / Zn / Co suitable for the carbonization process is obtained. The material is obtained. Preparation of CuO / ZnO / Co₃O₄@NPC Catalyst Cu / Zn / Co-containing metal-organic precursor for the production of CuO / ZnO / Co₃O₄@NPC catalyst The material undergoes two-stage heat treatment. In the first stage, the material is heated under an argon atmosphere at 800°C to 25°C. It is carbonized at °C for 3 hours. In the second stage, the carbonized product is left in an open air atmosphere for 500 hours. It is calcined at °C for 2 hours. As a result of this process, Cu, Zn and Co species are formed as CuO, ZnO and respectively. Co₃O₄ transforms into oxide phases. The nitrogen-doped carbon structure derived from benzimidazole acts as the support phase. It functions as such. The resulting product is defined as CuO / ZnO / Co₃O₄@NPC catalyst. 8 The temperature, time, concentration, and atmospheric conditions used within the scope of this invention affect the catalyst structure. It can be applied at specific intervals to ensure the following is achieved. Cu / Co based metal-organic Precursor synthesis is preferably carried out in a closed autoclave at 120 °C for 12 hours, This process can be applied at temperatures between 80–180 °C and for a duration of 4–24 hours. The resulting precursor materials are preferably dried at 60–80 °C. The drying process takes place at 40–120 °C. It can be applied within a temperature and time range of 6–48 hours. Carbon-supported metal-organic precursors. The carbonization process for converting them into catalysts is preferably carried out at 800 °C for 2–3 hours. It is carried out in an argon or nitrogen atmosphere. However, the carbonization temperature is 600– The temperature can be selected as 1000 °C, and the carbonization time can be chosen between 1–6 hours. For the preparation of metal oxide-containing catalysts, the calcination process is carried out in an open air atmosphere for 10 days. It is carried out at 500 °C for 2 hours. The calcination process is done at a temperature of 300–700 °C and for 0.5–5 hours. This process is applicable within this range. As a result of this process, Cu, Co, and Zn species are converted into their respective metal oxide phases. It is transforming. In the production of Cu / Zn / Co based nitrogen-doped porous carbon materials at room temperature Mixing processes are preferred, however, these processes are carried out at temperatures of 20–80 °C. This can be done within the following timeframes: Zn / benzimidazole precursor synthesis 0.5–12 hours, Cu addition 10 minutes. The 6-hour and CO addition process can be applied between 0.5–12 hours. Cu(NO₃)₂·3H₂O solution. The concentration is preferably 1 M, but can be selected in the range of 0.05–3 M. Within the scope of this invention, argon or nitrogen may be used as an inert atmosphere during carbonization. Heating rates can be applied in the range of 1–10 °C / min, and inert gas flow rates in the range of 20–200 mL / min. The calcination process can be carried out in air or in an oxygen-containing atmosphere. Table 1. ICP-MS analysis data for CuO / CoO@PC and CuO / ZnO / Co3O4@NPC catalysts. When the mechanism of CuAAC reactions was examined, the activity of Cu-centered catalysts was found to be 25. It is well known that this catalyst exhibits this behavior in different reaction environments (solvent, It is quite important that the catalyst consistently performs well (depending on temperature, etc.). This is quite possible with this catalyst. A catalytic effect is created with a stable CuO center, while CoO also provides synergistic contributions to CuO. It also imparts magnetic susceptibility to the catalyst. Thus, the reaction efficiency is improved with pure water. or in solvents with a high water content, very high values ​​(yield used 30 Catalyst Co (% m / m) Cu (% m / m) Zn (% m / m) CuO / CoO@PC 3-10 50-75 - CuO / ZnO / Co3O4@NPC 30-40 10-20 15-25 9 Although it varies depending on the types of chemicals, it is complex and catalytic. According to the mechanism, the yield is quite high even in reactions where unintended substrates are used. (high) results are obtained. This catalyst is used at least 5 times in CuAAC reactions and again Performance close to that of the catalyst used for the first time (small decreases in yield in the range of 1-3%). (possibly) it can exhibit performance. Due to the catalyst's magnetic properties, 5 The catalyst is separated with the help of a magnet and used with minimal loss in the amount of reaction. (because 100% separation of the catalyst in the environment is not possible) it is used repeatedly. It provides a significant advantage. 15 25

Claims

REQUESTS 1. It is a porous carbon-supported magnetic nanocatalyst, characterized by its porous carbon structure. CuO and CoO metals dispersed on the support and / or within a porous carbon support. It contains both oxide phases simultaneously. 5 2. This is the production method of the nanocatalyst defined in Claim 1, and its characteristics are: a. Preparation of a metal salt solution containing Cu salt and Co salt, b. Preparation of a ligand solution containing trimesic acid, c. Combining metal salt solution with ligand solution containing Cu and Co Synthesis of trimesic acid-based metal-organic precursor, 10 d. Separation, washing, and drying of the metal-organic precursor in question, e. Carbonization of the dried metal-organic precursor under an inert atmosphere to obtain Cu and Obtaining a porous carbon-supported carbonized interface containing Co, f. controlled carbonization of the aforementioned interface in an oxygen-containing atmosphere 15 containing CuO and CoO phases, subjected to oxidation / calcination process Synthesis of porous carbon-supported magnetic nanocatalysts It includes the steps.

3. It is a nitrogen-doped porous carbon-supported nanocatalyst, characterized by its nitrogen-doped properties. porous carbon support and / or nitrogen-doped porous carbon support It contains simultaneously dispersed metal oxide phases of CuO, ZnO, and Co₃O₄. 20 4. This is the production method of the nanocatalyst defined in Claim 3, and its characteristic is; a. Zn salt and benzimidazole are used in metal-organic solutions containing Zn and benzimidazole. Preparation of the premise, b. Cu species included in the aforementioned metal-organic precursor containing Zn and benzimidazole. done, 25 c. Co species are incorporated into the structure in the presence of benzimidazole, resulting in a structure containing Cu, Zn, and Co. Preparation of benzimidazole-based metal-organic precursor, d. the aforementioned benzimidazole-based metal-organic precursor containing Cu, Zn and Co separation, washing and drying, e. Carbonization of the dried metal-organic precursor under an inert atmosphere to obtain Cu, 30 Obtaining a nitrogen-doped porous carbon-supported carbonized interface containing Zn and Co. being done, f. controlled carbonization of the aforementioned interface in an oxygen-containing atmosphere By subjecting it to oxidation / calcination process, CuO, ZnO and Co₃O₄ phases are obtained. Preparation of nitrogen-doped porous carbon-supported nanocatalyst containing 35 It includes the steps.

5. It is a nanocatalyst according to claim 1, and its properties are: a metal-based trimesic acid containing Cu and Co. Porous carbon support formed as a result of carbonization of an organic precursor. It includes.

6. The method according to claim 2 or 4, characterized by the separation of CuO and CoO metal oxide phases into Cu and 40 A porous carbon-supported carbonized interface containing CO in an oxygen-containing atmosphere. 11 formed as a result of being subjected to a controlled oxidation / calcination process. It is the fact that.

7. It is a nanocatalyst according to claim 1, and its characteristic is that its Co content is as determined by ICP-MS analysis. The minimum fiber content should be 3-10% by weight, and 50-75% by weight.

8. Production method according to claim 2, characterized by; Cu salt to Cu(NO₃)₂·3H₂O and Co 5 Its salt is Co(NO₃)₂·6H₂O.

9. Production method according to claim 8, characterized by; Cu(NO₃)₂·3H₂O and Co(NO₃)₂·6H₂O metals. Examples include dissolving the salts in pure water and dissolving trimestic acid in ethanol.

10. The production method according to claim 9, characterized by the production of a ligand solution containing trimesic acid, Cu and is added to the metal salt solution containing Co salts under stirring. 10 11. Production method according to claim 10, characterized by; trimesic acid-based metal containing Cu and Co. Obtained by processing the organic precursor in a closed autoclave at 120°C for 12 hours. It is done.

12. It is a nanocatalyst according to claim 3, and its characteristic is that it is an organic structure derived from benzimidazole. It contains nitrogen-doped porous carbon supports formed as a result of carbonization. 15 13. Nanocatalyst according to claim 3 or 12, with the properties of CuO, ZnO and Co₃O₄ metal oxides. phases of nitrogen-doped porous carbon-supported carbonized intermediates containing Cu, Zn, and Co the structure undergoes a controlled oxidation / calcination process in an oxygen-containing atmosphere. It is formed as a result of being held captive.

14. It is a nanocatalyst according to claim 3, and its characteristic is that it contains Co, Cu and Zn according to ICP-MS analysis. and Co content 30-40% by weight, Cu content 10-20% by weight, Zn content It should be 15-25% by weight.

15. Production method according to claim 4, characterized by; Zn salt as Zn(NO₃)₂·6H₂O, Cu species The species is Cu(NO₃)₂·3H₂O and Co(NO₃)₂·6H₂O. 25 16. Production method according to claim 15, characterized by; metal-organic containing Zn and benzimidazole. During the preparation of the precursor, benzimidazole and Zn(NO₃)₂·6H₂O were mixed at a ratio of 1 mmol to 4 mmol. It is dissolved in methanol at a certain ratio.

17. Production method according to claim 16, characterized by; metal containing Zn and benzimidazole. 30 obtained by mixing the organic precursor at room temperature under atmospheric pressure It is done.

18. Production method according to claim 17, characterized by; metal containing Zn and benzimidazole. It is the dispersion of the organic precursor Cu(NO₃)₂·3H₂O in a methanol solution. 12 19. Production method according to claim 18, characterized by being an intermediate metal-organic material containing Cu and Zn. dispersing the material in methanol and adding benzimidazole to this mixture It is the addition of Co(NO₃)₂·6H₂O at a ratio of 1 mmol : 4 mmol.

Images