CN109759143B - Co3O4Preparation method and application of NP/CD/Co-MOF composite material - Google Patents
Co3O4Preparation method and application of NP/CD/Co-MOF composite material Download PDFInfo
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Abstract
The invention discloses a Co3O4A preparation method of NP/CD/Co-MOF composite material and application based on electrocatalysis of the composite material belong to the technical fields of nano catalysis, nano materials and the like. The method mainly comprises the steps of reacting cobalt nitrate, glucose, triethylene diamine and terephthalic acid at room temperature to prepare Co-MOF/glucose flaky microcrystals; oxidizing and pyrolyzing the microcrystal under microwave radiation to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites. The composite material has the advantages of low cost of raw materials, simple preparation process, low reaction energy consumption and industrial application prospect. The catalyst is used for electrocatalysis nitrogen fixation to ammonia, and has good electrochemical activity.
Description
Technical Field
The invention relates to a semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4A preparation method of NP/CD/Co-MOF composite material and application of the composite material in electrocatalysis nitrogen fixation to ammonia, belonging to the technical field of nano composite material and electrocatalysis.
Background
Ammonia is a vital chemical product in human society and is widely applied to the production of chemical fertilizers, medicaments, dyes and the like. Meanwhile, due to the strong hydrogen content and high energy density, the carbon dioxide is also widely concerned as an alternative energy carrier so as to promote the development of a low-carbon society. Thus, N2And H2Catalytic synthesis of NH3One of the most important chemical reactions on the earth, its inventors F-Haber and C-Bosch have also creditably won the Nobel chemical prize, a famous "Haber-Bosch" method. However, the industrial production of this reaction requires not only a high temperature of 500 to 600 ℃ but also a high pressure of 17 to 50 MPa (equivalent to 10.332 kg weight per square centimeter) to be carried outAnd iron-based catalyst. The energy consumed by the haber-bosch reaction in actual industrial production accounts for about 2 percent of the global energy consumption, and a large amount of hydrogen is consumed. In the current mainstream production process, fossil fuels are the main source of hydrogen, and the process of producing hydrogen also emits large amounts of carbon dioxide, which is one of the most important "greenhouse gases".
The electrocatalysis nitrogen fixation ammonia synthesis technology is one of the methods for replacing the reaction, can realize the advantages of ammonia synthesis at normal temperature and normal pressure, has low energy consumption and no carbon dioxide emission, has attracted the wide attention of global scholars in recent years, and is considered to be one of the most promising industrial ammonia synthesis technologies. However, the electrocatalysis nitrogen fixation is going to be applied to large-scale industry, and the development of non-noble metal catalysts to replace noble metal catalysts is an urgent problem to be solved in order to reduce the production cost.
The metal-organic frameworks (MOFs) are coordination polymers formed by self-assembly of metal ions and organic bridging ligands, and become a new-generation crystal porous material due to the characteristics of easy preparation, various structures, modification of pore channel surfaces and the like. Compared with the traditional inorganic materials, the MOFs material has organic-inorganic hybrid characteristics, such as large specific surface area, high porosity and diversified structure and function, is widely applied to the fields of gas adsorption, sensing, catalysis, optics, drug slow release and the like, and is a research hotspot in the research field of new functional materials at present. However, the defects of poor water stability and chemical stability of the MOFs still exist, and the surrounding chemical environment of the metal/metal coordination center in the framework structure of the MOFs is easy to change and is a direct reason for losing the stability of the material.
As is well known, the stability of the material is a precondition for realizing industrial application, and in order to compensate for these defects, MOFs is used as a precursor, and the MOFs-based composite materials such as nano metal particles, nano metal oxides and the like stably loaded on a substrate are prepared by pyrolysis.
Disclosure of Invention
One of the technical tasks of the invention is toMakes up the defects of the prior art and provides a semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4The preparation method of the NP/CD/Co-MOF composite material has the advantages of simple preparation process, low raw material cost, low reaction energy consumption and industrial application prospect.
The second technical task of the invention is to provide the application of the composite material, namely the composite material is used for high-efficiency electrocatalytic nitrogen fixation, and the composite material has good electrocatalytic nitrogen fixation activity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. co3O4Preparation method of NP/CD/Co-MOF composite material
(1) Preparation of Co-MOF/glucose microcrystals
Dissolving 0.9-1.1 mmol of triethylene diamine TED in 2-3 mL of absolute ethyl alcohol to prepare a TED solution;
taking 1.8-2.2 mmol of terephthalic acid H2BDC is dissolved in 6-8 mL of N, N-Dimethylformamide (DMF) to prepare H2A BDC solution;
mixing TED solution with H2Blending BDC solution, and dripping 1.0-1.2 mL of lithium hydroxide aqueous solution with the mass fraction of 3.7% to prepare ligand mixed solution;
dissolving 2.0-2.3mmol of cobalt nitrate and 1.5-1.7 mmol of glucose in 8-10 mL of DMF solution to obtain cobalt nitrate solution containing glucose;
mixing the ligand mixed solution and a cobalt nitrate solution containing glucose, standing at room temperature for 1-2 h, performing centrifugal separation, and washing with water and ethanol for 3 times respectively to obtain Co-MOF/glucose flaky microcrystals;
(2) oxidation-pyrolysis of Co-MOF/glucose platelet crystallites
Performing oxidation-pyrolysis on Co-MOF/glucose microcrystal under the microwave radiation of 400W power and temperature of 140-150 ℃, cooling to room temperature, washing the obtained powder with water and ethanol for 3 times respectively, and drying at 90 ℃ overnight to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites.
The Co-MOF/glucose flaky microcrystal is a composite flaky microcrystal of which the pores of a metal-organic framework Co-MOF are loaded with glucose; the yield of Co-MOF/glucose plate-like crystallites was 80-87%.
The Co-MOF has a chemical formula of [ Co2(BDC)2(TED)]·4DMF·H2O, one structural unit of which is composed of 2 Co (II) positive ions, 2 BDC (II) negative ions, one TED molecule, 4 guest DMF molecules and 5 guest H2And O molecules.
2. Co prepared by the preparation method described above3O4Application of NP/CD/Co-MOF composite material as electrocatalytic nitrogen fixation
(1) Preparation of working electrode
Taking 6 mg of Co3O4Dispersing NP/CD/Co-MOF composite material in a solution containing 720 mu L of water, 250 mu L of ethanol and 30 mu L of Nafion, forming a uniform suspension after ultrasonic treatment for 30 min, sucking 10 mu L of suspension liquid, dripping the suspension liquid on a glassy carbon electrode with the diameter of 4 mm, and airing overnight to obtain Co/CD/Co-MOF composite material3O4An NP/CD/Co-MOF composite working electrode;
(2) drawing a standard curve
Preparing series NH by adopting ammonium chloride and PBS buffer solution with concentration of 0.1M3A standard solution of (4);
taking 2 mL of standard solution, sequentially adding 2 mL of NaOH solution with the concentration of 0.1M, 1 mL of NaClO with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 656 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5% of salicylic acid and 5% of sodium citrate in percentage by mass;
(3) electrocatalytic nitrogen fixation
Connecting an H-shaped two-chamber electrolytic cell on an electrochemical workstation, separating the two chambers by a Nafion 115 proton exchange membrane, adding 30 mL of PBS buffer solution with the concentration of 0.1M into the two chambers, and coating Co3O4The glassy carbon electrode of the NP/CD/Co-MOF composite material is taken as a working electrode, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as an auxiliary electrode, N is introduced into a cathode chamber2After 30 min, setting an external voltage of-0.6 to-1.4V for electrocatalytic nitrogen fixation;
(4) taking the reaction liquid which catalyzes the reaction for 2 hours to replace 2 mL of standard solution in the step (2), and measuring the concentration of ammonia in the reaction liquid to test Co3O4The NP/CD/Co-MOF composite material has electrocatalytic nitrogen fixation performance;
when the applied voltage is-0.45V (vs RHE), the ammonia gas generation rate is 14.5-16.0 mu gNH3 h− 1mg catalyst -1The Faraday efficiency is more than or equal to 3.3-3.9%, which shows the high-efficiency electrocatalytic nitrogen fixation activity of the material; the presence of hydrazine was not detected, indicating that the catalyst had good selectivity.
The beneficial technical effects of the invention are as follows:
(1) co obtained by the invention3O4The NP/CD/Co-MOF composite material has the advantages of simple preparation process, simplicity and easy control, high product preparation efficiency and easy industrialization.
(2) Co prepared by the invention3O4NP/CD/Co-MOF composite material is based on oxidation-pyrolysis of Co-MOF/glucose flaky microcrystal under microwave radiation, partial oxidation-pyrolysis of Co-MOF in the process, and in-situ generation of Co3O4The nano particles are stably loaded on the porous Co-MOF, and glucose doped in Co-MOF crystals is pyrolyzed in situ to generate carbon dots, namely, semiconductor Co3O4The composite material is large in specific surface area and exposes more active sites; in addition, the material is Co3O4The multi-component composite material consisting of the nano particles, the carbon dots and the Co-MOF has the synergistic effect of all the components, so that the composite material catalyzes N2The activity of reducing the ammonia into ammonia is increased, and the rate of producing ammonia by electrocatalysis at room temperature is higher.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples, and modifications made by those skilled in the art to the technical solutions of the present invention should fall within the scope of the present invention.
Example 1A Co3O4Preparation method of NP/CD/Co-MOF composite material
(1) Preparation of Co-MOF/glucose microcrystals
Dissolving 0.9 mmol of triethylene diamine TED in 2 mL of absolute ethyl alcohol to prepare a TED solution;
1.8 mmol of terephthalic acid H is taken2BDC, dissolved in 6 mL of N, N-Dimethylformamide (DMF) to obtain H2A BDC solution;
mixing TED solution with H2Blending BDC solution, and dropwise adding 1.0 mL of lithium hydroxide aqueous solution with the mass fraction of 3.7% to prepare ligand mixed solution;
dissolving 2.0 mmol of cobalt nitrate and 1.5 mmol of glucose in 8 mL of DMF solution to obtain a cobalt nitrate solution containing glucose;
mixing the ligand mixed solution and a cobalt nitrate solution containing glucose, standing for 1h at room temperature, performing centrifugal separation, and washing with water and ethanol for 3 times respectively to obtain Co-MOF/glucose flaky microcrystals;
(2) oxidation-pyrolysis of Co-MOF/glucose platelet crystallites
Oxidizing and pyrolyzing Co-MOF/glucose microcrystal under 400W power and 140 ℃ microwave radiation for 3 min, cooling to room temperature, washing obtained powder with water and ethanol for 3 times respectively, and drying at 90 ℃ overnight to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites.
The Co-MOF/glucose flaky microcrystal is a composite flaky microcrystal of which the pores of a metal-organic framework Co-MOF are loaded with glucose; the yield of Co-MOF/glucose plate crystallites was 80%.
The Co-MOF has a chemical formula of [ Co2(BDC)2(TED)]·4DMF·H2O, one structural unit of which is composed of 2 Co (II) positive ions, 2 BDC (II) negative ions, one TED molecule, 4 guest DMF molecules and 5 guest H2And O molecules.
Example 2A Co3O4Preparation method of NP/CD/Co-MOF composite material
(1) Preparation of Co-MOF/glucose microcrystals
Dissolving 1.0 mmol of triethylene diamine TED in 2.5 mL of absolute ethyl alcohol to prepare a TED solution;
2.0 mmol of terephthalic acid H is taken2BDC, dissolved in 7 mL N, N-Dimethylformamide (DMF) to obtain H2A BDC solution;
mixing TED solution with H2Blending BDC solution, and dropwise adding 1.1 mL of lithium hydroxide aqueous solution with the mass fraction of 3.7% to prepare ligand mixed solution;
dissolving 2.1 mmol of cobalt nitrate and 1.6 mmol of glucose in 9 mL of DMF solution to obtain a cobalt nitrate solution containing glucose;
mixing the ligand mixed solution and a cobalt nitrate solution containing glucose, standing at room temperature for 1.5 h, performing centrifugal separation, and washing with water and ethanol for 3 times respectively to obtain Co-MOF/glucose flaky microcrystals;
(2) oxidation-pyrolysis of Co-MOF/glucose platelet crystallites
Oxidizing and pyrolyzing Co-MOF/glucose microcrystal under microwave radiation of 400W power and 145 ℃ for 5 min, cooling to room temperature, washing obtained powder with water and ethanol for 3 times respectively, and drying at 90 ℃ overnight to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites.
The Co-MOF/glucose flaky microcrystal is a composite flaky microcrystal of which the pores of a metal-organic framework Co-MOF are loaded with glucose; the yield of Co-MOF/glucose plate-like crystallites was 87%.
The chemical formula and the composition of the structural unit of the Co-MOF are the same as those of example 1.
Example 3A Co3O4Preparation method of NP/CD/Co-MOF composite material
(1) Preparation of Co-MOF/glucose microcrystals
Dissolving 1.1 mmol of triethylene diamine TED in 3 mL of absolute ethyl alcohol to prepare a TED solution;
2.2 mmol of terephthalic acid H are taken2BDC, dissolved in 8 mL N, N-Dimethylformamide (DMF) to obtain H2A BDC solution;
mixing TED solution with H2Blending BDC solution, and dropwise adding 1.2 mL of lithium hydroxide aqueous solution with the mass fraction of 3.7% to prepare ligand mixed solution;
dissolving 2.3mmol of cobalt nitrate and 1.7 mmol of glucose in 10 mL of DMF solution to prepare a cobalt nitrate solution containing glucose;
mixing the ligand mixed solution and a cobalt nitrate solution containing glucose, standing for 2 h at room temperature, performing centrifugal separation, and washing with water and ethanol for 3 times respectively to obtain Co-MOF/glucose flaky microcrystals;
(2) oxidation-pyrolysis of Co-MOF/glucose platelet crystallites
Oxidizing and pyrolyzing Co-MOF/glucose microcrystal under the microwave radiation of 400W power and 150 ℃ for 6 min, cooling to room temperature, washing obtained powder with water and ethanol for 3 times respectively, and drying at 90 ℃ overnight to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites.
The Co-MOF/glucose flaky microcrystal is a composite flaky microcrystal of which the pores of a metal-organic framework Co-MOF are loaded with glucose; the yield of Co-MOF/glucose plate crystallites was 84%.
The chemical formula of the Co-MOF and the composition of the structural units are the same as those of example 1.
Example 4A Co3O4Application of NP/CD/Co-MOF composite material as electrocatalytic nitrogen fixation
(1) Preparation of working electrode
Taking 6 mg of Co3O4Dispersing NP/CD/Co-MOF composite material in a solution containing 720 mu L of water, 250 mu L of ethanol and 30 mu L of Nafion, forming a uniform suspension after ultrasonic treatment for 30 min, sucking 10 mu L of suspension liquid, dripping the suspension liquid on a glassy carbon electrode with the diameter of 4 mm, and airing overnight to obtain Co/CD/Co-MOF composite material3O4An NP/CD/Co-MOF composite working electrode;
(2) drawing a standard curve
Preparing series NH by adopting ammonium chloride and PBS buffer solution with concentration of 0.1M3A standard solution of (4);
taking 2 mL of standard solution, sequentially adding 2 mL of NaOH solution with the concentration of 0.1M, 1 mL of NaClO with the concentration of 0.05M and 0.2 mL of sodium nitroferricyanide solution with the mass fraction of 1%, quickly shaking for several times, standing for 2 h at 25 ℃, detecting the absorbance peak value of the solution at the 656 nm wavelength by using a UV-vis spectrophotometer, and drawing an absorbance-concentration (A-c) standard curve;
the 1.0M NaOH solution contains 5% of salicylic acid and 5% of sodium citrate in percentage by mass;
(3) electrocatalytic nitrogen fixation
Connecting an H-shaped two-chamber electrolytic cell on an electrochemical workstation, separating the two chambers by a Nafion 115 proton exchange membrane, adding 30 mL of PBS buffer solution with the concentration of 0.1M into the two chambers, and coating Co3O4The glassy carbon electrode of the NP/CD/Co-MOF composite material is taken as a working electrode, Ag/AgCl is taken as a reference electrode, a platinum sheet is taken as an auxiliary electrode, N is introduced into a cathode chamber2After 30 min, setting an external voltage of-0.6 to-1.4V for electrocatalytic nitrogen fixation;
(4) taking the reaction liquid which catalyzes the reaction for 2 hours to replace 2 mL of standard solution in the step (2), and measuring the concentration of ammonia in the reaction liquid to test Co3O4The NP/CD/Co-MOF composite material has electrocatalytic nitrogen fixation performance;
when the applied voltage was-0.45V (vs RHE), the ammonia generation rate was 14.5. mu.gNH3 h−1mg catalyst -1The Faraday efficiency is more than or equal to 3.3 percent, which shows the high-efficiency electrocatalytic nitrogen fixation activity of the material; the presence of hydrazine was not detected, indicating that the catalyst had good selectivity.
Example 5A Co3O4Application of NP/CD/Co-MOF composite material as electrocatalytic nitrogen fixation
The method is the same as example 4, and only the Co obtained in example 2 is used3O4NP/CD/Co-MOF composite Material instead of Co prepared in example 13O4NP/CD/Co-MOF composites;
when the applied voltage was-0.45V (vs RHE), the ammonia gas generation rate was 16.0. mu.gNH3 h−1mg catalyst -1The Faraday efficiency is 3.9 percent, which shows that the material has high-efficiency electrocatalytic nitrogen fixation activity; the presence of hydrazine was not detected, indicating that the catalyst had good selectivity.
Example 6A Co3O4Application of NP/CD/Co-MOF composite material as electrocatalytic nitrogen fixation
The method is the same as example 4, and only the Co obtained in example 3 is used3O4NP/CD/Co-MOF composite Material instead of Co prepared in example 13O4NP/CD/Co-MOF composites;
when the applied voltage was-0.45V (vs RHE), the ammonia gas generation rate was 15.1. mu.gNH3 h−1mg catalyst -1The Faraday efficiency is more than or equal to 3.4 percent, which shows the high-efficiency electrocatalytic nitrogen fixation activity of the material; the presence of hydrazine was not detected, indicating that the catalyst had good selectivity.
Claims (2)
1. Co3O4The preparation method of the NP/CD/Co-MOF composite material is characterized by comprising the following steps:
(1) preparation of Co-MOF/glucose microcrystals
Dissolving 0.9-1.1 mmol of triethylene diamine TED in 2-3 mL of absolute ethyl alcohol to prepare a TED solution;
taking 1.8-2.2 mmol of terephthalic acid H2BDC is dissolved in 6-8 mL of N, N-Dimethylformamide (DMF) to prepare H2A BDC solution;
mixing TED solution with H2Blending BDC solution, and dripping 1.0-1.2 mL of lithium hydroxide aqueous solution with the mass fraction of 3.7% to prepare ligand mixed solution;
dissolving 2.0-2.3mmol of cobalt nitrate and 1.5-1.7 mmol of glucose in 8-10 mL of DMF solution to obtain cobalt nitrate solution containing glucose;
mixing the ligand mixed solution and a cobalt nitrate solution containing glucose, standing at room temperature for 1-2 h, performing centrifugal separation, and washing with water and ethanol for 3 times respectively to obtain Co-MOF/glucose flaky microcrystals;
(2) oxidation-pyrolysis of Co-MOF/glucose platelet crystallites
Performing oxidation-pyrolysis on Co-MOF/glucose microcrystal under the microwave radiation of 400W power and temperature of 140-150 ℃, cooling to room temperature, washing the obtained powder with water and ethanol for 3 times respectively, and drying at 90 ℃ overnight to obtain semiconductor Co3O4Nanoparticle and carbon dot CD Co-doped Co-MOF composites, i.e. Co3O4NP/CD/Co-MOF composites;
the Co-MOF/glucose flaky microcrystal is a composite flaky microcrystal of which the pores of a metal-organic framework Co-MOF are loaded with glucose; the yield of Co-MOF/glucose plate crystallites was 87%;
the Co-MOF has a chemical formula of [ Co2(BDC)2(TED)]·4DMF·H2O, one structural unit of which is composed of 2 Co (II) positive ions, 2 BDC (II) negative ions, one TED molecule, 4 guest DMF molecules and 5 guest H2And O molecules.
2. Co produced by the production method according to claim 13O4Application of NP/CD/Co-MOF composite material in electrocatalytic nitrogen fixation.
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