CN110862548A - Preparation method and new application of metal organogel catalyst based on MIL-53 - Google Patents

Preparation method and new application of metal organogel catalyst based on MIL-53 Download PDF

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CN110862548A
CN110862548A CN201911136362.2A CN201911136362A CN110862548A CN 110862548 A CN110862548 A CN 110862548A CN 201911136362 A CN201911136362 A CN 201911136362A CN 110862548 A CN110862548 A CN 110862548A
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organogel
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aluminum
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nickel
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CN110862548B (en
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李东升
魏君华
吴亚盘
张其春
兰亚乾
吴涛
张健
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Beijing Zhichanhui Technology Co ltd
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China Three Gorges University CTGU
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Abstract

The invention provides an MIL-53 multi-metal organogel catalyst for electrocatalytic methanol oxidation and a preparation method thereof, wherein the preparation method comprises the steps of preparing single-metal organogel by taking aluminum salt and terephthalic acid (BDC) as raw materials; preparing a bimetallic organogel by taking aluminum salt, nickel salt and terephthalic acid as raw materials; preparing trimetal organogel by taking aluminum salt, nickel salt, copper salt and terephthalic acid as raw materials; the synthetic materials were assembled into a three-electrode system for methanol oxidation testing. The method has the advantages of simple and convenient operation, high yield, good repeatability and controllable components, and the prepared multi-metal organogel has excellent electrocatalytic methanol oxidation performance.

Description

Preparation method and new application of metal organogel catalyst based on MIL-53
Technical Field
The invention belongs to the technical field of synthesis and application of catalysts, and particularly relates to a preparation method of a metal organic gel with electrocatalytic performance and application of the metal organic gel in electrocatalytic methanol oxidation.
Background
The direct methanol fuel cell is a proton exchange membrane fuel cell taking methanol as liquid fuel, and has the advantages of rich fuel source, low price, convenient and safe storage and transportation and the like, and the methanol has high energy density and is widely concerned. However, the development of methanol fuel cells is limited by the slow reaction kinetics of the anode methanol reaction and the susceptibility of the platinum metal catalysts to poisoning, which requires increased platinum loading. Therefore, the number of exposed active sites of the catalyst, the surface structure, the composition and the atomic arrangement are very important for improving the utilization rate and the catalytic performance of the platinum. At present, a great deal of research is focused on exploring the formation of alloy or heterostructure catalysts of different transition metals and platinum so as to modify a platinum electronic structure and achieve the purposes of reducing the platinum loading capacity and improving the platinum utilization rate. The open-pore structured nanomaterial such as nanocages, nano frames, hollow spheres and the like also maximizes the utilization of the active metal to reduce costs by imparting a high specific surface area, porosity to the catalyst and an active surface with which the reactants can come into contact in three-dimensional directions. The Metal Organic Gels (MOGs) are expanded on the basis of the structure of metal organic framework Materials (MOFs), and the metal organic framework material particles can form a three-dimensional network structure in a self-assembly mode. Therefore, MOGs become a porous metal organic material with a hierarchical structure, and the porous metal organic material has the characteristics of high specific surface area, size-adjustable pore channels, low density, inherent metal sites and the like, so that the porous metal organic material has potential application values in the aspects of mass transfer, adsorption, catalyst carrier and the like. As one of the porous materials, it has a characteristic that the pore diameter is adjustable as compared with an inorganic porous material (e.g., molecular sieve), which is generally fixed in pore size. Compared with the hotter MOFs (also belongs to a porous material) researched in recent years, the metal organogel has the characteristics of large pore diameter and stability, and for the MOFs, in order to obtain larger pore diameter, the length of a ligand is the most commonly used method, but the synthesized MOFs are unstable when the ligand is increased, so that the application of the MOFs is greatly limited. Therefore, the synthesis and performance research of the metal organogel have good application prospects. In general, a noble metal material is often used as an electrode material of a methanol fuel cell, but the noble metals Pt and Pb are expensive, have a small storage amount, and are easily poisoned by being combined with a CO intermediate. The alkaline direct methanol fuel cell can utilize non-noble metals Ni and Cu as electrode materials, but Ni and Cu react with ligands to generate MOF, so that gel cannot be formed generally, the yield of the electrode materials is too low, the use cost is increased, and the synthesis process of the MOF is complex and long in time consumption. Therefore, in the invention, the methanol oxidation performance of the MIL-53(Al) metal organic gel is improved by utilizing the multi-metal synergistic effect through synthesizing the MIL-53(Al) metal organic gel and introducing nickel/copper into the MIL-53(Al) metal organic gel.
Disclosure of Invention
The invention provides a method for preparing single metal, double metal and tri-metal organogel materials, and the composite material is applied to electrocatalytic methanol oxidation, and the preparation method is simple and convenient and has high yield. The invention aims at the application of polymetallic organogel in the field of methanol oxidation, and provides a preparation method and application of an electrocatalytic material, namely an aluminum-monometallic organogel material 1, an aluminum/nickel-bimetallic organogel material 2 and an aluminum/nickel/copper-trimetallic organogel material 3, which are obtained by assembling terephthalic acid and aluminum, nickel and copper metal ions.
The purpose of the invention is realized by the following technical scheme, the three materials are an aluminum-single metal organogel material 1, an aluminum/nickel-double metal organogel material 2 and an aluminum/nickel/copper-triple metal organogel material 3 which have stability in a 0.1M KOH solution, and the three materials are prepared by a hydrothermal method and comprise the following steps:
(1) dissolving metal salt in N, N-dimethylacetamide solvent, and performing ultrasonic treatment to obtain a mixed solution.
(2) Dissolving terephthalic acid in N, N-dimethylacetamide solvent, and performing ultrasonic treatment to prepare a ligand solution containing terephthalic acid.
(3) And (3) pouring the solution obtained in the step (1) into the solution obtained in the step (2), performing ultrasonic treatment at room temperature for a period of time to fully mix the solution, transferring the mixture into a reaction kettle, and reacting at the temperature of 120-.
(4) And (4) washing the wet gel obtained in the step (3) with ethanol for three times to obtain an MIL-53-based aluminum-single metal organic gel material 1, an aluminum/nickel-double metal organic gel material 2 and an aluminum/nickel/copper-triple metal organic gel material 3.
The metal salt is aluminum nitrate or nickel nitrate or copper nitrate.
The amount of the N, N-dimethylacetamide is only needed to be immersed in the metal salt and the terephthalic acid, and the molar ratio of the aluminum nitrate and/or the nickel nitrate and/or the copper nitrate to the ligand terephthalic acid is 1-2: 1.
3 kinds of metal organic gel materials prepared by the steps are used as electro-catalysts to carry out electro-catalytic methanol oxidation tests. The method comprises the following specific steps:
1) weighing 4mg of the obtained metal organogel material, adding 0.2ml of naphthol, 1.3ml of deionized water and 0.5ml of ethanol, and carrying out ultrasonic mixing for 30min to prepare an electrode solution for later use.
2) Coating 4 microliter of the electrode solution obtained in the step 1) on a glassy carbon electrode to form a working electrode, taking a platinum wire as a counter electrode and taking a Hg/HgO electrode as a reference electrode to form a three-electrode system, and inserting the three-electrode system into electrolyte to perform methanol oxidation reaction.
The invention has the following advantages:
(1) the gel synthesized by the method has simple reaction conditions, is easy to repeat mass synthesis, and has lower cost. The method synthesizes the aluminum-nickel-containing bimetallic gel and the aluminum-nickel-copper trimetal gel, provides reference for simplifying the preparation process and synthesizing other gels of different metal types, and has certain guiding significance.
(2) The metal in the multi-metal organogel has synergistic effect (geometric effect and electronic effect), and the introduction of nickel/copper can effectively enhance the methanol oxidation performance of the catalyst.
Drawings
FIG. 1 is a diagram of a metal organogel material prepared according to the present invention, wherein A is an aluminum-single metal organogel material, B is an aluminum/nickel-double metal organogel material, and C is an aluminum/nickel/copper-triple metal organogel material.
FIG. 2 is an X-ray powder diffraction pattern of the metal organogel material prepared in accordance with the present invention.
FIG. 3 is a Fourier infrared plot of a metal organogel material prepared according to the present invention.
FIG. 4 is SEM and energy spectrum of the aluminum-single metal organogel material prepared by the present invention.
Fig. 5 is SEM and energy spectrum of the aluminum/nickel-bimetal organogel material prepared by the present invention.
FIG. 6 is SEM and energy spectrum of the aluminum/nickel/copper-trimetal organogel material prepared by the present invention.
FIG. 7 is a cyclic voltammogram of a metal organogel material prepared according to the present invention in a 0.1M potassium hydroxide solution.
FIG. 8 is a cyclic voltammogram of the metal organogel material prepared in the invention in 0.1M potassium hydroxide and 1M methanol solution.
FIG. 9 is a graph showing the current decay degree of the metal organogel material prepared in the present invention in 0.1M KOH and 1M MeOH solutions.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention. The starting materials described in the present invention were all purchased commercially and the reagents were not further purified.
Example 1
225 mg of aluminum nitrate nonahydrate [ Al (NO) was weighed3)3•9H2O]All dissolved in 3mL of N, N-dimethylacetamide; weighing 99 mg of terephthalic acid, and dissolving in 3mL of N, N-dimethylacetamide; both the two solutions are ultrasonically treated until the solutions are completely dissolved, then the former solution is poured into the latter solution, and the mixed solution is ultrasonically treated for 5 minutes until the mixed solution is uniformly mixed; and then transferring the mixed solution into a 23mL reaction kettle, putting the reaction kettle into an air drying oven, preserving the temperature for 3h at 160 ℃, cooling, washing and drying to obtain the aluminum-monometal organogel material, wherein the physical diagram of the gel material is shown in figure 1, and the XRD, infrared and SEM are shown in figures 2, 3 and 4.
Example 2
112 mg of aluminum nitrate nonahydrate [ Al (NO) was weighed3)3•9H2O]87mg of nickel nitrate hexahydrate [ Ni (NO)3)2•6H2O]All dissolved in 3mL of N, N-dimethylacetamide; weighing 100 mg of terephthalic acid and dissolving in 3mL of N, N-dimethylacetamide; both the two solutions are ultrasonically treated until the solutions are completely dissolved, then the former solution is poured into the latter solution, and the mixed solution is ultrasonically treated for 5 minutes until the mixed solution is uniformly mixed; and then transferring the mixed solution into a 23mL reaction kettle, putting the reaction kettle into an air drying oven, preserving the temperature for 3h at 160 ℃, cooling, washing and drying to obtain the aluminum/nickel-bimetal organogel material, wherein the physical diagram of the gel material is shown in figure 1, and the XRD, infrared and SEM are shown in figures 2, 3 and 5.
Example 3
75 mg of aluminum nitrate nonahydrate [ Al (NO) was weighed3)3•9H2O]58 mg of nickel nitrate hexahydrate [ Ni (NO)3)2•6H2O]48mg of copper nitrate trihydrate [ Cu (NO)3)2•3H2O]All dissolved in 3mL of N, N-dimethylacetamide; weighing 100 mg of terephthalic acid and dissolving in 3mL of N, N-dimethylacetamide; both the two solutions are ultrasonically treated until the solutions are completely dissolved, then the former solution is poured into the latter solution, and the mixed solution is ultrasonically treated for 5 minutes until the mixed solution is uniformly mixed; and then transferring the mixed solution into a 23mL reaction kettle, putting the reaction kettle into an air-blowing drying oven, preserving the temperature for 3h at 160 ℃, cooling and washing to obtain the aluminum/nickel/copper-trimetal organogel material, wherein the physical diagram of the organogel material is shown in figure 1, and the XRD, infrared and SEM are shown in figures 2, 3 and 6. The XRD patterns of the three gels have good correspondence with the simulated peaks, and the three gels synthesized are proved to have an MIL-53 structure. Wherein the scan and energy spectra further reflect the presence of MIL-53(Al), MIL-53(AlNi) and MIL-53 (AlNiCu).
Example 4
The samples collected in examples 1-3 were weighed to 4mg respectively in a 4ml sample tube, added with 0.2ml naphthol, 0.5ml absolute ethyl alcohol and 1.3ml deionized water, and applied on a glassy carbon electrode after 30min of ultrasonic treatment. The cyclic voltammogram of the test material in 0.1M potassium hydroxide solution was scanned by CV until stable, and the test was as shown in FIG. 7. The cyclic voltammogram of the metal organogel material in 0.1M potassium hydroxide and 1M methanol solution was tested for material Methanol Oxidation (MOR) performance as shown in FIG. 8, MIL-53(Al) gel has no methanol oxidation peak, and MIL-53(AlNi) gel has a lower peak than MIL-53 (AlNiCu). Wherein the oxidation peak overpotentials of MIL-53(AlNi) and MIL-53(AlNiCu) are 0.831V and 1.008V respectively, and the mass activity is improved from 909mA/mg to 1014 mA/mg. FIG. 9 is a graph showing the current decay of the organogel material in 0.1M KOH and 1M MeOH, with MIL-53(Al) decaying significantly less than MIL-53(AlNi) and MIL-53(AlNiCu) and stable performance maintained up to 3600 seconds.
The metal organogel based on the MIL-53 structure, which is synthesized by the method, is found that the mass activity of the aluminum/nickel-bimetal organogel material is superior to that of the aluminum-single metal organogel material, and the mass activity of the aluminum/nickel/copper-trimetal organogel material is superior to that of the aluminum/nickel-single metal organogel material. The result shows that the Methanol Oxidation (MOR) performance of the metal organogel material is greatly improved due to the multi-metal concerted catalysis after the metal nickel and the metal copper are added.

Claims (4)

1. A preparation method of a MIL-53-based metal organic gel catalyst is characterized by comprising the following steps:
(1) aluminum nitrate nonahydrate Al (NO)3)3•9H2Dissolving O in N, N-dimethylacetamide;
(2) dissolving terephthalic acid in N, N-dimethylacetamide;
(3) pouring the solution in the step (1) into the solution in the step (2), and uniformly dispersing by ultrasonic; and then transferring the mixed solution into a reaction kettle, preserving the heat at the temperature of 120-180 ℃ for 2-10h, naturally cooling, and washing to obtain the aluminum-single metal organic gel material.
2. The method for preparing MIL-53 based metal organogel catalyst according to claim 1, wherein said step (1) further comprises mixing aluminum nitrate nonahydrate Al (NO)3)3•9H2O, Nickel nitrate hexahydrate Ni (NO)3)2•6H2Dissolving O in N, N-dimethyl acetamide to obtain the product of aluminum/nickel-bimetal organogel material.
3. The method for preparing MIL-53 based metal organogel catalyst according to claim 1 or 2, wherein the step (1) further comprises mixing aluminum nitrate nonahydrate Al (NO)3)3•9H2O, Nickel nitrate hexahydrate Ni (NO)3)2•6H2O, copper nitrate trihydrate Cu (NO)3)2•3H2Dissolving O in N, N-dimethylacetamide; the obtained product is an aluminum/nickel/copper-trimetal organogel material.
4. Use of a MIL-53 based metal organogel catalyst according to any of claims 1-3 for electrocatalytic methanol oxidation.
CN201911136362.2A 2019-11-19 2019-11-19 Preparation method and new application of metal organogel catalyst based on MIL-53 Active CN110862548B (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN112608488A (en) * 2020-12-15 2021-04-06 荆门市格林美新材料有限公司 MOFs-based precursor for cobalt-free lithium battery, positive electrode material and preparation method of MOFs-based precursor
CN113035575A (en) * 2021-03-05 2021-06-25 安徽大学 Conductive metal organic gel NiMn MOG and synthesis method and application thereof
CN113399003A (en) * 2021-06-04 2021-09-17 中国科学院上海硅酸盐研究所 Precious metal nanoparticle-MOFs gel block composite material and preparation method and application thereof
CN115651209A (en) * 2022-10-25 2023-01-31 常熟理工学院 Preparation method and application of MIL-53 (Al-Cu) nanosheet

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112608488A (en) * 2020-12-15 2021-04-06 荆门市格林美新材料有限公司 MOFs-based precursor for cobalt-free lithium battery, positive electrode material and preparation method of MOFs-based precursor
CN113035575A (en) * 2021-03-05 2021-06-25 安徽大学 Conductive metal organic gel NiMn MOG and synthesis method and application thereof
CN113399003A (en) * 2021-06-04 2021-09-17 中国科学院上海硅酸盐研究所 Precious metal nanoparticle-MOFs gel block composite material and preparation method and application thereof
CN115651209A (en) * 2022-10-25 2023-01-31 常熟理工学院 Preparation method and application of MIL-53 (Al-Cu) nanosheet
CN115651209B (en) * 2022-10-25 2024-02-23 常熟理工学院 Preparation method and application of MIL-53 (Al-Cu) nanosheets

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