CN113667131B - Functionalized metal organic framework nano material, preparation method and application thereof - Google Patents

Functionalized metal organic framework nano material, preparation method and application thereof Download PDF

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CN113667131B
CN113667131B CN202110833386.4A CN202110833386A CN113667131B CN 113667131 B CN113667131 B CN 113667131B CN 202110833386 A CN202110833386 A CN 202110833386A CN 113667131 B CN113667131 B CN 113667131B
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CN113667131A (en
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胡觉
张利波
张呈旭
戚强龙
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Kunming University of Science and Technology
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Abstract

The invention relates to a functionalized metal organic framework nano material, a preparation method and application thereof, belonging to the technical field of OER electro-catalysts. Dissolving 0.1mmol of organic ligand 2-nitroterephthalic acid or 2-formamido terephthalic acid and 0.1mmol of iron salt in an organic solvent, and heating at 130-180 ℃ for 2-5h for hydrothermal reaction to obtain a reaction product; cooling the obtained reaction product to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and then drying to obtain the functionalized metal organic framework nano material catalyst Fe-MOFs-X, wherein X = NO 2 Or NHCHO. According to the invention, by introducing nitro and formamido functional groups into the iron-based metal organic framework (Fe-MOFs-X) catalyst, the Fe-MOFs-X catalyst prepared by the method has high electrocatalytic activity and stability of oxygen precipitation in an alkaline environment.

Description

Functionalized metal organic framework nano material, preparation method and application thereof
Technical Field
The invention relates to a functionalized metal organic framework nano material, a preparation method and application thereof, belonging to the technical field of OER (organic electroluminescent) electrocatalysts.
Background
At present, natural resources are limited, and the development of efficient, safe and sustainable clean energy is more and more important. The development of renewable energy is considered as a promising solution to mitigate the global energy crisis and the environmental hazards posed by chemical fuels. Oxygen Evolution Reactions (OERs) are the core reaction processes of several electrochemical energy conversion and storage systems, including water splitting and metal air batteries.
OER kinetics are slow and an effective electrocatalyst is required to overcome the kinetic barrier. Noble metal oxide (RuO) 2 And IrO 2 ) Have been shown to have excellent OER activity, but their high cost and poor electrochemical stability limit their potential for practical large-scale applications. Therefore, exploring new electrocatalysts, it is crucial to find an effective catalyst design strategy. Among various novel materials, metal Organic Framework (MOFs) nanomaterials are considered as promising OER electrocatalyst materials. MOFs are a class of crystalline porous materials with periodic arrangement self-assembled by metal ion ' centers ' and organic ligand ' frameworksMOFs, a new class of porous materials, exhibit unique pore size structures, and abundant metal/ligand combinations compared to traditional porous materials.
At present, a great deal of research shows that the excellent OER performance of MOFs is often closely related to metals. For example, the metal is an active site of OER, a coordination unsaturated site of the metal, formation of a metal valence state, a coupling effect of different metal ions in the MOFs, addition and doping of the metal, and the like. However, little research has been done on the effect of organic ligands on electrocatalytic performance. The selection of the organic ligand can influence the final framework structure of the MOFs, and the catalytic performance of the MOFs is improved by influencing the appearance and the active site structure of the MOFs. The organic ligand can not only be matched with metal to form a specific framework structure, but also can obtain the flexibility of the organic ligand, the selectivity of functional groups and the like. In addition, different pore structures can be provided by different configurations, and the functional groups on the ligand can also adjust the properties of electrons, so that specific gas molecules are adsorbed, and the catalytic activity is improved.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a functionalized metal organic framework nano material, a preparation method and application thereof. The invention introduces nitro and formamido functional groups into an iron-based metal organic framework (Fe-MOFs-X) catalyst. The invention is realized by the following technical scheme.
A functionalized metal organic framework nano material has a simple structure of Fe-MOFs-X, wherein X = NO 2 Or NHCHO; the specific structure is as follows:
Figure BDA0003176329190000021
or
Figure BDA0003176329190000022
A preparation method of a functionalized metal organic framework nano material comprises the following specific steps:
step 1, dissolving 0.1mmol of organic ligand 2-nitroterephthalic acid or 2-formamido terephthalic acid and 0.1mmol of iron salt in an organic solvent, and heating at 130-180 ℃ for 2-5h for hydrothermal reaction to obtain a reaction product;
step 2, cooling the reaction product obtained in the step 1 to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and then drying to obtain the functionalized metal organic framework nano material catalyst Fe-MOFs-X, wherein X = NO 2 Or NHCHO.
The solid-liquid ratio of the organic ligand to the organic solvent in the step 1 is 1.5-1.
In the step 1, the ferric salt is ferric chloride hexahydrate.
The organic solvent in the step 1 is N, N-dimethylacetamide.
A functionalized metal organic framework nano material can be applied to electrocatalytic OER reaction.
The OER application method of the functionalized metal organic framework nano material comprises the following steps: adding 300 mu L of 0.5 percent Nafion ethanol solution and 200 mu L of deionized water into 10mg of MOFs catalyst, and then carrying out water bath ultrasonic treatment to uniformly disperse the mixture into suspension; then 25. Mu.L of the suspension was added dropwise to an area of 0.5cm 2 On the foamed nickel electrode; naturally drying the electrode at room temperature before measurement; the content of the catalyst is 1mg/cm 2 。
The invention has the beneficial effects that:
(1) The Fe-MOFs-X catalyst prepared by the method has consistent framework structure, and the introduction of the ligand substituent does not influence the framework structure of the Fe-MOFs.
(2) The Fe-MOFs-X catalyst prepared by the invention has higher electrocatalytic activity and stability of oxygen precipitation in an alkaline environment.
Drawings
FIG. 1 shows the Solvothermal method of Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And a comparison graph of a powder X-ray diffraction (XRD) pattern of Fe-MOFs-NHCHO prepared in example 2 and an XRD pattern of single crystal fitting thereof;
FIG. 2 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And Fourier Infrared Spectroscopy (FT-IR) of Fe-MOFs-NHCHO prepared in example 2;
FIG. 3 is a Field Emission Scanning Electron Microscope (FESEM) image of Fe-MOFs prepared in comparative example;
FIG. 4 shows Fe-MOFs-NO prepared in example 1 2 FESEM image of (B);
FIG. 5 is a FESEM photograph of Fe-MOFs-NHCHO prepared in example 2;
FIG. 6 is a Transmission Electron Microscope (TEM) image of Fe-MOFs prepared in comparative example;
FIG. 7 shows Fe-MOFs-NO prepared in example 1 2 A TEM image of (B);
FIG. 8 is a TEM image of Fe-MOFs-NHCHO prepared in example 2;
FIG. 9 is a High Resolution Transmission Electron Microscopy (HRTEM) image of Fe-MOFs prepared in comparative example;
FIG. 10 shows Fe-MOFs-NO prepared in example 1 2 HRTEM image of (A);
FIG. 11 is a HRTEM image of Fe-MOFs-NHCHO prepared in example 2;
FIG. 12 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And C1s high resolution X-ray photoelectron spectroscopy (XPS) spectra of Fe-MOFs-NHCHO prepared in example 2;
FIG. 13 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And a comparison graph of N1s high resolution XPS spectrum of Fe-MOFs-NHCHO prepared in example 2;
FIG. 14 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And a comparison graph of O1s high resolution XPS spectra of Fe-MOFs-NHCHO prepared in example 2;
FIG. 15 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And a comparative graph of Fe2p high resolution XPS spectrum of Fe-MOFs-NHCHO prepared in example 2;
FIG. 16 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And Fe-MOFs-NHCHO catalyst and commercial IrO prepared in example 2 2 IR-corrected polarization curves in 1M KOH solution at room temperature;
FIG. 17 shows Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And Fe-MOFs-NHCHO prepared in example 2 and commercial IrO 2 Tafel plot in electrocatalytic oxygen evolution reaction.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
In order to better compare the influence of the introduced functional group on the MOFs framework structure and the electrocatalytic OER performance thereof, the non-functional group iron-based metal organic frameworks (Fe-MOFs) were synthesized by the same synthesis method through the comparative example.
The flow charts of the invention and the comparative example are as follows
Figure BDA0003176329190000041
Example 1
The functionalized metal organic framework nano material has a simple structure of Fe-MOFs-X, wherein X = NO 2 (ii) a The specific structure is as follows:
Figure BDA0003176329190000042
the preparation method of the functionalized metal organic framework nano material comprises the following specific steps:
step 1, dissolving 0.1mmol of organic ligand 2-nitroterephthalic acid and 0.1mmol of iron salt (ferric salt is ferric chloride hexahydrate) in an organic solvent (N, N-dimethylacetamide), heating at 150 ℃ for 3h to perform hydrothermal reaction, wherein the solid-to-liquid ratio of the organic ligand to the organic solvent is 1;
step 2, cooling the reaction product obtained in the step 1 to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and then drying to obtain the functionalized metal organic framework nano material catalyst Fe-MOFs-X, wherein X = NO 2 。
Example 2
The functionalized metal organic framework nano material has a simple structure of Fe-MOFs-X, wherein X = NHCHO; the specific structure is as follows:
Figure BDA0003176329190000051
the preparation method of the functionalized metal organic framework nano material comprises the following specific steps:
step 1, dissolving 0.1mmol of organic ligand 2-formylamino terephthalic acid and 0.1mmol of iron salt (ferric salt is ferric chloride hexahydrate) in an organic solvent (N, N-dimethylacetamide), heating the organic ligand and the organic solvent at 150 ℃ for 3h to perform hydrothermal reaction to obtain a reaction product, wherein the solid-to-liquid ratio of the organic ligand to the organic solvent is 1;
and 2, cooling the reaction product obtained in the step 1 to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and drying to obtain the functionalized metal organic framework nano material catalyst Fe-MOFs-X, wherein X = NHCHO.
Comparative examples
Step 1, dissolving 0.1mmol of organic ligand 1, 4-terephthalic acid and 0.1mmol of iron salt (ferric salt is ferric chloride hexahydrate) in an organic solvent (N, N-dimethylacetamide), wherein the solid-to-liquid ratio of the organic ligand to the organic solvent is 1.7 g/L, and heating at 150 ℃ for 3h to carry out hydrothermal reaction to obtain a reaction product;
and 2, cooling the reaction product obtained in the step 1 to room temperature, carrying out suction filtration through an organic microporous filter membrane, washing the suction filtration object sequentially with deionized water and an ethanol organic solvent, and then drying to obtain the Fe-MOFs.
Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 And the Fe-MOFs-NHCHO prepared in the embodiment 2 is subjected to structural and morphological characterization:
shown in FIG. 1 as Fe-MOFs and Fe-MOFs-NO 2 And XRD patterns of Fe-MOFs-NHCHO show that XRD diffraction peaks of MOFs formed by assembling three organic ligands and iron salt correspond to peaks of single crystal fitting (CCDC: 695105). Functional group functionalized Fe-MOFs-X (X = NO) 2 NHCHO) are consistent with Fe-MOFs, which shows that the introduction of ligand substituent does not affect the framework structure of MOFs.
As shown in FIG. 2, the molecular structures of three MOFs were verified by FT-IR. Fe-MOFs-NO 2 And the FT-IR spectrum of the Fe-MOFs-NHCHO samples was similar to that of Fe-MOFs without functional group substitution. All samples were at 3423cm -1 ，750cm -1 ，536cm -1 All have the same characteristic absorption peak and are respectively attributed to stretching vibration of a benzene ring O-H, bending vibration of C-H and Fe-O bond vibration between ligand carboxyl and Fe ions. The three MOFs samples were at 1379cm -1 And 1580cm -1 Two strong absorption peaks corresponding to the symmetric vibration (v) of carboxyl respectively s -COO-) and asymmetric vibration (v) as -COO-), confirming the presence of the dicarboxylic acid linker. For Fe-MOFs-NO 2 ，1536cm -1 Characteristic absorption peak at (A) corresponding to the functional group-NO 2 The vibration of (2). For Fe-MOFs-NHCHO, at 1254cm -1 ，1295cm -1 ，1688cm -1 The characteristic peaks of (a) correspond to the C-N tensile vibration, N-H bending vibration and C = O vibration absorption peaks of the-NHCHO functional group, respectively.
As shown in FIG. 3, FESEM shows that the Fe-MOFs sample is a rod-like nano structure with rough surface, diameter of about 210nm and average length of about 940nm. However, the introduction of functional groups causes significant changes in the surface morphology of the catalyst. As shown in FIG. 4, fe-MOFs-NO 2 A sheet stacking structure is shown. As shown in FIG. 5, fe-MOFs-NHCHO showed a bulk structure with an average length of about 120 nm. Different functional groups are introduced through organic ligands to influence the morphology and the size of MOFs. The microstructure was further confirmed as shown in FIG. 6, which is a TEM image of Fe-MOFs as catalysts. Shown in FIGS. 7 and 8 as Fe-MOFs-NO, respectively 2 And TEM images of Fe-MOFs-NHCHO samples.
As shown in FIG. 9, highly ordered lattice fringes can be clearly seen in HRTEM images of Fe-MOFs, indicating better crystallinity. The distance of the lattice fringes is 0.28nm, corresponding to the (0-24) crystal planes of Fe-MOFs. As shown in FIGS. 10 and 11, fe-MOFs-NO 2 And the lattice fringe of the Fe-MOFs-NHCHO sample with the distance of 0.28nm shows that the skeleton of the MOFs is not changed after the functional group is introduced.
Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 XPS analysis with Fe-MOFs-NHCHO prepared in example 2:
the Fe-MOFs and Fe-MOFs-NO were further analyzed by XPS 2 And the chemical composition and state of the Fe-MOFs-NHCHO samples. XPS analysis shows that Fe, C and O, containing-NHCHO and-NO, are present in all MOFs 2 N is present in the MOFs of the functional group substituent.
FIG. 12 is a C1s high resolution XPS plot of three MOFs samples with peak distributions of 284.8eV, 286.04eV and 288.6eV assigned to C = C/C-C, C-O/C-N and O-C = O for the organic ligands. The fitting result shows that Fe-MOFs-NO 2 And the content of C-O/C-N in the Fe-MOFs-NHCHO sample is increased compared with that in the Fe-MOFs sample, which corresponds to the introduced functional group.
FIG. 13 shows Fe-MOFs-NO 2 And N1s high resolution XPS spectra of Fe-MOFs-NHCHO. For Fe-MOFs-NO 2 Wherein the peaks at 400.45eV and 399.8eV are assigned to C-N and N-O, respectively, of the nitro group. In addition, the N1s high resolution XPS spectra of Fe-MOFs-NHCHO, peaks at 400.42eV and 399.3eV, respectively, are attributed to C-N and C-N = O of the formylamino group.
FIG. 14 shows Fe-MOFs and Fe-MOFs-NO 2 And the O1s high resolution XPS spectrum of Fe-MOFs-NHCHO. Wherein 531.0, 531.7 and 533.1eV are associated with the Fe-O bond, the carboxylic acid group of the organic ligand and the absorbed water, respectively. For Fe-MOFs-NO 2 A new peak at 532.7eV occurs due to the N-O of the nitro group. A new peak at 532.3eV for Fe-MOFs-NCHO appears due to N-C = O of the formylamino group.
FIG. 15 shows Fe-MOFs and Fe-MOFs-NO 2 And Fe2p high resolution XPS spectra of Fe-MOFs-NHCHO. The binding energies of Fe2p XPS spectra of Fe-MOFs are respectively 711.4 and 725.1eV, and are assigned to Fe2p 3/2 And Fe2p 1/2 Indicating the presence of Fe 3+ In the oxidized state. Fe2p in comparison with Fe-MOFs 3/2 In Fe-MOFs-NO 2 And Fe-MOFs-NHCHO exhibit positive shifts of about 0.2eV and 0.4eV, respectively. This change in binding energy indicates that the defect strain causes a change in Fe-O bond length due to the introduction of functional groups in the ligandCaused by an enzyme. The defect strain of the material can improve the electrocatalytic activity of the catalyst, and the degree of the defect strain has different influences on the electrocatalytic activity.
Fe-MOFs prepared in comparative example, fe-MOFs-NO prepared in example 1 2 Application of OER reaction catalyst with Fe-MOFs-NHCHO prepared in example 2 for evaluation and comparison of Fe-MOFs, fe-MOFs-NO 2 And the catalytic activity of the Fe-MOFs-NHCHO catalyst, foamed Nickel (NF) is taken as a substrate, and the test conditions are as follows: the foam nickel electrode prepared by adopting an OER application method of the functionalized metal organic framework nano material, a three-electrode system, 1.0M KOH solution saturated by oxygen and room temperature conditions.
FIG. 16 shows Fe-MOFs and Fe-MOFs-NO 2 Fe-MOFs-NHCHO and commercial IrO 2 At 1mV s -1 At low scan rates, the polarization curve is obtained by IR rectification. Fe-MOFs-NHCHO at 10mA cm in all MOFs samples -2 Exhibits a minimum overpotential of 246mV, compared to Fe-MOFs-NO 2 (257 mV), fe-MOFs (283 mV), and commercial IrO 2 (335 mV) were low. These results indicate that introduced-NO 2 or-NHCHO functional group can improve the catalytic activity of OER.
FIG. 17 shows Fe-MOFs and Fe-MOFs-NO 2 Fe-MOFs-NHCHO and commercial IrO 2 Tafel slope based on polarization curve. The Tafel slope of the Fe-MOFs-NHCHO catalyst is 37.5mV dec -1 This ratio is Fe-MOFs-NO 2 (38.3mV dec -1 )、Fe-MOFs(41.6mV dec -1 ) And IrO 2 (85.4mV dec -1 ) Are small, indicating that the reaction kinetics are more favorable in the OER process.
Due to the functional group-NO of the benzene ring in the ligand 2 Or the steric hindrance of the-NHCHO group to cause rotation of the-COO-group. The larger the steric hindrance, the larger the angle between the-COO-group and the benzene ring, the strain effect can be caused by the rotation of the-COO-group in the ligand, and the electronic structure of iron is further influenced, which is consistent with the results of XRD and XPS. The introduction of functional groups weakens the coordination between carboxyl and Fe, promotes the low electron affinity of-COO-connector in unsaturated coordination ligand of metal to increase the unoccupied state density of Fe and strengthenThe bonding strength of the active Fe sites and the reaction intermediates is improved, so that the OER activity of the MOFs catalyst is improved.
Example 3
The functionalized metal organic framework nano material has a simple structure of Fe-MOFs-X, wherein X = NHCHO; the specific structure is as follows:
Figure BDA0003176329190000081
the preparation method of the functionalized metal organic framework nano material comprises the following specific steps:
step 1, dissolving 0.1mmol of organic ligand 2-formamido terephthalic acid and 0.1mmol of iron salt (ferric salt is ferric chloride hexahydrate) in an organic solvent (N, N-dimethylacetamide) with a solid-liquid ratio of the organic ligand to the organic solvent of 1.5g/L, and heating at 150 ℃ for 5h for hydrothermal reaction to obtain a reaction product;
and 2, cooling the reaction product obtained in the step 1 to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and drying to obtain the functionalized metal organic framework nano material catalyst Fe-MOFs-X, wherein X = NHCHO.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (4)

1. A functionalized metal organic framework nanomaterial for electrocatalytic OER reaction, characterized by: the functionalized metal organic framework nano material has a simple structure of Fe-MOFs-NHCHO, and the specific structure is as follows:
Figure FDF0000020461760000011
the preparation method of the functionalized metal organic framework nano material comprises the following specific steps:
step 1, dissolving 0.1mmol of organic ligand 2-formamido terephthalic acid and 0.1mmol of iron salt in an organic solvent, heating at 130-180 ℃ for 2-5h for hydrothermal reaction to obtain a reaction product;
and 2, cooling the reaction product obtained in the step 1 to room temperature, performing suction filtration through an organic microporous filter membrane, washing the filtrate with deionized water and an ethanol organic solvent in sequence, and drying to obtain the functionalized metal organic framework nano material catalyst.
2. The functionalized metal-organic framework nanomaterial of claim 1, wherein: the solid-liquid ratio of the organic ligand to the organic solvent in the step 1 is 1.5-1.
3. The functionalized metal-organic framework nanomaterial of claim 1, wherein: in the step 1, the ferric salt is ferric chloride hexahydrate.
4. The functionalized metal-organic framework nanomaterial of claim 1, wherein: the organic solvent in the step 1 is N, N-dimethylacetamide.
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