Cu-mof porous material and preparation method and application thereof

Abstract

The application discloses a Cu-MOF porous material and a preparation method and application thereof, and the preparation method comprises the following steps: S1, forming a 3D printing hydrogel matrix with a preset shape by 3D printing of a hydrogel precursor ink; and S2, obtaining the Cu-MOF porous material by reacting the hydrogel matrix in a copper source; the Cu-MOF is a metal organic framework material which is composed of copper ions as nodes and uniform benzenetricarboxylic acid ligands as pillars; the preparation method of the Cu-MOF porous material is simple, the yield is high, the prepared complex has good stability, is convenient to preserve, has good selectivity to CO2, and can realize efficient and simple specific detection of CO2.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal organic framework material preparation, and specifically relates to a Cu-MOF porous material and a preparation method and application thereof. Background Art

[0002] Global warming is mainly caused by carbon dioxide and other harmful gases (NO x ,SO x CO2 is caused by the emission of CO2 (and volatile organic compounds) into the atmosphere, which mainly comes from human industrial activities and vehicles. In addition, if the concentration of CO2 exceeds the safe level, it can cause symptoms such as fatigue, headaches, anxiety, lack of energy, jelly legs and lung ventilation. Therefore, it is crucial to have a reliable CO2 sensor. Currently, commonly used CO2 detection methods include CO2 sensors based on non-dispersive infrared (NDIR), solid-state electrolytes and metal oxides. However, high power consumption, high cost and harsh operating conditions limit their application.

[0003] Therefore, it is urgent to provide an efficient and simple method for detecting carbon dioxide. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a method for preparing a Cu-MOF porous material. The material preparation method is simple and has a high yield. The prepared complex is stable and easy to store. It also has good selectivity for CO2, enabling efficient and simple specific detection of CO2.

[0005] The second aspect of the present invention proposes an application of the Cu-MOF porous material prepared by the preparation method in carbon dioxide detection.

[0006] According to a first aspect of the present invention, a method for preparing a Cu-MOF porous material comprises:

[0007] S1: 3D printing the hydrogel precursor ink to form a 3D printed hydrogel matrix with a preset shape;

[0008] S2: reacting the hydrogel matrix in a copper source to obtain a Cu-MOF porous material;

[0009] The Cu-MOF is a metal organic framework material composed of copper ions as nodes and pyromellitic acid ligands as pillars.

[0010] According to the embodiments of the first aspect of the present invention, there are at least the following beneficial effects:

[0011] In the present invention, Cu-MOF is prepared by 3D printing. The preparation method is simple and the yield is high. The prepared complex has good stability and is easy to preserve. It also has good sensing performance for CO2 and can achieve specific recognition of CO2.

[0012] According to some preferred embodiments of the present invention, the method for preparing the Cu-MOF porous material includes:

[0013] S1: 3D printing and UV curing of hydrogel precursor ink to form a 3D printed hydrogel matrix with a preset shape;

[0014] S2: reacting the hydrogel matrix in a copper source to obtain a Cu-MOF porous material;

[0015] The Cu-MOF is a metal organic framework material composed of copper ions as nodes and pyromellitic acid ligands as pillars.

[0016] According to some embodiments of the present invention, the 3D printing printer includes a DLP printer.

[0017] According to some embodiments of the present invention, the UV curing uses a 405nm UV light source.

[0018] According to some embodiments of the present invention, in step S2, the reaction time is 24 to 25 hours.

[0019] According to some embodiments of the present invention, raw materials for preparing the hydrogel precursor ink include functional group monomers, a cross-linking agent, and a photoinitiator.

[0020] According to some embodiments of the present invention, the mass ratio of the functional group monomer, the cross-linking agent and the photoinitiator is 960:5 to 20:4.

[0021] According to some embodiments of the present invention, the raw materials for preparing the hydrogel precursor ink further include a solvent.

[0022] According to some embodiments of the present invention, the raw materials for preparing the hydrogel precursor ink further include ammonia water.

[0023] According to some embodiments of the present invention, the photoinitiator includes (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO).

[0024] According to some embodiments of the present invention, the functional group monomer includes at least one of acrylic acid and acrylamide.

[0025] The above functional group monomers and mass ratios ensure the excellent tensile properties of the Cu-MOF porous material.

[0026] According to some embodiments of the present invention, the cross-linking agent comprises polyethylene glycol (diol) diacrylate (PEGDA).

[0027] According to some embodiments of the present invention, the solvent includes water and N,N-dimethylacetamide.

[0028] According to some embodiments of the present invention, the molar ratio of the copper source to the trimesic acid is 5 to 10:1.

[0029] According to some embodiments of the present invention, the copper source includes copper nitrate.

[0030] According to some embodiments of the present invention, the method for preparing the hydrogel precursor ink includes mixing and reacting raw materials for preparing the hydrogel precursor ink.

[0031] According to some embodiments of the present invention, the reaction temperature is 60-80°C.

[0032] Application of the Cu-MOF porous material prepared by the above preparation method according to the second aspect of the present invention in carbon dioxide detection

[0033] The Cu-MOF prepared by 3D printing in the present invention has a fine microstructure and high sensing sensitivity in the detection of CO2. Using the 3D printed Cu-MOF as a sensor, the change in the conductivity of the Cu-MOF porous material is utilized to detect CO2 gas, thereby achieving specific identification of CO2. The operation is simple, convenient and efficient.

[0034] Other features and advantages of the present invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0036] Figure 1 A minimum asymmetric unit of the Cu-MOF prepared in Example 1;

[0037] Figure 2 This is a super depth-of-field image of the Cu-MOF prepared in Example 1;

[0038] Figure 3 This is the XRD pattern of Cu-MOF prepared in Example 1;

[0039] Figure 4 This is the infrared spectrum of the Cu-MOF prepared in Example 1;

[0040] Figure 5 This is the thermogravimetric analysis diagram of the Cu-MOF prepared in Example 1;

[0041] Figure 6 This is a diagram of the 3D printed Cu-MOF prepared in Example 1 as a CO2 sensor device;

[0042] Figure 7 Detail of the homemade electrode when the 3D-printed Cu-MOF prepared in Example 1 is used as a gas sensor;

[0043] Figure 8 IV curves of the 3D-printed Cu-MOF prepared in Example 1 in different gas atmospheres when used as a gas sensor. DETAILED DESCRIPTION

[0044] The following will be a clear and complete description of the concept of the present invention and the technical effects produced in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without paying creative work are within the scope of protection of the present invention. The raw materials of the present invention are all commercially available.

[0045] Example 1

[0046] This embodiment provides a method for preparing 3D printed Cu-MOF as follows:

[0047] (1) Acrylamide (10 g), acrylic acid (2 g), polyethylene glycol (glycol) diacrylate (PEGDA) (0.0625 g), (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) (0.05 g), trimesic acid ligand (0.42 g), water (15 g), N,N-dimethylacetamide (5 g) and 4 drops of ammonia were mixed and heated to 80 °C with stirring until completely dissolved to prepare a hydrogel precursor ink;

[0048] (2) The prepared hydrogel precursor ink was loaded into an ink cartridge, and the Cu-MOF hydrogel was printed by a DLP printer with a z-axis resolution of 50 μm and a 405 nm UV light source. The printed model was converted into an STL file using Solidworks. A three-dimensional solid model was obtained by bottom-up printing and layer-by-layer curing. The bottom layer irradiation time was set to 10 s to ensure that the model adhered to the printing stage, and the irradiation time of each layer was 7 s. Finally, the printed sample was washed with ethanol to remove the residual precursor solution on the surface;

[0049] (3) The 3D-printed sample was immersed in 0.02 L of Cu(NO3)2 (1 mol / L) solution for 24 h to promote the in situ synthesis of Cu-MOF, thereby obtaining the 3D-printed Cu-MOF porous material.

[0050] The structure of Cu-MOF is as follows Figure 1 As shown, the minimum asymmetric unit includes one crystallographically independent copper ion and one trimesic acid ligand.

[0051] Ultra-depth images of 3D printed Cu-MOF Figure 2 As shown, it shows that the material model has a microstructure with high accuracy.

[0052] The XRD and IR spectra of Cu-MOF are shown in Figure 2. Figure 3 、 Figure 4 shown.

[0053] The purity of the crystalline material of the substance was confirmed by X-ray diffraction (XRD) measurements at room temperature. Figure 3 The positions of all peaks in the experimental data of the substance are basically consistent with the positions of all peaks in the simulation (XRD) pattern produced by the corresponding X-ray diffraction, which clearly shows that the sample of the substance has a high purity.

[0054] Thermal stability is an important parameter of the complex. In order to study the thermal stability of the material, a thermogravimetric test was conducted on it. Under argon protection, the temperature was raised from 30℃ to 700℃ at a rate of 10℃ / min. Figure 5 As shown, the TG curve shows that the residual weight of the Cu-MOF hydrogel composite is about 17%, which is attributed to the fact that the main components of the residue are CuO and a small amount of carbon.

[0055] The three-necked flask was evacuated for 1 h as a closed space for gas sensing, and the conductivity test was performed using a homemade electrode through an electrochemical workstation under normal pressure of the corresponding gas, such as Figure 6 After each test, the three-necked flask was evacuated for 30 minutes.

[0056] The 3D printed Cu-MOF hydrogel was placed between stainless steel electrodes as a homemade electrode, e.g. Figure 7 shown.

[0057] Different gases were introduced into a three-necked flask containing a 3D printed Cu-MOF hydrogel self-made electrode to test the effect of different gases on conductivity. The results are as follows: Figure 8As shown, only CO2 has a significant enhancement on the conductivity, while other gases have almost no effect on the conductivity, indicating that the 3D printed Cu-MOF sensor has good selectivity for CO2. The present invention gives the Cu-MOF microstructure through 3D printing technology, which increases the contact area between the gas and the device, has higher sensitivity and lower detection limit, and can achieve specific identification and detection of CO2.

[0058] Example 2

[0059] This embodiment provides a method for preparing 3D printed Cu-MOF as follows:

[0060] (1) Acrylamide (10 g), acrylic acid (2 g), polyethylene glycol (glycol) diacrylate (PEGDA) (0.0625 g), (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) (0.05 g), trimesic acid ligand (0.42 g), water (15 g), N,N-dimethylacetamide (5 g) and 4 drops of ammonia were mixed and heated to 80 °C with stirring until completely dissolved to prepare a hydrogel precursor ink;

[0061] (2) The prepared hydrogel precursor ink was loaded into an ink cartridge, and the Cu-MOF hydrogel was printed by a DLP printer with a z-axis resolution of 50 μm and a 405 nm UV light source. The printed model was converted into an STL file using Solidworks. A three-dimensional solid model was obtained by bottom-up printing and layer-by-layer curing. The bottom layer irradiation time was set to 10 s to ensure that the model adhered to the printing stage, and the irradiation time of each layer was 7 s. Finally, the printed sample was washed with ethanol to remove the residual precursor solution on the surface;

[0062] (3) The 3D-printed sample was immersed in 0.015 L of Cu(NO3)2 (1 mol / L) solution for 24 h to promote the in situ synthesis of Cu-MOF, thereby obtaining the 3D-printed Cu-MOF porous material.

[0063] Example 3

[0064] This embodiment provides a method for preparing 3D printed Cu-MOF as follows:

[0065] (1) Acrylamide (10 g), acrylic acid (2 g), polyethylene glycol (glycol) diacrylate (PEGDA) (0.0625 g), (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) (0.05 g), trimesic acid ligand (0.42 g), water (15 g), N,N-dimethylacetamide (5 g) and 4 drops of ammonia were mixed and heated to 80 °C with stirring until completely dissolved to prepare a hydrogel precursor ink;

[0066] (2) The prepared hydrogel precursor ink was loaded into an ink cartridge, and the Cu-MOF hydrogel was printed by a DLP printer with a z-axis resolution of 50 μm and a 405 nm UV light source. The printed model was converted into an STL file using Solidworks. A three-dimensional solid model was obtained by bottom-up printing and layer-by-layer curing. The bottom layer irradiation time was set to 10 s to ensure that the model adhered to the printing stage, and the irradiation time of each layer was 7 s. Finally, the printed sample was washed with ethanol to remove the residual precursor solution on the surface;

[0067] (3) The 3D-printed sample was immersed in 0.01 L of Cu(NO3)2 (1 mol / L) solution for 24 h to promote the in situ synthesis of Cu-MOF, thereby obtaining the 3D-printed Cu-MOF porous material.

[0068] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. Application of a Cu-MOF porous material in carbon dioxide detection; characterized in that, The preparation method of the Cu-MOF porous material comprises: S1: 3D printing the hydrogel precursor ink to form a 3D printed hydrogel matrix with a preset shape; S2: reacting the hydrogel matrix in a copper source to obtain a Cu-MOF porous material; The Cu-MOF is a metal organic framework material composed of copper ions as nodes and pyromellitic acid ligands as pillars; The raw materials for preparing the hydrogel precursor ink include functional group monomers, cross-linking agents, photoinitiators and ammonia water; The photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO); The functional group monomers are acrylic acid and acrylamide; The cross-linking agent is polyethylene glycol (diol) diacrylate (PEGDA).

2. The use according to claim 1, characterized in that The molar ratio of the copper source to the trimesic acid is 5-10:

1.

3. The use according to claim 1, characterized in that The copper source includes copper nitrate.

4. The use according to claim 1, characterized in that The method for preparing the hydrogel precursor ink comprises mixing and reacting raw materials for preparing the hydrogel precursor ink.

5. The use according to claim 4, characterized in that The reaction temperature is 60-80°C.

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