CN113501964B - Three-dimensional copper carboxylate fullerene metal organic framework material and preparation method and application thereof - Google Patents
Three-dimensional copper carboxylate fullerene metal organic framework material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of photo-thermal functional coordination polymer materials, and discloses a three-dimensional copper carboxylate fullerene metal organic framework material, and a preparation method and application thereof. Wherein the chemical formula of the material is { [ Cu ] 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 ‑η 2 :η 2 :η 2 ) 2 ‑C 60 ]·2.5(C 11 H 10 )} n And n is a non-zero natural number. The preparation method of the material comprises the following steps: mixing hexafluoroglutaric acid, cuprous oxide and C 60 The 1-methylnaphthalene solution is prepared by mixing, and then carrying out ultrasonic treatment, heating, cleaning and drying. The invention realizes the rapid preparation of the three-dimensional copper carboxylate fullerene metal organic framework material in a single crystal form by a solvothermal synthesis method, the photo-thermal conversion efficiency of the prepared material is as high as 86.19 percent, and the material has better photo-thermal stability, can be recycled for many times, and has huge application prospect in the aspects of photo-thermal functional materials and laser-assisted treatment.
Description
Technical Field
The invention relates to the technical field of photo-thermal conversion functional coordination polymer materials, in particular to a three-dimensional copper carboxylate fullerene metal organic framework material and a preparation method and application thereof.
Background
C 60 Is the third carbon allotrope reported in 1985. C 60 Is a spherical molecule consisting of 60 carbon atoms and having a relative molecular mass of 720, C 60 Having 30 carbon-carbon double bonds, each carbon atom providing 1 p orbital electron overlapping each other to form a conjugated system containing 30 pairs of pi electrons. Due to its unique spherical molecular structure and its electronic structure, it is applicable to light and heatThe field of special materials such as electricity, magnetism, etc. has been widely studied. However, at present C 60 Related materials have not been studied on the photothermal functional material.
The design and synthesis of the photo-thermal functional material with high near-infrared light thermal conversion efficiency at present mainly starts from the following two aspects: 1. enhancing the absorption of near infrared light by the molecules; 2. limiting the radiative transitions of the molecule. And C 60 The complex has the two properties at the same time, and is an ideal molecule for designing and synthesizing the near infrared thermal conversion efficiency. C 60 The complex material mainly passes through [6,6 ]]The pi electrons on the bond are directly coordinated with metal ions. The coordination of the metal can obviously improve the absorption efficiency of the material to visible light, and is beneficial to improving the photo-thermal conversion efficiency of the material. But of the existing C 60 Most of transition metals adopted by the complex material are noble metals such as Pd, Pt, Ru, Os, Rh, Ir and the like, so that the cost is high, and the practical application of the complex material is severely restricted; in addition, most of C 60 The complex is prepared by a traditional low-temperature solution method, namely, the complex is prepared by a low-boiling-point solvent at normal temperature or at the temperature not higher than the boiling point of the solvent and under the condition of normal pressure (1 atmosphere). Most of the complexes prepared by the low-temperature solution method are oligonuclear molecular complexes, and the photothermal conversion capacity and the photothermal stability are very limited, so that the photothermal conversion efficiency is not high; meanwhile, a part of the complex belongs to amorphous nano materials, and the crystal structure of the complex is not clear, so that the study of the relationship between the structure and the functional property is not facilitated.
Disclosure of Invention
The invention provides a three-dimensional copper carboxylate fullerene metal organic framework material and a preparation method and application thereof.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
the chemical formula of the three-dimensional copper carboxylate fullerene metal organic framework material is { [ Cu { [ 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n And n is a non-zero natural number. Wherein, mu 3 Is represented by C 60 Coordinated to 3 Cu, eta 2 Represents Cu and C 60 In a coordination mode of one Cu and C 60 One C ═ C double bond coordination.
As a further improvement of the above scheme, the { [ Cu { [ 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n Is monoclinic system, P2/a space group.
The invention also provides a preparation method of the three-dimensional copper carboxylate fullerene metal organic framework material, which comprises the following steps:
step one, taking C 60 Adding the mixture into a 1-methylnaphthalene solution, and carrying out ultrasonic treatment to obtain a mixture A;
step two, mixing cuprous oxide, hexafluoroglutaric acid and the mixture A, sealing, and performing ultrasonic treatment to obtain a mixture B;
step three, heating the mixture B to 140-180 ℃, keeping the temperature for 48-72h, and cooling to room temperature at the speed of 2-5 ℃/h to obtain a substance C;
and step four, cleaning the substance C with an aromatic solvent, and then drying to obtain the three-dimensional copper carboxylate fullerene metal organic framework material.
Specifically, the method adopts 1-methylnaphthalene (with a boiling point of 244 ℃) with a high boiling point as a solvent to carry out reaction in a closed container, wherein the reaction temperature is 140 ℃ and 180 ℃, and the pressure generated in the closed container due to high temperature is far higher than normal 1 atmosphere. The method is a new method for preparing novel crystalline coordination polymer functional materials, and the materials have definite crystal structures and higher thermal stability and chemical stability.
As a further improvement of the above aspect, the aromatic solvent is selected from at least one of benzene, toluene, p-xylene, or chlorobenzene.
As a further improvement of the above aspect, said C 60 The molar mass ratio of the hexafluoroglutaric acid to the cuprous oxide is 1 (2-3) to (2-3); adding 0.020-0.045mmol of C into 1mL of 1-methylnaphthalene 60 。
As a further improvement of the scheme, in the step one, the time length of ultrasonic treatment is 10-30 min.
As a further improvement of the scheme, the second step and the third step are carried out under a sealed condition.
As a further improvement of the above solution, the drying in the fourth step is carried out in air.
The invention relates to application of a three-dimensional copper carboxylate fullerene metal organic framework material in a photo-thermal conversion functional material.
The invention directly utilizes C mainly through the self-assembly principle 60 The chemical activity of the C ═ C double bond on the surface is that cuprous oxide is taken as a copper source of cuprous ions, hexafluoroglutaric acid is taken as an auxiliary bridging ligand, methylnaphthalene is taken as an object template molecule, and the three-dimensional copper carboxylate fullerene metal organic framework material is prepared by one-step synthesis through a solvothermal synthesis method. The material can be used as a photo-thermal material, has high photo-thermal conversion efficiency, and has potential application prospects in the aspects of photo-thermal functional materials and laser-assisted treatment. The invention is a first example C 60 The metal complex is a material with the function of photo-thermal conversion.
The invention has the beneficial effects that: the method realizes the rapid preparation of the three-dimensional copper carboxylate fullerene metal organic framework material in a single crystal form by a solvothermal synthesis method, has the advantages of rapidness, convenience, simplicity, cheap raw materials, capability of large-scale preparation and contribution to industrial production and application. The prepared material can be used as a photothermal conversion material, has a high-efficiency photothermal function, has the photothermal conversion efficiency of 86.19 percent, has good photothermal stability, can be recycled for many times, and has a huge application prospect in the aspects of photothermal functional materials and laser-assisted treatment.
Drawings
FIG. 1 is a temperature-variable powder X-ray diffraction (PXRD) spectrum of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis (TGA) spectrum of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 4 is a temperature swing powder X-ray diffraction (PXRD) pattern of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 5 is a solid-state ultraviolet-visible-near infrared (UV-VIS-NIR) absorption spectrum of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 6 shows C in the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 60 A coordination environment map of the molecule;
FIG. 7 is a diagram showing the coordination environment of hexafluoropentanedioic acid anions in the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1;
FIG. 8 is a three-dimensional stacking view of the three-dimensional copper carboxylate fullerene metal-organic framework material in the a-axis direction according to example 1 of the present invention;
FIG. 9 is a three-dimensional stacking view of the three-dimensional copper carboxylate fullerene metal-organic framework material in the b-axis direction according to example 1 of the present invention;
FIG. 10 is a three-dimensional stacking view of the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 in the c-axis direction;
FIG. 11 is a three-dimensional stacking diagram of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 12 is a Scanning Electron Microscope (SEM) image of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 13 is a schematic view of a photothermal conversion test of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 14 is a temperature rise cycle chart of the three-dimensional copper carboxylate fullerene metal-organic framework material of the embodiment 1 of the present invention under laser irradiation with wavelength of 808nm and different power;
FIG. 15 is a Power-Temperature (Power-Temperature) linear graph of the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 16 is a graph of a single photo-thermal cycle of a three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 of the present invention;
FIG. 17 is a temperature lowering diagram of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 18 is a graph of Time-ln θ for cooling of the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1;
FIG. 19 is a photo-thermal cycling diagram of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 20 is a photo-thermal image of a three-dimensional copper carboxylate fullerene metal-organic framework material according to example 1 of the present invention;
FIG. 21 is a powder diffraction pattern of the three-dimensional copper carboxylate fullerene metal-organic framework material of example 1 before and after photo-thermal experiments.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1: synthesis of three-dimensional copper carboxylate fullerene metal organic framework material
Weigh 0.028mmol C 60 Dissolving in 1mL of 1-methylnaphthalene solution, performing ultrasonic treatment for 10min by an ultrasonic instrument, weighing 0.07mmol of hexafluoroglutaric acid and 0.07mmol of cuprous oxide, placing in a 8 x 12mm hard glass tube, and adding 1mL of 1-methylnaphthalene C with concentration of 0.028mmol/mL after ultrasonic treatment 60 Performing ultrasonic treatment on the solution, sealing the glass tube opening by using a water welder (oxyhydrogen machine), placing the glass tube opening into a stainless steel iron box, heating the glass tube opening to 180 ℃ in an oven, keeping the constant temperature for 72 hours, cooling the glass tube opening to the room temperature at the speed of 5 ℃/h,and (3) cleaning the mixture by using paraxylene after open-tube filtration, and naturally drying the mixture at room temperature to obtain a large number of black blocky crystals, namely the three-dimensional copper carboxylate fullerene metal organic framework material (complex for short, the same applies below).
Product performance test 1: characterization of three-dimensional copper carboxylate fullerene metal-organic framework material
The appropriate crystals from example 1 were picked under an optical microscope and placed on a Bruker D8 Venture (run at 25kW power: 45kV, 40 mA) single crystal diffractometer and scanned in an omega/theta fashion using Cu Ka radiation (λ ═ 1.5418) and diffraction data collected at low temperature (100K). The structure was resolved by the direct method (SHELXTL-2018) and F2 was refined using full-matrix minimum multiplication to obtain the coordinates and anisotropy parameters of all non-hydrogen atoms. Specific crystal data are shown in table 1.
The complex is basically characterized by powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) and ultraviolet visible near infrared absorption spectrum (UV-Vis), and the results are shown in figures 1-5, wherein figure 1 is a temperature-variable powder X-ray diffraction (PXRD) spectrum of the complex, and as can be seen from figure 1, the crystal phase of the complex is consistent with simulated powder and has better crystal phase purity (figure 1 is an X-ray diffraction diagram of the temperature-variable powder of the complex, which indicates that the synthesized products all exist in the form of crystals, and the simulated powder is obtained by simulating the crystal structure data measured by single crystal diffraction through software, each peak in figure 1 has one of the table crystal structure, if the actually measured powder diffraction and the single crystal diffraction can be well consistent, the obtained substance has better crystal phase purity, no other crystalline phase impurities). FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of the complex with C present 60 The characteristic peaks associated with hexafluoroglutaric acid indicate that the complex has been synthesized and the data relating to the crystal of the complex is shown in Table 1. FIG. 3 is a Thermogravimetric (TGA) analysis of the complex, showing that the thermal stability of the complex can be stabilized around 100 ℃. FIG. 4 is a temperature-variable powder-X-ray diffraction (PXRD) diagram of the complex, and it can be seen that the crystal phase of the complex can be stabilized to about 100 ℃. FIG. 5 is a solid ultraviolet-visible-near infrared (UV-VIS-NIR) absorbance of the complexAs can be seen from FIG. 5, the complex material has strong absorption in the whole ultraviolet visible near-infrared region.
TABLE 1{ [ Cu ] 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n Crystallographic data
a R 1 ＝∑ hkl (||F o |-|F C ||)/∑ hkl |F o |
As can be seen from Table 1, the chemical formula of the three-dimensional copper carboxylate fullerene organometallic framework material is { [ Cu ] 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n Wherein n is a non-zero natural number, and the material crystal belongs to a monoclinic system P2/a space group. Wherein, C 5 F 6 O 4 Represents a hexafluoropentanedioic acid anion, C 11 H 10 Represents a 1-methylnaphthalene guest molecule.
The crystal structure is shown in fig. 6, 7, 8, 9, 10 and 11. Wherein, FIG. 6 shows a three-dimensional copper carboxylate fullerene metal-organic framework material (middle C) of the present invention 60 Molecule) in a coordination environment (the inventors deleted the guest 1-methylnaphthalene for clarity); FIG. 7 is a diagram showing the coordination environment of the three-dimensional copper carboxylate fullerene metal-organic framework material (of hexafluoropentanedioic acid anion) of the present invention (the guest 1-methylnaphthalene has been deleted by the inventors for clarity of presentation); figure 8 is a three-dimensional packing diagram along the a-axis direction of a three-dimensional copper carboxylate fullerene metal-organic framework material of the present invention (for clarity,the inventors deleted guest 1-methylnaphthalene); FIG. 9 is a three-dimensional stacking view along the b-axis of the three-dimensional copper carboxylate fullerene metal-organic framework material of the present invention (for clarity, the inventors have deleted the guest 1-methylnaphthalene); FIG. 10 is a three-dimensional stacking view along the c-axis of a three-dimensional copper carboxylate fullerene metal-organic framework material of the present invention (the inventors have deleted the guest 1-methylnaphthalene for clarity); FIG. 11 is a three-dimensional packing diagram of a three-dimensional copper carboxylate fullerene metal-organic framework material of the present invention (without any atoms deleted, with a disordered guest molecule, 1-methylnaphthalene, present in the structure). FIG. 12 is a Scanning Electron Microscope (SEM) image of a sample of complex crystals, and FIG. 12 shows that the complex is bulk crystals.
As can be seen from FIG. 6, the copper atoms take a tetracoordinated form, each copper atom being coordinated to the O of two hexafluoroglutaric acids and then by Cu- (eta. -) 2 Form of a- (C ═ C)) bond with C 60 And (4) coordination, wherein the 4 th coordination point forms weak coordination with water molecules. Each C 60 The molecule passes through 6 [6,6 ] of two six-membered rings in opposite positions at both ends]The bond coordinates with 6 Cu (I) atoms to form a hexanuclear fullerene copper coordination unit. Hexafluoroglutaric acid bridges two such hexanuclear fullerene copper coordination units through an O-Cu (I) coordination bond to form a hexa-connection pcu topological network structure (NaCl type network) with the hexanuclear fullerene copper coordination units as hexanodes and with the characteristic of pores, and the pores of the material are filled and occupied by guest molecules of 1-methylnaphthalene. The porosity of the material after removal of the guest molecule 1-methylnaphthalene was 36.6% as calculated by the Platon software.
Product performance test 2: photothermal conversion experiment test of three-dimensional copper carboxylate fullerene metal organic framework material
The three-dimensional copper carboxylate fullerene metal-organic framework material prepared in example 1 is subjected to a photo-thermal conversion experimental test, fig. 13 is a schematic view of the photo-thermal conversion test of the complex, and the related test results and analysis results of the complex are shown in fig. 14-20. FIG. 14 is a temperature-rise cycle chart of the complex under laser irradiation with wavelength 808nm and different powers, and FIG. 15 is a linear dependence chart of the complex on the temperature under different laser powers. As can be seen in FIG. 15, the linear dependence of power on temperature is 0.99668, indicating that the relationship between laser power and temperature appearsBetter linear correlation. FIG. 16 shows that the complex has a wavelength of 808nm and a work rate of 0.570W/cm 2 The single photo-thermal cycle chart (temperature rising and reducing curve) under laser irradiation shows that the complex can reach the maximum temperature of 60.6 ℃ within 300 s.
The calculation formula of the photothermal conversion efficiency is as follows:
in the formula (1), η is the photothermal conversion efficiency; h is the heat transfer coefficient; s is the light receiving area of a sample in the quartz sample cell; delta T max Is the difference between the maximum temperature reached by the sample and the ambient temperature; i is the power of the irradiated laser; a. the 808 Is the ultraviolet-visible absorbance of the complex at 808nm of the wavelength of the irradiating laser.
In this formula (1), since two parameters of h and S are often difficult to be accurately determined, another experimental calculation formula of the photothermal conversion efficiency is usually derived from this formula in the experiment:
in this formula (2), m i The mass of the sample or quartz sample cell; c p,i The specific heat capacity of the sample or the quartz sample cell; tau. s Is the slope of the linear fit of the Time-ln θ curve (fig. 17 and 18). Wherein the content of the first and second substances,
t represents the sample temperature measured as the Time varies during natural cooling, T sur Indicating the ambient temperature, T max The maximum temperature to which the sample rises after being illuminated. Tau is s The method is used for comprehensively measuring the heat transfer (heat dissipation) properties of the sample and the quartz sample pool.
In the present example, the data determined are as follows: t is sur ＝23.8℃，T max ＝60.6℃，ΔT max ＝60.6℃–23.8℃＝36.8℃，I＝0.570W/cm 2 Quartz sample cell m Stone (stone) Specific heat capacity C of quartz is known as 1.3037g p, stone 0.8J/(g · K). τ is derived from the Time-ln θ plot of FIG. 17 s The absorbance a at 808nm was obtained from the solid uv-vis absorption spectrum of fig. 5 (104.4) ═ 104.4 808 ＝0.6875。
Mass m of sample Sample (A) Specific heat capacity C of sample 0.0477g p, sample The measurement calculation is carried out by the following method:
c was obtained by measuring the average specific heat capacity of samples in the range of 35.09384 ℃ to 60.55013 ℃ using a German relaxation-resistant differential thermal scanning calorimeter (NETZSCH DSC 204F1 Phoenix) at a temperature rise rate of 10 ℃/min p, sample ＝1.3549J/(g·K)
Substituting the above experimental data into the experimental calculation formula (2) of the photothermal conversion efficiency, we can obtain:
namely, the photo-thermal conversion efficiency eta of the three-dimensional copper carboxylate fullerene metal-organic framework material is measured and calculated to be 86.19%.
FIG. 19 shows the complex at 808nm and 0.570W/cm power 2 The photothermal cycle chart under laser irradiation of (2) shows that the complex is excellent in photothermal cycle stability as shown in FIG. 19. FIG. 20 is a photothermographic image of the complex. FIG. 21 is a powder diagram before and after photothermal testing of the complex, and it can be seen from FIG. 21 that the crystalline phases before and after photothermal testing of the complex remain perfectly consistent, indicating that the stability of the crystalline phases before and after photothermal testing of the complex is good.
The test and analysis results show that the three-dimensional copper carboxylate fullerene metal organic framework material has high-efficiency photo-thermal conversion efficiency and high photo-thermal stability for near infrared light, and has a great application prospect in the aspect of fullerene photo-thermal conversion functional materials.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the protection scope of the present invention.
Claims (6)
1. The application of the three-dimensional copper carboxylate fullerene metal organic framework material in a photo-thermal conversion functional material;
the preparation method of the three-dimensional copper carboxylate fullerene metal organic framework material comprises the following steps:
step one, taking C 60 Adding the mixture into a 1-methylnaphthalene solution, and carrying out ultrasonic treatment to obtain a mixture A;
step two, mixing cuprous oxide, hexafluoroglutaric acid and the mixture A, sealing, and performing ultrasonic treatment to obtain a mixture B;
step three, heating the mixture B to 140-180 ℃, keeping the temperature for 48-72h, and cooling to room temperature at the speed of 2-5 ℃/h to obtain a substance C;
step four, cleaning the substance C with an aromatic solvent, and then drying to prepare the three-dimensional copper carboxylate fullerene metal organic framework material;
said C is 60 The molar mass ratio of the hexafluoroglutaric acid to the cuprous oxide is 1 (2-3) to (2-3); adding 0.020-0.045mmol of C to each 1mL of 1-methylnaphthalene 60 ；
The chemical formula of the three-dimensional copper carboxylate fullerene metal organic framework material is { [ Cu { [ 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n And n is a non-zero natural number.
2. Use according to claim 1, wherein the aromatic solvent is selected from at least one of benzene, toluene, p-xylene or chlorobenzene.
3. The use according to claim 1, wherein in step one, the duration of the ultrasonic treatment is 10-30 min.
4. The use according to claim 1, wherein both step two and step three are carried out under closed conditions.
5. Use according to claim 1, wherein the drying in step four is carried out in air.
6. The use of claim 1, wherein { [ Cu { [ 3 (C 5 F 6 O 4 ) 3/2 (H 2 O) 3 ] 2 [(μ 3 -η 2 :η 2 :η 2 ) 2 -C 60 ]·2.5(C 11 H 10 )} n Is monoclinic system, P2/a space group.
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