CN111139065B - Bio-based luminescent nano material and preparation method and application thereof - Google Patents
Bio-based luminescent nano material and preparation method and application thereof Download PDFInfo
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- CN111139065B CN111139065B CN202010071084.3A CN202010071084A CN111139065B CN 111139065 B CN111139065 B CN 111139065B CN 202010071084 A CN202010071084 A CN 202010071084A CN 111139065 B CN111139065 B CN 111139065B
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Abstract
The invention relates to a biological-based luminescent nano material, a preparation method and application thereof, and belongs to the technical field of materials. The material takes cellulose nanocrystalline as a core and MOFs as a shell, wherein the cellulose nanocrystalline is directionally arranged in a MOFs cavity. Nanoparticles having a maximum emission wavelength and a maximum excitation wavelength that match the maximum emission wavelength and the maximum excitation wavelength of the cellulose nanocrystals are introduced into the pores of the MOFs in the material, thereby forming derivatives of the material. Because the bio-based luminescent nano material and the derivative thereof have higher luminescent intensity, the two materials can be well used in the fields of information anti-counterfeiting, active substance tracing, biological marking, catalysis or sensing, the two materials have simple preparation process, easy operation, low raw material cost and environmental protection, and are suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a bio-based luminescent nano material, and a preparation method and application thereof.
Background
Cellulose is one of the most abundant renewable biomass materials, and its crystalline form, cellulose nanocrystals, after inducing their regular arrangement, forms chiral nematic structures that selectively reflect circularly polarized light, thereby producing structural colors. By adjusting the periodic arrangement rule, the cellulose nanocrystals can emit light with specific frequency through enhanced resonance scattering under the stimulation of external illumination. Because the photoluminescence phenomenon is photoinduced virtual transition luminescence caused by Stokes scattering, compared with the traditional fluorescent luminescent material, the luminescent material has huge application potential in the related fields of luminescent materials because the luminescence of the luminescent material is not influenced by photobleaching and aggregation-induced quenching.
Metal-organic frameworks (MOFs) hold great promise in a variety of applications, including gas storage, chemical separation, catalysis, sensing, and fuel cells, as well as carrying many foreign species, including lanthanide cations, nanoparticles, and dyes. However, since MOFs have a crystalline nature, they exist mostly in the form of bulk powder or colloidal crystals whose crystal shape is controlled by the crystallization balance of the nucleation process and crystal growth. These MOFs crystal powders are very hard, on the one hand, reducing their required processability and practicality as films, filters and towers, thus limiting their use in these fields; on the other hand, their inherent microporous/mesoporous structure also limits the surface area and diffusion kinetics that they can use, thus rendering them hindered in the application of macromolecules and nanomaterials, which makes many high-value functional properties of nanomofr composites yet to be studied further.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a bio-based luminescent nanomaterial; the second purpose is to provide a preparation method of the bio-based luminescent nano material; thirdly, the application of the biological-based luminescent nano material in the fields of information anti-counterfeiting, active material tracing, biological marking, catalysis or sensing is provided; the fourth object is to provide derivatives of the bio-based luminescent nanomaterial; the fifth purpose is to provide a preparation method of the derivative of the biological-based luminescent nano material; the sixth purpose is to provide the application of the derivative of the biological-based luminescent nano material in the fields of information anti-counterfeiting, active substance tracing, biological marking, catalysis or sensing.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a bio-based luminescent nano material takes cellulose nanocrystals as cores and MOFs as shells, and the cellulose nanocrystals are arranged in a directional manner in a cavity of the MOFs.
Preferably, the MOFs are one of MOFs containing carboxylic acid ligands, MOFs containing nitrogen heterocyclic ligands, or MOFs containing a mixture of carboxylic acid and nitrogen heterocyclic ligands.
Preferably, the MOFs are one of ZIF-8, MIL-100 or UIO-66.
Preferably, the MOFs are one of ZIF-8 (Zn), MIL-100 (Fe) or UIO-66 (Zr).
2. The preparation method of the bio-based luminescent nano material comprises the following steps:
(1) Adding cellulose nanocrystals and MOFs organic ligands into a solvent until the cellulose nanocrystals are uniformly dispersed, and completely dissolving the MOFs organic ligands to obtain a solution I;
(2) Adding inorganic metal salt and MOFs organic ligand into the solvent until the inorganic metal salt and the MOFs organic ligand are completely dissolved, obtaining solution II, adding the solution II into the solution I at the speed of 0.05-0.2mL/s, stirring at normal temperature for reaction for 2-3h, standing until crystallization is completed, centrifuging and washing to obtain crystals, and drying to obtain the bio-based luminescent nanomaterial.
Preferably, the method is as follows:
(1) Adding cellulose nanocrystals and 2-methylimidazole into anhydrous methanol according to a molar ratio of 1:1 until the cellulose nanocrystals are uniformly dispersed, and completely dissolving the 2-methylimidazole to obtain a solution I;
(2) Under the condition that the mass of 2-methylimidazole is the same as that of 2-methylimidazole used in the step (1), zinc salt and 2-methylimidazole are added into absolute methanol according to the molar ratio of 1:2 until the zinc salt and the 2-methylimidazole are completely dissolved, solution II is obtained, the solution II is added into the solution I at the speed of 0.05-0.2mL/s, stirring reaction is carried out for 2-3h at normal temperature, standing is carried out until crystallization is completed, centrifugal washing is carried out, crystals are obtained, and drying is carried out, thus obtaining the bio-based luminescent nanomaterial.
Preferably, in step (2), the zinc salt is Zn (NO 3 ) 2 ·6H 2 O。
Preferably, in the step (2), the centrifugal washing specifically uses anhydrous methanol as a washing liquid, and the centrifugal washing is performed for more than 3 times at a rotation speed of 10000-12000rpm, and each time is 3-5min.
Preferably, in step (2), the drying is specifically vacuum drying at 55-65 ℃ for 12-24 hours.
3. The biological-based luminescent nano material is applied to the fields of information anti-counterfeiting, active material tracing, biological marking, catalysis or sensing.
Preferably, the application in the field of information anti-counterfeiting is particularly the application in preparing a permanent photo-bleaching-free invisible nano optical material.
4. A derivative of a bio-based luminescent nanomaterial, wherein cellulose nanocrystals are taken as cores and MOFs are taken as shells, the cellulose nanocrystals are directionally arranged in the MOFs cavity, nanoparticles are distributed in the pores of the MOFs, and the maximum emission wavelength and the maximum excitation wavelength of the nanoparticles are matched with those of the cellulose nanocrystals.
Preferably, the nanoparticle has a particle size of 20nm or less.
Preferably, the nanoparticle is one of a carbon quantum dot, a carbon nano dot, a metal nanoparticle or a metal quantum dot.
5. The preparation method of the derivative of the bio-based luminescent nanomaterial comprises the following steps: adding the biological-based luminescent nano material into the nanoparticle dispersion liquid, stirring and reacting for more than 7 hours, centrifugally washing to obtain a precipitate, and airing the precipitate to obtain the derivative of the biological-based luminescent nano material.
Preferably, the centrifugal washing specifically uses water as a washing liquid, and the washing is performed for more than 3 times at the rotating speed of 10000-12000rpm, and each time is 3-5min.
6. The derivative of the biological-based luminescent nano material is applied to the fields of information anti-counterfeiting, active substance tracing, biological marking, catalysis or sensing.
Preferably, the application in the field of information anti-counterfeiting is particularly the application in preparing a permanent photo-bleaching-free invisible nano optical material.
The invention has the beneficial effects that: the invention provides a bio-based luminescent nano material, a preparation method and application thereof, wherein the bio-based luminescent nano material is a degradable bio-non-toxic environment-friendly material, and by utilizing the interaction between MOFs and cellulose nanocrystals and controlling the material ratio and reaction conditions between raw materials, the cellulose nanocrystals can be distributed in the cavities of the MOFs in a certain sequence structure, and the structure is regulated to a stable state, so that the resonance scattering effect of the cellulose nanocrystals is enhanced, and the photoluminescence intensity of the cellulose nanocrystals is improved by 50%. Furthermore, by introducing nano particles with maximum emission wavelength and maximum excitation wavelength matched with the maximum emission wavelength and the maximum excitation wavelength of the cellulose nano crystal into MOFs pores of the bio-based luminescent nano material, the electromagnetic field resonance between the plasmon and the matrix is strongest, so that the photoinduced virtual luminescence of the material can be further enhanced. When the carbon quantum dot or the carbon nano dot is introduced, the carbon quantum dot or the carbon nano dot has a Dirac cone structure, so that the photoluminescence of the cellulose nano crystal can be further enhanced as a plasmon through a local plasmon effect, and the photoluminescence intensity of the material is further improved by 550%; when metal quantum dots or metal nanoparticles are introduced, since the surfaces of the metal quantum dots or metal nanoparticles inherently contain abundant electrons, the nanoparticles which are rich in electrons and can be induced under certain conditions and generate collective oscillation behaviors can serve as plasmons and further enhance the photoluminescence of cellulose nanocrystals through the local plasmon effect. Because the bio-based luminescent nano material and the derivative thereof have higher luminescent intensity, the two materials can be well used in the fields of information anti-counterfeiting, active substance tracing, biological marking, catalysis or sensing, the two materials have simple preparation process, easy operation, low raw material cost and environmental protection, and are suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an infrared spectrum test chart of SCNC, ZIF-8@SCNC and ZIF-8;
FIG. 2 is an XRD pattern for SCNC, ZIF-8@SCNC and ZIF-8;
FIG. 3 is an AFM diagram of an SCNC;
FIG. 4 is an AFM image of ZIF-8;
FIG. 5 is an AFM image of ZIF-8@SCNC;
FIG. 6 is a TEM image of ZIF-8@SCNC;
FIG. 7 is a fluorescence spectrum test chart of SCNC, ZIF-8 and ZIF-8@SCNC;
FIG. 8 is a TEM image of a CND@ZIF-8@SCNC;
FIG. 9 is a graph of the photoluminescence intensity enhancement ratio for SCNC, ZIF-8@SCNC, CND@ZIF-8@SCNC, CND@SCNC, CND@ZIF-8, and ZIF-8;
fig. 10 is a graph of nitrogen adsorption and desorption of derivatives of bio-based luminescent nanomaterial in example 3.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Example 1
A bio-based luminescent nano material takes cellulose nanocrystalline as a core and ZIF-8 as a shell, wherein the cellulose nanocrystalline is arranged in a ZIF-8 cavity in an oriented way. The material is prepared by the following steps:
(1) Firstly, soaking 20g of short cotton into sodium hydroxide alkali solution for alkali treatment, mechanically stirring at 3500rpm for reaction for 12 hours at normal temperature, washing the obtained cotton with clear water to be neutral, and drying at 55 ℃ in an oven for 24 hours to obtain the cotton after alkali treatment. Adding 5g of cotton subjected to alkali treatment into 45wt% sulfuric acid aqueous solution, mechanically stirring at a speed of 3500rpm for 30min at 50 ℃ to obtain a suspension, cooling the suspension in an ice bath to room temperature, pouring the cooled suspension into a dialysis bag with a molecular weight of 15000, dialyzing the solution until the solution is neutral to obtain cellulose nanocrystalline, and marking the cellulose nanocrystalline as SCNC;
(2) Adding the SCNC and the 2-methylimidazole prepared in the step (1) into 15mL of absolute methanol according to a molar ratio of 1:1, and carrying out ultrasonic treatment until the SCNC is uniformly dispersed in the absolute methanol, wherein the 2-methylimidazole is completely dissolved in the absolute methanol to obtain a solution I;
(3) In the case where the mass of 2-methylimidazole is the same as that of 2-methylimidazole used in step (1), zn (NO 3 ) 2 ·6H 2 O and 2-methylimidazole were added to 10mL of anhydrous methanol, and stirred to Zn (NO) 3 ) 2 ·6H 2 O and 2-methylimidazole are completely dissolved in absolute methanol to obtain a solution II; adding the solution II into the solution I obtained in the step (2) at the speed of 0.05mL/s, stirring at normal temperature for reacting for 2 hours, standing until crystallization is completed, washing with absolute methanol serving as a washing liquid at the speed of 12000rpm for 4 times for 5 minutes each time, and vacuum drying at 60 ℃ for 12 hours after crystals are obtained to obtain the bio-based luminescent nano material (ZIF-8@SCNC).
ZIF-8 was prepared by the method in step (3) of example 1
Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 10mL of anhydrous methanol to obtain Zn (NO) 3 ) 2 ·6H 2 O methanol solution; adding 2-methylimidazole into 15mL of anhydrous methanol, and adding Zn (NO) at a rate of 0.05mL/s after the 2-methylimidazole is completely dissolved 3 ) 2 ·6H 2 Stirring in O methanol solution at room temperature for 0.5 hr, standing until crystallization is completed, washing with anhydrous methanol as washing liquid at 12000rpm for 4 times and 5min each time, vacuum drying at 60deg.C for 24 hr to obtain ZIF-8, wherein Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:4.
Using infrared spectrometer at 4000-400cm -1 As a result of infrared testing of the above SCNC, ZIF-8@SCNC and ZIF-8, respectively, in the wave number range, as shown in FIG. 1, 1174cm originally present in the ZIF-8 structure was found from FIG. 1 -1 With 1140cm -1 The absorption peak of the C-N bond at this point became 1163cm in the ZIF-8@SCNC material -1 Indicating that the C-N bond is affected and 3346cm at ZIF-8@SCNC -1 The broadening of the peak of SCNC compared with that of SCNC suggests that the-OH bond of SCNC was affected, and it was inferred that there was a hydrogen bond between SCNC and ZIF-8.
As shown in FIG. 2, when the X-ray diffractometer XRD-6000 is used for testing the SCNC, ZIF-8@SCNC and ZIF-8 respectively, and compared with the standard patterns of the SCNC and ZIF-8, the patterns of the ZIF-8@SCNC have characteristic peaks of the SCNC and ZIF-8 at the same time, and the combined peaks of two diffraction peaks at 15.0 DEG and 16.8 DEG exist at about 16.0 DEG and the diffraction peaks at 20.7 DEG and 23.0 DEG of 2 theta are the corresponding diffraction peaks. Diffraction peaks corresponding to 2 theta of 6.7 degrees, 9.7 degrees, 12.1 degrees, 14.1 degrees, 15.8 degrees and 17.4 degrees are (011), (002), (112), (022), (013) and (222) respectively, and are consistent with a standard spectrogram simulated by a computer and ZIF-8 characteristic diffraction peaks reported in literature.
The atomic force microscope is adopted to test the SCNC, ZIF-8 and ZIF-8@SCNC respectively, and the results are shown in figures 3 to 5, wherein figure 3 is an atomic force microscope image of the SCNC, and the results show that the particle size of the SCNC is relatively uniform, the size distribution is relatively narrow, the whole nano particles are in a rod-shaped structure, but due to the self-aggregation effect of the nano particles, the products have certain accumulation, wherein the length distribution of the SCNC is 100-150nm, and the width distribution of the SCNC is 25-30nm; FIG. 4 is an atomic force microscope image of ZIF-8, showing that the ZIF-8 particles are spherical and have a diameter distribution of 75-150nm; FIG. 5 is an atomic force microscope image of ZIF-8@SCNC, and shows that the morphology of ZIF-8@SCNC and the morphology of SCNC basically maintain a rod-shaped structure, and the morphology of SCNC and ZIF-8 per se completely disappears, so that the ZIF-8 completely coats the SCNC, wherein the ZIF-8@SCNC has a length distribution of 100-200nm and a width distribution of 30-80nm.
As shown in FIG. 6, the edge of ZIF-8@SCNC presents a brighter part as shown in FIG. 6, because ZIF-8 wrapping layer is thinner, and SCNC exists inside, so that internal lining is deeper, and therefore ZIF-8@SCNC has an obvious shell-core structure.
Zeta potential tests were performed on the above SCNC, ZIF-8 and ZIF-8@SCNC using a nanoBrook Omni laser particle size analyzer, respectively, and the results are shown in Table 1.
TABLE 1
As is clear from Table 1, the average potential of SCNC was-28.18 mV, which indicates that SCNC was negatively charged in water and had a certain dispersibility. ZIF-8 has an average potential of 32.77mV, a side reflection of which is more prone to binding to negatively charged SCNC. The average potential of ZIF-8@SCNC was-11.03 mV. The reduction of the Zeta potential can reduce the charge by forming a certain force between ZIF-8 and SCNC.
As shown in FIG. 7, it is clear from FIG. 7 that the fluorescence of ZIF-8 is very weak and the SCNC solid has a certain luminous effect, but the ZIF-8@SCNC has a very strong luminous effect, so that the solid luminous intensity of the SCNC is obviously enhanced and the enhancement effect is improved by 50%.
Example 2
Preparation of derivatives of bio-based luminescent nanomaterials
(1) Adding citric acid and urea into distilled water according to a mass ratio of 1:1 until the citric acid and the urea are completely dissolved, stirring the solution at 150 ℃ for reaction for 7 hours, and dialyzing with distilled water for 3 days to obtain carbon nano dots which are marked as CND;
(2) Adding ZIF-8@SCNC prepared in the embodiment 1 into the carbon nano dot dispersion liquid obtained in the step (1), stirring and reacting for 15 hours, washing 3 times at 12000rpm with distilled water serving as a washing liquid for 3 minutes each time, and airing the obtained precipitate to obtain the derivative (CND@ZIF-8@SCNC) of the bio-based luminescent nano material.
As shown in FIG. 8, it is apparent from FIG. 8 that carbon nanodots exist in ZIF-8@SCNC, the size of the carbon nanodots is 20nm or less, and the lattice size is 0.226nm, when the CND@ZIF-8@SCNC is tested by using a Talos-f200x transmission electron microscope.
As shown in FIG. 9, the photoluminescence enhancement ratios of the SCNC, ZIF-8@SCNC, CND@ZIF-8@SCNC, CND@SCNC, CND@ZIF-8 and ZIF-8 were sequentially increased, i.e., the luminous intensity of each material was sequentially increased, as shown in FIG. 9. The CND@ZIF-8 and ZIF-8 emit light very weakly, which means that both ZIF-8 and CND have no strong photoluminescence effect, but after the two are respectively formed into a composite material with SCNC, the composite material has strong luminescence intensity, and the CND can better induce the SCNC to emit light compared with the ZIF-8, the luminescence intensity of a material formed by the combination of the CND, ZIF-8 and the SCNC is strongest, because the ZIF-8 coats the SCNC, the formed microcavity structure stabilizes the assembly induced luminescence of the SCNC, and after the CND is further introduced, the CND has a Dirac cone structure, so that the photoluminescence of the finally formed material can be further enhanced as a plasmon and is further enhanced through the local plasmon effect.
Example 3
Preparation of derivatives of bio-based luminescent nanomaterials
(1) Adding chloroplatinic acid with the mass fraction of 20% into distilled water, dropwise adding 1mL of sodium hydroxide solution with the mass fraction of 50% at the speed of 0.05mL/3s at the temperature of 0 ℃, keeping the temperature for stirring reaction for 1h, heating to the temperature of 25 ℃ and stirring reaction for 3h to obtain platinum nanoparticle solution;
(2) Adding ZIF-8@SCNC prepared in the embodiment 1 into the platinum nanoparticle solution obtained in the step (1), stirring and reacting for 15h, washing 3 times at 10000rpm with distilled water as a washing solution for 3min each time, and airing the obtained precipitate.
FIG. 10 is a graph showing the adsorption and desorption curves of nitrogen gas of the derivative of the above-mentioned bio-based luminescent nanomaterial, and as can be seen from FIG. 10, the specific surface area of the derivative is distributed at 50-55m 2 Between/g, a large specific surface area is present. The surface of the platinum nano-particles in the derivative is easy to adsorb hydrogen elements, can be used for catalyzing the catalytic hydrogenation reaction of small organic molecules, and can greatly improve the catalytic efficiency of the small organic molecules by virtue of the large specific surface area and rich adsorption sites of the derivative.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (3)
1. The derivative of the bio-based luminescent nanomaterial is characterized in that cellulose nanocrystals are taken as cores and ZIF-8 is taken as a shell, the cellulose nanocrystals are directionally arranged in a ZIF-8 cavity in a spiral manner through hydrogen bonding, nanoparticles are distributed in pores of the ZIF-8, and the maximum emission wavelength and the maximum excitation wavelength of the nanoparticles are matched with those of the cellulose nanocrystals;
the nano particles are any one of carbon nano points or platinum nano particles.
2. A method for preparing a derivative of a bio-based luminescent nanomaterial as claimed in claim 1, characterized in that the method comprises the following steps: adding the biological-based luminescent nano material into the nanoparticle dispersion liquid, stirring and reacting for more than 7 hours, centrifugally washing to obtain a precipitate, and airing the precipitate to obtain a derivative of the biological-based luminescent nano material;
the bio-based luminescent nanomaterial takes cellulose nanocrystals as cores and ZIF-8 as shells, and the cellulose nanocrystals are arranged in a spiral manner in a ZIF-8 cavity in an oriented manner through hydrogen bonding.
3. Use of a derivative of a bio-based luminescent nanomaterial according to claim 1 in the fields of information security, active substance tracking, biomarkers, catalysis or sensing.
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