CN109810272A - A kind of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film and preparation method thereof - Google Patents
A kind of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film to obtain oxidation nanometer cellulose suspension after cellulose nanometer fibril is successively dispersed, aoxidizes and is homogenized；By 1,4- naphthalenedicarboxylic acid [H2NDC] with Lanthanum trichloride hexahydrate based compound and DMF solvent it is mixed to get Ln-NDC mixed system, Ln-NDC mixed system is transferred to cooling after being reacted in reaction kettle after mixing evenly, obtains rare earth two-dimensional metallic organic backbone object after filtration drying；It is added after rare earth two-dimensional metallic organic backbone object obtains Ln-NDC-TOCNFs mixed system and stirs to oxidation nanometer cellulose suspension, then filter and be dried to obtain oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film；Raw cellulose is nontoxic, pollution-free, from a wealth of sources, environmentally protective, easily modified, good biocompatibility, passes through the H rich in conjugated pi electron between two components of composite fluorescent film2NDC is stronger in conjunction with the coordination of rare earth ion.
Description
Technical field
The invention belongs to field of new material preparation, and in particular to a kind of oxidation nanometer cellulose two-dimensional metallic organic backbone is multiple
Close fluorescence membrane and preparation method thereof.
Background technique
Cellulose is one of most ancient and the most abundant natural polymer on the earth, can be by photosynthesis by water and two
Carbonoxide synthesis, and can be degradable by microorganism in the Nature, therefore, it is a kind of renewable resource and environmental-friendly material
Material.Cellulose is the basis for constituting plant cell, and is up to 10,000,000,000 by the cellulose that photosynthesis generates every year
Ton.Meanwhile cellulose is nontoxic, water repelling property is strong, can occur in a variety of manners.Cellulose nano-fibrous (CNF) is a kind of day
Right polymer-based material has thermal expansion coefficient is low, optical transparence is good, mechanical strength is high etc. with petroleum base polymer phase ratio
Advantage can also be removed the moisture of CNF aqueous dispersions by modes such as vacuum filtrations, be often used in and prepare flexible electronic device
Thin-film carrier.Nano-cellulose fiber is wound mutually fine and close tridimensional network by hydrogen bond action etc., to make
The CNF film of standby excellent, satisfactory mechanical property, good biocompatibility with light transmittance.With excessively opening for non-renewable resources
It adopts and growing tension, the growing interest and attention of global environmental pollution and shortage of resources problem, people concentrates sight again
To on the research and development of renewable resource cellulose.Therefore, a kind of cellulose nano-fibrous flexible function for substrate is studied
Energy thin-film material and preparation method have important realistic meaning.
With deep and its application range the expansion of near-infrared area research, especially optical communication, public safety and life
The development and demand of the industries such as object medical treatment, there is an urgent need to a kind of near-infrared materials with good luminous performance.Organic material by
In the at low cost, simple process and structure easy-regulating the advantages that and be concerned, up to the present, primary study it is near-infrared luminous
Material is concentrated mainly on two major classes: first is that lanthanide complexes；Second is that organic ion dyestuff.Organic ion dyestuff can have one
A little problems, such as due to electrostatic interaction, molecule is easy to cause to shine because of aggregation to extract to go out.The f-f transition of rare earth element is
Prohibit, the excitation of molecule needs the energy transfer by ligand and central ion, improves its luminous efficiency.
Metal organic framework compound (metal organic frameworks, MOFs) is by metal ion or metal cluster
With organic ligand (binary or polybasic carboxylic acid, nitrogen-containing heterocycle compound etc.) self assembly and formed with periodic network structure
Porous compounds are widely used in gas with the advantages that large specific surface area, porosity is high, and structure is adjustable, and symmetry is good
The fields such as storage, separation, drug delivery, catalysis and sensing.The study found that partial organic substances and rare earth ion are with coordinate bond
Stronger fluorescence can be emitted after forming two-dimensional metallic organic backbone, these organic matters are referred to as ligand.Ligand mainly have with
Lower two features: first is that the energy of ligand to match with the f-f electron transition energy of rare earth ion and triplet energy level must
The lowest excited state energy level of rare earth ion must be higher than；Second is that ligand typically is provided with the conjugated structure of high absorptivity.Ligand
It transfers energy to rare earth ion after receiving extraneous light radiation and emits fluorescence, this effect of ligand is known as " antenna
Effect ".1,4- naphthalenedicarboxylic acid (H2NDC) frequently as the ligand of two-dimensional metallic organic backbone, have excellent conjugated structure and system
The standby simple feature of process.For three-dimensional MOFs, two-dimensional metal-organic framework materials have many good qualities, such as surface
There are more active sites, it is more flexible etc., it can apply to the fields such as electronics, photoelectron, molecule separation, catalysis.
With the development of luminescent material, synthetic method also can be more and more therewith.Researchers at home and abroad existed in recent years
A few thing has been carried out in this field, but most material substrate uses not environment friendly profile material, such as petroleum base
High molecular material etc., these materials not only to environment nocuousness, more seriously will lead to energy missing, and limits luminescent material and exist
The application of field of biomedicine.Therefore, preparing a kind of seems particularly necessary by the luminescent material of substrate of natural macromolecular material.
Summary of the invention
The purpose of the present invention is to provide a kind of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film and
Nano-cellulose is carried out oxidation processes, part is organic using natural macromolecular material as the luminescent material of substrate by preparation method
Object and rare earth ion obtain near-infrared luminous performance, mechanical property, light transmission with coordinate bond formation two-dimensional metallic organic backbone
The compound two-dimensional metallic organic backbone nano-cellulose fluorescence membrane of performance and biocompatibility.
To achieve the goals above, the technical solution adopted by the present invention is that, a kind of oxidation nanometer cellulose two-dimensional metallic has
The preparation method of machine skeleton composite fluorescent film, includes the following steps:
S1 takes cellulose nanometer fibril, after successively dispersing, aoxidize and being homogenized, obtains oxidation nanometer cellulose suspension；
S2 mixes Isosorbide-5-Nitrae-naphthalenedicarboxylic acid with Lanthanum trichloride hexahydrate based compound with DMF solvent according to mass ratio 1:0.9,
L n-NDC mixed system is obtained, Ln-NDC mixed system is transferred in reaction kettle after mixing evenly, is cooled to after the reaction was completed
Room temperature filters and obtains rare earth two-dimensional metallic organic backbone object after drying；
Rare earth two-dimensional metallic organic backbone prepared by S2 is added into the oxidation nanometer cellulose suspension of S1 preparation by S3
Object obtains Ln-NDC-TOCNFs mixed system, and Ln-NDC-TOCNFs mixed system is stirred under ultrasound condition, removes solvent,
It is dried to obtain oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film.
S1 specifically includes the following steps:
Cellulose powder is dispersed in aqueous solution and is ultrasonically treated, adds 0.01mmol/g's by S101
The NaBr aqueous solution of TEMPO and 6.0mmol/g obtains cellulose mixture aqueous dispersions system；
NaOH aqueous solution is added into cellulose mixture aqueous dispersions system by S102, and keeping pH value is 10.5；Gradually add again
Enter the NaClO solution of 6.0mmol/g, mixed liquor continues to stir 3h, obtains oxidation nanometer cellulose dispersion liquid；
Aqueous hydrochloric acid solution is added into oxidation nanometer cellulose dispersion liquid in S103, and pH value is adjusted to 7, oxidation is obtained and receives
Rice cellulose suspension；
S104 by resulting oxidation nanometer cellulose suspension through filtration of demineralized water and washing, then carries out 20 sub-high pressure homogenizing,
Pressure is 80MPa when high pressure homogenization, obtains uniform TOCNFs suspension.
There are store in the environment of 4 DEG C for TOCNFs suspension.
In S101, sonication treatment time 20min/g.
In S2, Lanthanum trichloride hexahydrate based compound is six Neodymium chloride hydrates, six hydrous ytterbium chlorides or six chloride hydrate erbiums.
In S2, stirred under ultrasound condition, 80 DEG C of reaction 3d be heated in autoclave, in autoclave after reaction with
The rate of 5 DEG C/h is cooling.
In S2, washed using deionized water；Autoclave uses the autoclave of polytetrafluoroethyllining lining.
In S3, TEMPO oxidation nanometer cellulose suspension and rare earth two-dimensional metallic organic backbone object dosage are every gram of rare earth
Two-dimensional metallic organic backbone object 1~5mL TEMPO oxidation nanometer cellulose suspension.
In S3, mixing time 30min is removed solvent using suction method, is filtered by vacuum using glass sand core funnel.
Another technical solution of the invention is the oxidation nanometer cellulose two-dimensional metallic obtained according to above-mentioned preparation method
Organic backbone composite fluorescent film.
Compared with prior art, the present invention at least has the advantages that
Two-dimensional metallic organic backbone object is introduced into nano-cellulose fiber substrate by the present invention, is then filtered by vacuum, is dry
Nano-cellulose fluorescence membrane can be made after dry, since nano-cellulose size is small, surface can easily reunite greatly, and will
Rare earth two-dimensional metallic organic backbone object mixes that will lead to material property in pure cellulose substrate unstable；It is aoxidized using TEMPO
For method by the part primary hydroxy group of CNF at carboxyl, the anionic CNF after oxidation has good dispersibility in aqueous solution,
And carboxylic group can carry out coordination with rare earth ion, enhance the stability of material, and the preparation process is simple,
Reaction condition is mild, and raw material sources are extensive and environmentally protective, low in cost；
Raw cellulose of the present invention is nontoxic, pollution-free, from a wealth of sources, environmentally protective, easily modified, biofacies
Capacitive is good, renewable；The TEMPO oxidation nanometer cellulose aqueous dispersions of preparation stablize not coagulation and preparation manipulation is simple；TEMPO
Oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film have excellent near-infrared luminous performance, light transmission,
Mechanical property and biocompatibility, and pass through the H rich in conjugated pi electron between two components of composite fluorescent film2NDC with it is dilute
The coordination of earthmetal cations combines stronger, and the stability of film itself is improved；Biological cell mark,
Cell imaging, the fields such as fluorescence falsification preventing, optical sensor have broad prospects.
Detailed description of the invention
Fig. 1 is TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone (NDC-Nd3+) composite fluorescent film excitation spectrum
Figure and transmitting spectrogram；
Fig. 2 is TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone (NDC-Yb3+) composite fluorescent film excitation spectrum
Figure and transmitting spectrogram；
Fig. 3 is TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone (NDC-Er3+) composite fluorescent film excitation spectrum
Figure and transmitting spectrogram.
Specific embodiment
Embodiment in detail below is the technology of the present invention to be further described, and the raw material in embodiment can pass through
Commercial channel is bought.
Embodiment 1
The preparation of S1, TEMPO oxidation nanometer cellulose aqueous dispersions, specifically comprises the following steps:
It is that raw material aoxidizes that resulting cellulose nanometer fibril (CNF), which will be bought, using TEMPO/NaClO/NaBr as oxygen
Change system aoxidizes the hydroxyl on cellulose fibre.By cellulose nanometer fibril (1g, dry weight) sonicated 20min
Afterwards, according to mass ratio be 1:0.16 sequentially add 6.0mmol/g NaBr and 0.01mmol/g TEMPO aqueous solution, then plus
Enter NaOH aqueous solution, its pH value is adjusted to 10.5；Then, it is gradually added into the NaClO solution of 6.0mmol/g, mixed liquor continues
3h is stirred, dilute hydrochloric acid is added, adjusts the pH value of reaction solution to 7；Resulting oxidation nanometer cellulose suspension is through filtration of demineralized water
And washing, then cellulose fibre suspension is homogenized at 80MPa with 20 sub-high pressure homogenizers, it is generated
TOCNFs suspension is collected, for using later in the environment of being stored in 4 DEG C.
S2, the preparation of two-dimensional metallic organic backbone object, specifically comprises the following steps:
By 1,4- naphthalenedicarboxylic acid (0.1mmol) and six Neodymium chloride hydrate [NdCl3·6H2O (0.006mmol)] according to quality
Than being added in beaker for 1:0.9, takes 8ml n,N-Dimethylformamide (DMF) to mix into beaker, above-mentioned mixed system is existed
Stirring a period of time is uniformly mixed it under ultrasound condition, is transferred in the autoclave of 25ml polytetrafluoroethyllining lining later,
3d is heated at 80 DEG C.It is slowly cooled to room temperature reaction kettle with 5 degrees Celsius per hour of temperature, which is washed with deionized
Filtration drying finally obtains lavender granular crystals.
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Nd for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 5mLS1 to prepare3+Crystal is in room temperature
Lower ultrasonic mixing stirs 1h, the mixed liquor after stirring is filtered by vacuum using glass sand core funnel, what is obtained after suction filtration is thin
Film be placed in 40 DEG C of vacuum oven it is dry after that TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone can be obtained is multiple
Close fluorescence membrane.
Embodiment 2
S1 and S2 are same as Example 1；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Nd for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 15mLS1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, is filtered by vacuum using glass sand core funnel to the mixed liquor after stirring, is obtained after suction filtration
Film, which is placed in 40 DEG C of vacuum oven, can be obtained TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone after drying
Composite fluorescent film.
Embodiment 3
S1 and S2 are same as Example 1；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Nd for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 25mLS1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, is filtered by vacuum using glass sand core funnel to the mixed liquor after stirring, is obtained after suction filtration
Film, which is placed in 40 DEG C of vacuum oven, can be obtained TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone after drying
Composite fluorescent film.
Embodiment 4
S1 embodiment 1 is identical；
S2, by Isosorbide-5-Nitrae-naphthalenedicarboxylic acid (0.1mmol) and six hydrous ytterbium chloride [YbCl3·6H2O (0.006mmol)] according to matter
Amount takes 8ml n,N-Dimethylformamide (DMF) to mix into beaker, by above-mentioned mixed system than being that 1:0.9 is added in beaker
Stirring a period of time is uniformly mixed it under ultrasound condition, is transferred in the autoclave of 25ml polytetrafluoroethyllining lining later,
3d is heated at 80 DEG C.It is slowly cooled to room temperature reaction kettle with 5 degrees Celsius per hour of temperature, which is washed with deionized water
Filtration drying is washed, white rhabdolith is finally obtained.
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Yb for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 5mLS1 to prepare3+Crystal is in room temperature
Lower ultrasonic mixing stirs 1h, the mixed liquor after stirring is filtered by vacuum using glass sand core funnel, what is obtained after suction filtration is thin
Film be placed in 40 DEG C of vacuum oven it is dry after that TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone can be obtained is multiple
Close fluorescence membrane.
Embodiment 5
S1 and S2 are same as Example 4；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Yb for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 15mLS1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, and the mixed liquor after stirring is filtered by vacuum using glass sand core funnel, after vacuum filtration
To film be placed in 40 DEG C of vacuum oven it is dry after that TEMPO oxidation nanometer cellulose two-dimensional metallic can be obtained is organic
Skeleton composite fluorescent film.
Embodiment 6
S1 and S2 are same as Example 4；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Yb for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 25mLS1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, is filtered by vacuum using glass sand core funnel to the mixed liquor after stirring, is obtained after suction filtration
Film, which is placed in 40 DEG C of vacuum oven, can be obtained TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone after drying
Composite fluorescent film.
Embodiment 7
S1 embodiment 1 is identical；
S2, by Isosorbide-5-Nitrae-naphthalenedicarboxylic acid (0.1mmol) and six chloride hydrate erbium [ErCl3·6H2O (0.006mmol)] according to matter
Amount takes 8ml n,N-Dimethylformamide (DMF) to mix into beaker, by above-mentioned mixed system than being that 1:0.9 is added in beaker
Stirring a period of time is uniformly mixed it under ultrasound condition, is transferred in the autoclave of 25ml polytetrafluoroethyllining lining later,
3d is heated at 80 DEG C.It is slowly cooled to room temperature reaction kettle with 5 degrees Celsius per hour of temperature, which is washed with deionized water
Filtration drying is washed, pink colour rhabdolith is finally obtained.
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Er for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 5mL S1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, is filtered by vacuum using glass sand core funnel to the mixed liquor after stirring, is obtained after suction filtration
Film, which is placed in 40 DEG C of vacuum oven, can be obtained TEMPO oxidation nanometer cellulose two-dimensional metallic organic backbone after drying
Composite fluorescent film.
Embodiment 8
S1 and S2 are same as Example 7；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Er for TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 15mL S1 to prepare3+Crystal is in room
The lower ultrasonic mixing of temperature stirs 1h, and the mixed liquor after stirring is filtered by vacuum using glass sand core funnel, after vacuum filtration
To film be placed in 40 DEG C of vacuum oven it is dry after that TEMPO oxidation nanometer cellulose two-dimensional metallic can be obtained is organic
Skeleton composite fluorescent film.
Embodiment 9
S1 and S2 are same as Example 7；
S3 prepares oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film
The NDC-Er for 0TEMPO oxidation nanometer cellulose suspension and 5mg the S2 preparation for taking 25mL S1 to prepare3+Crystal exists
Ultrasonic mixing stirs 1h at room temperature, is filtered by vacuum using glass sand core funnel to the mixed liquor after stirring, is obtained after suction filtration
Film be placed in 40 DEG C of vacuum oven it is dry after the organic bone of TEMPO oxidation nanometer cellulose two-dimensional metallic can be obtained
Frame composite fluorescent film；
The TEMPO- oxidation nanometer cellulose two-dimensional metallic organic backbone laminated film of comparative example 1-9 preparation, makes two
The additive amount for tieing up metal organic framework object is constant, as the dosage of TEMPO oxidation nanometer cellulose suspension increases, composite fluorescence
The transparency of film constantly declines, but the thickness of film, tensile strength, mechanical property are continuously improved.In embodiment dosage model
In enclosing, the luminescent properties of two kinds of films, which do not have, significantly to be changed, and different rare earth two-dimensional metallic organic backbones is to film
Translucency, mechanical performance, tensile strength have no influence.
Using sepectrophotofluorometer research TEMPO- oxidation nanometer cellulose two-dimensional metallic organic backbone laminated film
Photoluminescent property；Fig. 1 show when at 359nm monitor excitation wavelength when, NDC-Nd3+- TOCNFs film (TEMPO- oxidation nanometer fiber
Plain two-dimensional metallic organic backbone composite fluorescent film) detect three characteristic emission peaks, these characteristic emission peaks show sharply
Shape, be located at 887nm, 1061nm and 1331nm, and these frequency bands are attributed to respectively4F3/2-4I9/2,4F3/2-4I11/2,4F3/2-4I13/2, strongest emission peak is located at 1061nm, this, which shows the film here, has with near-infrared luminous characteristic；
This excitation spectrum is shown in NDC-Nd3+In-TOCNFs film, NDC ligand is by antenna effect successfully by the energy of absorption
It is transferred to Nd3+Ion.
Fig. 2 show when at 376nm monitor excitation wavelength when, NDC-Yb3+- TOCNFs film (TEMPO- oxidation nanometer fiber
Plain two-dimensional metallic organic backbone composite fluorescent film) detect that a characteristic emission peak, the characteristic emission peak show sharply
Shape, be located at 980nm, and frequency band is attributed to2F5/2-2F7/2, this, which shows the film here, has with near-infrared luminous spy
Property.This excitation spectrum is shown in NDC-Yb3+In-TOCNFs film, NDC ligand is by antenna effect successfully by the energy of absorption
Amount is transferred to Yb3+Ion.
Fig. 3 show when at 380nm monitor excitation wavelength when, NDC-Er3+- TOCNFs film (TEMPO- oxidation nanometer fiber
Plain two-dimensional metallic organic backbone composite fluorescent film) detect that a characteristic emission peak, the characteristic emission peak show sharply
Shape, be located at 1539nm, and frequency band is attributed to4I13/2-4I15/2, this, which shows the film here, has with near-infrared luminous
Characteristic；This excitation spectrum is shown in NDC-Er3+In-TOCNFs film, NDC ligand is by antenna effect successfully by absorption
Energy transfer is to Er3+Ion.
Claims (10)
1. a kind of preparation method of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film, which is characterized in that packet
Include following steps:
S1 takes cellulose nanometer fibril, after successively dispersing, aoxidize and being homogenized, obtains oxidation nanometer cellulose suspension；
Isosorbide-5-Nitrae-naphthalenedicarboxylic acid is mixed with Lanthanum trichloride hexahydrate based compound with DMF solvent according to mass ratio 1:0.9, is obtained by S2
Ln-NDC mixed system is transferred in reaction kettle after mixing evenly, is cooled to room temperature after the reaction was completed by Ln-NDC mixed system,
It filters and obtains rare earth two-dimensional metallic organic backbone object after drying；
S3 is added rare earth two-dimensional metallic organic backbone object prepared by S2 into the oxidation nanometer cellulose suspension of S1 preparation and obtains
To Ln-NDC-TOCNFs mixed system, Ln-NDC-TOCNFs mixed system is stirred under ultrasound condition, removes solvent, it is dry
Obtain oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film.
2. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that S1 specifically includes the following steps:
Cellulose powder is dispersed in aqueous solution and is ultrasonically treated by S101, add 0.01mmol/g TEMPO and
The NaBr aqueous solution of 6.0mmol/g obtains cellulose mixture aqueous dispersions system；
NaOH aqueous solution is added into cellulose mixture aqueous dispersions system by S102, and keeping pH value is 10.5；It is gradually added into again
The NaClO solution of 6.0mmol/g, mixed liquor continue to stir 3h, obtain oxidation nanometer cellulose dispersion liquid；
Aqueous hydrochloric acid solution is added into oxidation nanometer cellulose dispersion liquid in S103, and pH value is adjusted to 7, oxidation nanometer fibre is obtained
Tie up plain suspension；
S104 by resulting oxidation nanometer cellulose suspension through filtration of demineralized water and washing, then carries out 20 sub-high pressure homogenizing, high pressure
Pressure is 80MPa when homogenizing, obtains uniform TOCNFs suspension.
3. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 2
Method, which is characterized in that there are store in the environment of 4 DEG C for TOCNFs suspension.
4. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 2
Method, which is characterized in that in S101, sonication treatment time 20min/g.
5. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that in S2, Lanthanum trichloride hexahydrate based compound is six Neodymium chloride hydrates, six hydrous ytterbium chlorides or six hydrations
Erbium chloride.
6. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that in S2, stirred under ultrasound condition, 80 DEG C of reaction 3d are heated in autoclave, knot is reacted in autoclave
It is cooling with the rate of 5 DEG C/h after beam.
7. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that in S2, washed using deionized water；Autoclave uses the autoclave of polytetrafluoroethyllining lining.
8. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that in S3, TEMPO oxidation nanometer cellulose suspension and rare earth two-dimensional metallic organic backbone object dosage are every
Gram rare earth two-dimensional metallic organic backbone object 1~5mLTEMPO oxidation nanometer cellulose suspension.
9. the preparation side of oxidation nanometer cellulose two-dimensional metallic organic backbone composite fluorescent film according to claim 1
Method, which is characterized in that in S3, mixing time 30min removes solvent using suction method, is carried out using glass sand core funnel true
Empty pump filter.
10. the oxidation nanometer cellulose two-dimensional metallic organic backbone that preparation method according to claims 1 to 9 obtains is compound
Fluorescence membrane.
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| CN111253599A (en) * | 2020-03-11 | 2020-06-09 | 陕西科技大学 | Preparation method of anti-counterfeiting nanocellulose film capable of switching upper and lower conversion double channels |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
| CN113801651A (en) * | 2021-09-24 | 2021-12-17 | 广东省科学院化工研究所 | Composite luminescent material and preparation method and application thereof |
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| CN110767075A (en) * | 2019-12-05 | 2020-02-07 | 南方科技大学 | Flexible anti-counterfeiting layer based on metal micro-nano network, and preparation method and application thereof |
| CN111253599A (en) * | 2020-03-11 | 2020-06-09 | 陕西科技大学 | Preparation method of anti-counterfeiting nanocellulose film capable of switching upper and lower conversion double channels |
| CN112458795A (en) * | 2020-11-24 | 2021-03-09 | 陕西科技大学 | Photochromic fluorescent nano-paper based on lanthanide metal organic framework and preparation method thereof |
| CN113801651A (en) * | 2021-09-24 | 2021-12-17 | 广东省科学院化工研究所 | Composite luminescent material and preparation method and application thereof |
| CN113801651B (en) * | 2021-09-24 | 2023-10-13 | 广东省科学院化工研究所 | Composite luminescent material and preparation method and application thereof |
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