CN109897317A - A kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe and its preparation method and application - Google Patents
A kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe and its preparation method and application Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 71
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 71
- 239000000523 sample Substances 0.000 title claims abstract description 68
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- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- JVYYYCWKSSSCEI-UHFFFAOYSA-N europium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JVYYYCWKSSSCEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
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Abstract
The invention belongs to field of polymer composite material, a kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe and its preparation method and application is disclosed.Study fluorescence probe --- Rare Earth Europium Complex, which is preferably implemented in, to be crosslinked in reversible hydrogel, realizes the heavy metal ion easily and fast, sensitively detected in water environment, while solving the problems, such as that previous fluorescence probe is not readily portable.Heavy metal ions of the hydrogel fluorescence probe in detection water environment are with good application prospect.
Description
Technical field
The invention belongs to field of polymer composite material, are related to a kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol
Composite hydrogel fluorescence probe and its preparation method and application.
Background technique
Fluorescence probe method is a kind of rapid detection method, using rare earth compounding as fluorescence indicator, since electronics is mainly located
In high-lying level, so that fluorescence emission peak is concentrated mainly on high energy order transition, to pass through fluorescence power or Fluorescent peal
Variation realization is moved to the qualitative or quantitative analysis of metal ion.This method is convenient, simple, easily operated, and have selectivity it is good,
The advantages that high sensitivity, so being usually used in the real-time detection and in situ detection of heavy metal ion.
Hydrogel is made of high molecular polymer is crosslinked through chemical bonding or physical entanglement, using water as the tool of decentralized medium
There is the high molecular material of three-dimensional net structure.Intelligent aqueous gel is the hydrogel for having responsiveness to the stimulation of external environment,
In, the hydrogel with ion identification response function is a member of intelligent aqueous gel family.Utilize the fluorescence of rare earth nano crystal
Performance synthesizes the composite hydrogel with fluorescent characteristic, can be used for detecting to the metal ion in water environment.Polyvinyl alcohol is most
One of important water-soluble polymer, has a degradability, non-toxic and biological phase permeability curve, and there are a large amount of hydroxyls on strand
Base, can be by being physically or chemically cross-linked to form hydrogel.However, using polyvinyl alcohol as the hydrogel intensity of matrix relatively low and toughness
Poor, there are the deficiencies of physical mechanical property etc., cannot achieve industrial applications.
Since Cellulose nanocrystal is close with polyvinyl alcohol polarity, interface compatibility is preferable, Cellulose nanocrystal/polyethylene
The great researching value of the performance of alcohol composite material.Cellulose nanocrystal is a kind of ideal polyvinyl alcohol hydrogel reinforcing material,
Compared with other reinforced phases, Cellulose nanocrystal has high intensity, and draw ratio is big, can be in matrix material as reinforcement
Reticular structure is formed in material, improves material property.Cellulose nanocrystal/polyvinyl alcohol plural gel both maintains conventional polyethylene
The biocompatibility of alcohol hydrogel, and in terms of having the advantages that Cellulose nanocrystal mechanical property, as high tensile, toughness with
And high elastic modulus.
There is presently no rare earth compounding is preferably implemented in hydrogel, realize easily and fast, sensitively detect water
The report of heavy metal ion in environment.Currently on the market also that not there is preferable mechanical property and heavy metal ion can be detected
Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe.
Summary of the invention
The object of the present invention is to provide a kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence
Probe.
It is a further object to provide the preparation methods of above-mentioned composite hydrogel fluorescence probe.
It is also another object of the present invention to provide above-mentioned composite hydrogel fluorescence probes in detection water environment heavy metal ion
In application.By being crosslinked reversible fluorescence probe, while realizing the portability of solid state fluorescence probe and under liquid environment
Detect heavy metal quick and precisely.
The purpose of the present invention is what is realized by following technical proposal:
A kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe, under which uses
Column method is prepared:
A. Cellulose nanocrystal CNC is prepared；
B. rare earth compounding Eu (DPA) is prepared3；
C. to Cellulose nanocrystal CNC and rare earth compounding Eu (DPA)3In mixing suspension be added pva powder and
Crosslinking agent, stirring form gel and visit to get to Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence
Needle.
Further, (cellulosic material is delignification plant fiber to Cellulose nanocrystal CNC, is preferably floated in step a
Whitewood's pulp fibres or absorbent cotton) preparation method using chemical bonding mechanical treatment process, specific steps include:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 50%~70%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 40-50 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, by delignification plant fiber: sulfuric acid solution is mixed by the mass ratio of 1:10~1:40
It closes, the delignification plant fiber is preferably bleached wood pulp fiber or degreasing cotton fiber；It should lasting stirring in the process；It is being added
During delignification plant fiber, it is careful not to for delignification plant fiber being poured on wall of cup and agitating paddle, after preventing
To generate impurity in transfer process；After delignification plant fiber is added, continue heating stirring 1~3 hour；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, 20~50min of ultrasound removes cellulose for Cellulose nanocrystal under 300~500W power,
Cellulose nanocrystal CNC suspension is prepared, the Cellulose nanocrystal suspension being prepared into is placed on stored under refrigeration in refrigerator
It is spare.
Further, the rare earth compounding preparation in step b, step include:
(1) 2 are weighed, in a round bottom flask, the two molar ratio is 2:1~4 for dipicolimic acid 2 and europium nitrate hexahydrate:
1, it is dissolved in 10~40ml dehydrated alcohol, 2, the mass ratio of dipicolimic acid 2 and dehydrated alcohol is 1:200~1:800；
(2) 3~5 drop ammonia spirits are added into system and are adjusted to pH=7；
(3) round-bottomed flask for filling mixture solution is placed in reflux unit, it is small to be heated to reflux 1~2 at 70~90 DEG C
When and be cooled to room temperature；
(4) it collects obtained precipitating to be washed with distilled water twice, then carries out filtering removing excessive moisture using vacuum pump,
Obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
Further, Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe in step c
Preparation method the following steps are included:
(1) rare earth compounding Eu (DPA) is added into the Cellulose nanocrystal CNC suspension that solid content is 0.1-2%3With
Pva powder, at 80~95 DEG C of water-bath 30~70min of mechanical stirring, wherein Cellulose nanocrystal CNC suspension is consolidated
The mass ratio of content and polyvinyl alcohol is 1:2~1:10, and the mass ratio of rare earth compounding and polyvinyl alcohol is 1:200~1:
2000；
(2) when the temperature stabilizes, addition borate crosslink continues stirring until forming gel, makes after cooling completely
Obtain Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe.Wherein borate crosslink and polyethylene
The mass ratio of alcohol is 1:2~1:6.
Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe preparation method, feature exist
Include the following steps: in this method
A. Cellulose nanocrystal CNC is prepared；
B. rare earth compounding Eu (DPA) is prepared3；
C. to Cellulose nanocrystal CNC and rare earth compounding Eu (DPA)3Pva powder and friendship are added in mixed solution
Join agent, stirring forms gel to get Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe is arrived.
Further, it is characterised in that the preparation method of Cellulose nanocrystal CNC uses at chemical bonding machinery in step a
Logos, specific steps include:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 50%~70%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 40-50 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, by delignification plant fiber: sulfuric acid solution is mixed by the mass ratio of 1:10~1:40
It closes, the delignification plant fiber is preferably bleached wood pulp fiber or degreasing cotton fiber；It should lasting stirring in the process；It is being added
During delignification plant fiber, it is careful not to for delignification plant fiber being poured on wall of cup and agitating paddle, after preventing
To generate impurity in transfer process；After delignification plant fiber is added, continue heating stirring 1~3 hour；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, 20~50min of ultrasound removes cellulose for Cellulose nanocrystal under 300~500W power,
Cellulose nanocrystal CNC suspension is prepared, the Cellulose nanocrystal suspension being prepared into is placed on stored under refrigeration in refrigerator
It is spare.
Further, the rare earth compounding preparation in step b, step include:
(1) 2 are weighed, in a round bottom flask, the two molar ratio is 2:1~4 for dipicolimic acid 2 and europium nitrate hexahydrate:
1, it is dissolved in 10~40ml dehydrated alcohol, 2, the mass ratio of dipicolimic acid 2 and dehydrated alcohol is 1:200~1:800；
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7；
(3) round-bottomed flask for filling mixture solution is placed in reflux unit, it is small to be heated to reflux 1~2 at 70~90 DEG C
When and be cooled to room temperature；
(4) it collects obtained precipitating to be washed with distilled water twice, then carries out filtering removing excessive moisture using vacuum pump,
Obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
Further, Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe in step c
Preparation method the following steps are included:
(1) rare earth compounding Eu (DPA) is added into the Cellulose nanocrystal CNC suspension that solid content is 0.1-2%3With
Pva powder, 30~70min of mechanical stirring at 80~95 DEG C of water-bath, the wherein matter of the solid content of CNC and polyvinyl alcohol
Ratio is measured as 1:2~1:10, the mass ratio of rare earth compounding and polyvinyl alcohol is 1:200~1:2000；
(2) when the temperature stabilizes, addition borate crosslink continues stirring until forming gel, makes after cooling completely
Obtain Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe.Wherein borate crosslink and polyethylene
The mass ratio of alcohol is 1:2~1:6.
Weight of the Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe in detection water environment
The application of metal ion.
What technical solution of the present invention was realized has the beneficial effect that
Rare earth compounding is distributed to using polyvinyl alcohol/borate as in the hydrogel of matrix, with sulphuric acid hydrolysis by this research
Cellulose nanocrystal CNC as reinforcing material, to obtain maintain CNC and 2,3 pyridinedicarboxylic acid europium Eu (DPA)3Respectively
Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe material of advantageous feature.The material can have
A variety of excellent properties.
1. hydrogel is using water as the high molecular material with three-dimensional net structure of decentralized medium, have bio-compatibility and
Natural biomass materials cellulose and nontoxic polyvinyl alcohol are introduced into hydrogel, will not generate two by readily degradable
Secondary pollution.
2. making to realize hydrogen bond association between CNC and polyvinyl alcohol by chemical crosslink technique, in colloid internal build 3D network
Structure realizes nanometer enhancing；
3. the hydrogel fluorescence probe of new generation that the present invention prepares has good mechanical property and excellent fluorescence
Energy.In actual use, subject hydrogel probe is more easily portable than fluorescent liquid probe.However existing fluorescence divides on the market
The fluorescence intensity of light photometric determination liquid is more accurate, and the fluorescence intensity for measuring solid is influenced to lead to error by thickness of sample
It is larger.The superiority of hydrogel prepared by the present invention is that the crosslinking of hydrogel is reversible, and adds water and stirs rear hydrogel again
Become liquid, directly survey the fluorescence intensity of liquid, avoids that fluorescence spectrophotometer measurement solid fluorescence intensity error is big to be lacked
It falls into.Accuracy that is easy to operate while ensure that measurement result.Hydrogel fluorescence probe of new generation can be realized weight in water environment
The detection on the spot of metal ion, it is convenient and sensitive, a kind of effective new way is provided for the detection of heavy metal ion in water environment
Diameter.By being crosslinked reversible fluorescence probe, while realizing the portability of solid state fluorescence probe and detecting weight under liquid environment
Metal is quick and precisely.
4. realizing Eu (DPA)3Dual function: within the scope of additive amount of the invention, on the one hand played fluorescence,
Complex reaction occurs with heavy metal ion such as copper ions makes subject hydrogel can be used in heavy metal to make fluorescent quenching
Detection, and sensitivity is higher.On the other hand, Eu (DPA)3As reinforced phase, since there are two hydroxyl, gel-in-matrix polyethylene
The hydroxyl formation hydrogen bond of alcohol, nano-cellulose, increases the mechanical property of hydrogel, improves the mechanical strength of hydrogel.
Detailed description of the invention
Fig. 1 is the stress-strain diagram of embodiment 7-9 hydrogel.
Fig. 2 is the stress-strain diagram of embodiment 4-6,9 hydrogel fluorescence probe of embodiment.
Fig. 3 is the fluorescence intensity of embodiment 1-6 hydrogel fluorescence probe.
Fig. 4 is fluorescence intensity of the fluorescence probe of embodiment 5 in various concentration copper ion solution.
Fig. 5 is 5 Fluorimetric Quenching Method of embodiment detection Cu2+Linear relationship.
Fig. 6 is fluorescence intensity of the fluorescence probe of embodiment 5 in copper ion solution and coexisting ion solution.
Fig. 7 is the examination of infrared spectrum figure of the hydrogel fluorescence probe of embodiment 5, embodiment 7, embodiment 9.
Fig. 8 is the SEM image of the porosity aeroge formed after the hydrogel sample of embodiment 5 is lyophilized.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the requested protection scope of the present invention.
Abbreviation in following embodiment:
Polyvinyl alcohol is abbreviated as PVA, and the English name of crosslinking agent borax is Borax, and the present invention takes PVA and Borax to start
Letter, i.e. PB indicate polyvinyl alcohol hydrogel；
CNC is Cellulose nanocrystal；
Eu(DPA)3It is reduced to Eu3+。
Embodiment 1 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- I (CNC concentration 0.5wt%, Eu3+0.001g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- II, specific method step includes:
(1) take 2g pva powder that the CNC suspension that 100mL solid content is 0.5% is added, 90 DEG C of water-bath, machinery stirs
Mix 50min；
(2) the rare earth compounding Eu (DPA) of 0.001g is added3After continue to stir；
(3) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- II (CNC concentration 0.5wt%, Eu3+0.001g)。
Embodiment 2 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- II (CNC concentration 0.5wt%, Eu3+0.006g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- I, specific method step include:
(1) take 2g pva powder that the CNC suspension that 100mL solid content is 0.5% is added, 90 DEG C of water-bath, machinery stirs
Mix 50min；
(2) the rare earth compounding Eu (DPA) of 0.006g is added3After continue to stir；
(3) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- I (CNC concentration 0.5wt%, Eu3+0.006g)。
Embodiment 3 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- III (CNC concentration 0.5wt%, Eu3+0.01g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- III, specific method step includes:
(1) take 2g pva powder that the CNC suspension that 100mL solid content is 0.5% is added, 90 DEG C of water-bath, machinery stirs
Mix 50min；
(2) the rare earth compounding Eu (DPA) of 0.01g is added3After continue to stir；
(3) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- III (CNC concentration 0.5wt%, Eu3+0.01g)。
Embodiment 4 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- IV (CNC concentration 1wt%, Eu3+0.001g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- V, specific method step includes:
(1) take 2g pva powder be added 100mL solid content be 1% CNC suspension, 90 DEG C of water-bath, mechanical stirring
50min；
(2) the rare earth compounding Eu (DPA) of 0.001g is added3After continue to stir；
(3) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- V (CNC concentration 1wt%, Eu3+0.001g)。
Embodiment 5 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- V (CNC concentration 1wt%, Eu3+0.006g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- IV, specific method step includes:
(1) take 2g pva powder be added 100mL solid content be 1% CNC suspension, 90 DEG C of water-bath, mechanical stirring
50min；
(2) the rare earth compounding Eu (DPA) of 0.006g is added3After continue to stir；
(3) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- IV (CNC concentration 1wt%, Eu3+0.006g)。
Embodiment 6 prepares Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe PB-CNC-
Eu3+- VI (CNC concentration 1wt%, Eu3+0.01g)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) sulfuric acid solution for preparing mass fraction 60% is spare；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, prepares rare earth compounding, and specific steps include:
(1) 2 are weighed, dipicolimic acid 2 50.1mg and europium nitrate hexahydrate 44.6mg in a round bottom flask, add anhydrous
Ethyl alcohol 25ml.
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7.
(3) round-bottomed flask for filling mixture solution is placed in reflux unit and is heated to reflux 1.5 hours and cools down for 85 DEG C
To room temperature.
(4) it collects obtained precipitating to be washed with distilled water twice, then be filtered using vacuum pump, remove superfluous water
Point, obtain the white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
It is compound that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol is prepared in step 3, processes for chemically crosslinked polyethylene alcohol
Hydrogel fluorescence probe, is named as PB-CNC-Eu3+- VI, specific method step includes:
(4) take 2g pva powder be added 100mL solid content be 1% CNC suspension, 90 DEG C of water-bath, mechanical stirring
50min；
(5) the rare earth compounding Eu (DPA) of 0.01g is added3After continue to stir；
(6) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-Eu is obtained afterwards3+- VI (CNC concentration 1wt%, Eu3+0.01g)。
The preparation of embodiment 7 is for control, polyvinyl alcohol composite hydrogel PB
Step 1, processes for chemically crosslinked polyethylene alcohol/borax prepare hydrogel, are named as PB, and specific method step includes:
(1) take 2g pva powder that 100mL deionized water, at 90 DEG C of water-bath, mechanical stirring 50min is added；
(2) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB hydrogel is obtained afterwards.
The preparation of embodiment 8 is for control, and (CNC's Cellulose nanocrystal-polyvinyl alcohol composite hydrogel PB-CNC-I suspends
0.5%) fluid solid content is
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 60%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, chemical crosslinking preparation Cellulose nanocrystal-polyvinyl alcohol composite hydrogel, is named as PB-CNC-I,
Specific method step includes:
(1) take 2g pva powder be added 100mL0.5% CNC suspension, 90 DEG C of water-bath, mechanical stirring 50min；
(2) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-I is obtained afterwards.
Embodiment 9 prepares Cellulose nanocrystal-polyvinyl alcohol composite hydrogel PB-CNC-II, and (CNC suspension solid content is
1%)
Step 1, cellulose are prepared into CNC by being chemically combined mechanical treatment process, and specific method step includes:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 60%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 45 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, cotton fiber is carefully added into sulfuric acid by the mass ratio of 1:20, should be held in the process
Continuous stirring；It during cotton fiber is added, is careful not to for cotton fiber being poured on wall of cup and agitating paddle, prevents from shifting later
Impurity is generated in journey；After cotton fiber is added, continue heating stirring 2 hours；
4) gained suspension is poured into a beaker, supernatant liquor after distilled water is stood is added and pours out, this is repeated several times
Operated wash；Suspension is poured into bag filter, is dialysed in flowing water to neutrality.
(2) mechanical treatment process:
In ice-water bath, ultrasound 30min removes cellulose for Cellulose nanocrystal under 400W power, that is, prepares fiber
The nanocrystalline CNC suspension of dimension element, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
Step 2, chemical crosslinking preparation Cellulose nanocrystal-polyvinyl alcohol composite hydrogel, is named as PB-CNC-II,
Specific method step includes:
(1) take 2g pva powder be added 100mL1% CNC suspension, 90 DEG C of water-bath, mechanical stirring 50min；
(2) when the temperature stabilizes, 0.4g borax is added as crosslinking agent, continues stirring until formation gel, completely cooling
PB-CNC-II is obtained afterwards.
The application of heavy metal ion of 10 hydrogel of embodiment in detection water environment
Take 1g PB-CNC-Eu3+Hydrogel, adds 10mL deionized water, and stirring is to being completely dissolved.
Take 1g PB-CNC-Eu3+Hydrogel is dissolved in the aqueous solution of 10g copper ion containing various concentration, copper ion concentration point respectively
It Wei 10-6mol/L、10-5mol/L、2×10-5mol/L、3×10-5mol/L、4×10-5mol/L。
In on 55 sepectrophotofluorometer of LS (Perkin Elmer), if excitation wavelength is 285nm, launch wavelength is
610-640nm, slit 2.5nm, scanning speed are set as 200, measure the fluorescence intensity (Fig. 5) of solution.
The application of heavy metal ion of 11 hydrogel of embodiment in detection water environment
Take 1g PB-CNC-Eu3+Hydrogel, adds 10mL deionized water, and stirring is to being completely dissolved.
Take 1g PB-CNC-Eu3+Hydrogel is dissolved in 10g 10-6Mol/L copper ion solution.
Take 1g PB-CNC-Eu3+Hydrogel is dissolved in 10g 10-6The mixed solution that mol/L copper, cadmium ion coexist.
In on 55 sepectrophotofluorometer of LS (Perkin Elmer), if excitation wavelength is 285nm, launch wavelength is
610-640nm, slit 2.5nm, scanning speed are set as 200, measure the fluorescence intensity (Fig. 6) of solution.
Fig. 1 be embodiment 7 prepare PB, embodiment 8 prepare PB-CNC-I, embodiment 9 prepare PB-CNC-II water-setting
The compression performance of glue is tested, and has figure it is found that the compression strength of PB hydrogel is minimum, the compression strength of PB-CNC-I at 40%
About the 2 of PB times, the compression strength of PB-CNC-II is about 6 times of PB.Show that the addition of CNC can significantly improve water-setting matrix
The compression strength of body, and CNC solid content be 1% when, compression strength is more excellent；
Fig. 2 is PB-CNC-Eu prepared by embodiment 43- IV, PB-CNC-Eu prepared by embodiment 53+- V, embodiment 6 is made
Standby PB-CNC-Eu3+- VI, the compression performance test of the hydrogel of PB-CNC-II prepared by embodiment 9 is added as seen from the figure
Eu3+Afterwards, the PB-CNC-II that hydrogel compressive property is prepared relative to embodiment 9 is further enhanced, and PB-CNC-Eu3-Ⅳ、
PB-CNC-Eu3+-Ⅴ、PB-CNC-Eu3+- VI compression strength successively enhances, and shows to increase Eu (DPA)3Amount can effectively mention
The compression strength of high hydrogel fluorescence probe.
Fig. 3 is PB-CNC-Eu prepared by embodiment 13PB-CNC-Eu prepared by-I, embodiment 23It is prepared by-II, embodiment 3
PB-CNC-Eu3PB-CNC-Eu prepared by-III, embodiment 43- IV, PB-CNC-Eu prepared by embodiment 53+- V, embodiment
The PB-CNC-Eu of 6 preparations3+The fluorescence intensity of-VI hydrogel.As seen from the figure in a certain range the fluorescence intensity of sample with Eu
(DPA)3Increase and enhance, be more than optimum range after, fluorescence intensity is begun to decline.Influence of the addition of TOCN to fluorescence intensity
It is little.
Fig. 4 is PB-CNC-Eu prepared by example 53+- V is added the fluorescence intensity in the copper ion solution of various concentration.
620nm nearby generates fluorescence emission peak, mainly by high level5D→7F transition generates.Fluorescent quenching shows after immersion copper ion
As obvious, due to Cu2+It can be effectively coordinated with rare earth compounding, the electronics or energy transfer of intramolecular lead to fluorescent quenching.It says
Bright Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe of the invention can be used to detect water ring
Heavy metal ion in border.When copper ion concentration is 10-6When mol/L, it still is able to accurately detect.
Fig. 5 is PB-CNC-Eu prepared by example 53+- V hydrogel fluorescence probe (PB-CNC-Eu3+) relative fluorescence it is strong
Spend Δ F and lnC (Cu2+) linear relationship, this experiment process method such as embodiment 10, equation of linear regression y=0.1366x
+ 2.0253, linearly dependent coefficient R2=0.9201.Show that the fluorescence probe of preparation can be to Cu2+Carry out quantitative detection.
Fig. 6 is PB-CNC-Eu prepared by embodiment 53+- V is added 10-6Mol/L copper ion solution and 10-6Mol/L copper, cadmium
The mixed solution that ion coexists.It is respectively designated as PB-CNC-Eu3+- Cu and PB-CNC-Eu3+-Cu-Cd.This experiment process method
Such as embodiment 11, as shown in figure, PB-CNC-Eu3+The fluorescence intensity of-Cu-Cd is lower, illustrates coexistent metallic ion to copper ion
Detection has an impact, and hydrogel fluorescence probe prepared by the present invention being capable of various heavy effectively in detection of complex water environment.
Fig. 7 is prepared by the PB hydrogel of the preparation of embodiment 7, the PB-CNC-II hydrogel of the preparation of embodiment 9 and example 5
PB-CNC-Eu3+The infrared spectrogram of-V hydrogel fluorescence probe.By the test of chemical functional group, find PB in 1429cm-1
The absorption peak at place is the asymmetric stretching vibration of B-O-C, in 845cm-1And 661cm-1The absorption peak at place is respectively B-O and B-O-B
Stretching vibration, it was confirmed that the crosslinking of PVA and borax.PB hydrogel, PB-CNC-II hydrogel and PB-CNC-Eu3+Hydrogel by
In O-H key stretching vibration and in 3326cm-1Nearby there is a wider absorption peak, and PB-CNC-Eu3+The peak of hydrogel
Intensity ratio PB-TOCN hydrogel, the peak intensity of PB hydrogel are high, it was demonstrated that form hydrogen between CNC, PVA, rare earth compounding and borax
Key.To sum up, CNC and rare earth compounding, which crosslink under the effect of crosslinking agent borax with polyvinyl alcohol, reacts, and generates Hydrogenbond,
Tridimensional network is formed, hydrogel is made to keep better stability.
Fig. 8 is PB-CNC-Eu prepared by example 53+The SEM of the porosity aeroge formed after the freeze-drying of-V hydrogel sample
Image.Show that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe porous structure forms surely
Fixed three-dimensional net structure.
Claims (9)
1. a kind of Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe, it is characterised in that the water-setting
What glue was prepared using following method:
A. Cellulose nanocrystal CNC is prepared；
B. rare earth compounding Eu (DPA) is prepared3；
C. to Cellulose nanocrystal CNC and rare earth compounding Eu (DPA)3Pva powder and crosslinking are added in mixing suspension
Agent, stirring form gel to get Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe is arrived.
2. Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe according to claim 1,
It is characterized in that the preparation method of Cellulose nanocrystal CNC is using chemical bonding mechanical treatment process, specific steps packet in step a
It includes:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 50%~70%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 40-50 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, by delignification plant fiber: sulfuric acid solution is mixed by the mass ratio of 1:10~1:40, institute
Stating delignification plant fiber is preferably bleached wood pulp fiber or degreasing cotton fiber；It should lasting stirring in the process；Wood is removed in addition
It during quality plant fiber, is careful not to for delignification plant fiber being poured on wall of cup and agitating paddle, prevents from turning later
Impurity is generated during moving；After delignification plant fiber is added, continue heating stirring 1~3 hour；
4) gained suspension is poured into a beaker, is added after distilled water is stood and pours out supernatant liquor, this behaviour is repeated several times
It washs；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, 20~50min of ultrasound removes cellulose for Cellulose nanocrystal under 300~500W power, that is, makes
Standby Cellulose nanocrystal CNC suspension out, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
3. Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe according to claim 1,
It is characterized in that prepared by the rare earth compounding in step b, step includes:
(1) 2 are weighed, in a round bottom flask, the two molar ratio is 2:1~4:1, molten for dipicolimic acid 2 and europium nitrate hexahydrate
In 10~40ml dehydrated alcohol, 2, the mass ratio of dipicolimic acid 2 and dehydrated alcohol is 1:200~1:800；
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7；
(3) round-bottomed flask for filling mixture solution is placed in reflux unit, 1~2 hour is heated to reflux at 70~90 DEG C simultaneously
It is cooled to room temperature；
(4) it collects obtained precipitating to be washed with distilled water twice, then carries out filtering removing excessive moisture using vacuum pump, obtain
The white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
4. Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe according to claim 1,
It is characterized in that Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe preparation method in step c
The following steps are included:
(1) rare earth compounding Eu (DPA) is added in the Cellulose nanocrystal CNC suspension for being 0.1~2% to solid content3With poly- second
Enol powder, 30~70min of mechanical stirring at 80~95 DEG C of water-bath, the wherein mass ratio of the solid content of CNC and polyvinyl alcohol
For 1:2~1:10, the mass ratio of rare earth compounding and polyvinyl alcohol is 1:200~1:2000；
(2) when the temperature stabilizes, addition borate crosslink continues stirring until forming gel, obtains fibre after cooling completely
Tie up plain nanocrystalline-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe；Wherein borate crosslink and polyvinyl alcohol
Mass ratio is 1:2~1:6.
5. Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe preparation side described in claim 1
Method, it is characterised in that this method includes the following steps:
A. Cellulose nanocrystal CNC is prepared；
B. rare earth compounding Eu (DPA) is prepared3；
C. to Cellulose nanocrystal CNC and rare earth compounding Eu (DPA)3Pva powder and crosslinking are added in mixing suspension
Agent, stirring form gel to get Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe is arrived.
6. preparation method according to claim 5, it is characterised in that the preparation method of Cellulose nanocrystal CNC in step a
Using chemical bonding mechanical treatment process, specific steps include:
(1) method of chemical treatment:
1) it is spare to prepare the sulfuric acid solution that mass fraction is 50%~70%；
2) the sulfuric acid solution oil bath prepared heating is stablized to 40-50 DEG C and continues to stir；
3) when sulfuric acid temperature is constant, by delignification plant fiber: sulfuric acid solution is mixed by the mass ratio of 1:10~1:40, institute
Stating delignification plant fiber is preferably bleached wood pulp fiber or degreasing cotton fiber；It should lasting stirring in the process；Wood is removed in addition
It during quality plant fiber, is careful not to for delignification plant fiber being poured on wall of cup and agitating paddle, prevents from turning later
Impurity is generated during moving；After delignification plant fiber is added, continue heating stirring 1~3 hour；
4) gained suspension is poured into a beaker, is added after distilled water is stood and pours out supernatant liquor, this behaviour is repeated several times
It washs；Suspension is poured into bag filter, is dialysed in flowing water to neutrality；
(2) mechanical treatment process:
In ice-water bath, 20~50min of ultrasound removes cellulose for Cellulose nanocrystal under 300~500W power, that is, makes
Standby Cellulose nanocrystal CNC suspension out, it is spare to be placed on stored under refrigeration in refrigerator for the Cellulose nanocrystal suspension being prepared into.
7. preparation method according to claim 5, it is characterised in that the rare earth compounding preparation in step b, step include:
(1) 2 are weighed, in a round bottom flask, the two molar ratio is 2:1~4:1, molten for dipicolimic acid 2 and europium nitrate hexahydrate
In 10~40ml dehydrated alcohol, 2, the mass ratio of dipicolimic acid 2 and dehydrated alcohol is 1:200~1:800；
(2) 3~5 drop ammonia spirits are added into system and adjust pH=7；
(3) round-bottomed flask for filling mixture solution is placed in reflux unit, 1~2 hour is heated to reflux at 70~90 DEG C simultaneously
It is cooled to room temperature；
(4) it collects obtained precipitating to be washed with distilled water twice, then carries out filtering removing excessive moisture using vacuum pump, obtain
The white powder of the fluorescent material containing europium, i.e. rare earth compounding Eu (DPA)3。
8. preparation method according to claim 5, it is characterised in that Cellulose nanocrystal-rare earth compounding-is poly- in step c
The preparation method of vinyl alcohol composite hydrogel fluorescence probe the following steps are included:
(1) rare earth compounding Eu (DPA) is added in the Cellulose nanocrystal CNC suspension for being 0.1~2% to solid content3With poly- second
Enol powder, 30~70min of mechanical stirring at 80~95 DEG C of water-bath, the wherein mass ratio of the solid content of CNC and polyvinyl alcohol
For 1:2~1:10, the mass ratio of rare earth compounding and polyvinyl alcohol is 1:200~1:2000；
(2) when the temperature stabilizes, addition borate crosslink continues stirring until forming gel, obtains fibre after cooling completely
Tie up plain nanocrystalline-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe；Wherein borate crosslink and polyvinyl alcohol
Mass ratio is 1:2~1:6.
9. Cellulose nanocrystal-rare earth compounding-polyvinyl alcohol composite hydrogel fluorescence probe described in claim 1 is detecting
The application of heavy metal ion in water environment.
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