CN115011343B - Composite nanomaterial based on up-conversion nanocrystalline and Au nanoparticle as well as preparation method and application thereof - Google Patents
Composite nanomaterial based on up-conversion nanocrystalline and Au nanoparticle as well as preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 55
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002159 nanocrystal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 230000005284 excitation Effects 0.000 claims description 10
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000002835 absorbance Methods 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002082 metal nanoparticle Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 4
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- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 70
- 238000001308 synthesis method Methods 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000003911 water pollution Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- -1 pharmaceutical Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000010223 real-time analysis Methods 0.000 description 2
- 238000002165 resonance energy transfer Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 208000032140 Sleepiness Diseases 0.000 description 1
- 206010041349 Somnolence Diseases 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002866 fluorescence resonance energy transfer Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention relates to a composite nano material based on up-conversion nano crystal and Au nano particles, a preparation method and application thereof, and prepared NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material is formed by combining noble metal nano particles and up-conversion nano crystals, has uniform size, good dispersibility, and good water solubility, and can be used for specific up-conversion fluorescence detection of 4-NP in aqueous solution and catalytic reduction of 4-NP in aqueous solution, and noble metal is loaded on the surface of up-conversion nano crystals, so that the problems of reduced catalytic activity and cycle catalytic performance of the noble metal nano particles caused by small size and easy aggregation of the noble metal nano particles are solvedThe problem of reduction can effectively improve the phenomenon of reduction of catalytic performance caused by precious metal agglomeration. Furthermore, the present invention relates to the use of deionized water as a solvent in the synthesis process, and a rapid, energy-efficient and low cost one-step synthesis process.
Description
Technical Field
The invention belongs to the technical field of up-conversion nanocrystalline materials, and relates to a composite nanomaterial based on up-conversion nanocrystalline and Au nanoparticles, a preparation method and application thereofThe method is used, in particular to a composite NaYF based on up-conversion nanocrystalline and Au nano-particles 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nanomaterial can be used for specific fluorescence detection of 4-NP in aqueous solution and catalytic reduction of 4-NP in aqueous solution.
Background
One of the main causes of current water pollution is the release of compounds, especially dyes and other organic chemicals, into the water supply. Among organic compounds, compounds containing a phenol functional group are a major threat to water pollution due to their high solubility and stability in aqueous solutions. Among them, 4-nitrophenol (4-NP), one of the phenolic compounds, is widely used in the dye, paper, pharmaceutical, agricultural chemical, petroleum industries, and is also a chemical precursor of 4-aminophenol. Although 4-NPs have high utility, the maximum allowable limit in drinking water is 0.06 μg/mL, 4-NPs are toxic to humans, animals and plants, and short-term exposure can lead to headache, nausea and somnolence. In addition, 4-NP is poorly biodegradable and highly stable, complicating its removal in soil and contaminated wastewater. It is therefore necessary to remove it from the wastewater and water source. Currently, various strategies for detecting 4-NPs have been involved, including liquid chromatography-mass spectrometry, electrochemical, photochemical, high performance liquid chromatography, and fuel cell-based sensing platforms, but these methods often require cumbersome, expensive instrumentation, complex sample pretreatment or electrode modification, and time-consuming detection procedures, limiting their widespread use. Among various analysis methods, the 4-NP fluorescence spectrum detection technology is an analysis technology with the advantages of high sensitivity, high selectivity, quick response, convenience, real-time analysis and the like, and is widely applied to the field of analytical chemistry. However, the absorption wavelength of 4-NP is relatively short (300 nm-425 nm), the currently reported 4-NP fluorescence detection method is based on that the absorption wavelength of 4-NP is consistent with the excitation light wavelength of a fluorescent material, and the 4-NP absorbs part of excitation light to cause the fluorescence of the fluorescent material to be weakened, so that the 4-NP concentration in water pollution is sensitively and accurately detected based on Electron Transfer (ET) or Forst Resonance Energy Transfer (FRET) induced fluorescence quenching. In addition, the catalytic reduction of 4-NP based on noble metal nano particles is easy to aggregate due to the small size of the noble metal nano particles, so that the catalytic activity of the noble metal nano particles is reduced and the circulating catalytic performance is reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide NaYF formed by combining noble metal Au nano particles and up-conversion nano crystals in order to overcome the problems existing in the prior art 4 :Yb 3+ /Tm 3+ @NaYF 4 The invention can not only sensitively and accurately detect the concentration of 4-NP in water pollution based on the up-conversion fluorescence quenching induced by the FRET of the Forst resonance energy transfer, but also be used for the catalytic reduction degradation of 4-NP in water solution.
Another object of the present invention is to provide NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 A preparation method of an Au composite nano-material.
It is a further object of the present invention to provide NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Application of an Au composite nano-material.
The technical scheme adopted for solving the technical problems of the invention is as follows:
NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nano material is prepared by adopting a high-temperature solvothermal method, and comprises the following components in percentage by weight:
(1)NaYF 4 :Yb 3+ /Tm 3+ nanocrystalline: 0.415mmol YCl 3 ·6H 2 O、0.58mmol YbCl 3 ·6H 2 O、0.005mmol TmCl 3 ·6H 2 O；
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Nanocrystalline: 0.5mmol YCl 3 ·6H 2 O、1 mmolNaYF 4 :Yb 3+ /Tm 3+ A nanocrystalline;
(3)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @ Au composite nanomaterial: 0.125mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Nanocrystalline, 1mg HAuCl 4 。
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 The preparation method of the@Au composite nanomaterial is characterized by comprising the following steps of:
(1)NaYF 4 :Yb 3+ /Tm 3+ the preparation method of the nanocrystalline comprises the following steps: will be 0.415mmolYCl 3 ·6H 2 O、 0.58mmol YbCl 3 ·6H 2 O、0.005mmol TmCl 3 ·6H 2 Stirring and heating O, 6mL oleic acid and 15mL 1-octadecene under nitrogen, heating to 100-110deg.C, displacing oxygen and residual water with vacuum system for 2-3 times, heating to 150-160deg.C, maintaining under 6-8mL/min nitrogen flow for 60-70min to obtain transparent yellow solution, cooling to room temperature, adding 4mmol NH under stirring 4 F and 8-10mL of 2.5 mmoles of NaOH in methanol, stirring at room temperature for 30-120min, heating to 50-60 ℃, reacting for 20-30min under 38-42mL/min nitrogen flow, replacing 2-3 times at 100-110 ℃ by using a vacuum system, heating to 300-305 ℃ under 6-8mL/min nitrogen flow, preserving heat for 60-90min, adding excessive ethanol when the reaction system is cooled to room temperature, and centrifuging to obtain a product;
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the preparation method of the nanocrystalline comprises the following steps: will be 0.5mmol YCl 3 ·6H 2 Stirring O, 6mL of oleic acid and 15mL of 1-octadecene under nitrogen, heating to 100-110 ℃ and replacing for 2-3 times by a vacuum system, then heating to 150-160 ℃ and maintaining for 60-70min under nitrogen flow, obtaining transparent yellow solution, cooling to room temperature, and then cooling 1mmol of NaYF prepared in the step (1) 4 :Yb 3+ /Tm 3+ Nanocrystalline, containing 2mmolNH 4 F and 8-10mL of methanol solution of 1.25 mmole of NaOH are uniformly stirred and added into transparent yellow solution to react for 30-120min, then the mixture is heated to 50-60 ℃, the mixture reacts for 20-30min under the nitrogen flow of 38-42mL/min to remove methanol in the reaction mixture, oxygen, residual water and methanol in the system are replaced by a vacuum system at 100-110 ℃, then the mixture is heated to 300-305 ℃ under the nitrogen flow of 6-8mL/min to keep the temperature for 60-90min, and when the reaction system is cooled to room temperature, excessive ethanol is added to centrifuge to obtain a product;
(3)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @Authe preparation method of the composite nano material comprises the following steps: taking 0.125mmol clean NaYF prepared in the step (2) 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing the nanocrystalline into 20-25mL deionized water, stirring, sequentially adding 100-200mg polyvinylpyrrolidone PVP and 100-200mg 2-morpholinoethanesulfonic acid MES, ultrasonically dissolving, and adding 0.1mL 1g/100mL HAuCl 4 Adding 0.5mgNaBH into the aqueous solution 4 Stirring and reacting the solid powder for 10-20 minutes, and finally centrifuging for 7-10 minutes at 9000-10000r to obtain NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @au composite nanomaterial.
The clean NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Nanocrystalline is prepared by subjecting 0.5mmol NaYF prepared in step (2) 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing the nanocrystalline in 6-10mL chloroform by ultrasonic wave, adding into 10-15mL aqueous solution dissolved with 0.2g cetyltrimethylammonium bromide CTAB, stirring for 30-60 min, placing into 50-60 ℃ water bath, stirring for 20-30min, centrifuging, washing the centrifuged precipitate with 60-80 ℃ hot water, centrifuging to obtain clean NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @au composite nanomaterial.
The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nano-material is used for specific fluorescence detection of 4-NP in an aqueous solution or catalytic reduction of 4-NP in an aqueous solution.
The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The method for specific fluorescence detection of 4-NP in aqueous solution by the@Au composite nanomaterial comprises the following steps: 1/64mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The nano Au composite material is ultrasonically dispersed in 3mL of aqueous solution with the concentration of 4-NP of 0.01 mug/mL, 0.1 mug/mL, 1 mug/mL, 10 mug/mL, 25 mug/mL, 50 mug/mL, 75 mug/mL and 100 mug/mL respectively, and the peak intensity of the collected up-conversion fluorescence spectrum is analyzed for quantitative detection of 4-NP in the aqueous solution under the excitation of 980nm excitation light sources with the same test conditions and the same intensity.
The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The relative up-conversion fluorescence spectrum peak intensity ratio R of the@Au composite nano material accords with the exponential relation with the optical system of 4-NP concentration C in the aqueous solution, and R= 1.20309 ×e 0.03524C The optical system between the lnR value and the 4-NP concentration C accords with the linear relation, lnR=0.09418+0.03524C, and the two relations can be used for quantitative detection of 4-NP in aqueous solution, wherein R is the ratio of the intensity of an emission peak at 450nm to the intensity of an emission peak at 350 nm.
The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nano-material is used for catalytic reduction of 4-NP in an aqueous solution, and the specific method is as follows: at room temperature, a 4mL quartz cuvette is used as a reaction vessel for catalytic reaction, and a 722N visible spectrophotometer is used for monitoring the absorbance of the solution in the reaction process, specifically: 1/64mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nanomaterial was sonicated to 3mL of 4-NP aqueous solution of varying concentrations diluted with deionized water, wherein the 4-NP aqueous solution was at a concentration of 0.01. Mu.g/mL, 0.1. Mu.g/mL, 1. Mu.g/mL, 10. Mu.g/mL, 25. Mu.g/mL, 50. Mu.g/mL, 75. Mu.g/mL, 100. Mu.g/mL, respectively, and then 100. Mu.L of 0.2mmol/mLNaBH was added 4 The change in absorbance of the solution was monitored and recorded at λ=400 nm for the aqueous solution.
The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nanomaterial can be repeatedly used for catalytic reduction of 4-NP in an aqueous solution.
NaYF prepared by the invention 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material is formed by combining noble metal nano particles and upper conversion nano crystals, has uniform size and good dispersity, and the surface is uniformly loaded with the Au nano particles with the size of a few nanometers, so that the composite nano material has good water solubility. The method can be used for not only the specific up-conversion fluorescence detection of 4-NP in aqueous solution, but also the catalytic reduction of 4-NP in aqueous solution, and the noble metal is loaded on the surface of up-conversion nanocrystalline, so that the problems of reduced catalytic activity and reduced cyclic catalytic performance of noble metal nanoparticles caused by small size and easy aggregation of noble metal nanoparticles are solved, and the phenomenon of reduced catalytic performance caused by agglomeration of noble metal can be effectively improvedLike a Chinese character. In addition, the present invention relates to the use of deionized water as a solvent in the synthesis process, and a rapid, energy-efficient and low cost one-step synthesis process, thereby providing a more green process for nanocomposite fabrication.
The invention (1) NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The up-conversion nanocrystalline has unique up-conversion fluorescence characteristics, namely ultraviolet-visible light is radiated under Near Infrared (NIR) excitation, the emission band is clear (sharp line spectrum), the attenuation time is long, and the photochemical stability is good. Therefore, up-conversion fluorescence as a fluorescence signal under Near Infrared (NIR) excitation can effectively reduce background noise in complex detection systems.
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Partial up-conversion fluorescence of the @ Au composite nanomaterial is overlapped with absorption of 4-NP, and NaYF is utilized 4 :Yb 3+ /Tm 3+ @NaYF 4 The up-conversion fluorescence spectrum technology for detecting 4-NP in the aqueous solution by the Au composite nano-material has the advantages of high sensitivity, high selectivity, high accuracy, quick response, convenience, real-time analysis and the like.
(3) The NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The optical system of the ratio R (the ratio of the intensity of an emission peak at 450nm to the intensity of an emission peak at 350 nm) of the relative up-conversion fluorescence intensity of the@Au composite nanomaterial accords with the exponential relation between the concentration C of 4-NP, and R= 1.20309 ×e 0.03524C The optical system between the ln value of the up-conversion fluorescence intensity R and the 4-NP concentration C accords with the linear relation, lnR=0.09418+0.03524C, can be used for quantitative detection of 4-NP in aqueous solution, and has very low detection limit of 0.01 mug/mL. NaYF of the invention 4 :Yb 3+ /Tm 3+ (core) Yb for rare earth ion pair 3+ -Tm 3+ Codoping, up-conversion by energy transfer into a primary energy transfer mechanism: yb 3+ Absorbing 980nm near infrared light 2 F 7/2 → 2 F 5/2 ) The resulting energy is then transferred to the adjacent Tm 3+ The respective excited state energy levels of the ions can then radiate the violet up-conversion fluorescence of two-photon and three-photon processes through a radiative relaxation processLight. NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@Shell) in NaYF 4 :Yb 3+ /Tm 3+ Epitaxial growth of a layer of inert NaYF on the surface of (core) nanocrystals 4 The layer can obviously enhance up-conversion fluorescence. NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Composite nanomaterial of @ Au (core @ shell @ Au): the core@shell nanocrystal is converted into water solubility, and the surface of the core@shell nanocrystal is converted into Au nanoparticle by utilizing intermolecular acting force to form the core@shell@Au composite nanomaterial.
Drawings
FIG. 1 is a NaYF of the invention 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@shell) nanocrystals and NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Transmission Electron Microscope (TEM) image of the composite nano material of the core@shell@Au;
FIG. 2 is a NaYF of the invention 4 :Yb 3+ /Tm 3+ @NaYF 4 Up-conversion fluorescence spectrum and ultraviolet-visible absorption spectrum of 4-NP of a core@shell@Au composite nanomaterial;
FIG. 3 shows NaYF of the present invention in the range of 0-100. Mu.g/mL 4 :Yb 3+ /Tm 3+ @NaYF 4 @Au
The relative up-conversion fluorescence intensity ratio R of the (core@shell@Au) composite nanomaterial is exponentially related to the concentration C of 4-NP: r= 1.20309 ×e 0.03524C And a linear correlation between the relative up-conversion fluorescence intensity lnR of the composite nanomaterial and the 4-NP concentration C: lnr=0.09418+0.03524c;
FIG. 4 is a sample of the invention of example 4 with 1/64mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @Au
(core@Shell@Au) up-conversion fluorescence spectrogram measured by ultrasonic dispersion in 3mL of 4-NP aqueous solution with unknown concentration;
FIG. 5 shows the same concentration of NaYF according to the invention 4 :Yb 3+ /Tm 3+ @NaYF 4 Nano composite material of copper and shell and in process of catalyzing and reducing 4-NP water solution with different concentration 0 ) Reaction withA relationship diagram of time t;
FIG. 6 is a NaYF of the invention 4 :Yb 3+ /Tm 3+ @NaYF 4 The recycling performance of the 4-NP aqueous solution of which the catalyst is reduced for 25 mug/ml for 5 times continuously is achieved by the composite nano material of core@shell@Au.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Example 1
NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The @ Au composite nano material is prepared by adopting a high-temperature solvothermal method, and comprises the following components in percentage by weight:
(1)NaYF 4 :Yb 3+ /Tm 3+ (core) nanocrystals: YCl 3 ·6H 2 O(0.415mmol)、YbCl 3 ·6H 2 O (0.58mmol)、TmCl 3 ·6H 2 O(0.005mmol)
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@shell) nanocrystals: 0.5mmol YCl 3 ·6H 2 O、 1mmolNaYF 4 :Yb 3+ /Tm 3+ (core) nanocrystals
(3)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Composite nanomaterial of @ Au (core @ shell @ Au): 1/8mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@Shell) nanocrystalline, 1mg HAuCl 4 。
Example 2
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 The preparation method of the@Au composite nanomaterial comprises the following specific synthesis method:
(1)NaYF 4 :Yb 3+ /Tm 3+ the specific synthesis method of the nanocrystalline comprises the following steps: YCl was added to each 100mL three-necked flask 3 ·6H 2 O(0.415mmol)、YbCl 3 ·6H 2 O(0.58mmol)、TmCl 3 ·6H 2 O (0.005 mmol), oleic acid (6 mL) and 1-octadecene (15 mL) were heated to 100deg.C with a temperature-controlled electric heating mantle under nitrogen flow and magnetic stirring, and a vacuum system was usedDisplacing oxygen and residual water for 2 times, heating the mixture to 150deg.C, maintaining under nitrogen flow of 8mL/min for 60min to obtain transparent yellow solution, cooling to room temperature, and adding 8mL of NH-containing solution under stirring 4 F (4 mmol) and NaOH (2.5 mmol) in methanol, stirring at room temperature for 120min, heating the solution to 50 ℃, reacting for 20min under a nitrogen flow with the flow of 38mL/min to remove methanol in a reaction mixture, replacing oxygen, residual water and methanol by a vacuum system for 3 times at 100 ℃ at the vacuum system, heating to 300 ℃ under a nitrogen flow atmosphere with the flow of 6mL/min, preserving heat for 60min, adding excessive ethanol when the reaction system is cooled to room temperature, centrifuging to obtain a product, washing the product with cyclohexane for multiple times, and dispersing the product into cyclohexane for use;
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the specific synthesis method of the (core@shell) nanocrystalline comprises the following steps: will be 0.5mmol YCl 3 ·6H 2 O, oleic acid (6 mL) and 1-octadecene (15 mL) are respectively added into a three-neck flask with 100mL, the mixture is heated to 100 ℃ by a temperature-controlled electric heating sleeve under the condition of nitrogen flow and magnetic stirring, the mixture is replaced by a vacuum system for 2 times, oxygen and residual water in the system are replaced by the vacuum system, then the mixture is heated to 150 ℃ and kept under the condition of nitrogen flow for 60min, a transparent yellow solution is obtained, and after the mixture is cooled to room temperature, the prepared NaYF is obtained 4 :Yb 3+ /Tm 3+ (core) nanoparticles (1 mmol) were added to the flask, and then 8mL NH-containing 4 F (2 mmol) and NaOH (1.25 mmol) are uniformly stirred and added into a transparent yellow solution for 120min, then the solution is heated to 50 ℃, the reaction is carried out for 20min under a nitrogen flow of 40mL/min to remove methanol in a reaction mixture, oxygen, residual water and methanol in the system are replaced out for 2 times under the temperature of 100 ℃ by a vacuum system, then the mixture is heated to 300 ℃ under the atmosphere of 6mL/min nitrogen flow, the temperature is kept for 60min, and when the reaction system is cooled to room temperature, excessive ethanol is added, and the product is obtained by centrifugation;
(3)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the specific synthesis method of the composite nano material of the@Au (core@shell@Au) comprises the following steps: coating NaYF with 0.5mmol oleic acid 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@Shell) nanocrystals were dispersed ultrasonically in 6mL of chloroform, then added to 10mL of a CTAB aqueous solution in which 0.2g was dissolved, magnetically stirred for 30 minutes, then the mixture was placed in a water bath at 60℃for 20 minutes to remove chloroform, a transparent solution was obtained, the product was centrifuged, washed once with hot water at 60℃and centrifuged again, and 1/8mmol of centrifuged NaYF was obtained 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing (core@Shell) nanocrystals into 20mL deionized water, sequentially adding 100mg PVP and 200mg MES under stirring, ultrasonically dissolving, and adding 0.1mL 1g/100mL HAuCl 4 Aqueous solution and 0.5mg NaBH 4 The solid powder is stirred for 10 minutes and centrifuged for 10 minutes at 9000r/min to obtain NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @Au
(core@shell@Au) composite nanomaterial.
Example 3
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 The preparation method of the@Au composite nanomaterial comprises the following specific synthesis method:
(1)NaYF 4 :Yb 3+ /Tm 3+ the specific synthesis method of the nanocrystalline comprises the following steps: YCl was added to each 100mL three-necked flask 3 ·6H 2 O(0.415mmol)、YbCl 3 ·6H 2 O(0.58mmol)、TmCl 3 ·6H 2 O (0.005 mmol), oleic acid (6 mL) and 1-octadecene (15 mL) under nitrogen flow and magnetic stirring, heating the mixture to 110deg.C with a temperature-controlled electric heating jacket, displacing 3 times with a vacuum system to displace oxygen and residual water, heating the mixture to 160deg.C, maintaining under 6mL/min nitrogen flow for 70min to obtain transparent yellow solution, cooling to room temperature, and uniformly adding 10mL of solution containing NH under stirring 4 F (4 mmol) and NaOH (2.5 mmol) under stirring at room temperature for 30min, heating to 60deg.C, reacting under 42mL/min nitrogen flow for 20min to remove methanol in the reaction mixture, displacing oxygen, residual water and methanol with vacuum system at 110deg.C for 2 times, heating to 305 deg.C under 8mL/min nitrogen flow atmosphere, maintaining the temperature for 90min, cooling to room temperature, adding excessive ethanol, centrifuging to obtain the final productThe product is washed by cyclohexane for a plurality of times and then dispersed into cyclohexane for use;
(2)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the specific synthesis method of the (core@shell) nanocrystalline comprises the following steps: will be 0.5mmol YCl 3 ·6H 2 O, oleic acid (6 mL) and 1-octadecene (15 mL) are respectively added into a three-neck flask with 100mL, the mixture is heated to 110 ℃ by a temperature-controlled electric heating sleeve under the condition of nitrogen flow and magnetic stirring, the mixture is replaced by a vacuum system for 3 times, oxygen and residual water in the system are replaced by the vacuum system, then the mixture is heated to 160 ℃ and kept under the condition of nitrogen flow for 70min, a transparent yellow solution is obtained, and after the mixture is cooled to room temperature, the prepared NaYF is obtained 4 :Yb 3+ /Tm 3+ (core) nanoparticles (1 mmol) were added to the flask, followed by 10mL of NH-containing 4 F (2 mmol) and NaOH (1.25 mmol) are uniformly stirred and added into a transparent yellow solution for 30min, then the solution is heated to 60 ℃, the reaction is carried out for 30min under a nitrogen flow of 38mL/min to remove methanol in a reaction mixture, oxygen, residual water and methanol in the system are replaced by a vacuum system for 3 times at 110 ℃, then the mixture is heated to 305 ℃ under a nitrogen flow atmosphere of 8mL/min, the temperature is kept for 90min, excessive ethanol is added when the reaction system is cooled to room temperature, and the product is obtained after centrifugation;
(3)NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the specific synthesis method of the composite nano material of the@Au (core@shell@Au) comprises the following steps: coating NaYF with 0.5mmol oleic acid 4 :Yb 3+ /Tm 3+ @NaYF 4 (core@Shell) nanocrystals were dispersed ultrasonically in 10mL of chloroform, then added to 15mL of CTAB aqueous solution in which 0.2g was dissolved, magnetically stirred for 60 minutes, then the mixture was placed in a 50 ℃ water bath and stirred for 30 minutes to remove chloroform, a transparent solution was obtained, the product was centrifuged, washed once with 80 ℃ hot water and centrifuged again, and 1/8mmol of centrifuged NaYF was taken 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing (core@Shell) nanocrystals into 25mL deionized water, sequentially adding 200mg PVP and 100mg MES under stirring, ultrasonically dissolving, and adding 0.1mL 1g/100mL HAuCl 4 Aqueous solution and 0.5mg NaBH 4 The solid powder is stirred for 20 minutes and centrifuged for 7 minutes at 10000r/min to obtainNaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Composite nano material of copper@shell@Au.
Example 4
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 The application of the @ Au composite nano-material is used for the specific fluorescence detection of 4-NP in aqueous solution. As shown in FIG. 2, 4-NP has a strong absorption peak at 300-400nm, whereas NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material of the@Au (core@shell@Au) has stronger fluorescence signals at 350nm and 450 nm. Thus NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The up-conversion fluorescence spectrum of the composite nano material at core@shell@Au and the ultraviolet-visible absorption spectrum of the 4-NP are mutually overlapped at 350nm, and the 4-NP can quench the fluorescence intensity of the composite nano material at the wavelength of 350nm, while the fluorescence intensity at the wavelength of 450nm is basically unchanged. Thus NaYF can be utilized 4 :Yb 3+ /Tm 3+ @NaYF 4 And (3) quantitatively measuring the concentration of 4-NP in the solution by fluorescence resonance energy transfer between the core@shell@Au composite nanomaterial and the 4-NP. The method comprises the following steps: 1/64mmol of core@Shell@Au (1/64 mmol) was ultrasonically dispersed in 3mL of 4-NP aqueous solutions of different concentrations (4-NP concentrations 0.01. Mu.g/mL, 0.1. Mu.g/mL, 1. Mu.g/mL, 10. Mu.g/mL, 25. Mu.g/mL, 50. Mu.g/mL, 75. Mu.g/mL, 100. Mu.g/mL, respectively). And (3) quantitatively analyzing the peak intensity of the collected up-conversion fluorescence spectrum under the excitation of 980nm excitation light sources with the same test conditions and the same intensity. The results are shown in FIG. 3, naYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The area product ratio R of the emission peak intensities at 450nm and 350nm in the composite nano material at the temperature of copper@shell@Au conforms to an exponential function relationship (R=1.20309×e0.03524C) with the concentration C of 4-NP, and the lnR conforms to a linear function relationship (lnR=0.09418+0.03524C) with the concentration C of 4-NP. Therefore, the up-conversion fluorescence of the composite nano material can be utilized to quantitatively detect the 4-NP in the aqueous solution. FIG. 4 is a graph showing the fluorescence spectrum of the up-conversion of 1/64mmol core@shell@Au by ultrasonic dispersion in 3mL of 4-NP aqueous solution having an unknown concentration, and it was found from the analysis that the area ratio R of the intensities of the emission peaks at 450nm and 350nm was 2.8, and therefore, according to R=1.20309 x 0.03524c or lnr=0.09418+0.03524c, the concentration of 4-NP in the solution was calculated to be 26.54 μg/mL.
Example 5
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 The application of the composite nano material of the core@shell@Au is used for catalyzing and reducing 4-NP in an aqueous solution. At room temperature, a 4mL quartz cuvette is used as a reaction vessel for catalytic reaction, and a 722N visible spectrophotometer is used for monitoring the absorbance of the solution in the reaction process. The specific operation steps are that 1/64mmol of core@shell@Au (1/64 mmol) is ultrasonically dispersed in 3mL of 4-NP aqueous solutions with different concentrations (the 4-NP concentrations are respectively 0.01,0.1,1,10,25,50,75 and 100 mug/mL). Adding newly-formulated NaBH 4 Immediately after the aqueous solution (100 μl,0.2 mmol/mL), the change in absorbance of the solution was monitored and recorded at λ=400 nm. As a result, as shown in FIG. 5, naYF was present at the same concentration 4 :Yb 3+ /Tm 3 + @NaYF 4 In-process-ln (A/A) of catalytic reduction of 4-NP (0.01,0.1,1,10,25,50,75,100 mug/mL) with different concentrations by aqueous solution of composite nano-material of core@shell@Au 0 ) Curve with reaction time t. The slope of the curve indicates the reaction rate of the 4-NP reduction reaction, i.e., K app . Although the catalytic rate decreased slightly with increasing 4-NP concentration, the overall catalytic rate was still very high. NaYF at a 4-NP concentration of 0.01, 0.1. Mu.g/mL 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material of the@Au (core@shell@Au) can instantaneously and completely catalyze 4-NP (less than 1 s). NaYF when the 4-NP concentration was 1. Mu.g/mL 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material nano catalyst of the core@shell@Au can completely catalyze 4-NP only by 10 s. NaYF at a 4-NP concentration of 100. Mu.g/mL 4 :Yb 3+ /Tm 3+ @NaYF 4 The nano catalyst of the composite nano material of the@Au (core@shell@Au) can completely catalyze 4-NP within 20min, so that the concentration of the 4-NP can be completely catalyzed within the range of 0-100 mug/mL, and the catalysis rate is very fast.
Example 6
NaYF described above 4 :Yb 3+ /Tm 3+ @NaYF 4 @Au(core@shell@Au) composite nanomaterial is repeatedly used for catalytic reduction of 4-NP in aqueous solution, and the reusability is good. The method comprises the following steps: naYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Continuous catalytic reduction of 25 mug/mL 4-NP five times with composite nano material of core@shell@Au, naYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The 4-NP reduction reaction catalyzed by the composite nano material of the core@shell@Au can be performed in NaBH 4 The cycle proceeds in the presence. In order to avoid loss of catalyst during the separation, a cyclic test was performed on site. Namely, after each catalytic reaction is finished, 4-NP with the same concentration and NaBH with new configuration are directly added into the reaction system 4 Aqueous solution, naBH in solution must be waited after one catalytic reaction is completed 4 Adding freshly prepared NaBH after decomposition 4 Aqueous solution to ensure the addition of NaBH 4 The amount was then tested for the next catalytic reduction 4-NP experiment. FIG. 6 shows NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 After 5 times of cyclic use, the catalytic reduction efficiency of the composite nano material of the@Au (core@shell@Au) is still high. And NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The composite nano material of the@Au (core@shell@Au) can be recovered by simple centrifugation.
Claims (7)
1. The preparation method of the composite nano material based on the up-conversion nano crystal and the Au nano particles is characterized by comprising the following specific steps:
（1）NaYF 4 :Yb 3+ /Tm 3+ the preparation method of the nanocrystalline comprises the following steps: will be 0.415mmolYCl 3 ·6H 2 O、0.58mmolYbCl 3 ·6H 2 O、0.005mmolTmCl 3 ·6H 2 Stirring and heating O, 6mL oleic acid and 15mL 1-octadecene under nitrogen, heating to 100-110deg.C, displacing oxygen and residual water with vacuum system for 2-3 times, heating to 150-160deg.C, maintaining under 6-8mL/min nitrogen flow for 60-70min to obtain transparent yellow solution, cooling to room temperature, adding 4mmol NH under stirring 4 8-10mL of methanol solution of F and 2.5mmol of NaOH, stirring at room temperature for 30-120min, heating to 50-60 ℃, and stirring at 38-42mLReacting for 20-30min under nitrogen flow, replacing with vacuum system at 100-110deg.C for 2-3 times, heating to 300-305 deg.C under 6-8mL/min nitrogen flow, maintaining for 60-90min, cooling to room temperature, adding excessive ethanol, and centrifuging to obtain product;
（2）NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the preparation method of the nanocrystalline comprises the following steps: will be 0.5mmol YCl 3 ·6H 2 Stirring O, 6mL of oleic acid and 15mL of 1-octadecene under nitrogen, heating to 100-110 ℃ and replacing for 2-3 times by a vacuum system, then heating to 150-160 ℃ and maintaining for 60-70min under nitrogen flow, obtaining transparent yellow solution, cooling to room temperature, and then cooling 1mmol of NaYF prepared in the step (1) 4 :Yb 3+ /Tm 3+ Nanocrystalline, containing 2mmolNH 4 F and 8-10mL of methanol solution of 1.25 mmole of NaOH are uniformly stirred and added into transparent yellow solution to react for 30-120min, then the mixture is heated to 50-60 ℃, the mixture reacts for 20-30min under the nitrogen flow of 38-42mL/min to remove methanol in the reaction mixture, oxygen, residual water and methanol in the system are replaced by a vacuum system at 100-110 ℃, then the mixture is heated to 300-305 ℃ under the nitrogen flow of 6-8mL/min to keep the temperature for 60-90min, and when the reaction system is cooled to room temperature, excessive ethanol is added to centrifuge to obtain a product;
（3）NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 the preparation method of the@Au composite nanomaterial comprises the following steps: taking 0.125mmol clean NaYF prepared in the step (2) 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing the nanocrystalline into 20-25mL deionized water, stirring, sequentially adding 100-200mg polyvinylpyrrolidone PVP and 100-200mg 2-morpholinoethanesulfonic acid MES, ultrasonically dissolving, and adding 0.1mL 1g/100mL HAuCl 4 Adding 0.5mgNaBH into the aqueous solution 4 Stirring and reacting the solid powder for 10-20 minutes, and finally centrifuging for 7-10 minutes at 9000-10000r to obtain NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @au composite nanomaterial.
2. The method for preparing the composite nanomaterial based on the up-conversion nanocrystal and the Au nanoparticle according to claim 1, wherein: the clean NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Nanocrystalline is prepared by subjecting 0.5mmol NaYF prepared in step (2) 4 :Yb 3+ /Tm 3+ @NaYF 4 Dispersing the nanocrystalline in 6-10mL chloroform by ultrasonic wave, adding into 10-15mL aqueous solution dissolved with 0.2g cetyltrimethylammonium bromide CTAB, stirring for 30-60 min, placing into 50-60 ℃ water bath, stirring for 20-30min, centrifuging, washing the centrifuged precipitate with 60-80 ℃ hot water, centrifuging to obtain clean NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 @au composite nanomaterial.
3. The use of the composite nanomaterial produced by the method for producing a composite nanomaterial based on upconverting nanocrystals and Au nanoparticles according to claim 1, characterized in that: for specific fluorescence detection of 4-NP in aqueous solution or for catalytic reduction of 4-NP in aqueous solution.
4. The use of the composite nanomaterial produced by the method for producing a composite nanomaterial based on upconverting nanocrystals and Au nanoparticles as claimed in claim 3, characterized in that: 1/64mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 The nano Au composite material is ultrasonically dispersed in 3mL of aqueous solution with the concentration of 4-NP of 0.01 mug/mL, 0.1 mug/mL, 1 mug/mL, 10 mug/mL, 25 mug/mL, 50 mug/mL, 75 mug/mL and 100 mug/mL respectively, and the peak intensity of the collected up-conversion fluorescence spectrum is analyzed for quantitative detection of 4-NP in the aqueous solution under the excitation of 980nm excitation light sources with the same test conditions and the same intensity.
5. The use of the composite nanomaterial produced by the method for producing a composite nanomaterial based on upconverting nanocrystals and Au nanoparticles as claimed in claim 4, characterized in that: the NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Relative up-conversion fluorescence spectrum peak intensity ratio of@Au composite nanomaterialRConcentration of 4-NP in aqueous solutionCThe light system accords with the exponential relation, R= 1.20309 ×e 0.03524C Optical system between lnR value and 4-NP concentration CIn line with the relationship lnr=0.09418+0.03524c, two relationships can be used for quantitative detection of 4-NP in aqueous solutions, where R is the ratio of the intensity of the emission peak at 450nm to the intensity of the emission peak at 350 nm.
6. The use of the composite nanomaterial produced by the method for producing a composite nanomaterial based on upconverting nanocrystals and Au nanoparticles according to claim 2, characterized in that: at room temperature, a 4mL quartz cuvette is used as a reaction vessel for catalytic reaction, and a 722N visible spectrophotometer is used for monitoring the absorbance of the solution in the reaction process, specifically: 1/64mmol NaYF 4 :Yb 3+ /Tm 3+ @NaYF 4 Ultrasound dispersing of the Au composite nanomaterial into 3mL aqueous 4-NP solutions of different concentrations diluted with deionized water, wherein the concentration of the aqueous 4-NP solution is 0.01. Mu.g/mL, 0.1. Mu.g/mL, 1. Mu.g/mL, 10. Mu.g/mL, 25. Mu.g/mL, 50. Mu.g/mL, 75. Mu.g/mL, 100. Mu.g/mL, respectively, and then adding 100. Mu.L of 0.2mmol/mLNaBH 4 The change in absorbance of the solution was monitored and recorded at λ=400 nm for the aqueous solution.
7. The use of the composite nanomaterial produced by the method for producing a composite nanomaterial based on upconverting nanocrystals and Au nanoparticles according to claim 2, characterized in that: repeated catalytic reduction of 4-NP in aqueous solution.
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