CN104596994B - Europium-doped titanium dioxide/graphene oxide composite film and preparation method thereof - Google Patents
Europium-doped titanium dioxide/graphene oxide composite film and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000004528 spin coating Methods 0.000 claims abstract description 10
- 239000002096 quantum dot Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 56
- 229910052693 Europium Inorganic materials 0.000 claims description 21
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 20
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002738 chelating agent Substances 0.000 claims description 11
- 239000010408 film Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002538 Eu(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000010668 complexation reaction Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims 1
- 229910000348 titanium sulfate Inorganic materials 0.000 claims 1
- 102000004169 proteins and genes Human genes 0.000 abstract description 13
- 108090000623 proteins and genes Proteins 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 238000012512 characterization method Methods 0.000 abstract description 3
- 238000004113 cell culture Methods 0.000 abstract description 2
- 238000000338 in vitro Methods 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 102000009027 Albumins Human genes 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000010609 cell counting kit-8 assay Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 210000002950 fibroblast Anatomy 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910004337 Ti-Ni Inorganic materials 0.000 description 1
- 229910011209 Ti—Ni Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- -1 europium ions Chemical class 0.000 description 1
- ZLLLNBMJZUQURU-UHFFFAOYSA-N europium titanium Chemical compound [Ti][Eu] ZLLLNBMJZUQURU-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a europium-doped titanium dioxide/graphene oxide composite film and a preparation method thereof. According to the film, a substrate is provided with a europium-doped titanium dioxide nanodot and graphene oxide mixed layer, wherein titanium dioxide nanodots in the mixed layer are 30-150nm in size and 1.0*10＜10＞-1.0*10＜11＞/cm＜2＞ in density, the molar concentration of Eu＜3+＞ is 0.005-0.015mol/L, and the concentration of graphene oxide is 5-15mg/L. The preparation method is based on a sol-gel method and comprises the steps of preparing europium-doped titanium dioxide/graphene oxide precursor sol and then performing thermal treatment of the precursor sol on the substrate by a spin-coating method. The film provided by the invention has favorable biocompatibility, protein adsorption property and luminescence property, and can be used for in-situ semi-quantitative characterization of the protein adsorption capacity of a film surface. The film can be applied in the biomedical engineering fields of cell culture in vitro, tissue engineering and the like.
Description
Technical field
The invention belongs to bio-medical film applications, and in particular to can be applicable to sxemiquantitative in situ and characterize material surface albumen
The a kind of of adsorbance mixes titanium dioxide/graphene composite thin film of europium and preparation method thereof.
Background technology
Titanium dioxide is a kind of nontoxic, material with good biocompatibility and chemical stability, in medical domain
In be widely used and have developed rapidly.Research shows that skeletonization is thin before titanium dioxide nanometer points surface mice cranium is derivative
Born of the same parents MC3T3-E1 growing states it is good [Y. Hong, M. F. Yu, W. J. Weng, K. Cheng, H. M. Wang,
J. Lin. Light-induced cell detachment for cell sheet technology.
Biomaterials, 2013,34(1):11-18], no cytotoxicity.
Graphene oxide is widely studied as one of the derivant of Graphene, and because of its unique structure and performance and
It is considered as that there is in biomaterial application project very big development prospect, research shows that the graphene oxide of low concentration has
Good biocompatibility and protein adsorption performance [J. Q. Liu, L. Cui, D. S. Losic. Graphene and
graphene oxide as new nanocarriers for drug delivery applications. Acta
biomaterialia. 2013, 9(12):9243-9257]。
Eu now3+Extensive concern is caused in field of photoelectric devices.Eu3+Cause5D0 − 7FjTransition and showing
Some characteristic luminescence peaks, and5D0 − 7F2The luminous intensity at place is very high, Eu3+It is titania-doped to form Eu-O-Ti keys, make
Obtain TiO2With more preferable luminescent properties [H. Liu and L. X. Yu. Preparation and
photoluminescence properties of europium ions doped TiO2 nanocrystals.
Journal of Nanoscience and Nanotechnology. 2013,(13):5119-5125]。
Now, many methods such as BCA can detect protein adsorption quantity, but these methods all can not be inhaled to albumen substantially
Attached amount carries out in-situ characterization.
The content of the invention
It is an object of the invention to provide a kind of have good luminous performance, protein adsorption performance, preparation method is simple, cost
It is low can be applied to sxemiquantitative in situ characterize protein adsorption quantity the titanium dioxide/graphene composite thin film for mixing europium and its
Preparation method.
Titanium dioxide/the graphene composite thin film for mixing europium of the present invention, has the titanium dioxide for mixing europium to receive in substrate
The mixed layer of nanodot and graphene oxide, in mixed layer the size of titanium dioxide nanometer points be 30～150 nm, density be 1.0 ×
1010～1 × 1011/ cm2, Eu3+Molar concentration is 0.005～0.015 mol/L, and graphene oxide concentration is 5 mg/L～15
mg/L。
Heretofore described substrate is quartz glass, silicon chip, tantalum piece, titanium sheet or Ti-Ni alloy piece.
The preparation method of the titanium dioxide/graphene composite thin film of europium is mixed, step is as follows：
1）First graphene oxide and europium source are added in dehydrated alcohol, are stirred to europium source after being completely dissolved, add titanium source,
The mol ratio of chelating agent and deionized water, titanium source and chelating agent is 1:0.2～0.4, the mol ratio of titanium source and deionized water is 1:
0.8～1.2, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, titanium atom concentration is configured to for 0.1～0.5
Mol/L, polyvinylpyrrolidoneconcentration concentration are 10～100 g/L, and Eu concentration is 0.005～0.015 mol/L, and graphene oxide is dense
Spend the TiO 2 precursor colloidal sol for 5 mg/L～15 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net substrate surface of cleaning to be paved with to which, and with 4000～8000 rpm
20～60 s of speed spin coating, be then placed at 400～600 DEG C 0.5～2 h of insulation.
Heretofore described europium source is Eu (TMHD)3(three (DPM dpm,dipivalomethane acid) europium (III))
Or Eu (NO3)3·6H2O。
Heretofore described titanium source can be butyl titanate, titanium tetrachloride, titanous chloride., titanium fluoride or sulphuric acid.
Heretofore described chelating agent can be acetylacetone,2,4-pentanedione or ethanolamine.
The present invention is based on titanium dioxide nanometer points, compound with graphene oxide, improves the egg of titanium dioxide nanometer points
White absorption property；Doping Eu elements, improve the luminescent properties of titanium dioxide nanometer points, and using sending out at characteristic peak in PL spectrums
The change of light intensity, carrys out the variation relation of in-situ study luminous intensity and protein adsorption quantity.Present invention incorporates titanium dioxide is good
Biocompatibility well, the avirulence of low-concentration oxidizing Graphene and good protein adsorption performance and Eu3+Doping is to titanium dioxide
The improvement of titanium luminescent properties, albumen adsorb all right in material surface, using the very high feature of luminous intensity in thin film PL spectrums
Peak, carries out semiquantitative sign in situ to the adhesion protein of material surface.The nanodot films of the present invention are prepared using colloidal sol-solidifying
Glue method, low cost, it is easy to accomplish, PL tests are simple, easy to operate, have one to some situations for needing in-situ characterization protein adsorption quantity
It is fixed to help, can be applicable to the biomedical engineering fields such as Cell culture invitro, organizational project.
Description of the drawings
Fig. 1 is the SEM figures for mixing Eu titanium deoxid films.
Fig. 2 is the SEM figures for mixing Eu titanium dioxide/graphene composite thin film.
Fig. 3 is the PL spectrograms for mixing Eu titanium dioxide/graphene composite thin film of different albumin adsorbances；
In figure：Curve 1 be not adhesion protein, curve 2 be absorption 1 h albumen, curve 3 be that 2 h albumen of absorption, curve 4 are
Adsorb 16 h albumen.
Fig. 4 is to mix the OD after 6 h of fibroblast, 1 d, 3 d are cultivated on Eu titanium dioxide/graphene composite thin film
Value.
Specific embodiment
Describe the present invention with reference to embodiment and accompanying drawing in detail, but the present invention is not limited to this.
Embodiment 1
1）Using sol-gel process, TiO 2 precursor colloidal sol using butyl titanate (TBOT) as titanium source, make by ethanol
For solvent, wherein adding europium source Eu (TMHD)3, chelating agent acetylacetone,2,4-pentanedione (AcAc) and polyvinylpyrrolidone (PVP), metatitanic acid four
Butyl ester concentration is 0.1 mol/L, Eu (TMHD)3Concentration is 0.01 mol/L, acetylacetone,2,4-pentanedione, deionized water and butyl titanate
Mol ratio is 0.3:1:1, it is stirred at room temperature to form uniform colloidal sol；Then, the 20 μ L precursor colloidal sols are taken with 8000 rpm's
Speed is spin-coated on silicon chip surface, and spin-coating time is set to 40 s；Do not contained after the good sample of spin coating is incubated 2 h at 500 DEG C
Graphene oxide mixes europium titanium deoxid film（SEM figures are shown in Fig. 1）.It is 95～110 that the size of titanium dioxide nanometer points is most of
Nm, density about 5.4 × 1010/ cm2。
Embodiment 2
1）First by graphene oxide and Eu (TMHD)3In adding dehydrated alcohol, stir to Eu (TMHD)3After being completely dissolved, then
Add butyl titanate (TBOT), chelating agent acetylacetone,2,4-pentanedione (AcAc) and deionized water, acetylacetone,2,4-pentanedione, deionized water and metatitanic acid four
The mol ratio of butyl ester is 0.3:1:1, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, be configured to four fourth of metatitanic acid
Ester concentration is 0.1 mol/L, and polyvinylpyrrolidoneconcentration concentration is 40 g/L, Eu (TMHD)3Concentration is 0.01 mol/L, aoxidizes stone
The concentration of black alkene is the TiO 2 precursor colloidal sol of 10 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net silicon chip surface of cleaning to be paved with to which, and with the speed of 8000 rpm
40 s of spin coating, is then placed at 500 DEG C and is incubated 2 h, obtains mixing Eu titanium dioxide/graphene composite thin film.Its SEM
Figure is shown in Fig. 2, and the size of titanium dioxide nanometer points is most of for 90～105 nm, density about 5.2 × 1010/ cm2。
This example is compared with embodiment 1, it is seen that graphene oxide add after nano dot pattern and be not added with graphite oxide
Alkene is essentially identical, and is evenly distributed.
Embodiment 3
1）First by graphene oxide and Eu (TMHD)3In adding dehydrated alcohol, stir to Eu (TMHD)3After being completely dissolved, then
Add butyl titanate, chelating agent acetylacetone,2,4-pentanedione and deionized water, the mol ratio of acetylacetone,2,4-pentanedione, deionized water and butyl titanate
For 0.3:1:1, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, butyl titanate concentration is configured to for 0.1
Mol/L, polyvinylpyrrolidoneconcentration concentration are 35 g/L, Eu (TMHD)3Concentration be 0.012 mol/L, the concentration of graphene oxide
For the TiO 2 precursor colloidal sol of 8 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net quartz glass plate surface of cleaning to be paved with to which, and with 8000 rpm
40 s of speed spin coating, be then placed at 500 DEG C and be incubated 2 h, obtain mixing Eu titanium dioxide/graphene oxide THIN COMPOSITE
Film, the size of titanium dioxide nanometer points are most of for 94～110 nm, density about 5.1 × 1010/ cm2。
PL tests are carried out to sample obtained in this example, excitation wavelength is 300 nm, and the peak position and peak intensity of Eu characteristic peaks are all very
Substantially, characteristic peak luminous intensity highest at 614 nm, and the luminous intensity compared with remaining peak is higher by a lot.
Embodiment 4
1）First by graphene oxide and Eu (TMHD)3In adding dehydrated alcohol, stir to Eu (TMHD)3After being completely dissolved, then
Add butyl titanate, chelating agent acetylacetone,2,4-pentanedione and deionized water, the mol ratio of acetylacetone,2,4-pentanedione, deionized water and butyl titanate
For 0.3:1:1, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, butyl titanate concentration is configured to for 0.1
Mol/L, polyvinylpyrrolidoneconcentration concentration are 50 g/L, Eu (TMHD)3Concentration is 0.01 mol/L, and the concentration of graphene oxide is
The TiO 2 precursor colloidal sol of 15 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net quartz glass plate surface of cleaning to be paved with to which, and with 8000 rpm
40 s of speed spin coating, be then placed at 500 DEG C and be incubated 2 h, obtain mixing Eu titanium dioxide/graphene oxide THIN COMPOSITE
Film, the size of titanium dioxide nanometer points are most of for 84～100 nm, density about 5.4 × 1010/ cm2。
The albumin solution of 1 mg/mL concentration is prepared, and the egg of 1 h, 2 h, 16 h is carried out in sample surfaces obtained in this example
It is white to adsorb, PL tests are carried out to sample, excitation wavelength is 300 nm, obtains PL spectrograms（See Fig. 3）.As can be seen that with albumen
The increase of adsorbance, PL luminous intensities reduce.
Embodiment 5
1）First by graphene oxide and Eu (TMHD)3In adding dehydrated alcohol, stir to Eu (TMHD)3After being completely dissolved, then
Add butyl titanate, chelating agent acetylacetone,2,4-pentanedione and deionized water, the mol ratio of acetylacetone,2,4-pentanedione, deionized water and butyl titanate
For 0.3:1:1, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, butyl titanate concentration is configured to for 0.1
Mol/L, polyvinylpyrrolidoneconcentration concentration are 40 g/L, Eu (TMHD)3Concentration be 0.012 mol/L, the concentration of graphene oxide
For the TiO 2 precursor colloidal sol of 12 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net titanium plate surface of cleaning to be paved with to which, and with the speed of 8000 rpm
40 s of spin coating, is then placed at 500 DEG C and is incubated 2 h, obtains mixing Eu titanium dioxide/graphene composite thin film, dioxy
The size for changing titanium nano dot is most of for 90～104 nm, density about 5.2 × 1010/ cm2。
Fibroblasts in vitro culture is carried out on thin film obtained in this example and pure titinium dioxide nanodot films respectively, is trained
After supporting 6 h, 1 d, 3 d, OD values are determined using CCK-8 (Cell Counting Kit-8) method（Optical Density, and
Claim light absorption value）, the OD values of thin film obtained in this example compare the OD value differences of pure titinium dioxide nanodot films away from little（See Fig. 4）,
Illustrate that the compound and Eu doping of graphene oxide is had little to no effect to the biocompatibility of titanium dioxide nanometer points.
Embodiment 6
1）First by graphene oxide and Eu (TMHD)3In adding dehydrated alcohol, stir to Eu (TMHD)3After being completely dissolved, then
Add butyl titanate, chelating agent acetylacetone,2,4-pentanedione and deionized water, the mol ratio of acetylacetone,2,4-pentanedione, deionized water and butyl titanate
For 0.3:1:1, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, butyl titanate concentration is configured to for 0.1
Mol/L, polyvinylpyrrolidoneconcentration concentration are 45 g/L, Eu (TMHD)3Concentration is 0.01 mol/L, and the concentration of graphene oxide is
The TiO 2 precursor colloidal sol of 15 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net quartz glass plate surface of cleaning to be paved with to which, and with 8000 rpm
35 s of speed spin coating, be then placed at 500 DEG C and be incubated 2 h, obtain mixing Eu titanium dioxide/graphene oxide THIN COMPOSITE
Film, the size of titanium dioxide nanometer points are most of for 87～104 nm, density about 5.3 × 1010/ cm2。
Prepare the albumin solution of 1 mg/mL concentration, sample surfaces obtained in this example carry out 10 min, 20 min, 30
Min, 40 min, 50 min, 1 h, the protein adsorption of 2 h, carry out PL tests to sample, and excitation wavelength is 300 nm, as a result table
Bright, with the increase of protein adsorption quantity, the luminous intensity at characteristic peak is reduced.
Claims (4)
1. a kind of preparation method of the titanium dioxide/graphene composite thin film for mixing europium, this mixes the titanium dioxide/oxidation stone of europium
Black alkene laminated film has the mixed layer of the titanium dioxide nanometer points and graphene oxide of mixing europium, titanium dioxide in mixed layer in substrate
The size of titanium nano dot is 30～150 nm, and density is 1.0 × 1010～1.0 × 1011/ cm2, Eu3+Molar concentration is 0.005
～0.015 mol/L, graphene oxide concentration are 5 mg/L～15 mg/L, and its preparation process is as follows：
1）First graphene oxide and europium source are added in dehydrated alcohol, is stirred to europium source after being completely dissolved, is added titanium source, complexation
The mol ratio of agent and deionized water, titanium source and chelating agent is 1:0.2～0.4, the mol ratio of titanium source and deionized water is 1:0.8～
1.2, polyvinylpyrrolidone is subsequently adding, is sufficiently stirred at room temperature, it is 0.1～0.5 mol/L to be configured to titanium atom concentration,
Polyvinylpyrrolidoneconcentration concentration is 10～100 g/L, and Eu concentration is 0.005～0.015 mol/L, and graphene oxide concentration is 5
The TiO 2 precursor colloidal sol of mg/L～15 mg/L；
2) TiO 2 precursor colloidal sol is dropped to the net substrate surface of cleaning to be paved with to which, and with the speed of 4000～8000 rpm
Degree 20～60 s of spin coating, is then placed on 0.5～2 h of insulation at 400～600 DEG C.
2. the preparation method of the titanium dioxide/graphene composite thin film for mixing europium according to claim 1, its feature exist
In described europium source be Eu (TMHD)3Or Eu (NO3)3·6H2O。
3. the preparation method of the titanium dioxide/graphene composite thin film for mixing europium according to claim 1, its feature exist
In described titanium source be butyl titanate, titanium tetrachloride, titanous chloride., titanium fluoride or titanium sulfate.
4. the preparation method of the titanium dioxide/graphene composite thin film for mixing europium according to claim 1, its feature exist
In described chelating agent be acetylacetone,2,4-pentanedione or ethanolamine.
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