CN113267483A - Precious metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristic and preparation method and application thereof - Google Patents
Precious metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristic and preparation method and application thereof Download PDFInfo
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- CN113267483A CN113267483A CN202110507317.4A CN202110507317A CN113267483A CN 113267483 A CN113267483 A CN 113267483A CN 202110507317 A CN202110507317 A CN 202110507317A CN 113267483 A CN113267483 A CN 113267483A
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- titanium dioxide
- nanorod array
- dioxide nanorod
- modified titanium
- noble metal
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- 239000002073 nanorod Substances 0.000 title claims abstract description 167
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 56
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000010970 precious metal Substances 0.000 title description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000000523 sample Substances 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 31
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
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- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 11
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- 239000002105 nanoparticle Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims description 8
- 229960003405 ciprofloxacin Drugs 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 229960003376 levofloxacin Drugs 0.000 claims description 8
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 claims description 7
- 229960005091 chloramphenicol Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000010931 gold Substances 0.000 description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 22
- 239000002086 nanomaterial Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 14
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- 238000000479 surface-enhanced Raman spectrum Methods 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
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- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 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
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
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Abstract
The invention provides a noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics, and a preparation method and application thereof. The preparation method comprises the following steps: soaking the FTO conductive glass substrate in a mixed solution obtained by mixing hydrochloric acid, deionized water and tetrabutyl titanate, and performing hydrothermal reaction, washing, drying and annealing to obtain a titanium dioxide nanorod array; soaking the titanium dioxide nanorod array in Au precursor solution obtained by mixing chloroauric acid aqueous solution, ethanol and deionized water, and performing continuous ultraviolet laser irradiation and washing to obtain an Au-modified titanium dioxide nanorod array; and soaking the Au modified titanium dioxide nanorod array in an Ag precursor solution obtained by mixing silver nitrate aqueous solution, ethanol and deionized water, and carrying out continuous ultraviolet laser irradiation, washing and drying to obtain the Au modified titanium dioxide nanorod array. The material obtained by the invention is non-toxic, and simultaneously, the loaded probe molecules have excellent SERS performance, and can effectively detect active molecules with extremely low concentration.
Description
Technical Field
The invention relates to a noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics, and a preparation method and application thereof, and belongs to the field of preparation and application of novel nano materials.
Background
The discovery and application of antibiotics by human beings have great milestone significance for the development of human beings. However, with the wide use of antibiotics, a large amount of antibiotics are discharged into the environment, so that the drug resistance of sensitive bacteria is enhanced, and the potential threat to the survival of human beings is caused. Solving the problem of pollution of antibiotics is an important problem in the current society, and controllably preparing excellent detection materials by adopting a novel synthesis technology is a field which is mainly explored by current scientific researchers.
The intrinsic Local Surface Plasmon Resonance (LSPR) mode of the noble metal Au and Ag nano material can be efficiently adjusted in a visible light-near infrared region, so that a stronger electromagnetic field can be generated when the noble metal Au and Ag nano material is excited by illumination, a Raman signal of a load molecule can be obviously enhanced, and the Surface Enhanced Raman Scattering (SERS) spectrum diagnosis technology formed by the method has obvious application value in the field of micro detection of antibiotics.
Researchers mainly realize the regulation and control preparation of the single metal nanometer material of Ag and Au by using the classical chemical synthesis technology comprising a seed growth method, a hydrothermal method, a polyol reduction method and the like. At present, a great deal of research results show that the SERS enhancement factor of a single Au or Ag nano material to a loaded probe molecule is 106-109Lack of SERS performancePreferably; the detection limit is high, and the method cannot be effectively used for detecting trace active molecules. If the Ag @ Au bimetallic nano-material can be controllably synthesized, the SERS performance of the probe molecules loaded on the surface of the nano-material is expected to be further improved. However, Ag and Au mainly used for SERS tend to form alloy nanoparticles through a complicated chemical synthesis process due to extremely similar lattice structures, and their effects and synergistic effects cannot be sufficiently and effectively achieved. Therefore, the Ag @ Au bimetallic nano material is prepared by any method, and respective effects and synergistic effects of the Ag @ Au bimetallic nano material can be effectively realized, so that the Ag @ Au bimetallic nano material is worthy of further research. In addition, researchers have also noted that even during the preparation of single-metal nanomaterials, chemical synthesis techniques suffer from certain deficiencies, including the inevitable use of large amounts of toxic, hazardous chemical reagents, and activators, stabilizers, curing agents, etc. having benzene rings or halogens; even if the late-stage strict and complicated purification process is carried out, the nano material still carries toxic residual substances, and the SERS detection of trace active molecules is difficult to be substantially and deeply popularized in the fields of biomedicine and the like.
Therefore, the exploration of obtaining the nonhazardous Ag @ Au bimetallic nanomaterial by a green, environment-friendly and simple preparation method can obviously improve the SERS performance of the loaded probe molecules and effectively detect the active molecules with extremely low concentration, and is an important problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering property and a preparation method and application thereof. The preparation method is simple, green and environment-friendly, and the obtained material is non-toxic and is suitable for the fields of biomedicine and the like. The composite nano material obtained by the invention is used as a substrate loaded probe molecule and not only has the molecular weight derived from TiO2The loaded probe molecule has excellent SERS performance due to the chemical enhancement provided by the charge transfer between the loaded probe molecule and the electromagnetic enhancement provided by the bimetal; the obtained composite material shows excellent surface enhanced Raman scattering characteristics for low-concentration detection of antibiotics levofloxacin, ciprofloxacin and chloramphenicolThe method can be effectively used for detecting trace antibiotics, and the detection limit is low.
The noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics is characterized in that the noble metal is Ag and Au, and in the noble metal modified titanium dioxide nanorod array, the molar content of Au is 2-4%, and the molar content of Ag is 4-6%.
According to the invention, the micro-morphology of the noble metal modified titanium dioxide nanorod array is as follows: ag nano particles and Au nano particles are loaded on the surface of the titanium dioxide nano rod array; the diameter of the titanium dioxide nano rod in the titanium dioxide nano rod array is 80-120nm, and the length of the titanium dioxide nano rod is 1.5-1.9 mu m; the particle size of the Au nano-particles is 5-30nm, and the particle size of the Ag nano-particles is 70-90 nm; the Ag nano-particles are loaded on the surface of the Au nano-particles.
The preparation method of the noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics comprises the following steps:
(1) mixing hydrochloric acid, deionized water and tetrabutyl titanate to obtain a mixed solution; soaking the FTO conductive glass substrate in the mixed solution, and then carrying out hydrothermal reaction; after the hydrothermal reaction is finished, cooling to room temperature, taking out the FTO conductive glass substrate material, and washing, drying and annealing to obtain the FTO conductive glass substrate loaded with the titanium dioxide nanorod array;
(2) uniformly mixing chloroauric acid aqueous solution, ethanol and deionized water to obtain Au precursor solution; soaking the FTO conductive glass substrate loaded with the titanium dioxide nanorod array in the Au precursor solution, and performing continuous ultraviolet laser irradiation and washing to obtain the FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array;
(3) uniformly mixing silver nitrate aqueous solution, ethanol and deionized water to obtain Ag precursor solution; and soaking the FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array in the Ag precursor solution, and performing continuous ultraviolet laser irradiation, washing and drying to obtain the noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering property.
According to the invention, in the step (1), the mass fraction of the hydrochloric acid is 37%, and the volume ratio of the hydrochloric acid to the deionized water to the tetrabutyl titanate is 25-35: 25-35: 1, preferably 30:30: 1.
Preferably, in the step (1), when the FTO conductive glass substrate is immersed in the mixed solution, the conductive coating of the FTO conductive glass substrate faces downward, which is beneficial for the titanium dioxide nanorod array to grow and load on the surface of the conductive coating. The FTO conductive glass substrate forms an angle of 45 degrees with the side wall of the reaction vessel, and the conductive surface faces downwards or directly faces upwards, so that the growth of the titanium dioxide nanorod array is not facilitated to be loaded on the surface of the conductive coating, and the formation of a compact titanium dioxide film is not facilitated. The FTO conductive glass substrate needs to be immersed in the mixed liquid.
Preferably, in step (1), the ratio of the volume of tetrabutyl titanate to the area of the conductive surface of the FTO conductive glass substrate is 0.1-1mL/cm2。
Preferably, in the step (1), the hydrothermal reaction temperature is 100-200 ℃, and the hydrothermal reaction time is 5-7 h; preferably, the hydrothermal reaction temperature is 150 ℃ and the hydrothermal reaction time is 6 h.
According to the invention, in the step (1), annealing is carried out in air at 450-550 ℃ for 0.5-2 hours, and the heating rate is 1-8 ℃/min; preferably, the annealing temperature is 500 ℃, the annealing time is 1 hour, and the heating rate is 5 ℃/min.
Preferably, according to the present invention, in the step (1), the washing is washing with deionized water; the drying is room temperature drying.
Preferably, in step (2), the concentration of the aqueous chloroauric acid solution is 0.02-0.1mol/L, and the volume ratio of the aqueous chloroauric acid solution, the ethanol and the deionized water is 1: 35-45: 180-220; preferably, the concentration of the chloroauric acid aqueous solution is 0.05mol/L, and the volume ratio of the chloroauric acid aqueous solution, the ethanol and the deionized water is 1: 40: 200.
preferably, in the step (2), when the FTO conductive glass substrate loaded with the titanium dioxide nanorod array is soaked in the Au precursor solution, the surface loaded with the titanium dioxide nanorod array faces upward. The FTO conductive glass substrate loaded with the titanium dioxide nanorod array needs to be immersed in the Au precursor solution.
According to the invention, the ratio of the volume of the aqueous chloroauric acid solution in step (2) to the volume of tetrabutyltitanate in step (1) is preferably 0.01 to 0.1:1, preferably 0.05: 1.
According to the invention, in the step (2), the continuous ultraviolet laser irradiation is performed for 10-20 minutes by using the ultraviolet laser with the power of 350-; preferably, the continuous ultraviolet laser irradiation is ultraviolet laser irradiation with a power of 400mW and a wavelength of 375nm for 15 minutes.
Preferably, in step (2), the washing is performed with deionized water.
Preferably, in the step (3), the concentration of the silver nitrate aqueous solution is 0.005-0.05mol/L, and the volume ratio of the silver nitrate aqueous solution, the ethanol and the deionized water is 1: 5-15: 45-55; preferably, the concentration of the silver nitrate aqueous solution is 0.01mol/L, and the volume ratio of the silver nitrate aqueous solution to the ethanol to the deionized water is 1: 10: 50.
preferably, in the step (3), when the FTO conductive glass substrate loaded with the Au-modified titanium dioxide nanorod array is immersed in the Ag precursor solution, the surface loaded with the Au-modified titanium dioxide nanorod array faces upward. The FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array needs to be immersed in the Ag precursor solution.
Preferably, according to the invention, the molar ratio of silver nitrate in step (3) to chloroauric acid in step (2) is 1:1 to 2, preferably 1: 1.25.
According to the invention, in the step (3), the continuous ultraviolet laser irradiation is performed for 10-20 minutes by using the ultraviolet laser with the power of 350-; preferably, the continuous ultraviolet laser irradiation is ultraviolet laser irradiation with a power of 400mW and a wavelength of 375nm for 15 minutes.
Preferably, according to the present invention, in the step (3), the washing is performed by using ethanol; drying is carried out at room temperature in air.
The application of the noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering property is used as a substrate for loading probe molecules, and the concentration of the probe molecules is detected through the surface enhanced Raman scattering property.
Preferably, the probe molecule is crystal violet, levofloxacin, ciprofloxacin or chloramphenicol.
According to a preferred embodiment of the invention, the method for loading probe molecules as a substrate is as follows: and immersing the noble metal modified titanium dioxide nanorod array in the water solution of the probe molecules for 4-8 hours, and drying to obtain the noble metal modified titanium dioxide nanorod array loaded with the probe molecules.
The invention has the following technical characteristics and beneficial effects:
1. the reaction conditions in the preparation process of the titanium dioxide nanorod array are required to be appropriate. The hydrothermal reaction time needs to be proper, and the longer the reaction time is, the longer the length of the nano rod is; however, the reaction time is too long, the titanium dioxide nanorod array can fall off from the FTO, and therefore, the appropriate hydrothermal reaction time is selected. The hydrothermal reaction temperature also plays an important role in the growth of the nano-rod, and when the temperature is less than 100 ℃, TiO plays an important role2The nanorods cannot grow on the FTO substrate; too high reaction temperature and too long reaction time can lead to TiO2The nano-rods fall off. Therefore, the hydrothermal reaction time and the reaction temperature need to be appropriate. In addition, the amount of the used initial raw materials also has influence on the synthesis of the titanium dioxide nanorod array. The density of the nanorods can be changed by regulating the concentration of the initial reactant (tetrabutyl titanate). The regulation and control of acid (HCl) in the reaction system can also influence the synthesis of the nano-rod; in the absence of hydrochloric acid or low hydrochloric acid concentrations, all titanium precursors will precipitate and become TiO2The titanium dioxide nano-rod array cannot be obtained because the titanium dioxide nano-rod array is precipitated to the bottom of the reaction vessel, so that the tetrabutyl titanate needs to be slowly hydrolyzed in a stronger acidic aqueous medium for the directional growth of the titanium dioxide nano-rods.
2. The Ag @ Au bimetal modified TiO is prepared by adopting a laser-induced photochemical method2The nano-rod array material has simple preparation method, environmental protection and high efficiency. In the steps (2) and (3) of the invention, the TiO loaded metal nanoparticles is realized by a photochemical method2Controllable synthesis of nano rod array. The control parameters mainly include laser wavelength and power densityIrradiation time and ion solution concentration (AgNO)3And HAuCl4). Wherein the excitation wavelength and power density of the continuous laser beam mainly determine the synthesis efficiency and the crystallization characteristics of the composite nanostructure. And the efficiency of exciting the semiconductor to generate electron-hole pairs by the long excitation wavelength (such as 532nm,633nm and 808nm) is relatively low due to the shorter excitation wavelength, so that metal ions cannot be effectively reduced, and the load growth amount of metal particles on the semiconductor nanorods is small, so that 375nm ultraviolet laser beams are selected as an excitation light source, and the semiconductor can be effectively excited to generate the electron-hole pairs. The high-power laser beam can accelerate the load growth rate of the metal elements, the agglomeration phenomenon occurs, the later performance exploration is not facilitated, and the low-power laser beam can reduce the agglomeration phenomenon of the load growth of the metal elements. Therefore, the laser power of the reaction process is regulated. The shape regulation and control of the laser-induced photochemical reaction are realized by changing the irradiation time of continuous laser and the concentration of the ionic solution. The irradiation time and the concentration of the ionic solution need to be appropriate. When the irradiation time is shorter and the concentration of the ionic solution is lower, the load growth amount of the metal nano particles is less and the dispersity is better. The irradiation time and the concentration of the ionic solution are too high, so that metal particles further grow on the array structure, an agglomeration phenomenon is generated, the number of hot spots is reduced, and the SERS activity is reduced. In addition, for bimetallic modified TiO2The nanorod array effectively regulates and controls the components of the bimetal by changing reaction conditions, so that the synergistic coupling effect between the bimetal is more fully exerted, and more excellent SERS performance is generated.
3. The loading sequence of the noble metal on the surface of the titanium dioxide nanorod array has an important influence on obtaining the material with the shape of the invention. Such as in TiO2Noble metal Ag is loaded on the surface of the nanorod array, Ag nanoparticles are only attached to the top ends of the nanorods, and no nanoparticles are loaded on the surface of the nanorods for growth; the method loads Au firstly, which is beneficial to uniform loading of subsequent Ag.
4. The preparation method is simple, green and environment-friendly, and the obtained material is non-toxic and is suitable for the fields of biomedicine and the like. Ag @ Au modified TiO prepared by the invention2A nanorod array material, wherein,compared with a nano shell layer or a hollow structure, the nanorod array has the advantages that the abundant and dense slender dendritic structures of the nanorod array can generate incomparable strong magnetic fields under the excitation of external light, and an ideal nano carrier is provided for improving the SERS effect. The material prepared by the invention has small noble metal nano particles, and the small noble metal nano particles are more beneficial to exerting better surface enhanced Raman scattering effect. Ag @ Au modified TiO prepared by the invention2The nanorod array material can utilize a remarkable array structure, simultaneously plays a unique synergistic effect of gold and silver, and can generate an additional electromagnetic field enhancement effect; and the prepared Ag @ Au modified TiO2The nanorod array material is small in size and can exert the synergistic effect of gold and silver, so that the excellent SERS characteristic is shown.
5. Ag @ Au modified TiO prepared by the invention2The nanorod array material is used as a high-performance substrate and shows excellent performance in the aspect of surface enhanced Raman scattering. The composite nano material obtained by the invention not only has the TiO-derived nano material2The loaded probe molecules have excellent SERS performance and are beneficial to detecting molecular Raman scattering signals with extremely low concentration. The composite material prepared by the invention has excellent surface enhanced Raman scattering performance for detecting probe molecule CV (crystal violet). The composite material prepared by the invention shows excellent surface enhanced Raman scattering characteristics for low-concentration detection of antibiotics levofloxacin, ciprofloxacin and chloramphenicol, can be effectively used for detection of trace antibiotics, has low detection limit, and has important application value in the aspect of antibiotic enhanced Raman scattering analysis.
Drawings
FIG. 1 is a top view of the structure of the titanium dioxide nanorod array prepared in step (1) of example 1 and an SEM image obtained by tilting the structure by 52 degrees;
FIG. 2 is Au-TiO prepared in step (2) of example 12A cross section view of the nanorod array structure and SEM top views under different magnifications;
FIG. 3 is Au-TiO prepared in step (2) of example 12High-power TEM images and element analysis maps of the nanorod array structural material under different magnifications;
FIG. 4 is Ag @ Au-TiO prepared in step (3) of example 12A cross section view of the nano-rod array structure material and SEM top views under different magnifications;
FIG. 5 shows Ag @ Au-TiO prepared in step (3) of example 12EDS energy spectrogram of the nanorod array structure material;
FIG. 6 is Ag @ Au-TiO prepared in step (3) of example 12High-power TEM images and element analysis maps of the nanorod array structural material under different magnifications;
FIG. 7 is Ag @ Au-TiO prepared in example 12Nanorod array structure material and Au-TiO prepared in step (2) of example 12Nanorod array structure material and TiO prepared in step (1) of example 12Nanorod array structure material, Ag-TiO prepared in comparative example 12Comparing X-ray diffraction patterns of the nanorod array structure material and the FTO conductive glass substrate;
FIG. 8 is Ag-TiO prepared in comparative example 12A cross-sectional view of the nanorod array structural material and SEM top views at different magnifications;
FIG. 9 is Ag-TiO prepared in comparative example 12High-power TEM images and element analysis maps of the nanorod array structural material under different magnification factors;
FIG. 10 shows that the concentration of the aqueous solution of probe molecules (CV) in test example 1 was 10-8Au-TiO loaded with probe molecules prepared in mol/L mode2、Ag@Au-TiO2And Ag-TiO2Raman spectrogram of the nanorod array structural material;
FIG. 11 is Ag @ Au-TiO-Supported Probe molecules prepared by varying the concentration of the aqueous Probe molecule (CV) solution in Experimental example 12Raman spectrogram of the nanorod array structural material;
FIG. 12 shows that the concentration of the aqueous solution of probe molecules (CV) in test example 1 was 10-8Prepared by mol/L loaded probe molecule (CV) Ag @ Au-TiO2The SERS spectrum of the nanorod array structure material is tested after the nanorod array structure material is placed at room temperature for a period of time;
FIG. 13 is Ag @ Au-TiO in test example 12A Raman spectrogram measured under the excitation of laser with different wavelengths after the nano-rod array structural material adsorbs CV and different antibiotics;
FIG. 14 is a graph of Ag @ Au-TiO adsorbed with different concentrations of antibiotic in Experimental example 12And a Raman spectrum measured by the nanorod array structure material under the excitation of 785nm laser.
Detailed description of the invention
The present invention will be further described with reference to specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
A preparation method of a noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics comprises the following steps:
(1) at room temperature, 15mL of hydrochloric acid with a mass fraction of 37% was dissolved in 15mL of deionized water, and the solution was slowly stirred for 5 minutes. Subsequently, 0.5mL of tetrabutyltitanate was added dropwise to the resulting solution, and stirring was continued for 5 minutes. The resulting mixed solution was then transferred to a teflon-lined autoclave having a capacity of 50mL, and an FTO conductive glass substrate having a length × width × height of 1cm × 1cm × 2mm, which was cleaned with ethanol, was immersed therein with the conductive coating facing downward. The hydrothermal synthesis was started and carried out in a laboratory oven at 150 degrees celsius for 6 hours. After cooling to room temperature, taking out the FTO substrate, repeatedly washing with deionized water, drying at room temperature, and finally, thermally annealing the sample in 500 ℃ air for 1h (the heating rate is 5 ℃ for min)-1) And crystallizing, namely finally obtaining the titanium dioxide nanorod array only on the conductive coating of the FTO conductive glass substrate.
(2) Fully mixing 25 mu L/0.05M chloroauric acid aqueous solution, 1mL of ethanol and 5mL of deionized water to prepare precursor liquid, soaking the titanium dioxide nanorod array obtained in the step (1) in the precursor liquid, and irradiating by using laser with the wavelength of 375nm and the power of 400mWFor 15 minutes. Then, taking out the FTO substrate, and thoroughly cleaning the FTO substrate by using deionized water to obtain an Au modified titanium dioxide nanorod array, namely Au-TiO nanorod array2A nanorod array structure.
(3) Preparing 100 mu L/0.01M silver nitrate aqueous solution, 1mL ethanol and 5mL deionized water into a mixed solution, soaking the Au modified titanium dioxide nanorod array obtained in the step (2) in the mixed solution, irradiating for 15 minutes by using laser with the wavelength of 375nm and the power of 400mW, then taking out an FTO substrate, repeatedly and alternately washing by using ethanol and deionized water, drying in the air at room temperature, and finally obtaining the noble metal modified titanium dioxide nanorod array, namely Ag @ Au-TiO nanorod array2A nanorod array structure.
The top view and SEM image with 52 degree inclination of the titanium dioxide nanorod array obtained in step (1) of this example are shown in FIG. 1. As can be seen from FIG. 1, the prepared titanium dioxide nanorod array has a rod-like structure with an average diameter of 100nm and a length of about 1.7 μm.
Au-TiO obtained in step (2) of this example2The cross-sectional view and SEM top view at different magnifications of the nanorod array structure are shown in FIG. 2. As can be seen from FIG. 2, a large number of small spherical gold nanoparticles were attached to TiO2The surface of the nano rod is about 5-30nm in size.
This example, Au-TiO prepared in step (2)2The TEM spectrum and the element distribution spectrum of the nanorod array structure under different magnifications are shown in FIG. 3. From FIG. 3, Au-TiO was obtained2The nanorod array structure is formed by stacking nanoparticles on a slender nanorod structure, the average size of the nanoparticles is 5-30nm, the distribution of Au, Ti and O elements can be respectively seen, and the element distribution map further proves that Au particles are loaded and grown on the slender nanorod structure.
Ag @ Au-TiO obtained in step (3) of this example2The cross-sectional view of the nanorod array structure and the top view of the SEM taken at different magnifications are shown in FIG. 4. As can be seen from FIG. 4, the prepared Ag @ Au-TiO2The nanorod array structure is formed by stacking nanoparticles on a slender nanorod structure, Ag nanoparticles are further loaded on the surface of Au nanoparticles, and the average size of the Ag nanoparticles is 80nm。
Ag @ Au-TiO obtained in this example2The EDS energy spectrum of the nanorod array structure is shown in FIG. 5, wherein the molar content of gold is 3.1% and the molar content of silver is 4.9%.
Ag @ Au-TiO prepared in step (3) of this example2The TEM spectrum and the element distribution spectrum of the nanorod array structure under different magnifications are shown in FIG. 6. From FIG. 6, Ag @ Au-TiO was obtained2The nano-rod array structure is formed by stacking nano-particles on a slender nano-rod structure, and Ag is loaded on TiO2The top end of the nano rod is also supported and grown on the TiO2The surface of the nano-rod.
Example Ag @ Au-TiO Final preparation2X-ray diffraction pattern (AgAu-TiO) of nanorod array structure2) The Au-TiO prepared in the step (2)2X-ray diffraction pattern (Au-TiO) of nanorod array structure2) TiO prepared in step (1)2Nanorod array structure (TiO)2) And a contrast graph of the X-ray diffraction pattern of the FTO conductive glass substrate is shown in fig. 7. TiO prepared in step (1) in the figure2The sharp diffraction peak of the nanorod array suggests good crystallinity of the material, wherein a series of diffraction peaks with 2 theta values of 27.4 degrees, 36.1 degrees, 41.1 degrees and 54.4 degrees respectively correspond to TiO2The (110), (101), (111), and (211) crystal planes (JCPDS, No. 21-1276). For Ag @ Au-TiO2The nano-rod array has a series of diffraction peaks with 2 theta values of 38.2 degrees, 44.4 degrees and 64.5 degrees between pure gold (JCPDS, No.65-2870) and Ag (JCPDS, No.65-1271), which indicates that the bimetal nano-material is successfully deposited on TiO2And forming a metal-semiconductor heterostructure on the surface of the nanorod array.
Example 2
A method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering characteristics, as described in example 1, except that in the step (1), the hydrothermal reaction temperature is 200 ℃; the other steps and conditions were identical to those of example 1.
Examples 3 to 4
A method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering characteristics, as described in example 1, except that in the step (2), the laser irradiation time is 10 and 20 minutes, respectively; the other steps and conditions were identical to those of example 1.
Examples 5 to 6
A method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering characteristics, as described in example 1, except that in the step (3), the laser irradiation time is 10 and 20 minutes, respectively; the other steps and conditions were identical to those of example 1.
Comparative example 1
A preparation method of a precious metal modified titanium dioxide nanorod array comprises the following steps:
(1) at room temperature, 15mL of hydrochloric acid with a mass fraction of 37% was dissolved in 15mL of deionized water, and the solution was slowly stirred for 5 minutes. Subsequently, 0.5mL of tetrabutyltitanate was added dropwise to the resulting solution, and stirring was continued for 5 minutes. The resulting mixed solution was then transferred to a teflon-lined autoclave having a capacity of 50mL, and an FTO conductive glass substrate having a length × width × height of 1cm × 1cm × 2mm, which was cleaned with ethanol, was immersed therein with the conductive coating facing downward. The hydrothermal synthesis was started and carried out in a laboratory oven at 150 degrees celsius for 6 hours. And cooling to room temperature, taking out the FTO substrate, repeatedly washing with deionized water, drying at room temperature, and finally, thermally annealing the sample in 500 ℃ air for 1h (with the heating rate of 5 ℃ for min-1) for crystallization, namely finally obtaining the titanium dioxide nanorod array only on the conductive coating of the FTO conductive glass substrate.
(2) Preparing 200 mu L/0.01M silver nitrate aqueous solution, 1mL ethanol and 5mL deionized water into a mixed solution, soaking the titanium dioxide nanorod array obtained in the step (1) in the mixed solution, irradiating for 15 minutes by using laser with the wavelength of 375nm and the power of 400mW, then taking out the FTO substrate, repeatedly and alternately washing by using ethanol and deionized water, drying in the air at room temperature, and finally obtaining the Ag-TiO2A nanorod array structure.
Ag-TiO obtained in this comparative example2Cross section view of nano-rod array structure and different magnificationsThe top view of the SEM is shown in fig. 8. As can be seen from FIG. 8, Ag-TiO compounds were produced2The nanorod array structure is formed by attaching nanoparticles to the top of a rod-shaped structure, and the average size of the nanoparticles is 100 nm.
Ag-TiO obtained in this comparative example2The TEM spectrum and the element distribution spectrum of the nanorod array structure under different magnifications are shown in FIG. 9. From FIG. 9, it is obtained that Ag nanoparticles are only attached to the top of the nanorods, the surface has no nanoparticle supported growth, and the distribution of Ag, Ti and O elements and Ag, TiO elements can be seen2The lattice structure of (1).
Ag-TiO obtained in this comparative example2The X-ray diffraction pattern of the nanorod array structure is shown in FIG. 7.
As can be seen from the comparison of the comparative examples, the loading sequence of the noble metal of the invention has an important influence on obtaining the material with the morphology of the invention. Such as in TiO2Noble metal Ag is loaded on the surface of the nanorod array, Ag nanoparticles are only attached to the top ends of the nanorods, and no nanoparticles are loaded on the surface of the nanorods for growth; the method loads Au firstly, which is beneficial to uniform loading of subsequent Ag.
As can be seen from the comparison of the comparative example, the addition of the silver nitrate aqueous solution affects the loading speed of Ag particles, and the addition of excessive silver nitrate aqueous solution causes the growth of large Ag blocks on TiO due to loading2A surface.
Test example 1
The surface enhanced raman scattering performance of antibiotics levofloxacin, ciprofloxacin and chloramphenicol was tested.
Test samples: EXAMPLE 1 Au-TiO prepared in step (2)2Nanorod array structure, Ag @ Au-TiO prepared in step (3)2Nanorod array structure, Ag-TiO prepared in comparative example 12A nanorod array structure.
The test method comprises the following steps:
(1) the test samples were immersed in 1mL of aqueous solutions containing probe molecules at different concentrations (wherein the concentration of the probe molecules was 10, respectively)-8mol/L、10-9mol/L、10-10mol/L、10-11mol/L、10-12mol/L) inSoaking for 6 hours under the condition of magnetic stirring, and then drying for 12 hours in a room temperature environment to ensure that the substrate is absolutely dry to obtain the Ag @ Au-TiO loaded with probe molecules2Nanorod array structures, and then SERS testing.
(2) The completely dried sample is subjected to Raman spectrum test by using visible light 532nm,633nm and near infrared light 785nm as excitation wavelengths.
In the process of Raman spectrum testing, the laser power is set to be 1mW, the exposure time is 15s, the same testing result needs to be repeated for multiple times so as to ensure the repeatability of the testing result, and the obtained result is shown in the figure.
Uses Crystal Violet (CV) as probe molecule to compare Au-TiO2、Ag@Au-TiO2And Ag-TiO2SERS performance of the substrate material with the nanorod array structure. The concentration of the probe molecule (CV) in the aqueous solution was 10-8The SERS spectrum of the nanorod array structure material loaded with probe molecules prepared in mol/L is shown in FIG. 10, and Ag @ Au-TiO can be clearly seen2SERS signal of nanorod array structure is far higher than that of Au-TiO2And Ag-TiO2The nanorod array structure and the enhancement of SERS signals are attributed to the synergistic coupling effect between Au and Ag in the composite nanomaterial. In addition, to further verify the sensitivity of composite nanomaterial SERS, at 10-8～10-12Preparation of Ag @ Au-TiO loaded with Probe molecules by varying the concentration of the Probe molecule (CV) aqueous solution within the mol/L range2Nanorod array structure, SERS test, optimized Ag @ Au-TiO as shown in FIG. 112The detection limit of the nanorod array structure can reach pM magnitude.
The concentration of the probe molecule (CV) in the aqueous solution was 10-8mol/L, preparing Ag @ Au-TiO loaded with probe molecules (CV)2And (3) carrying out SERS test on the nanorod array structure after being placed at room temperature for a period of time. Fig. 12 shows changes in SERS spectra before and after 30 days of standing. It was found that neither the peak position nor the intensity changed significantly, and that the SERS intensity remained 92.6% of the initial intensity after 30 days of exposure. The result shows that the prepared Ag @ Au-TiO2The nanorod array structure has the SERS substrate characteristics required by practical applicationHigh sensitivity, uniformity, reproducibility and stability.
The concentration of the probe molecule (CV) in the aqueous solution was 10-8mol/L, preparing Ag @ Au-TiO loaded with probe molecules (CV)2The nanorod array structure, when SERS tests are performed with different laser light sources (532nm, 633nm and 785nm), as shown in fig. 13(a), it can be clearly observed that the main characteristic band derived from the CV molecule can be clearly identified in the SERS spectrum, indicating that the CV molecule is suitable for different laser wavelengths.
The concentration of the probe molecule aqueous solution is 10-6mol/L, the probe molecules are levofloxacin, ciprofloxacin and chloramphenicol respectively, and Ag @ Au-TiO loaded with the probe molecules are prepared respectively2A nanorod array structure; SERS spectra were measured at 532nm,633nm and 785nm as excitation wavelengths at the same power. It can be seen that some raman peaks of the antibiotic can be identified, but some peaks are not detected due to fluorescence interference. Wherein, under the excitation of 785nm near infrared laser, the fluorescence interference is further weakened, and the characteristic peaks of all antibiotics can be clearly identified. By changing the concentration of the probe molecule aqueous solution, we further studied the adsorption of antibiotics with different concentrations on Ag @ Au-TiO2In the nanorod array structure, 785nm is taken as an excitation wavelength, SERS spectra are tested and shown in FIG. 14, and it can be clearly seen that the detection limits of levofloxacin, ciprofloxacin and chloramphenicol are respectively as low as 10-9M,10-9M,10-8M, is superior to many previous studies.
The final Ag @ Au-TiO prepared by the invention2The enhancement effect of the nanorod array structure as a substrate on the Raman spectra of levofloxacin, ciprofloxacin and chloramphenicol is obviously superior to that of other base materials, and a large number of repeated experiments are carried out in order to ensure that the method is absolutely non-accidental.
Claims (9)
1. The noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering characteristics is characterized in that the noble metal is Ag and Au, and in the noble metal modified titanium dioxide nanorod array, the molar content of Au is 2-4%, and the molar content of Ag is 4-6%.
2. The noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering properties according to claim 1, wherein the micro-morphology of the noble metal-modified titanium dioxide nanorod array is as follows: ag nano particles and Au nano particles are loaded on the surface of the titanium dioxide nano rod array; the diameter of the titanium dioxide nano rod in the titanium dioxide nano rod array is 80-120nm, and the length of the titanium dioxide nano rod is 1.5-1.9 mu m; the particle size of the Au nano-particles is 5-30nm, and the particle size of the Ag nano-particles is 70-90 nm; the Ag nano-particles are loaded on the surface of the Au nano-particles.
3. The method for preparing the noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property as set forth in any one of claims 1-2, comprising the steps of:
(1) mixing hydrochloric acid, deionized water and tetrabutyl titanate to obtain a mixed solution; soaking the FTO conductive glass substrate in the mixed solution, and then carrying out hydrothermal reaction; after the hydrothermal reaction is finished, cooling to room temperature, taking out the FTO conductive glass substrate material, and washing, drying and annealing to obtain the FTO conductive glass substrate loaded with the titanium dioxide nanorod array;
(2) uniformly mixing chloroauric acid aqueous solution, ethanol and deionized water to obtain Au precursor solution; soaking the FTO conductive glass substrate loaded with the titanium dioxide nanorod array in the Au precursor solution, and performing continuous ultraviolet laser irradiation and washing to obtain the FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array;
(3) uniformly mixing silver nitrate aqueous solution, ethanol and deionized water to obtain Ag precursor solution; and soaking the FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array in the Ag precursor solution, and performing continuous ultraviolet laser irradiation, washing and drying to obtain the noble metal modified titanium dioxide nanorod array with excellent surface enhanced Raman scattering property.
4. The method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property according to claim 3, wherein the step (1) comprises one or more of the following conditions:
i. the mass fraction of the hydrochloric acid is 37 percent, and the volume ratio of the hydrochloric acid to the deionized water to the tetrabutyl titanate is 25-35: 25-35: 1, preferably 30:30: 1;
ii. When the FTO conductive glass substrate is soaked in the mixed liquid, the conductive coating of the FTO conductive glass substrate faces downwards;
iii, the volume of the tetrabutyl titanate and the area ratio of the conductive surface of the FTO conductive glass substrate are 0.1-1mL/cm2；
iv, the hydrothermal reaction temperature is 100-; preferably, the hydrothermal reaction temperature is 150 ℃, and the hydrothermal reaction time is 6 h;
v, annealing is to anneal for 0.5-2 hours at the temperature of 450-550 ℃ in the air, and the heating rate is 1-8 ℃/min; preferably, the annealing temperature is 500 ℃, the annealing time is 1 hour, and the heating rate is 5 ℃/min.
5. The method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property according to claim 3, wherein the step (2) comprises one or more of the following conditions:
i. the concentration of the chloroauric acid aqueous solution is 0.02-0.1mol/L, and the volume ratio of the chloroauric acid aqueous solution to the ethanol to the deionized water is 1: 35-45: 180-220; preferably, the concentration of the chloroauric acid aqueous solution is 0.05mol/L, and the volume ratio of the chloroauric acid aqueous solution, the ethanol and the deionized water is 1: 40: 200 of a carrier;
ii. When the FTO conductive glass substrate loaded with the titanium dioxide nanorod array is soaked in the Au precursor solution, one surface loaded with the titanium dioxide nanorod array faces upwards;
iii, the volume ratio of the chloroauric acid aqueous solution to the tetrabutyl titanate in the step (1) is 0.01-0.1:1, preferably 0.05: 1;
iv, the continuous ultraviolet laser irradiation is performed for 10-20 minutes by using 350-450mW and 375nm ultraviolet laser irradiation power; preferably, the continuous ultraviolet laser irradiation is ultraviolet laser irradiation with a power of 400mW and a wavelength of 375nm for 15 minutes.
6. The method for preparing a noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property according to claim 3, wherein the step (3) comprises one or more of the following conditions:
i. the concentration of the silver nitrate aqueous solution is 0.005-0.05mol/L, and the volume ratio of the silver nitrate aqueous solution to the ethanol to the deionized water is 1: 5-15: 45-55 parts of; preferably, the concentration of the silver nitrate aqueous solution is 0.01mol/L, and the volume ratio of the silver nitrate aqueous solution to the ethanol to the deionized water is 1: 10: 50;
ii. When the FTO conductive glass substrate loaded with the Au modified titanium dioxide nanorod array is soaked in the Ag precursor solution, one surface loaded with the Au modified titanium dioxide nanorod array faces upwards;
iii, the molar ratio of the silver nitrate in the step (3) to the chloroauric acid in the step (2) is 1:1-2, preferably 1: 1.25;
iv, the continuous ultraviolet laser irradiation is performed for 10-20 minutes by using 350-450mW and 375nm ultraviolet laser irradiation power; preferably, the continuous ultraviolet laser irradiation is ultraviolet laser irradiation with a power of 400mW and a wavelength of 375nm for 15 minutes.
7. Use of the noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property as claimed in any one of claims 1-2 as a substrate for supporting probe molecules, and detecting the concentration of the probe molecules through the surface-enhanced raman scattering property.
8. The use of the noble metal-modified titanium dioxide nanorod array with excellent surface-enhanced raman scattering property according to claim 7, wherein the probe molecules are crystal violet, levofloxacin, ciprofloxacin or chloramphenicol.
9. The application of the noble metal modified titanium dioxide nanorod array with excellent surface-enhanced Raman scattering property according to claim 7, wherein the method for loading the probe molecules as the substrate is as follows: and immersing the noble metal modified titanium dioxide nanorod array in the water solution of the probe molecules for 4-8 hours, and drying to obtain the noble metal modified titanium dioxide nanorod array loaded with the probe molecules.
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