CN109932351B - TiO 22Preparation method of/ZnO semiconductor heterojunction SERS active substrate - Google Patents
TiO 22Preparation method of/ZnO semiconductor heterojunction SERS active substrate Download PDFInfo
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Abstract
一种TiO2/ZnO半导体异质结SERS活性基底的制备方法，它涉及SERS活性基底的制备方法。它是要解决现有的TiO2/ZnO半导体异质结制备方法复杂、用作SERS基底时活性低的技术问题。本方法：将钛酸四丁酯溶液滴入乙醇、水和浓硝酸混合液中制备溶胶，再经水热和焙烧，得到TiO2纳米粒子；将TiO2纳米粒子加入到Zn(NO3)2.6H2O水溶液中，再加入NaOH水溶液和促进剂，搅拌、沉降、烘干、焙烧，得到TiO2/ZnO半导体异质结新型SERS活性基底。它对4‑巯基吡啶的最低检出浓度达到1×10‑9M，可用于表面增强拉曼检测领域。
A preparation method of a TiO 2 /ZnO semiconductor heterojunction SERS active substrate relates to the preparation method of the SERS active substrate. It is to solve the technical problems of complicated preparation method of the existing TiO 2 /ZnO semiconductor heterojunction and low activity when used as a SERS substrate. This method: dropping tetrabutyl titanate solution into a mixed solution of ethanol, water and concentrated nitric acid to prepare a sol, then hydrothermally and calcining to obtain TiO 2 nanoparticles; adding TiO 2 nanoparticles to Zn(NO 3 ) 2 .6H 2 O aqueous solution, then add NaOH aqueous solution and accelerator, stir, settle, dry and bake to obtain a new type of SERS active substrate of TiO 2 /ZnO semiconductor heterojunction. Its lowest detection concentration for 4-mercaptopyridine reaches 1×10 ‑9 M, and it can be used in the field of surface-enhanced Raman detection.
Description
Technical Field
The invention relates to a preparation method of a SERS active substrate.
Background
The Surface-enhanced Raman Scattering (SERS) effect is due to the phenomenon that when a species such as a molecule is adsorbed or is very close to the Surface of a certain nanostructure (i.e., a so-called SERS-active substrate), the Raman signal intensity is significantly enhanced compared to the bulk molecule. SERS has been applied in many fields, especially in environmental catalysis, chemical and biological sensors, surface science and material science, because of its advantages such as high sensitivity, high selectivity, high accuracy, fast and nondestructive detection. The generation of SERS relies on a substrate having SERS activity, which has undergone the development process from metal materials to semiconductor materials to metal/semiconductor composite materials, and research on the preparation and enhancement mechanism of the SERS active substrate has been a hot spot of interest.
Wide band gap semiconductor nanomaterials (TiO)2ZnO, etc.) has the advantages of stable chemical performance, good acid and alkali resistance, no toxicity and harm to organisms, good biocompatibility and the like, and is widely applied to the fields of environmental protection, photocatalysis and the like. Due to the excellent performance and wide application of wide-bandgap semiconductor nanomaterials, SERS based on wide-bandgap semiconductors is gradually drawing much attention, but at present, SERS research based on semiconductors is still in a preliminary stage, the substrate form is single, and the SERS enhancement capability is significantly weaker than that of noble metal substrates. Therefore, the development of novel high-performance semiconductor-based SERS active substrates has important theoretical and practical significance.
The SERS enhancement of the semiconductor to the adsorbed molecules mainly comes from charge transfer contribution between a semiconductor substrate and the molecules and depends on the special surface property of the semiconductor substrate, so that the improvement of the charge transfer efficiency between the substrate and the molecules and the improvement of the specific surface enhanced Raman activity of the substrate can be one of effective ways for developing a novel high-performance semiconductor-based SERS active substrate.
Semiconductor heterostructures are typically composed of two or more different materials, each having a different bandgap. Due to the formation of the heterojunction structure, the change of the electronic state and the surface property causes the obvious change of the surface and interface properties of the heterostructure, thereby possibly bringing excellent photophysical or photochemical properties. At present, TiO is used2The research of the/ZnO heterojunction is limited to some fields such as photocatalysis. A nano-scale (Nanoscale) article published on 588-593 at 5 th stage of 2013, a highly effective TiO2@ ZnO n-p-n heterojunction nanorod photocatalyst (A Highly effective TiO)2@ ZnO n-P-n heterojunction nanocrystalline photcatalyzet) by using P25TiO 252In combination with ZnO, a heterojunction material was formed and used as a photocatalyst in the study of photocatalytic activity. In the synthetic process, on one hand, the pH value needs to be controlled, and on the other hand, P25TiO is adopted2Suspended on the synthesized ZnO nano-rod by a hydrothermal method due to non-synchronous combination of the heterojunction and the constituent unit thereofTherefore, the heterojunction obtained by the method is not beneficial to forming good interface effect, and has poor activity when used as a SERS substrate. Article ZnO @ TiO published in Royal Seisakusho Chemie Adv (RSC Adv.) 8.8.2018, 8064-80702Thermal decomposition method for preparing nanotube heterostructure thin film and photocatalysis performance thereof (Preparation of ZnO @ TiO)2The nanotubes nanostructured film by thermal decomposition and the same photocatalytic performances) are adopted to prepare ZnO @ TiO by a thermal decomposition method2The nanotube heterojunction film is also used for researching the photocatalytic performance. However, the method has complex synthesis conditions and needs to add zinc acetate to TiO2In nanotubes, the harsh preparation process presents great difficulties for the preparation of samples.
To date, TiO has been added2The research of the/ZnO semiconductor heterojunction serving as the SERS substrate is not reported yet. And, TiO reported in the field of photocatalysis at present2The preparation method of the/ZnO heterojunction does not have specific contribution to the SERS effect, and the obtained large-size nanorod (or tube) and the interface combination mode thereof are not suitable for application in the SERS field.
Disclosure of Invention
The invention aims to solve the problem of the existing TiO2The preparation method of the ZnO semiconductor heterojunction is complex, and the activity is low when the ZnO semiconductor heterojunction is used as an SERS substrate, so that the TiO semiconductor heterojunction is provided2A preparation method of a novel SERS active substrate of a ZnO semiconductor heterojunction.
TiO of the invention2The preparation method of the/ZnO semiconductor heterojunction SERS active substrate comprises the following steps:
firstly, according to the volume ratio of 1:1, stirring and mixing tetrabutyl titanate and absolute ethyl alcohol uniformly to obtain a solution A;
secondly, according to the volume ratio (5-7): (5-7): 1, uniformly mixing ethanol, water and concentrated nitric acid to obtain a solution B; dripping the solution A into the solution B, and stirring for 100-120 min after the dripping is finished to obtain sol;
thirdly, transferring the sol into a hydrothermal kettle, putting the sol into an oven for hydrothermal reaction at 155-165 ℃ for 6-7 h, naturally cooling to room temperature, pouring out waste liquid, putting the obtained hydrothermal product into the oven for drying at 75-80 ℃ for 6-7 h, naturally cooling, and grinding into powder to obtain a precursor;
fourthly, placing the precursor in a muffle furnace, heating to 450-460 ℃, and roasting for 2-3 hours to obtain TiO2Nanoparticles;
fifthly, preparing NaOH aqueous solution, and marking as solution I;
sixthly, Zn (NO) is prepared3)2.6H2The O aqueous solution is marked as a solution II; then adding TiO2The nanoparticles are added to the solution II, where TiO2With Zn (NO)3)2.6H2The molar ratio of O is (1-1.2): 1; stirring uniformly to obtain a suspension;
adding the solution I into the suspension under the stirring condition, uniformly stirring, then adding an accelerant at one time, stirring for 50-70 min, settling for 30-40 min, removing a supernatant, drying in an oven, and grinding into powder to obtain a heterojunction precursor; wherein the promoter is NH4HCO3In which NH4HCO3With Zn (NO)3)2.6H2The mass ratio of O is 1: (2-3) or the promoter is NH4HCO3In combination with sodium laureth sulfate, NH wherein4HCO3With Zn (NO)3)2.6H2The mass ratio of O is 1: (2-3) sodium laureth sulfate and Zn (NO)3)2.6H2The molar ratio of O is (1-1.6): 200 of a carrier;
eighthly, placing the heterojunction precursor in a muffle furnace, heating to 400-410 ℃, and roasting for 2-3 h to obtain TiO2The ZnO semiconductor heterojunction SERS active substrate.
Furthermore, in the second step, 1 drop is added at the speed of 2-3 seconds when the solution A is added into the solution B;
furthermore, in the fifth step, the concentration of the NaOH aqueous solution is 0.02-0.03 g/mL;
further, in step six, Zn (NO)3)2.6H2The concentration of the O water solution is 0.02-0.04 g/mL;
further, step sevenIn the solution I, the mass of NaOH and the Zn (NO) in the suspension3)2.6H2The mass ratio of O is 1: (2-4);
furthermore, in the seventh step, the drying is carried out at 75-80 ℃ for 19-20 h.
The invention adopts a drying method to prepare TiO2The method is simple, low in raw material cost, non-toxic, harmless and environment-friendly. The promoter NH is added during the preparation of the heterojunction4HCO3So that TiO is present2With Zn2+Ion generation of uniform TiO on the basis of molecular level mixing2a/ZnO heterojunction structure; NH (NH)4HCO3The accelerating agent combined with sodium laureth sulfate can not only generate uniform TiO on the basis of molecular level mixing2The structure of the ZnO heterojunction, and the sodium lauryl polyether sulfate can control the generation rate and the interface performance of the heterojunction, so that the formed heterojunction has a higher specific SERS effect.
The TiO prepared by the invention2the/ZnO heterojunction has specific SERS effect, so that the/ZnO heterojunction has higher SERS activity. 4-mercaptopyridine (4-MPY) probe molecules in the TiO of the invention2The lowest detected concentration on the ZnO heterojunction substrate can reach 1 x 10-9M, which is the highest detection sensitivity among semiconductor substrates reported so far. TiO of the invention2the/ZnO heterojunction expands the range of the SERS technology and the semiconductor SERS active substrate.
Drawings
FIG. 1 is the TiO prepared in example 12Pure anatase TiO active substrate prepared by ZnO semiconductor heterojunction SERS (surface enhanced Raman scattering) active substrate and comparative experiment 12Nanoparticles, ZnO nanoparticles prepared in comparative experiment 2, TiO prepared in comparative experiment 3 using the unfired precursor2Enhanced Raman spectrum of ZnO semiconductor heterojunction;
FIG. 2 shows TiO prepared at 400 ℃ in example 12ZnO semiconductor heterojunction SERS active substrate and TiO prepared in example 2 at 450 ℃, 500 ℃ and 550 ℃ respectively2Enhanced Raman spectroscopy of/ZnO semiconductor heterojunctionA drawing;
FIG. 3 shows the results obtained in example 1 in TiO2With Zn (NO)3)2.6H2TiO prepared under the condition that the molar ratio of O is 1:12ZnO semiconductor heterojunction SERS active substrate and example 3 on TiO2With Zn (NO)3)2.6H2TiO prepared under the condition that the molar ratio of O is 2:1, 3:1, 4:1 and 5:12Enhanced Raman spectrum of ZnO semiconductor heterojunction;
FIG. 4 shows the adsorption of ethanol solutions of 4-mercaptopyridine (4-MPY) at different concentrations on TiO prepared in example 12Enhanced Raman spectrogram on a ZnO semiconductor heterojunction SERS active substrate;
FIG. 5 is the TiO prepared in example 12Enhanced raman spectra of/ZnO semiconductor heterojunction SERS-active substrate and the semiconductor heterojunction SERS-active substrate prepared in example 4.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: TiO of this example2The preparation method of the/ZnO semiconductor heterojunction SERS active substrate comprises the following steps:
firstly, adding 15mL of tetrabutyl titanate into 15mL of absolute ethyl alcohol, and stirring for 10min to obtain a solution A;
mixing 15mL of absolute ethyl alcohol, 15mL of water and 3mL of concentrated nitric acid with the mass percentage concentration of 65%, and stirring for 10min to obtain a solution B; under the condition of stirring, dropwise adding the solution A into the solution B, controlling the dropwise adding speed to be 2-3 seconds per drop, and stirring for 120min after dropwise adding is finished to obtain light yellow transparent sol;
thirdly, transferring the sol into a hydrothermal kettle, putting the hydrothermal kettle into an oven for hydrothermal reaction for 6 hours at 160 ℃, naturally cooling the hydrothermal kettle to room temperature, pouring out waste liquid, putting the obtained hydrothermal product into the oven for drying for 6 hours at 80 ℃, naturally cooling the hydrothermal product, and grinding the hydrothermal product into powder to obtain a precursor;
fourthly, placing the precursor in a muffle furnace, heating to 450 ℃ and roasting for 2h to obtain TiO2Nanoparticles;
fifthly, weighing 1.6g of NaOH and dissolving the NaOH in 80mL of deionized water to obtain NaOH aqueous solution, and marking as solution I;
sixthly, weighing 5.9498g of Zn (NO)3)2.6H2Dissolving O in 200mL of deionized water, and marking as a solution II; 1.5973 g of TiO were further mixed2The nanoparticles are added to the solution II, TiO2With Zn (NO)3)2.6H2The molar ratio of O is 1: 1; stirring uniformly to obtain a suspension;
seventhly, adding the solution I into the suspension under the stirring condition, uniformly stirring, and then adding 2.4g of NH in one step4HCO3Then adding 5mL of 0.02mol/L lauryl alcohol polyether sulfate sodium aqueous solution, stirring for 60min, settling for 30min, removing supernatant, drying in an oven at 80 ℃ for 20h, and grinding into powder to obtain a heterojunction precursor;
eighthly, placing the heterojunction precursor in a muffle furnace, heating to 400 ℃, and roasting for 2h to obtain TiO2The ZnO semiconductor heterojunction SERS active substrate.
Comparative experiment 1: preparation of pure anatase TiO2Nanoparticles were used for comparison, and the specific preparation steps were as follows: firstly, adding 15mL of tetrabutyl titanate into 15mL of absolute ethyl alcohol, and stirring for 10min to obtain a tetrabutyl titanate solution, and marking as a solution A; mixing 15mL of absolute ethyl alcohol, 15mL of water and 3mL of concentrated nitric acid with the mass percentage concentration of 65%, and stirring for 10min to obtain a solution B; slowly dripping the solution A into the solution B for hydrolysis under the stirring condition, keeping the dripping speed for 2-3 seconds per drop, and continuously stirring for 2 hours after the dripping is finished to obtain light yellow transparent sol; then transferring the prepared sol into a hydrothermal kettle, putting the hydrothermal kettle into an oven for hydrothermal reaction for 6h at 160 ℃, naturally cooling the hydrothermal kettle to room temperature, pouring out waste liquid, uniformly dispersing the obtained hydrothermal product into a watch glass, putting the watch glass into the oven for drying for 6h at 80 ℃, naturally cooling the watch glass, and putting the watch glass into a mortar for grinding the watch glass into powder to obtain a precursor; roasting the precursor for 2 hours at the temperature of 450 ℃ to obtain pure anatase TiO2Nanoparticles.
Comparative experiment 2: preparation of ZnO nanoparticles for comparison, the specific preparation steps were as follows: weighing 1.6g of NaOH and dissolving in 80mL of deionized water to obtain a NaOH solution; weighing 5.9498g Zn (NO)3)2.6H2Dissolving O in 200mL of deionized water to obtain Zn (NO)3)2A solution; dropping the obtained NaOH solution into Zn (NO) under stirring3)2In the solution, the dropping speed is kept at 2-3 seconds per drop, after the dropping is finished, the solution is stirred for 60min and then settled for 30min, and the supernatant is poured out to obtain white suspension; drying the suspension in a drying oven at 80 ℃ for 19h, naturally cooling, and grinding into powder to obtain a precursor; and then the precursor is placed in a muffle furnace to be roasted for 2 hours at the temperature of 400 ℃, and the ZnO nano particles are obtained.
Comparative experiment 3: the difference between this comparative experiment and example 1 is that step four was omitted, i.e. the precursor was not calcined; in the sixth step, the precursor is used to replace TiO2Carrying out operation on the nano particles; otherwise, TiO was obtained in the same manner as in example 12A/ZnO semiconductor heterojunction.
TiO prepared in example 12Pure anatase TiO active substrate prepared by ZnO semiconductor heterojunction SERS (surface enhanced Raman scattering) active substrate and comparative experiment 12Nanoparticles, ZnO nanoparticles prepared in comparative experiment 2, and TiO prepared in comparative experiment 32the/ZnO semiconductor heterojunction is dispersed in 8mL of the solution with concentration of 1 × 10-3M in 4-mercaptopyridine (4-MPY) ethanol, and stirring for 6 hours at room temperature by magnetic force. Then, the mixture was centrifuged in a centrifuge 9500 rpm for 12 minutes, washed with ethanol, and centrifuged, and the operation was repeated 2 times. And naturally drying to obtain the probe molecule 4-MPY surface modified material. The enhanced Raman spectrum obtained by Raman spectroscopy using a HORIBA LabRam ARAMIS Raman spectrometer with an excitation light source wavelength of 633nm is shown in FIG. 1, and it can be seen from FIG. 1 that TiO prepared in example 12The performance of the/ZnO semiconductor heterojunction SERS active substrate is obviously better than that of TiO2ZnO itself; calcined TiO at 450 ℃2The resulting heterojunction has SERS performance better than that of the precursor, i.e. unbaked TiO2Formed TiO2a/ZnO heterojunction. This indicates that the stabilized TiO2The framework is favorable for the successful formation of heterojunction, has excellent surface and interface properties, and adopts TiO in a 450 ℃ calcination state2Is to form high performance TiO2Method for preparing ZnO semiconductor heterojunction SERS substrateThe key is that.
Example 2: TiO of this example2The preparation method of the/ZnO semiconductor heterojunction SERS active substrate is different from the embodiment 1 in that the roasting temperature in the step eight is respectively 450 ℃, 500 ℃ and 550 ℃; the rest is the same as in example 1.
TiO prepared in example 1 at 400 deg.C2ZnO semiconductor heterojunction SERS active substrate and TiO prepared in example 2 at 450 ℃, 500 ℃ and 550 ℃ respectively2the/ZnO semiconductor heterojunction is dispersed in 8mL of the solution with concentration of 1 × 10-3M in 4-mercaptopyridine (4-MPY) ethanol, and stirring for 6 hours at room temperature by magnetic force. Then, the mixture was centrifuged in a centrifuge 9500 rpm for 12 minutes, washed with ethanol, and centrifuged, and the operation was repeated 2 times. And naturally drying to obtain the probe molecule 4-MPY surface modified material. The Raman spectroscopy test is carried out by using a HORIBA LabRam ARAMIS type Raman spectrometer with the excitation light source wavelength of 633nm, and the obtained enhanced Raman spectrogram is shown in figure 2, which can be clearly seen when TiO is2The roasting temperature of the ZnO heterojunction in the step eight is 400 ℃, and the ZnO heterojunction and TiO prepared at other roasting temperatures2Compared with ZnO, the SERS enhancement capability is highest. The reason is that the forming efficiency of the heterojunction is reduced along with the rise of the temperature, so that the number of surface bindable sites is reduced, and the SERS performance of the prepared substrate is influenced, and the roasting temperature of 400-410 ℃ selected by the invention obtains good SERS activity.
Example 3: TiO of this example2The difference between the preparation method of the/ZnO semiconductor heterojunction SERS active substrate and the example 1 is that in the sixth step, TiO2With Zn (NO)3)2.6H2The molar ratio of O is 2:1, 3:1, 4:1 and 5: 1; the rest is the same as in example 1.
Example 1 is performed on TiO2With Zn (NO)3)2.6H2TiO obtained under the condition that the molar ratio of O is 1:12ZnO semiconductor heterojunction SERS active substrate and example 3 on TiO2With Zn (NO)3)2.6H2TiO prepared under the condition that the molar ratio of O is 2:1, 3:1, 4:1 and 5:12ZnO semiconductor hetero-junctionThe mixture was dispersed in 8mL of 1X 10-3M in 4-mercaptopyridine (4-MPY) ethanol, and stirring for 6 hours at room temperature by magnetic force. Then, the mixture was centrifuged in a centrifuge 9500 rpm for 12 minutes, washed with ethanol, and centrifuged, and the operation was repeated 2 times. And naturally drying to obtain the probe molecule 4-MPY surface modified material. The method comprises performing Raman spectroscopy test by using HORIBA LabRam ARAMIS type Raman spectrometer with excitation light source wavelength of 633nm to obtain enhanced Raman spectrogram as shown in FIG. 3, wherein the enhancement degree of semiconductor heterojunction obtained by different composition ratios is different, and 4-MPY molecules are adsorbed on TiO2With Zn (NO)3)2.6H2TiO prepared with molar ratio of O1: 12The maximum SERS enhancement is shown on the/ZnO semiconductor heterojunction SERS active substrate. This is due to the addition of TiO2An excessive amount of nanoparticles may inhibit the formation of a heterojunction. TiO selected by the invention2With Zn (NO)3)2 .6H2The molar ratio of O is (1-1.2): 1 prepared TiO2the/ZnO substrate can improve the SERS signal of the probe molecule.
20mg of TiO prepared as in example 12Respectively dispersing the/ZnO semiconductor heterojunction SERS active substrates to 8mL of SERS active substrates with the concentration of 1 multiplied by 10-3、1×10-4、1×10-5、1×10-6、1×10-7、1×10-8、1×10-9And 1X 10-10M in 4-mercaptopyridine (4-MPY) ethanol, and stirring for 6 hours at room temperature by magnetic force. Then, the mixture was centrifuged in a centrifuge 9500 rpm for 12 minutes, washed with ethanol, and centrifuged, and the operation was repeated 2 times. Naturally drying to obtain the TiO modified on the surface of the probe molecule 4-MPY2a/ZnO heterojunction material. The Raman spectrometer of HORIBA LabRam ARAMIS type is adopted, the wavelength of an excitation light source is 633nm, and the obtained Raman spectrogram is shown in figure 4. As can be seen from FIG. 4, TiO2The minimum detection limit of the/ZnO heterojunction SERS substrate reaches 10-9And M. Thus, the novel TiO compound was found to be2The detection capability of the/ZnO semiconductor heterojunction SERS active substrate is higher than that of the common TiO2And is superior to common ZnO substrate. Thus, it is possible to provideThe novel TiO2the/ZnO semiconductor heterojunction has excellent SERS performance as an SERS substrate.
Example 4: TiO of this example2The preparation method of the/ZnO semiconductor heterojunction SERS active substrate is different from that of the example 1 in that: the operation of the seventh step is as follows: under stirring, the solution I is added to the suspension and stirred uniformly, and then 2.4g of NH are added in one portion4HCO3Stirring for 60min, settling for 30min, removing supernatant, drying in an oven, and grinding into powder to obtain heterojunction precursor; the rest is the same as in example 1. To obtain TiO2The ZnO semiconductor heterojunction SERS active substrate.
TiO prepared in example 12ZnO surface enhanced Raman scattering active substrate and TiO prepared in example 42Respectively dispersing the/ZnO semiconductor heterojunction SERS active substrates to 8mL of SERS active substrates with the concentration of 1 multiplied by 10-3M in 4-mercaptopyridine (4-MPY) ethanol, and stirring for 6 hours at room temperature by magnetic force. Then, the mixture was centrifuged in a centrifuge 9500 rpm for 12 minutes, washed with ethanol, and centrifuged, and the operation was repeated 2 times. And naturally drying to obtain the probe molecule 4-MPY surface modified material. Raman spectroscopy was performed using a HORIBA LabRam ARAMIS type Raman spectrometer with an excitation light source wavelength of 633nm, and the resulting enhanced Raman spectrogram was shown in FIG. 5. As can be seen from FIG. 5, NH is used4HCO3TiO obtained by composite accelerator combined with sodium laureth sulfate2NH with single SERS performance ratio of ZnO substrate4HCO3The accelerator is further improved. In the preparation process, sodium laureth sulfate can control the generation rate of the heterojunction and obtain the interface performance which has specific contribution to the SERS effect, so that the formed heterojunction structure has higher SERS activity to probe molecules.
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