CN113484302B - SnS with capillary effect 2 Microsphere SERS substrate and preparation method and application thereof - Google Patents
SnS with capillary effect 2 Microsphere SERS substrate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a SnS with capillary effect 2 A microsphere SERS substrate and a preparation method and application thereof are provided. The SnS 2 The micro-sphere SERS substrate is composed of SnS 2 The nano-sheets are curled, and the average particle size is 1-10 mu m.
Description
Technical Field
The invention relates to a SnS 2 A microsphere SERS substrate and a preparation method thereof, in particular to SnS which is prepared by a hydrothermal method and has an average size of 2-10 micrometers (for example, 5 micrometers) and is formed by curling nano sheets 2 A microsphere Surface Enhanced Raman Scattering (SERS) substrate and a preparation method thereof belong to the technical field of laser Raman spectroscopy and detection.
Background
The Surface Enhanced Raman Scattering (SERS) sensor can efficiently and quickly detect substances in trace quantity and give fine structural vibration information. Therefore, the SERS sensor can be used for detecting biomacromolecules such as bacteria, viruses, glucose, DNA and the like in the field of biosensing. However, since all the time, virus infection seriously threatens human health, and people are forced to realize that the detection of biomacromolecules such as viruses is necessary. At present, a great deal of application research of the SERS technology finds that the SERS substrate widely used for detecting biomolecules is mostly a precious metal, however, poor biocompatibility and the ability to denature proteins are two main culprits limiting the practical application of precious metal substrates in virus detection. Compared with a noble metal substrate, the semiconductor material has many attractive advantages in the aspects of biocompatibility, high spectral stability, strong anti-interference capability, selective SERS enhancement of targeted molecules and the like, so that the semiconductor-based SERS substrate has wide application prospects in identification and sensing of biomolecules. And because most protein molecules or virus particles have large molecular weight, the semiconductor substrate with the main effect of charge transfer is difficult to obviously enhance the chemical bond vibration of the whole biomacromolecule by SERS. Therefore, there is a strong need to achieve ultra-high SERS sensitivity in semiconductor-based substrates, comparable to noble metal substrates.
For semiconductor-based SERS substrates, the SERS enhancement to the probe molecule results primarily from charge transfer between the two increasing the polarizability of the molecule, thereby enhancing the chemical bond vibrations of the molecule. Common approaches are to increase the carrier concentration (excited electrons) or to add intermediate energy levels by elemental doping, amorphizing the substrate material, structuring the heterojunction substrate, thereby facilitating charge transfer. In addition, the HOMO and LUMO energy levels of the substrate material can be regulated and controlled through processing means such as element doping, phase change, annealing, crystal face regulation and the like, so that the best energy level matching can be realized with the energy level of the probe molecule, and the coupling resonance effect of multiple components (charge transfer, molecular resonance and exciton resonance) can be realized. Currently, a large number of researchers have optimized SERS detection limits for most pure semiconductor-based substrates to 10 -9 M nearby, but breakthrough 10 -10 M becomes a new SERS detection bottleneck. In recent years, metal sulfides have been receiving attention from many scholars due to their low band gaps, special crystal structures and excellent electrochemical reactivity. SnS 2 As a typical two-dimensional (2D) layered semiconductor material, the material has huge application potential in the SERS detection field due to the unique photoelectric characteristics, no toxicity, low price and high stability under acidic and alkaline conditions. Due to SnS 2 S vacancy existing on the surface of the nanosheet is an n-type semiconductor with an indirect band gap, the average carrier diffusion length of the n-type semiconductor is 0.19 mu m, and charge transfer is facilitated. SnS 2 The nano sheets are only connected through weak van der Waals interaction, the thickness of the nano sheets is reduced to a single layer, the band gap of the nano sheets is changed between 1 to 3eV, and the HOMO and LUMO energy levels of the substrate material can be adjusted and controlled. And SnS 2 The material can not only be compounded with most other semiconductors to form a heterojunction structure to activate excited electrons of the material, but also be doped with most metal elements (Mo \ V \ In/Co/Fe/Er/Ho/Co/Zn/Ni/Sb/Cu) to regulate and control the material band gap. Due to the fact thatThis SnS 2 The nanoplatelets can generate a great amount of charge transfer with probe molecules to realize multi-component coupling resonance enhancement of charge transfer resonance, molecular resonance and exciton resonance, which shows that SnS 2 The nano sheet is expected to be developed into an active material with ultrahigh sensitivity of SERS. But only SnS 2 The smooth surface of the nanosheet is free of wrinkles, so that the phenomenon that probe molecules are converged on the surface of the substrate under low concentration is not facilitated, and the sensitivity of the nanosheet as the SERS substrate is low.
Disclosure of Invention
Therefore, the invention aims to provide an SnS with special novel morphology and ultrahigh SERS sensitivity 2 The material and the preparation method thereof are used as a hypersensitive SERS substrate to directly detect biological macromolecules such as viruses and the like in the field of biosensing.
In one aspect, the invention provides an SnS 2 A microsphere SERS substrate, said SnS 2 SnS substrate of microsphere SERS 2 The nano-sheets are curled, and the average particle size is 1-10 mu m.
In the present invention, snS 2 The microsphere is directly synthesized through simple one-step hydrothermal reaction, no surfactant or template agent is added in the reaction, and the nano-sheets are directly self-assembled into the microsphere curled by the nano-sheets by adjusting the concentration of reactants. The SnS 2 The microsphere is used as an SERS substrate, so that ultra-sensitive detection of methylene blue dye molecules (MeB) can be realized, and the detection limit of the microsphere can be even comparable to a noble metal substrate with a hot spot effect. Such SnS 2 The synthesis process of the microspheres is simple and controllable, and the microspheres can be produced and applied in large batch. Preferably, the SnS 2 The microsphere SERS substrate has ultrasensitive surface enhanced Raman scattering activity, and the SERS detection limit of methylene blue molecules is at least 10 -13 M。SnS 2 The SERS enhancement factor of the microsphere to MeB is at least 1.2 multiplied by 10 10 。
Preferably, the SnS 2 The thickness of the nano sheet is 2-10 nm; preferably, the SnS 2 The average particle size of the microsphere SERS substrate was 5.37 μm.
Preferably, the SnS 2 Crimped SnS on microsphere SERS substrate surface 2 Gaps (or gaps) with the width smaller than 300nm are formed between the nano sheets, and gaps with the width smaller than 300nm are formed between the nano sheets.
Preferably, the SnS 2 The exposed crystal face of the microsphere SERS substrate is a (011) face.
Preferably, the SnS 2 The microsphere SERS substrate has hydrophilicity, and the water contact angle is 10-30 degrees, preferably 10-20 degrees.
On the other hand, the invention also provides SnS 2 The preparation method of the microsphere SERS substrate comprises the following steps:
(1) Will K 2 SnO 3 ·3H 2 O powder and Na 2 SnO 3 ·3H 2 Adding at least one of O powder into deionized water solution of a sulfur source, and uniformly mixing at 40-60 ℃ to obtain precursor solution; preferably, the sulfur source is at least one of thioacetamide and thiourea;
(3) Putting the precursor solution into a reaction kettle, and carrying out hydrothermal reaction at 120-240 ℃ for 16-36 hours to obtain brown precipitate, namely SnS 2 Microsphere SERS substrate.
In the present invention, K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 Dissolving O powder in a deionized water solution of a sulfur source to obtain a precursor solution, wherein the chemical reaction comprises the following steps: na (Na) 2 SnO 3 ·3H 2 O＝Na 2 SnO 3 +3H 2 And O. Then, putting the precursor solution into a 100mL reaction kettle, carrying out hydrothermal reaction for 24-36 hours at 160-200 ℃, and then carrying out centrifugation, washing and freeze drying to obtain the SnS 2 And (4) micro-spheres. The chemical reactions that occur in the hydrothermal reaction are: na (Na) 2 SnO 3 +2H 2 S＝ SnS 2 ↓+2NaOH+H 2 And O. In the whole hydrothermal reaction, na 2 SnO 3 ·3H 2 O provides a Sn source and thioacetamide provides an S source.
Preferably, thioacetamide (TTA) is added into deionized water, and is electromagnetically stirred at the temperature of 40-60 ℃ to rapidly dissolve the powder, so that an aqueous thioacetamide solution is obtained. Chemical reaction taking placeThe method comprises the following steps: CH (CH) 3 CSNH 2 +H 2 O＝ CH 3 CONH 2 +H 2 S。
Preferably, said K 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The mass ratio of the O powder to the sulfur source is 1: (1.8 to 2.2), preferably 1:2; the mixing mode is electromagnetic stirring, the rotating speed is 400-600 r/min, and the time is 10-30 min.
Preferably, said K 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The ratio of O powder to deionized water is (1.4-4.8 mmol): (40 mL-70 mL), preferably (2.5 mmol-3.5 mmol): (40 mL-70 mL), more preferably (2.9 mmol-3.1 mmol): (50 mL-60 mL).
Preferably, the ratio of the sulfur source to the deionized water is (10-33 mmol): (40 mL-70 mL), preferably (18 mmol-25 mmol): (40 mL-70 mL), more preferably (20 mmol-22 mmol): (50 mL-60 mL).
Preferably, the hydrothermal reaction temperature is 180 ℃ and the hydrothermal reaction time is 24 hours.
Has the advantages that:
in the present invention, snS 2 The microsphere has ultrahigh SERS sensitivity, and can be used for directly detecting various biological macromolecules, such as various biological markers of new coronavirus which needs to be detected at present. The experimental result shows that the method is based on SnS 2 The microsphere SERS substrate, SARS-CoVS, SARS-CoV-2S protein, inactivated SARS-CoV-2 virus and SARS-CoV-2S pseudovirus, were all sensitively detected and recognized, and it is believed that SnS 2 The microsphere has great potential in practical application such as biosensing.
Drawings
FIG. 1 shows three topographies of trigonal SnS dominated by three exposed surfaces prepared in examples 1, 2, and 3 2 A nanosheet. Wherein, snS 2 The exposed surface of the microsphere is (011) surface, snS 2 Exposed surface of micrometer flower is (100) surface, snS 2 The exposed surface of the stacked regular hexagonal nanosheets is the (001) surface;
FIG. 2 isSnS prepared in example 1 2 SEM image of the microsphere, from which SnS is known 2 The micro-sphere is made of SnS 2 The nano-sheet is formed by rolling nano-sheets, has uneven particle size and fluctuates approximately within the range of 2-10 mu m. And the SnS 2 The surface of the microsphere has a large number of wide-top and narrow-bottom 'ravines' formed by SnS adjacent to the crimp 2 Between the nano-sheets, the width is less than 300nm, and the SnS 2 The thickness of the nano-sheet is about 5.8 nm;
FIG. 3 shows SnS prepared in example 1 2 TEM image (a), SAED image (b), HRTEM image (c) of the microspheres. TEM image showing SnS 2 The nanosheets are crimped into a microspherical morphology wherein the exfoliated nanosheets are approximately 300nm in size. SnS is shown by SAED diagram 2 The exposed surface of the microsphere is (011) plane, and HRTEM image shows significant lattice diffraction fringes with interplanar spacing of 2.78nm corresponding to SnS 2 The (011) plane of the trigonal system of the nanosheet, which is consistent with the XRD analysis results;
FIG. 4 shows SnS prepared in example 1 2 A histogram (a) and a histogram (b) of the particle size distribution of the microspheres. As can be seen, snS 2 The size of the microsphere particles is not uniform and fluctuates approximately within the range of 2-10 microns, and the average size of the microsphere is 5.37 microns by statistics;
FIG. 5 shows SnS prepared in example 1 2 Micro-ball pair 10 -11 M (notation "1"), 10 -12 M (notation "2"), 10 -13 Raman spectrum of M (symbol "3") methylene blue (MeB), and SnS was found from the spectrum 2 Micro-sphere pair MeB reaches 10 -13 M, and at a very low MeB concentration of 10 -12 M and 10 -13 Under M, snS 2 There was no significant drop in the raman intensity of MeB under microspheric SERS enhancement, which is comparable to SnS 2 The unique "gully" morphology of the microsphere surface is related to the capillary effect due to good hydrophilicity. SnS 2 The capillary attraction on the surface of the microsphere can guide the low-concentration probe molecules to converge on the surface of the substrate, so that visual Raman detection is realized, and the detection sensitivity of the probe molecules is greatly improved. This also results in SnS 2 The SERS enhancement factor of the microsphere to MeB is up to 1.2 multiplied by 10 10 To achieve 10 -13 SERS detection limit of M (the inventors tested 3 times, and the detection limit of M can reach 10 each time -13 M). Due to SnS 2 The capillary effect existing on the surface of the microsphere has the convergence effect on the probe molecules, and the Raman peak of the molecules can be detected as long as the convergence region of the molecules is searched on the surface of the SERS substrate, so that the characteristic Raman peak intensity of the detected MeB is 10 -13 The concentration of M is still as high as 16697a.u. at ultralow concentration, so that the detection limit can be reasonably predicted to be lower (10) -14 M)。
FIG. 6 is SnS prepared in example 1 2 The visible image (a) and the Raman Mapping image (b) of the aggregation effect of the microspheres on MeB molecules in the solution are shown. Due to SnS 2 The unique "ravine" morphology of the microsphere surface is related to the capillary effect caused by good hydrophilicity, so that the probe molecule water solution will flow to the "ravine" region during evaporation, thereby generating the probe molecule aggregation. The phenomenon can realize visual detection of Raman, which can greatly reduce the detection limit of SERS;
FIG. 7 is a stacked regular hexagonal SnS prepared in example 2 2 SEM image of nanoplatelets. As can be seen from the figure, the SnS of the regular hexagon 2 A helical stack of nanosheets having a particle size of about 3.0 μm;
FIG. 8 is a stacked regular hexagonal SnS prepared in example 2 2 TEM image (a), SAED image (b), HRTEM image (c) of nanosheets. TEM image showing SnS stacked in regular hexagon 2 Nanoplatelets having a particle size of approximately 1.6 μm. Stacked regular hexagonal SnS shown by SAED diagram 2 The exposed face of the nanoplatelets is the (001) face, and HRTEM images show significant lattice diffraction fringes with interplanar spacings of 5.75nm and 3.17nm corresponding to SnS 2 The (001) and (100) planes of the trigonal systems of the nanosheets, which is consistent with XRD analysis results;
FIG. 9 is SnS prepared in example 3 2 SEM images of the popcorn. As shown in the figure, snS 2 The micro-flower is formed by crossing nano-sheets, and the particle size of the micro-flower is about 6.0 μm;
FIG. 10 is SnS prepared in example 3 2 TEM image of the micro-flowers (a),SAED image (b), HRTEM image (c). TEM image shows the pattern formed by SnS 2 The nano sheets are crossed to form a micro popcorn structure, and the particle size is about 1.6 mu m. Stacked regular hexagonal SnS shown by SAED diagram 2 The exposed surface of the nanosheet was the (100) surface and the diffraction points tended to form sharp diffraction rings, indicating that SnS 2 Crystallinity of the micro-flowers compared to stacked regular hexagonal SnS 2 Nanosheet and SnS 2 The micro-spheres dropped somewhat. HRTEM image showed clear lattice diffraction fringes with interplanar spacing of 3.2nm corresponding to SnS 2 The (100) face of the trigonal system of the nanosheet, which is consistent with the XRD analysis results;
FIG. 11 is a SnS with three profiles dominated by three exposed surfaces prepared by examples 1, 2, 3 2 Powder photograph. Wherein (011) surface controlled SnS 2 The microspheres are brown in color, and (001) plane controlled SnS 2 The stacked regular hexagonal nanoplates are yellow, (100) face-controlled SnS 2 Micro flowers are dark brown;
FIG. 12 shows three patterns of SnS with three exposed surface masters prepared in examples 1, 2 and 3 2 Hydrophilicity and specific surface area data of the nanoplatelets. As can be seen from the figure, though SnS with three morphologies 2 The specific surface areas of the nano sheets are all small and are respectively 7.22m 2 /g， 9.35m 2 /g，10.18m 2 (ii)/g; however, the appearance of the (001) surface master-control stacked regular hexagonal nano-sheets and the appearance of the micro-flowers formed by crossing the (100) surface master-control nano-sheets do not have the hydrophilic characteristic, but SnS 2 The microspheres show good hydrophilicity;
FIG. 13 shows three patterns of SnS prepared in example 1 (labeled "1"), 2 (labeled "2"), 3 (labeled "3") 2 Nanosheet pair 10 -6 Raman Spectroscopy of M MeB (a), snS 2 Stacking regular hexagonal nanosheet pairs 10 -11 M (notation "1"), 10 -12 M (notation "2"), 10 -13 Raman spectrum (b) of M (notation "3") MeB, snS 2 Micro-flower pair 10 -7 M～10 -11 Raman spectrum (c) of MeB with M (labeled "1, 2, 3, 4, 5" in this order). As can be seen from the graph (a), snS with three morphologies 2 SERS enhancement of nanosheets to high concentration of MeBThe strength is: snS 2 Stacked orthohexagonal nanosheet > SnS 2 Micro-sphere > SnS 2 Micro-flowers (this is a comparison of the characteristic Raman peak intensities of high concentration MeB molecules, since at higher probe molecule concentrations the probe molecular weight is huge and can directly cover the entire SnS 2 The substrate causes the gathering effect of the micro-spheres on the molecules to be not obvious, and at the moment, snS 2 The Raman intensity of the stacked regular hexagonal nanosheets to MeB is slightly higher than that of SnS 2 Microspheres are reasonable. At relatively low concentrations (less than 10) -10 M) MeB molecules, the convergence region of the probe molecules in a microscopic field can be seen due to the convergence of the microspheres on the molecules, so that the high Raman intensity of the MeB can be obtained through detection, namely SnS 2 What stacked regular hexagonal nanosheets do not). As shown in FIGS. b and c, snS 2 The detection limit of the stacked nanosheets to MeB reaches 10 -13 M (inventor pair 10) -13 M MeB carries out a plurality of Raman tests to detect the Raman peak data of one MeB, the intensity of the Raman characteristic peak is only 8500, and therefore the fact that the detection limit cannot break through 10 can be determined -13 M), SERS enhancement factor is 4.02X 10 9 。SnS 2 The detection limit of MeB on the micro-flower reaches 10 -11 M, SERS enhancement factor 8.16 is multiplied by 10 6 ；
FIG. 14 is SnS prepared by adjusting the volume of deionized water to 50mL (a), 55mL (b), and 60mL (c) in example 4 2 SEM image of microspheres. As can be seen from FIG. 14, the volume of deionized water was slightly changed versus SnS 2 The micron spherical appearance does not have obvious influence;
FIG. 15 is stacked orthohexagonal SnS prepared by adjusting hydrothermal reaction temperature of 160 deg.C (a), 180 deg.C (b), 200 deg.C (c) of example 5 2 SEM image of nanosheets. As can be seen from the figure, the non-regular hexagonal SnS is obtained after the hydrothermal reaction at the temperature of 160 DEG C 2 Stacking the nano sheets, and carrying out hydrothermal reaction at 180 ℃ to obtain regular-hexagon SnS 2 Stacking the nano sheets, and performing hydrothermal reaction at the temperature of 200 ℃ to obtain most of vertically crossed regular hexagon SnS 2 A nanosheet;
FIG. 16 shows the hydrothermal reaction time controlled in example 6SnS prepared in 2h, 8h, 16h and 24h 2 XRD pattern of microspheres;
FIG. 17 shows SnS prepared in example 6 by adjusting hydrothermal reaction times of 2h, 8h, 16h and 24h 2 SEM image of micro-spheres, snS is reflected in FIG. 17 2 The growth process and mechanism of the microspheres;
FIG. 18 shows SnS prepared in example 7 by adjusting hydrothermal reaction times of 2h, 8h, 16h and 24h 2 XRD pattern of stacked nanoplates;
FIG. 19 shows SnS prepared in example 7 by adjusting hydrothermal reaction times of 2h, 8h, 16h and 24h 2 SEM image of stacked nanosheets, regular hexagonal SnS reflected by FIG. 19 2 The growth process and mechanism of the stacked nanosheets;
FIG. 20 is a graph of SnS prepared by adjusting hydrothermal reaction times of 2h, 8h, 16h and 24h in example 8 2 XRD pattern of the popcorn;
FIG. 21 shows that SnS is prepared in example 8 by adjusting hydrothermal reaction time for 2h, 8h, 16h and 24h 2 SEM image of micro-flower rice, snS is reflected by FIG. 21 2 The growth process and mechanism of the micro-flowers;
FIG. 22 is SnS prepared in example 1 2 The microsphere powder is used as Raman spectra of SARS-CoV-S protein and SARS-CoV-2S protein detected by SERS substrate Raman detection (a), and SARS-CoV-2S protein, inactivated SARS-CoV-2 virus and SARS-CoV-2S pseudovirus (b). As can be seen, all marker molecules of coronavirus are adsorbed to SnS 2 Obvious Raman peaks appear on the microspheres. Wherein, SARS-CoV-2S protein has a characteristic Raman peak which is different from SARS-CoV S protein and is 918cm respectively -1 And 1520cm -1 Raman peak of (d). While SARS-CoV-2S protein, inactivated SARS-CoV-2 virus and SARS-CoV-2S pseudovirus show almost completely identical Raman peaks, which are mainly attributed to SnS 2 The main part contacted by the micro-sphere substrate is SARS-CoV-2S protein, thus showing Raman peak identical to SARS-CoV-2S protein.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In this disclosure, snS 2 The micro-sphere SERS substrate is composed of SnS 2 The nano-sheets are coiled, the size of the particles is not uniform, the average size can be 1-10 μm, preferably 2-10 μm, more preferably 3-6 μm, and most preferably about 5.37 μm, and the ultra-high surface-enhanced Raman scattering activity is achieved.
In an alternative embodiment, the SnS 2 A plurality of gaps with wide upper parts and narrow lower parts exist on the surface of the microsphere SERS substrate, the gaps are formed among the curled nano sheets, and the maximum width of the gaps on the surface of the nano sheets is distributed between 20nm and 300nm.
In an alternative embodiment, the SnS 2 The exposed surface of the microsphere SERS substrate is SnS 2 (011) plane of (S), advantageous for SnS 2 And (4) forming the morphology of the microspheres. The band gap of crystals controlled by different crystal planes is different, so that the charge transfer is influenced, and the band gap of the (011) plane is 1.87eV.
In an alternative embodiment, the SnS 2 The specific surface area of the microsphere SERS substrate is smaller and is distributed at 6m 2 /g～ 8m 2 The ratio of the carbon atoms to the carbon atoms is between/g.
In an alternative embodiment, the SnS 2 The microsphere SERS substrate has good hydrophilicity, which endows SnS with good hydrophilicity 2 The gully shape of the surface of the micron sphere has a special function: a capillary effect.
Due to SnS 2 The microsphere SERS substrate has good hydrophilicity and surface gully appearance, so that the microsphere SERS substrate has a converging effect on probe molecules in an aqueous solution, and the SnS is caused 2 SERS detection limit of micro-spheres to methylene blue molecules is as low as 10 -13 M (break through 10) -10 M SERS detection bottleneck), the SERS enhancement factor is up to 3.4 × 10 13 The material is a material with the highest detection sensitivity in the reported pure semiconductor SERS substrate at present, and can be compared with a part of noble metal substrates with hot spot effects.
In one embodiment of the invention, snS with special new appearance and ultrahigh SERS sensitivity is directly synthesized by adjusting the concentration of reactants without adding any surfactant or template 2 And (4) micro-spheres. It can realize 10 to methylene blue dye molecule -13 The ultra-low detection limit of M can meet the requirement of ultra-high SERS sensitivity for detecting biomacromolecules such as viruses and the like in the field of biosensing. In addition, the invention adopts a simple and controllable one-step hydrothermal method, the product is pollution-free, green and economical, and can be produced and applied in large batch. The following exemplarily illustrates SnS 2 A preparation method of a microsphere SERS substrate.
An amount of commercially available thioacetamide (TTA) powder was dissolved in deionized water. Specifically, 10-33 mmol thioacetamide (TTA) is added into 50-60 mL deionized water, and the mixture is electromagnetically stirred for about 10 minutes at the temperature of 40-60 ℃ to rapidly dissolve the powder, so that a mixed transparent solution (namely the deionized water solution of thioacetamide) is obtained. The reaction equation during this dissolution process is: CH (CH) 3 CSNH 2 +H 2 O＝CH 3 CONH 2 +H 2 S, the sulfur source of the obtained hydrothermal reaction: h 2 S。
Then a certain amount of Na is added 2 SnO 3 ·3H 2 The O powder was dissolved in the thioacetamide solution described above. As an example, 1.4 to 4.8mmol of Na 2 SnO 3 ·3H 2 Adding O powder into the thioacetamide solution of 50-60 mL, and continuing to electromagnetically stir at the temperature of 40-60 ℃ (for example, the rotating speed can be 400-600 r/min for 10-30 min, preferably 20 min) so as to rapidly dissolve the powder and uniformly mix the powder to obtain a precursor solution. The reaction equation during this dissolution process is: na (Na) 2 SnO 3 ·3H 2 O＝Na 2 SnO 3 +3H 2 O, tin source of the resulting hydrothermal reaction: na (Na) 2 SnO 3 。
The precursor solution is subjected to hydrothermal reaction to prepare SnS 2 And (4) micro-spheres. As an example, 50-60 mL of the precursor solution is placed in a 100mL reaction kettle and undergoes hydrothermal reaction at 160-200 ℃ for 24-36 hours to obtain brown precipitate, namely SnS 2 Microsphere SERS substrate. Then centrifuging, washing and freeze-drying to obtain the brown SnS 2 And (4) micro-sphere powder. Wherein the rotation speed of the centrifuge can be 1100012000r/min, 15-20 min. For example, the rotation speed of the centrifugation is 12000r/min, and the time is 20min. The chemical reactions that occur in this hydrothermal reaction are: na (Na) 2 SnO 3 + 2H 2 S＝SnS 2 ↓+2NaOH+H 2 O。
In the present invention, the lining material of the hydrothermal reaction kettle used in the hydrothermal reaction process is Polytetrafluoroethylene (PTFE) or polyparaphenylene (PPL). In the invention, the SERS enhancement factor is calculated according to the characteristic Raman peak intensity of the detection limit.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples and comparative examples, the rotation speed of the centrifuge used was 12000r/min and the time was 20min, unless otherwise specified.
Example 1
1.6g of TTA powder (21.3 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.8g of Na was added 2 SnO 3 ·3H 2 O powder (3 mmoL) is added into the TTA solution, and the mixture is continuously stirred electromagnetically for about 20 minutes at the temperature of 60 ℃ so that the powder is quickly dissolved and uniformly mixed to obtain a precursor solution. The precursor solution was placed in a 100mL PPL lined hydrothermal reaction kettle and subjected to hydrothermal reaction at 180 ℃ for 24 hours to obtain a brown precipitate, as shown in fig. 11. Finally, centrifuging the brown precipitate, washing the brown precipitate with deionized water for three times, and freeze-drying the washed brown precipitate to obtain brown SnS 2 And (4) micro-sphere powder.
Example 2
0.8g of TTA powder (10.7 mmoL) was first added55mL of deionized water and placed at a temperature of 60 ℃ for about 10 minutes with magnetic stirring to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.4g of Na was added 2 SnO 3 ·3H 2 O powder (1.5 mmoL) was added to the above TTA solution, and electromagnetic stirring was continued at 60 ℃ for about 20 minutes to rapidly dissolve the powder and mix uniformly, to obtain a precursor solution. The precursor solution was then placed in a 100mL PPL lined hydrothermal reaction kettle and subjected to hydrothermal reaction at 180 ℃ for 24 hours to obtain a yellow precipitate, as shown in fig. 11. Finally, centrifuging the yellow precipitate, washing the yellow precipitate with deionized water for three times, and freeze-drying the yellow precipitate to obtain yellow SnS 2 Stacked regular hexagonal nanosheet powder.
Example 3
2.4g of TTA powder (32 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 1.2g of Na was added 2 SnO 3 ·3H 2 O powder (4.5 mmoL) was added to the above TTA solution, and electromagnetic stirring was continued at 60 ℃ for about 20 minutes to rapidly dissolve the powder and uniformly mix, to obtain a precursor solution. The precursor solution was then placed in a 100mL hydrothermal reaction kettle lined with PPL and subjected to hydrothermal reaction at 180 ℃ for 24 hours to obtain a dark brown precipitate, as shown in fig. 11. Finally, centrifuging the dark brown precipitate, washing the precipitate with deionized water for three times, and freeze-drying the precipitate to obtain dark brown SnS 2 The nano-sheets are crossed to form micro popcorn powder.
Example 4
First, 1.6g of TTA powder (21.3 mmoL) was added to 50, 55, and 60mL of deionized water, respectively, and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed transparent solution. Then, 0.8g of Na was added 2 SnO 3 ·3H 2 O powder (3 mmoL) is added into the TTA solution respectively, and the mixture is stirred electromagnetically for about 20 minutes at the temperature of 60 ℃ continuously to enable the powder to be dissolved rapidly and mixed uniformly, so that precursor solution is obtained. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃ to obtain brown precipitate. Most preferablyCentrifuging the brown precipitate, washing with deionized water for three times, and freeze drying to obtain brown SnS 2 And (3) powder.
Example 5
0.8g of TTA powder (10.7 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.4g of Na was added 2 SnO 3 ·3H 2 O powder (1.5 mmoL) was added to the above TTA solution, and electromagnetic stirring was continued at 60 ℃ for about 20 minutes to rapidly dissolve the powder and mix uniformly, to obtain a precursor solution. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction for 24 hours at 160 ℃,180 ℃ and 200 ℃ respectively to obtain brown precipitate. Finally, centrifuging the brown precipitate, washing the brown precipitate with deionized water for three times, and freeze-drying the washed brown precipitate to obtain brown SnS 2 And (3) powder.
Example 6
1.6g of TTA powder (21.3 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.8g of Na was added 2 SnO 3 ·3H 2 O powder (3 mmoL) is added into the TTA solution, and the mixture is continuously stirred electromagnetically for about 20 minutes at the temperature of 60 ℃ so that the powder is quickly dissolved and uniformly mixed to obtain a precursor solution. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction at 180 ℃ for 2, 8, 16 and 24 hours respectively to obtain precipitates, as shown in figure 11. Finally, centrifuging the precipitate, washing the precipitate with deionized water for three times, and freeze-drying the precipitate to obtain SnS 2 And (3) powder.
Example 7
0.8g of TTA powder (10.7 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.4g of Na was added 2 SnO 3 ·3H 2 O powder (1.5 mmoL) was added to the above TTA solution, and electromagnetic stirring was continued at a temperature of 60 ℃ for about 20 minutes to rapidly dissolve the powder and mix uniformly,and obtaining a precursor solution. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction at 180 ℃ for 2, 8, 16 and 24 hours respectively to obtain precipitates, as shown in FIG. 11. Finally, centrifuging the precipitate, washing the precipitate with deionized water for three times, and freeze-drying the precipitate to obtain SnS 2 And (3) powder.
Example 8
2.4g of TTA powder (32 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 1.2g of Na was added 2 SnO 3 ·3H 2 O powder (4.5 mmoL) was added to the above TTA solution, and electromagnetic stirring was continued at 60 ℃ for about 20 minutes to rapidly dissolve the powder and uniformly mix, to obtain a precursor solution. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction at 180 ℃ for 2, 8, 16 and 24 hours respectively to obtain precipitates, as shown in FIG. 11. Finally, centrifuging the precipitate, washing the precipitate with deionized water for three times, and freeze-drying the precipitate to obtain SnS 2 And (3) powder.
Examples 1, 2, and 3 were performed by controlling the concentration of the reactants, and Na was adjusted without adding any template agent or surfactant 2 SnO 3 ·3H 2 Addition amount of O powder and TTA powder (Na) 2 SnO 3 ·3H 2 Mass ratio of O powder 2:1:3. mass ratio of TTA powder =2:1: 3) Three-form trigonal SnS with three exposed surfaces for main control 2 Nanoplatelets as shown in figure 1. Example 3 is SnS 2 (100) Micron flower morphology formed by crossing nano sheets controlled by surfaces is shown in figure 9; example 2 is SnS 2 (001) The surface-master-controlled stacked regular hexagonal nanosheet morphology is as shown in fig. 7; and example 1 is SnS 2 (011) The micron spherical appearance formed by curling of the surface-controlled nano-sheets is shown in figure 2, and the micron spherical appearance is also a novel SnS 2 The shape of the nano-sheet. Although the three patterns of SnS are shown in FIG. 12 2 The specific surface areas of the nano sheets are all small and are respectively 7.22m 2 /g，9.35m 2 /g，10.18m 2 (iv) g; but stacking of (001) plane mastersThe morphology of the regular hexagonal nano-sheets and the morphology of the micro popcorn formed by crossing the nano-sheets controlled by the (100) surface do not have the hydrophilic characteristic. Thus, with SnS 2 The micro-spheres have different SERS properties, snS 2 Neither the stacked nanosheets nor the micro flowers can generate the convergence effect on the probe molecule aqueous solution, so that the SERS enhancement effect on methylene blue dye molecules is weaker than that of SnS 2 The morphology of the microspheres is shown in FIG. 13. SnS 2 The detection limit of stacked nanosheets to MeB reaches 10 -13 M, SERS enhancement factor is 4.02 multiplied by 10 9 ；SnS 2 The detection limit of MeB on the micro-flower reaches 10 -11 M, SERS enhancement factor 8.16 is multiplied by 10 6 (ii) a And SnS 2 The detection limit of the micro-spheres on MeB reaches 10 -13 M, in conclusion, snS with three morphologies 2 All the nano sheets break through 10 -10 SERS of M detects bottlenecks.
Example 4 the volume of deionized water, 50, 55, 60mL, snS was slightly changed based on example 1 2 The morphology of the microspheres did not change significantly as shown in fig. 14. Example 5 the reaction temperature was controlled at 160 deg.C, 180 deg.C, 200 deg.C based on example 2. As shown in FIG. 15, non-regular hexagonal SnS was obtained after hydrothermal reaction at 160 deg.C 2 Stacking the nanosheets; obtaining the regular hexagonal SnS after the hydrothermal reaction at the temperature of 180 DEG C 2 Stacking the nanosheets; obtaining most of vertically crossed regular hexagon SnS after hydrothermal reaction at the temperature of 200 DEG C 2 Nanosheets. Example 6 on the basis of example 1, example 7 on the basis of example 2, and example 8 on the basis of example 3, hydrothermal reaction times of 2, 8, 16, and 24 hours are all regulated and controlled to study the growth principle of the morphology, and as shown in fig. 16-21, two hours after hydrothermal reaction, three types of SnS with three morphologies controlled by different crystal planes are grown 2 The nuclei were aggregated and a large amount of unreacted S (Fddd space group) was present, and after 8 hours of hydrothermal reaction, snS controlled by the (001) plane 2 Stacked nanosheets, snS controlled by (011) plane 2 Microsphere and SnS controlled by (100) plane 2 The appearance of the popcorn is already rudimentary, and XRD images all show complete SnS 2 Characteristic peak of (2). After hydrothermal reaction for 16 hoursExample 7 hexagonal SnS has been formed 2 The nanosheet morphology, example 6, has also grown to a perfect micron-spherical morphology of about 7-9 μm in size, and example 8 has also grown to a micron-flower morphology of about 8 μm in size. Further extension of the reaction time to 24 hours, example 7 resulted in the formation of more regular hexagonal nanoplates. The nanoplatelets in the microspheres of example 6 will grow further and extend, making the microsphere size larger and the "ravine" morphology more pronounced. Example 8 resulted in a more complete micro-flower topography.
Example 9
1.6g of TTA powder (21.3 mmoL) was first added to 55mL of deionized water and placed under electromagnetic stirring at 60 ℃ for about 10 minutes to rapidly dissolve the powder, resulting in a mixed clear solution. Then, 0.9g of K was added 2 SnO 3 ·3H 2 O powder (3.0 mmoL) is added into the TTA solution, and the mixture is continuously electromagnetically stirred for about 20 minutes at the temperature of 60 ℃ so as to quickly dissolve the powder and uniformly mix the powder, thus obtaining a precursor solution. And then placing the precursor solution into a 100mL hydrothermal reaction kettle with a PPL lining, and carrying out hydrothermal reaction for 24 hours at 180 ℃ to obtain brown precipitate. Finally, centrifuging the brown precipitate, washing the brown precipitate with deionized water for three times, and freeze-drying the washed brown precipitate to obtain brown SnS 2 And (4) micro-sphere powder.
The main difference between the present example 9 and example 1 is that the material providing the Sn source is changed to K 2 SnO 3 ·3H 2 O powder when mixing K 2 SnO 3 ·3H 2 When O powder is dissolved in TTA solution, na and Na are generated 2 SnO 3 ·3H 2 O＝Na 2 SnO 3 + 3H 2 O＝2Na + +SnO 3 2ˉ +3H 2 O is a similar chemical reaction as K 2 SnO 3 ·3H 2 O＝K 2 SnO 3 +3H 2 O＝2K + + SnO 3 2ˉ +3H 2 And O. And K is used in the subsequent hydrothermal reaction + And Na + All do not participate in the reaction, only made of SnO 3 ˉ Providing a source of Sn to participate in the following chemical reaction: snO 3 2ˉ +2H 2 S＝SnS 2 ↓+2OH ˉ +H 2 And O. Thus, as shown in FIG. 22, the Sn source material becomes K 2 SnO 3 ·3H 2 O powder does not significantly change SnS 2 The morphology of the microspheres.
Claims (16)
1. SnS 2 The microsphere SERS substrate is characterized in that the SnS substrate 2 The micro-sphere SERS substrate is composed of SnS 2 The nano-sheets are curled, and the average particle size is 1-10 mu m; the SnS 2 Curled SnS of microsphere SERS substrate surface 2 Ravines with the width of less than 300nm are formed among the nano sheets; the SnS 2 The exposed crystal face of the microsphere SERS substrate is a (011) face.
2. The SnS of claim 1 2 The SERS substrate of the microsphere is characterized in that the SnS substrate 2 The thickness of the nano sheet is 2-10 nm.
3. The SnS of claim 2 2 The microsphere SERS substrate is characterized in that the SnS substrate 2 The average particle size of the microsphere SERS substrate was 5.37 μm.
4. The SnS of any of claims 1-3 2 The microsphere SERS substrate is characterized in that the SnS substrate 2 The microsphere SERS substrate has hydrophilicity, and the water contact angle is 10-30 degrees; the SnS 2 The microsphere SERS substrate has ultrasensitive surface enhanced Raman scattering activity, and the SERS detection limit of methylene blue molecules is at least 10 -13 M。
5. The SnS of claim 4 2 The microsphere SERS substrate is characterized in that the SnS substrate 2 The microsphere SERS substrate has hydrophilicity, and the water contact angle is 10-20 degrees.
6. The SnS of any one of claims 1-5 2 The preparation method of the microsphere SERS substrate is characterized by comprising：
(1) Will K 2 SnO 3 ·3H 2 O powder and Na 2 SnO 3 ·3H 2 Adding at least one of O powder into deionized water solution of a sulfur source, and uniformly mixing at 40-60 ℃ to obtain precursor solution;
(3) Putting the precursor solution into a reaction kettle, and carrying out hydrothermal reaction at 120-240 ℃ for 16-36 hours to obtain brown precipitate, namely SnS 2 Microsphere SERS substrate.
7. The method according to claim 6, wherein the sulfur source is at least one of thioacetamide and thiourea.
8. The method of claim 6, wherein K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The mass ratio of the O powder to the sulfur source is 1: (1.8-2.2); the mixing mode is electromagnetic stirring, the rotating speed is 400-600 r/min, and the time is 10-30 min.
9. The method of claim 8, wherein K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The mass ratio of the O powder to the sulfur source is 1:2.
10. the method of claim 6, wherein K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The ratio of the O powder to the deionized water is (1.4-4.8 mmoL): (40 mL-70 mL).
11. The method of claim 10, wherein K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The ratio of the O powder to the deionized water is (2.5-3.5 mmoL): (40 mL-70 mL).
12. The method of claim 11, wherein K is 2 SnO 3 ·3H 2 O powder or Na 2 SnO 3 ·3H 2 The ratio of O powder to deionized water is (2.9-3.1 mmoL): (50 mL-60 mL).
13. The method of claim 6, wherein the ratio of the sulfur source to the deionized water is (10 to 33 mmoL): (40 mL-70 mL).
14. The method of claim 13, wherein the ratio of the sulfur source to the deionized water is (18-25 mmoL): (40 mL-70 mL).
15. The method of claim 14, wherein the ratio of the sulfur source to the deionized water is (20-22 mmoL): (50 mL-60 mL).
16. The method according to any one of claims 6 to 15, wherein the hydrothermal reaction temperature is 180 ℃ and the hydrothermal reaction time is 24 hours.
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