CN110907428B - Method for preparing reusable porous SERS metal substrate by reduction induction method and application thereof - Google Patents
Method for preparing reusable porous SERS metal substrate by reduction induction method and application thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a recyclable porous SERS metal substrate by a reduction induction method and application thereof, and relates to porous goldThe method belongs to a preparation method and application of materials, and aims to solve the problems that the existing preparation method of the SERS substrate is complex, and the prepared SERS substrate cannot be reused. The preparation method comprises the following steps: 1. obtaining an oxide metal material precursor; 2. preparing a mixed reduction solution: using water as solvent, the solute comprising NaBH 4 NaOH and polyethylene glycol 4000; 3. and putting the oxidized metal material precursor into a mixed reduction solution for reduction-induced porous treatment. The invention is carried out by NaBH 4 The reducibility of the metal oxide can enable the metal oxide to quickly react with the reducing solution to remove oxygen components, thereby forming a micro-nano porous structure. The prepared porous metal is applied to SERS, so that single-molecule-level high-performance SERS enhancement and repeated utilization are realized, and the method is reliable, economic and high in commercial value.
Description
Technical Field
The invention relates to a preparation method and application of a porous metal material, in particular to a simple method for removing oxygen components of a solid-phase oxidized metal material by using solution reduction so as to prepare a micro-nano porous structure, and the prepared porous metal is applied as a high-performance and recyclable Surface Enhanced Raman Scattering (SERS) substrate.
Background
Raman spectroscopy is a non-destructive analytical technique in which raman scattered light is generated based on the interaction of light and chemical bonds within a material, and provides detailed information about the chemical structure, phase and morphology, crystallinity, and molecular interactions of a sample. Raman spectroscopy is also considered to be a chemical fingerprint unique to a particular molecule or material, and is an effective means of rapidly identifying the type of material. The application range of the compound is wide in various fields of chemistry, physics, biology, medicine and the like. One important drawback of raman spectroscopy, however, is its weak signal, primarily due to the fact that about one million parts of the incident photons are scattered by the sample molecules, most of the scattered light being rayleigh scattering, whereas raman scattering is only about one thousandth of the rayleigh scattering intensity. The Surface Enhanced Raman Scattering (SERS) developed from the seventies of the last century well solves the problem of weak Raman spectrum signals, has the characteristics of high sensitivity, difficulty in being interfered by fluorescence, capability of providing a characteristic spectrum of a detected object and the like, and is widely applied to the fields of surface science, analytical science, biological environment monitoring, drug explosive detection and the like.
The detection of the SERS spectroscopy is influenced by a plurality of factors, and one very important factor is the SERS substrate. At present, precious metals such as gold, silver and copper are the most popular SERS materials, but in consideration of size effect, the main SERS substrate materials at present use these metal nanoparticles or sols of these metals. However, the biggest defects of the reinforced substrate are that the reinforced substrate is inconvenient to store and transport, high in cost (hundreds of yuan/mL), only capable of being used once and poor in reusability. In recent years, some researchers find that nano-porous metal can be prepared by a dealloying method to serve as an efficient SERS substrate, however, the dealloying method needs an alloy-dealloying process and needs introduction of two-phase metal, and the problems of complex preparation process, long preparation period and the like exist. More importantly, the mechanical strength of the porous metal prepared in the dealloying process is poor, the repeated use of the SERS substrate cannot be realized, and the cost is high. Therefore, a new efficient, simple and rapid preparation process is developed, and the preparation of the economic and efficient SERS substrate with high sensitivity and reusability remains an important direction for the development of metal materials at present.
Disclosure of Invention
The invention aims to solve the problems that the existing SERS substrate preparation method is complex, the process requirement and the preparation cost are high, and the prepared SERS substrate cannot be recycled, and provides a method for preparing a recyclable porous metal Raman enhanced substrate by a reduction induction method and application thereof.
The method for preparing the porous SERS metal substrate by the reduction induction method is realized by the following steps:
1. utilizing a commercialized metal oxide material as an oxide metal material precursor, or carrying out oxidation treatment on the metal material to obtain a metal oxide material as the oxide metal material precursor;
2. preparing a mixed reduction solution: water is used as a solvent, and the solute comprises the following components in concentration: 0.1 to 1mol L -1 NaBH of (a) 4 ，0.1～6mol L -1 NaOH and 2 to 40g L of -1 Polyethylene glycol 4000 (PEG 4000) to obtain a mixed reduction solution;
3. and (3) reducing the mixed reducing solution at the temperature of 20-85 ℃, putting the oxidized metal material precursor in the step one into the mixed reducing solution for reduction-induced porous treatment, and cleaning and airing the oxidized metal material precursor by using absolute ethyl alcohol and water after the porous treatment, thereby completing the preparation of the porous SERS metal substrate.
The invention applies the porous SERS metal substrate as an enhanced substrate material in Surface Enhanced Raman Scattering (SERS). For detecting and analyzing trace probe molecules.
NaBH in the invention 4 Reducing the oxidized metal by using a reducing agent to remove oxygen components; the effect of NaOH is to prevent NaBH 4 Hydrolyzing; PEG4000 acts as a pore-forming protective agent to protect irregular porous structures generated during the reduction reaction. Without the participation of PEG4000, the surface of the metal atoms is spontaneously reconstructed according to the principle of minimizing the free energy, and a porous structure cannot be formed. PEG is a nonionic surfactant, ether bond is used as hydrophilic group, ethylidene group is used as hydrophobic group, the hydrophobic group is in contact with silver surface, and the hydrophilic groupThe micro-nano porous particles can be coated in the generation process by contacting with the solution, so that the protection effect is realized to prevent the porous structure from agglomerating. When the method is used for preparing the porous metal, the reduction reaction is violent, the oxygen removal process is quick, so that the metal atoms in an action area are quickly moved and diffused, and the quick shrinkage of the material volume is favorable for the quick formation of a porous structure; and PEG4000 can provide protection for the porous structure generated in the reaction process in time, and is beneficial to reducing the size of the formed porous structure.
The invention adopts a reduction induction method to prepare the porous metal SERS substrate, and the performance of the preparation method and the prepared substrate has the following remarkable advantages:
1. at present, the commercial SERS substrate is gold-silver sol, is inconvenient to store and transport, has high cost (hundreds yuan/mL), and cannot be recycled. The SERS enhanced substrate prepared by reduction induction has a uniform all-solid-state porous structure, has certain mechanical strength, is convenient to store and transport, has low cost and can be recycled.
2. The method for preparing the solid porous SERS substrate is generally a dealloying method, requires complex alloying and dealloying processes, and has long preparation period and complex process. The preparation method directly takes the metal oxide as the precursor to prepare the porous metal SERS substrate, avoids the complex alloy-dealloying process, does not need the introduction of two-phase metal, and has the advantages of simple, convenient and quick preparation method.
3. The invention can utilize commercial chemical reagents and metal oxide materials to construct the microstructure of the metal surface, the whole reaction system is an open system, no special technical process is involved, the requirement on equipment is low, the cost is low, and the large-scale commercial production is convenient to realize.
4. The reduction induction method can be regarded as a secondary processing technology, and porous processing can be carried out on the basis of metal material (device) precursors in various shapes according to requirements, so that the porous metal SERS substrate in a complex shape is prepared, and the method is suitable for special industrial requirements.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a silver oxide flake precursor of example one;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the micro-nano porous silver sheet prepared in the first embodiment;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the silver wire after cleaning in example two;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a surface silver oxide wire obtained in example two;
FIG. 5 is a Scanning Electron Microscope (SEM) image of the micro-nano porous silver wire prepared in example II;
FIG. 6 shows an application example of the method 10, in which a porous silver plate SERS and glass are used as substrates -6 A Raman spectrum of the M Crystal Violet (CV) methanol solution, wherein 1 represents a porous silver sheet SERS, and 2 represents glass;
FIG. 7 shows SERS with a porous silver plate and a glass substrate 10 in one application example -6 A Raman spectrum of an M rhodamine (R6G) aqueous solution, wherein 1 represents porous silver sheet SERS, and 2 represents glass;
FIG. 8 shows an application example I in which SERS (surface enhanced Raman Scattering) is used as a substrate 10 -11 A raman spectrum of a solution of M Crystal Violet (CV) in methanol;
FIG. 9 shows an application example I in which SERS (surface enhanced Raman Scattering) is used as a substrate 10 -11 A Raman spectrum of an M rhodamine (R6G) aqueous solution;
FIG. 10 shows an SERS substrate with a porous silver plate, 10 -11 Raman spectra of the respiratory effect of the M rhodamine (R6G) molecule;
FIG. 11 illustrates a SERS substrate with a porous silver plate 10 at different positions according to an embodiment -6 M Crystal Violet (CV) at Raman shift 1179cm -1 The peak intensity of (b);
FIG. 12 shows SERS substrates with porous silver flakes at different positions 10 according to an embodiment -6 M rhodamine (R6G) at Raman shift 1650cm -1 The peak intensity of (b);
FIG. 13 shows a schematic diagram of a first embodiment 10 -6 SERS enhanced raman spectroscopy with 20 reuses of M Crystal Violet (CV);
FIG. 14 shows a block diagram of the first embodiment 10 -6 SERS enhancement factor of M Crystal Violet (CV) for 20 replicates;
FIG. 15 shows a schematic diagram of a first exemplary embodiment 10 -6 SERS enhanced Raman spectroscopy with 12 repeated applications of M rhodamine (R6G);
FIG. 16 shows a schematic diagram of a first exemplary embodiment 10 -6 SERS enhancement factor of M rhodamine (R6G) 12 times of repeated use;
FIG. 17 shows an example of a second embodiment of a porous silver wire SERS substrate 10 -6 A Raman spectrum of the M Crystal Violet (CV) methanol solution, wherein 1 represents porous silver wire SERS, and 2 represents glass;
FIG. 18 shows a porous silver wire SERS substrate 10 according to an embodiment -6 M Crystal Violet (CV) at Raman shift 1179cm -1 The peak at (a) is strong.
Detailed Description
The first embodiment is as follows: the method for preparing the porous SERS metal substrate by the reduction induction method is implemented according to the following steps:
1. utilizing a commercialized metal oxide material as an oxide metal material precursor, or carrying out oxidation treatment on the metal material to obtain a metal oxide material as the oxide metal material precursor;
2. preparing a mixed reduction solution: water is used as a solvent, and the solute comprises the following components in percentage by weight: 0.1 to 1mol L -1 NaBH of 4 ，0.1～6mol L -1 NaOH and 2-40 g L -1 To obtain a mixed reducing solution;
3. and (2) reducing the mixed reducing solution at the temperature of 20-85 ℃, putting the oxidized metal material precursor in the step one into the mixed reducing solution for reduction-induced porosification treatment, and cleaning and airing the oxidized metal material precursor by using absolute ethyl alcohol and water after porosification treatment, thereby completing the preparation of the porous SERS metal substrate.
In the present embodiment, from the viewpoints of the interaction between the reducing agent and the solid-phase metal oxide and the protective effect of the surfactant on the microstructure, naBH is used 4 The precursor is reduced, and the metal atoms in the action region are violently moved and diffused through higher concentration, so that the formation of a small-scale porous structure is facilitated. The surfactant PEG4000 is utilized to react in timeThe porous structure generated in the process provides protection, and provides a novel method for preparing a micro-nano porous structure on a solid oxidized metal precursor by using a mixed reduction solution reduction induction method. The method for producing a porous metal by the reduction induction method of the present embodiment can be applied to metal materials (devices) of various shapes.
The second embodiment is as follows: the difference between this embodiment and the specific embodiment is that the metal oxide material in step one is aluminum oxide, gallium oxide, indium oxide, thallium oxide, germanium oxide, tin oxide, lead oxide, antimony oxide, bismuth oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, silver oxide, ruthenium oxide, rhodium oxide, palladium oxide, osmium oxide, iridium oxide, iron oxide, nickel oxide, or copper oxide.
The third concrete implementation mode: different from the first or second embodiment, in the first step, the metal material is aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth, polonium, manganese, iron, cobalt, nickel, copper, gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, nickel, copper or titanium alloy.
The fourth concrete implementation mode is as follows: this embodiment is different from the first to third embodiments in that the oxidation treatment in the first step is a high-temperature oxidation treatment, a chemical oxidation treatment, or an electrochemical oxidation treatment.
The fifth concrete implementation mode: this embodiment is different from one of the first to fourth embodiments in that the oxide metal material precursor is in the form of an oxide metal powder, an oxide metal wire, an oxide metal sheet, or an oxide metal film.
The present embodiment can press commercial oxidized metal powder into an oxidized metal sheet with a die.
The embodiment takes the commercialized metal wire as a processing object, mainly because the filamentous metal has the advantages of small volume, convenient bending and the like, the prepared porous metal wire can be directly used for the SERS probe, and has huge application potential in a plurality of fields.
The sixth specific implementation mode is as follows: the present embodiment is different from one of the first to fifth embodiments in that the oxidation degree of the oxide metal material precursor in the first step is complete oxidation or surface partial oxidation.
The reduction induction method of the present embodiment is applied to oxidized metal precursors of different oxidation degrees.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the solute in the second step has the following components and concentrations: 0.5 to 1mol L -1 NaBH of 4 ，0.1～1mol L -1 NaOH and 20-40 g L of -1 Polyethylene glycol 4000 (PEG 4000).
The specific implementation mode is eight: the present embodiment is different from one of the first to seventh embodiments in that the oxidized metallic material precursor is horizontally, vertically or obliquely immersed in the mixed reducing solution in the third step.
The specific implementation method nine: the present embodiment is different from the first to eighth embodiments in that the time for the reduction-induced porosification treatment in the third step is 0.5 to 3 hours.
The detailed implementation mode is ten: the present embodiment applies porous metal substrates as an enhanced substrate material in Surface Enhanced Raman Scattering (SERS).
The first embodiment is as follows: the method for preparing the micro-nano porous structure by reducing and inducing the silver oxide sheet by the mixed reducing solution is realized by the following steps:
1. weighing commercially available silver oxide powder (purity 99.0%) 0.20g, and dry-pressing into tablet with diameter of 13mm and thickness of 240 μm by using tablet press to obtain silver oxide tablet precursor;
2. preparing a mixed reduction solution: water is used as a solvent, and the solute components and the concentrations are respectively as follows: 1mol L -1 NaBH of 4 ，0.1mol L -1 40g L of NaOH -1 The polyethylene glycol 4000 (PEG 4000) is prepared by firstly adding NaOH to prevent NaBH 4 Hydrolyzing;
3. and heating the mixed reduction solution in a water bath to 85 ℃, putting the oxidized metal material precursor into the mixed reduction solution for reduction induction porosification treatment for 1h, and cleaning and airing the oxidized metal material precursor by using absolute ethyl alcohol and water after porosification treatment, thereby completing the preparation of the porous SERS metal substrate.
As can be seen from comparison between fig. 1 and fig. 2, after the mixed reducing solution is processed, a large number of micro-nano particles with a diameter of 14 to 192nm (average particle diameter of 133 nm) are formed on the surface of the silver flake.
Example two: the method for preparing the micro-nano porous structure by reducing and inducing the surface silver oxide wires by the mixed reducing solution is realized by the following steps:
1. commercially available silver wire (diameter 300 μm, purity 99.9%) was subjected to surface oxidation: cutting a 3cm silver wire, cleaning the silver wire by using absolute ethyl alcohol, airing to obtain the cleaned silver wire, using the silver wire as a working electrode in a three-electrode system, taking Pt as a counter electrode, taking Hg/HgO as a reference electrode and 0.1mol L of electrolyte -1 Using a Shanghai Chenghua electrochemical workstation in the surface oxidation process, treating for 10min by adopting a constant voltage mode of 0.42V, taking out a working electrode, and cleaning a sample by using absolute ethyl alcohol and deionized water to obtain a surface silver oxide wire precursor;
2. preparing a mixed reduction solution: the solution components and concentrations were: 1mol L -1 NaBH of (a) 4 ，0.1mol L -1 40g L of NaOH -1 The polyethylene glycol 4000 (PEG 4000) is prepared by firstly adding NaOH to prevent NaBH 4 Hydrolyzing;
3. and heating the mixed reduction solution in a water bath to 85 ℃, putting the oxidized metal material precursor into the mixed reduction solution for reduction induction porosification treatment for 1h, and cleaning and airing the oxidized metal material precursor by using absolute ethyl alcohol and water after porosification treatment, thereby completing the preparation of the porous SERS metal substrate.
As can be seen by comparing the graphs in FIGS. 3, 4 and 5, after the silver wire is subjected to surface oxidation and mixed reducing liquid treatment, a large number of micro-nano particles of 30-487 nm are formed on the surface of the silver wire.
The first application embodiment: and testing the enhancement effect of the micro-nano porous silver SERS substrate obtained in the first embodiment. In the present application example, two molecules, i.e., crystal Violet (CV) and rhodamine 6G (R6G), were used for the study, and a methanol solution of CV and an aqueous solution of R6G were used. Starting CV and R6G from 10 -2 M begins to dilute to 1 step by step0 -11 And M, soaking the porous silver SERS substrate in the solution for 10min, then taking out, drying the solution on the surface of the sample, and measuring the Raman spectrum by using a NanoBase XperRam 200 micro-Raman spectrometer, wherein the excitation wavelength is 532nm, the spot size is 2 microns, and the laser power is 5.0mW. In the enhanced repeatability test of the porous silver SERS substrate, a sample tested last time is subjected to ultrasonic cleaning by using absolute ethyl alcohol and then is cleaned for multiple times by using clear water, and the next SERS test is carried out after an obvious Raman signal is no longer detected.
As can be seen from FIGS. 6 and 7, 10 is dropped on the glass substrate -6 M CV and R6G molecular solutions can not detect any Raman characteristic peak, but the detection on the porous silver sheet enhanced substrate can obtain obvious typical Raman characteristic peaks of CV and R6G. Therefore, the porous silver sheet has strong SERS enhancement performance. From FIGS. 8 and 9, CV and R6G molecular solutions were diluted to 10 -11 After M, SERS test is carried out by using the porous silver sheet, an obvious Raman characteristic peak of the test molecule can still be seen, and through calculation, the porous silver sheet pair 10 -11 The SERS enhancement factor of M CV reaches 9.63 multiplied by 10 9 The enhancement factor of R6G reaches 2.75 multiplied by 10 9 . The research results show that the porous silver sheet has extremely high sensitivity on the detection of trace molecules, and has great prospects in the fields of trace fruit and vegetable pesticide residue detection, toxic substance detection, sewage detection, biomacromolecule detection and the like.
Fig. 10 shows that the porous silver sheet SERS substrate detects the scintillation effect of the R6G molecule, that is, the intensity of the raman spectrum changes periodically with the stretching change of the molecule, and the period is about 10s. The method is a single-molecule detection behavior, can further prove the high SERS performance of the porous silver sheet, is a strong evidence that single-molecule detection can be realized, and shows the excellent practical application value of the porous silver sheet.
As can be seen from fig. 11 and 12, the SERS enhancement factor of the porous silver sheet SERS substrate is 10 at any selected 40 positions for both CV and R6G 6 Therefore, the prepared porous silver sheet is uniform in appearance, good in reinforcing effect consistency and capable of ensuring reliability in practical application.
From FIG. 13-16, it can be seen that the raman spectrum SERS enhancement effect of each repeatability test is very stable, at 10 -6 In the repeatability test of the M CV methanol solution, the Raman shift of the previous 20 experiments is 1179cm -1 All peak enhancement factors of (2) are 10 6 Above, at 10 -6 In the repeatability test of the M R6G aqueous solution, the Raman shift of the previous 11 experiments is 1650cm -1 All peak enhancement factors of (1) are 10 6 Above, the data according to the enhancement factor show that the porous silver sheet prepared by the method has good recycling performance. Therefore, the use cost can be further reduced for practical application.
Application example two: and testing the SERS effect of the micro-nano porous silver wire obtained in the second example. In the present application example, a study was conducted using a Crystal Violet (CV) molecule, using a methanol solution of CV. CV from 10 -2 M begins to dilute to 10 -6 And M, soaking the porous silver sheet in the solution for 10min, then taking out, drying the solution on the surface of the sample, and measuring the Raman spectrum by using a NanoBase XperRam 200 micro-Raman spectrometer, wherein the excitation wavelength is 532nm, the spot size is 2 microns, and the laser power is 5.0mW.
As can be seen from FIG. 17, 10 is dropped on the glass substrate -6 The M CV molecular solution can not detect any Raman characteristic peak, but can obtain a very obvious typical CV Raman characteristic peak when the detection is carried out on the porous silver wire enhanced substrate. Calculated, the porous silver wire pair 10 -6 SERS enhancement factor of M CV is 3.21 multiplied by 10 5 The method shows that the porous silver wire prepared by the reduction induction method also has strong SERS enhancement performance, and also proves the universality of the micro-nano porous metal structure prepared by the reduction induction method.
As can be seen from FIG. 18, for 10 -6 M CV, the enhancement factor of the porous silver wire SERS substrate is 10 at 40 different positions 5 Therefore, the prepared porous silver wire is uniform in appearance, stable in reinforcing effect and consistent, and reliability of the porous silver wire in practical application is guaranteed.
Claims (1)
1. The application of the reusable porous SERS metal substrate prepared by a reduction induction method in crystal violet molecule detection is characterized in that:
the preparation method is realized by the following steps:
1. commercially available silver wire was subjected to surface oxidation: the diameter of the silver wire is 300 mu m, the purity is 99.9 percent, 3cm silver wire is cut, the silver wire is cleaned by absolute ethyl alcohol and dried to obtain the cleaned silver wire, the silver wire is used as a working electrode in a three-electrode system, pt is a counter electrode, hg/HgO is used as a reference electrode, and 0.1mol L of electrolyte is used -1 Treating the working electrode for 10min by using a 0.42V constant voltage mode with NaOH solution, taking out the working electrode, and cleaning the sample by using absolute ethyl alcohol and deionized water to obtain a surface silver oxide wire precursor;
2. preparing a mixed reduction solution: the solution components and concentrations were: 1mol L -1 NaBH of 4 ，0.1mol L -1 NaOH,40g L -1 The polyethylene glycol 4000, naOH is added firstly when preparing the solution to prevent NaBH 4 Hydrolyzing;
3. heating the mixed reduction solution to 85 ℃ in a water bath, putting the surface silver oxide wire precursor into the mixed reduction solution for reduction induction porosification treatment for 1h, cleaning with absolute ethyl alcohol and water after porosification treatment, and drying in the air to complete the preparation of the porous SERS metal substrate;
after the silver wire is subjected to surface oxidation and mixed reduction liquid treatment, a large number of micro-nano particles of 30-487 nm are formed on the surface of the silver wire;
when the porous metal is prepared, the reduction reaction is violent, the oxygen removal process is quick, so that the metal atoms in an action area are quickly moved and diffused, and the quick contraction of the material volume is favorable for the quick formation of a porous structure;
using a solution of crystal violet in methanol, the crystal violet is dissolved from 10 -2 M begins to dilute to 10 -6 And M, soaking the porous silver sheet in the solution for 10min, then taking out, and after the solution on the surface of the sample is dried, carrying out Raman spectrum measurement, wherein the excitation wavelength is 532nm, the spot size is 2 microns, and the laser power is 5.0mW.
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