CN112159994B - Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof - Google Patents

Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof Download PDF

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CN112159994B
CN112159994B CN202010947065.2A CN202010947065A CN112159994B CN 112159994 B CN112159994 B CN 112159994B CN 202010947065 A CN202010947065 A CN 202010947065A CN 112159994 B CN112159994 B CN 112159994B
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淡振华
袁园
罗家钰
徐子豪
周子杰
秦凤香
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Abstract

The invention discloses a (111) plane orientation enrichment-based superfine nanoporous silver SERS substrate material, wherein a pore channel of the superfine nanoporous silver SERS substrate material is connected with a metal ligament to form a three-dimensional continuous nanoporous structure; the metal ligaments have ordered lattice stripes; the lattice spacing of the lattice stripes on the metal ligament is 0.237 nm; the superfine nano porous silver material corresponds to epsilon-AgZn3The diffraction peaks of the phases all disappeared, and there were diffraction peaks corresponding to the (111) and (222) crystal planes of fcc-Ag at 38.1 ° and 81.6 °; the superfine nano-porous silver material has (111) plane orientation enrichment. The invention also discloses a preparation method of the superfine nanoporous silver SERS substrate material based on (111) plane orientation enrichment. The superfine nano-porous silver material has (111) plane orientation enrichment and stronger molecular adsorption capacity, thereby having stronger chemical enhancement effect on SERS.

Description

Superfine nano porous silver SERS substrate material based on (111) plane orientation enrichment and preparation method thereof
Technical Field
The invention relates to the technical field of nano metal functional materials, in particular to an ultrafine nano porous silver SERS substrate material based on (111) plane orientation enrichment and a preparation method thereof.
Background
The Surface Enhanced Raman Scattering (SERS) has the capability of ultrasensitiveness, and can detect trace detection molecules rapidly and ultrasensitively. It is generally believed that raman enhancement comes primarily from the enhanced local electromagnetic field in close proximity to the noble metals (Ag and Au), while chemical enhancement is another important factor, which depends primarily on the size, shape and exposed surface of the metal nanostructures.
The faces in the crystal are directly related to their physical and chemical properties, which results in different SERS enhancements. Currently, nanoporous silver materials have been used in substrate materials for SERS, and nanosilver single crystals with a typical face-centered-cubic (fcc) structure contain four major faces, where the differences between the (111) face and the other faces include not only surface atomic density, but also electronic structure, bonds and possible chemical reactivity. (111) The (111) plane has the lowest free energy, which makes it more capable of adsorbing molecules than other planes, thereby increasing chemical enhancement in SERS. Therefore, when preparing the nano-porous silver material, the material with rich (111) plane orientation is expected to be obtained so as to better enhance the Raman signal. However, although all of the existing nano-porous silver materials have the crystal form of the (111) plane, the (111) plane orientation enrichment cannot be obtained.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the (111) plane orientation enrichment-based ultrafine nanoporous silver SERS substrate material, which has (111) orientation enrichment and stronger molecular adsorption capacity, thereby having stronger chemical enhancement effect on SERS.
The invention also aims to provide a preparation method of the ultrafine nanoporous silver SERS substrate material based on (111) plane orientation enrichment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a kind ofBased on the (111) plane orientation enriched ultrafine nano-porous silver SERS substrate material, the pore channel of the ultrafine nano-porous silver material and a metal ligament are connected with each other to form a three-dimensional continuous nano-porous structure; the metal ligaments have ordered lattice stripes; the lattice spacing of the lattice stripes on the metal ligament is 0.237 nm; the superfine nano porous silver material corresponds to epsilon-AgZn3The diffraction peaks of the phases all disappeared, and there were diffraction peaks corresponding to the (111) and (222) crystal planes of fcc-Ag at 38.1 ° and 81.6 °; the superfine nano-porous silver material has (111) plane orientation enrichment.
Furthermore, the average pore diameter of the pore channel is 16.8-19.9 nm.
Further, the width of the metal ligament is 18.9-23 nm.
A preparation method of an ultrafine nanoporous silver SERS substrate material based on (111) plane orientation enrichment comprises the following steps:
s1: preparation of precursor alloy
Weighing Ag and Zn pure metal particles according to the component proportion, mixing, smelting an Ag-Zn alloy ingot through a high-frequency induction smelting furnace under the protection of inert gas, repeatedly smelting the alloy ingot obtained by smelting, and preparing an Ag-Zn alloy strip by adopting a single-roller strip-spinning process;
s2: polarization at constant potential
And (3) adopting a three-electrode system, taking KOH aqueous solution as electrolyte, carrying out constant potential polarization, washing the prepared sample with deionized water and ethanol for several times, and drying to obtain the nano porous silver material.
Further, the atomic expression of the Ag-Zn alloy is AgxZn100-xWherein, x is 19.6-23.6 at.%.
Further, the smelting frequency of the alloy ingot is 3-4.
Further, the three-electrode system specifically comprises: with said AgxZn100-xThe alloy strip is used as a working electrode, a platinum sheet is used as an auxiliary electrode, Ag-AgCl-saturated KCl is used as a reference electrode, KOH aqueous solution is used as electrolyte, and constant potential polarization is carried out.
Further, the concentration of the KOH aqueous solution is 0.1-1M.
Furthermore, the constant potential is within the range of-0.5V to-0.35V, the polarization time of the constant potential is not less than 24h, and the number of times of cleaning is 2-3.
The invention has the beneficial effects that:
1. the invention takes Ag-Zn alloy with specific proportion as a working electrode, and obtains the superfine nano-porous silver material with thinner aperture and (111) plane orientation enrichment under the action of constant potential polarization, and the nano-porous silver material passes through AgxZn100-xUnder constant potential polarization of alloy strip, corresponding to epsilon-AgZn in alloy3The diffraction peaks of the phases disappear completely, only one group of diffraction peaks corresponding to (111) and (222) crystal faces of fcc-Ag appear at 38.1 degrees and 81.6 degrees, the (111) face of the nano-porous silver single crystal has the lowest free energy, so that the (111) face has stronger molecular adsorption compared with other planes, and the material has stronger molecular adsorption capacity due to the strong enrichment of the (111) face, so that the nano-porous silver single crystal can be used as a substrate substance to have stronger chemical enhancement effect when trace probe molecules are rapidly detected by surface enhanced Raman scattering; meanwhile, the nano porous silver material has a high specific surface area which can reach 13.1m2g-1The average pore diameter can reach 16.8nm at the minimum, the R6G molecule is easier to adsorb the surface due to the higher specific surface area and the unique three-dimensional continuous nano porous structure, and high-density active hot spots are generated, so that the nano porous silver material prepared by the method has a stronger Raman signal enhancing effect due to the synergistic effect with strong adsorption brought by (111) plane orientation enrichment.
2. The method for preparing the (111) orientation-enriched superfine nano porous silver material by the potentiostatic method has the advantages of simple required instruments and equipment, less used chemical reagents, simple preparation, environmental protection, low cost and the like, solves the problems of complex process, environmental pollution, high cost and the like in the prior art, and realizes the preparation of the nano porous metal with smaller aperture from the precursor alloy with the single-phase intermetallic compound.
Drawings
FIG. 1 is a potentiodynamic polarization plot of a precursor alloy of the preparation procedure of example 5.
Figure 2 is an XRD of the precursor alloy of the preparation procedure of example 5.
Fig. 3 is an XRD pattern of the ultra-fine nano-porous silver material prepared in example 4.
Fig. 4 is an XRD pattern of the ultra-fine nano-porous silver material prepared in example 5.
Fig. 5 is an XRD pattern of the ultra-fine nano-porous silver material prepared in the comparative example.
Fig. 6 is a microscopic SEM image of the ultra fine nano porous silver material prepared in example 4.
Fig. 7 is a pore diameter statistical diagram of the ultra-fine nano-porous silver material prepared in example 4.
Fig. 8 is a microscopic SEM image of the ultra fine nano porous silver material prepared in example 5.
Fig. 9 is a pore diameter statistical diagram of the ultra-fine nano-porous silver material prepared in example 5.
Fig. 10 is a TEM image of the ultra fine nano porous silver material prepared in example 5.
Fig. 11 is a microscopic SEM image of the ultra fine nano porous silver material prepared by the comparative example.
Fig. 12 is a pore diameter statistical diagram of the ultra-fine nano-porous silver material prepared by the comparative example.
Fig. 13 is BET of the ultra fine nano porous silver material prepared in example 5.
FIG. 14 shows the nanoporous silver adsorbates 10 obtained in examples 4, 5 and comparative examples-6M R6G.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
The raw materials in the following examples were all purchased from commercial sources unless otherwise specified.
Example 1
S1: the weight ratio of the components is 19.6: 80.4, weighing Ag and Zn pure metal particles according to the proportion, mixing, and smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas19.6Zn80.4Alloy ingot, Ag obtained by smelting19.6Zn80.4The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process19.6Zn80.4A strip of an alloy, the strip having,
placing the crushed alloy ingot into a quartz tube (diameter) with an opening at the lower end
Figure BDA0002675653100000031
) Vertically placing the alloy into an induction melting coil of a single-roller melt-spinning device, and reheating the alloy to a molten state through high-frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag19.6Zn80.4And (3) taking the alloy strip as a working electrode, taking a platinum sheet as an auxiliary electrode, taking Ag-AgCl-saturated KCl as a reference electrode, taking a 0.1M KOH aqueous solution as electrolyte, applying-0.5V constant potential polarization, after 24h of polarization, washing the obtained sample for 2-3 times by deionized water and ethanol, and drying to obtain the (111) orientation-enriched nano porous silver catalytic material.
Example 2
S1: according to the mixture ratio of 23.6: 76.4, weighing Ag and Zn pure metal particles according to the proportion, mixing, and smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas23.6Zn76.4Alloy ingot, Ag obtained by smelting23.6Zn76.4The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process23.6Zn76.4Alloy strip, placing the broken alloy ingot into quartz tube (diameter) with opening at lower end
Figure BDA0002675653100000041
) In the middle, vertically put into an induction melting coil of a single-roller melt-spinning device and pass through a highRe-heating the alloy to a molten state by frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag23.6Zn76.4And (3) taking the alloy strip as a working electrode, taking a platinum sheet as an auxiliary electrode, taking Ag-AgCl-saturated KCl as a reference electrode, taking a 1.0M KOH aqueous solution as electrolyte, applying-0.35V constant potential polarization, after 24h of polarization, washing the obtained sample for 2-3 times by deionized water and ethanol, and drying to obtain the (111) orientation-enriched nano porous silver material.
Example 3
S1: according to the mixture ratio of 23: 77, weighing Ag and Zn pure metal particles according to the proportion, mixing, and smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas23Zn77Alloy ingot, Ag obtained by smelting23Zn77The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process23Zn77Alloy strip, placing the broken alloy ingot into quartz tube (diameter) with opening at lower end
Figure BDA0002675653100000042
) Vertically placing the alloy into an induction melting coil of a single-roller melt-spinning device, and reheating the alloy to a molten state through high-frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag23Zn77The alloy strip is used as a working electrode, a platinum sheet is used as an auxiliary electrode, Ag-AgCl-saturated KCl is used as a reference electrode, 0.5M KOH aqueous solution is used as electrolyte, constant potential polarization of-0.4V is applied, and after 24 hours of polarization, the obtained sample is usedWashing with ionized water and ethanol for 2-3 times, and drying to obtain (111) orientation-enriched nano porous silver material.
Example 4
S1: according to the proportion of 22: 78, weighing Ag and Zn pure metal particles, mixing, and smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas22Zn78Alloy ingot, Ag obtained by smelting22Zn78The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process22Zn78Alloy strip, placing the broken alloy ingot into quartz tube (diameter) with opening at lower end
Figure BDA0002675653100000043
) Vertically placing the alloy into an induction melting coil of a single-roller melt-spinning device, and reheating the alloy to a molten state through high-frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag22Zn78And (3) taking the alloy strip as a working electrode, taking a platinum sheet as an auxiliary electrode, taking Ag-AgCl-saturated KCl as a reference electrode, taking a 0.5M KOH aqueous solution as electrolyte, applying-0.5V constant potential polarization, after 24h of polarization, washing the obtained sample for 2-3 times by deionized water and ethanol, and drying to obtain the (111) orientation-enriched nano porous silver material.
Example 5
S1: according to the proportion of 20: 80, mixing, smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas20Zn80Alloy ingot, Ag obtained by smelting20Zn80The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process20Zn80Alloy strip to be brokenPlacing the crushed alloy ingot into a quartz tube (diameter) with an opening at the lower end
Figure BDA0002675653100000051
) Vertically placing the alloy into an induction melting coil of a single-roller melt-spinning device, and reheating the alloy to a molten state through high-frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag20Zn80And (3) taking the alloy strip as a working electrode, taking a platinum sheet as an auxiliary electrode, taking Ag-AgCl-saturated KCl as a reference electrode, taking a 0.5M KOH aqueous solution as electrolyte, applying-0.5V constant potential polarization, after 24h of polarization, washing the obtained sample for 2-3 times by deionized water and ethanol, and drying to obtain the (111) orientation-enriched nano porous silver material.
Comparative example
S1: according to the mixture ratio of 18: 82, weighing Ag and Zn pure metal particles according to the proportion, mixing, and smelting into Ag by a high-frequency induction smelting furnace under the protection of inert gas18Zn82Alloy ingot, Ag obtained by smelting18Zn82The alloy ingot is repeatedly smelted for 3-4 times to ensure the uniformity of the internal components of the ingot.
Ag is prepared by adopting single-roller melt-spinning process18Zn82Alloy strip, placing the broken alloy ingot into quartz tube (diameter) with opening at lower end
Figure BDA0002675653100000052
) Vertically placing the alloy into an induction melting coil of a single-roller melt-spinning device, and reheating the alloy to a molten state through high-frequency induction;
introducing high-pressure argon gas into the quartz tube, spraying the melt to a copper roller with the rotating speed of 1500rpm under the action of pressure, rapidly solidifying the melt into an alloy thin strip by utilizing the chilling action of the copper roller, and finally preparing the alloy strip with the thickness of about 50 mu m and the width of about 5 mm.
S2: with Ag18Zn82And (3) taking the alloy strip as a working electrode, taking a platinum sheet as an auxiliary electrode, taking Ag-AgCl-saturated KCl as a reference electrode, taking 0.5M KOH aqueous solution as electrolyte, applying-0.5V constant potential polarization, after 24h of polarization, washing the obtained sample for 2-3 times by deionized water and ethanol, and drying to obtain the nano porous silver material.
FIG. 1 shows Ag, Zn and single-phase Ag20Zn80Potentiodynamic polarization curves of the alloys in 0.5M KOH solutions. The working potential of constant potential polarization is determined by the self-corrosion potential of each component in the alloy, and is dissolving single-phase Ag20Zn80The Zn in the alloy strip is selected to have a working potential higher than that of the Zn and single-phase Ag20Zn80The self-corrosion potential of the Ag is lower than that of the corrosion resisting component, so that only a diffusion process is carried out on Ag atoms in the polarization process, and active dissolution is not carried out. According to Ag20Zn80The electrochemical property of the alloy is selected to be applied to Ag at a potential of-0.5V to-0.35V20Zn80The alloy is subjected to constant potential polarization.
[ characterizations ] of
1、XRD
FIG. 2 shows Ag in example 520Zn80XRD spectrum of alloy strip, from which Ag can be seen20Zn80The alloy strip is composed of close-packed hexagonal epsilon-AgZn3Single phase composition.
FIG. 3 is an XRD pattern of the ultra-fine nano-porous silver material prepared in example 4, from which it is apparent that the alloy corresponds to ε -AgZn3The diffraction peaks of the phases all disappeared, and only one set of diffraction peaks corresponding to the (111) and (222) crystal planes of fcc-Ag (JCPDS-87-0717) appeared at 38.1 DEG and 81.6 DEG, and the material had an orientation enrichment of the (111) plane.
FIG. 4 is an XRD pattern of the ultra-fine nano-porous silver material prepared in example 5, from which it is seen that the material corresponds to ε -AgZn3The diffraction peaks of the phases all disappeared, and only one set of diffraction peaks corresponding to the (111) and (222) crystal planes of fcc-Ag (JCPDS-87-0717) appeared at 38.1 DEG and 81.6 DEG, and the material had an orientation enrichment of the (111) plane.
FIG. 5 shows the nano-scale particles obtained by the comparative exampleXRD pattern of porous silver material, it can be seen that the alloy corresponds to epsilon-AgZn3The diffraction peaks of the phases all disappeared, but diffraction peaks corresponding to the fcc-Ag (JCPDS-87-0717) crystal plane appeared at 38.1 °, 44.4 °, 64.5 °, 77.7 ° and 81.6 °, and the material at this ratio did not yield a (111) orientation-enriched porous silver material.
2. SEM and TEM
Fig. 6 is an SEM image of the ultra-fine nano-porous silver material prepared in example 4, which shows that the pores and the metal ligaments of the material are connected to each other to form a three-dimensional continuous nano-porous structure. FIG. 7 is a distribution diagram of pore sizes of the ultra-fine nano-porous silver material prepared in example 4 based on SEM image statistics, and it can be seen from the figure that the average pore size is 19.9nm, the ligament width is 23.0nm, and the pore structure is uniform.
Fig. 8 is an SEM image of the ultra-fine nano-porous silver material prepared in example 5, and it can be seen from the SEM image that the pores and the metal ligaments of the material are connected with each other to form a three-dimensional continuous through nano-porous structure, and the pore structure is relatively uniform. Fig. 9 is a SEM-based pore size distribution diagram from which it can be seen that the porous silver with (111) orientation has an average pore size of 16.8nm and ligament width of 18.9 nm. The pore structure is uniform.
Fig. 10 is a TEM image of the ultrafine nano-porous silver material with (111) orientation prepared in example 5, which shows good correspondence with the SEM of example 5 in terms of tissue morphology, further demonstrating the three-dimensional bicontinuous porous structure of the nano-porous silver material. From the selected area electron diffraction inset in fig. 10a, it can be seen that the prepared porous silver material is a single crystal structure, and the internal hexagonal lattice represents 1/3(422) bragg reflection with a stripe spacing of 0.250nm, which is consistent with the lattice stripes in the HRTEM image in fig. 10b, and the forbidden reflection can be attributed to the (111) plane parallel to the plane. From the high resolution image, it can be seen that another lattice fringe spacing is 0.237nm, corresponding to the (111) crystal plane of Ag. TEM analysis therefore also further demonstrates that the porous silver catalytic material has a (111) orientation.
Fig. 11 is an SEM image of the nano-porous silver material prepared in the comparative example, and it is seen from the image that the pore size and ligament of the material are connected to each other to form a nano-porous structure, but the ligament width is 44.5nm, ligament coarsening is severe, and the pore structure is not uniform, compared to the previous example 4 and example 5. The pore size distribution based on the SEM image statistics is shown in fig. 12, and the average pore size of the material is 24.5nm, and the pore size cannot reach 20nm or less.
3、BET
For more accurate statistics of the pore size of the nanoporous silver prepared in this example 5, the material was subjected to BET test.
FIG. 13 shows N of the ultra-fine nano-porous silver material prepared in example 52Adsorption and desorption curves. An obvious hysteresis loop can be observed, which indicates that the obtained nano-porous silver has mesopores (2 nm-50 nm) and the pore channels in the prepared nano-porous silver are nearly cylindrical through holes according to the shape of the hysteresis loop. Further, the specific surface area of the nanoporous silver was measured by BET to be 13.1m2g-1. The inset in fig. 11 shows the pore size distribution of nano-silver calculated by BJH model, with pore size mainly distributed in the 4-25nm range, with an average pore size of 16.8nm, consistent with pore size based on SEM statistics. The high specific surface area and the unique three-dimensional continuous nano-porous structure enable the R6G molecules to be adsorbed on the surface more easily, and high-density active 'hot spots' are generated, so that the Raman signal is enhanced.
[ application test ]
The materials of example 4, example 5 and comparative example were used as the active matrix for surface enhanced raman for detection of rhodamine 6G. FIG. 14 shows the nano-porous silver adsorption 10 obtained in different embodiments-6M R6G. It can be seen from the figure that the raman signal of the porous silver material without (111) orientation is the lowest, the pore size is smaller and the raman signal of the porous silver material with (111) orientation is the strongest. The phenomena can be attributed to that (111) surfaces adsorb molecules stronger than other surfaces, so that chemical enhancement of Surface Enhanced Raman Spectroscopy (SERS) is increased, nano-porous silver with smaller pore diameter has higher specific surface area, and high-density SERS hot spots are created between adjacent nano-porous structures, so that the phenomenon has a synergistic effect with strong adsorption brought by (111) surface orientation enrichment, and better enhancement is achievedThe effect of the raman signal.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims (6)

1. A superfine nanometer porous silver SERS substrate material based on (111) plane orientation enrichment is characterized in that: the pore channel of the superfine nano-porous silver SERS substrate material is connected with a metal ligament to form a three-dimensional continuous nano-porous structure; the metal ligaments have ordered lattice stripes; the lattice spacing of the lattice stripes on the metal ligament is 0.237 nm; the XRD pattern of the superfine nano-porous silver SERS substrate material corresponds to epsilon-AgZn3The diffraction peaks of the phases all disappeared, with diffraction peaks only at 38.1 ° and 81.6 °, corresponding to the (111) and (222) crystallographic planes of fcc-Ag, respectively; the superfine nanoporous silver SERS substrate material has (111) plane orientation enrichment; the average pore diameter of the pore channel is 16.8-19.9 nm; the width of the metal ligament is 18.9-23 nm.
2. A method for preparing the (111) plane orientation enrichment-based ultra-fine nanoporous silver SERS substrate material according to claim 1, comprising the steps of:
s1: preparation of precursor alloy
Weighing Ag and Zn pure metal particles according to the component proportion, mixing, smelting an Ag-Zn alloy ingot through a high-frequency induction smelting furnace under the protection of inert gas, repeatedly smelting the alloy ingot obtained by smelting, and preparing an Ag-Zn alloy strip by adopting a single-roller strip-spinning process; the atomic expression of the Ag-Zn alloy is AgxZn100-xWherein, x =19.6-23.6 at.%;
s2: polarization at constant potential
And (3) adopting a three-electrode system, taking KOH aqueous solution as electrolyte, carrying out constant potential polarization, washing the prepared sample with deionized water and ethanol for several times, and drying to obtain the superfine nano porous silver SERS substrate material.
3. The preparation method of the (111) plane orientation enrichment-based ultrafine nanoporous silver SERS substrate material according to claim 2, wherein the preparation method comprises the following steps: the smelting frequency of the alloy ingot is 3-4 times.
4. The preparation method of the (111) plane orientation enrichment-based ultrafine nanoporous silver SERS substrate material according to claim 2, wherein the three-electrode system specifically comprises: with said AgxZn100-xThe alloy strip is used as a working electrode, a platinum sheet is used as an auxiliary electrode, Ag-AgCl-saturated KCl is used as a reference electrode, KOH aqueous solution is used as electrolyte, and constant potential polarization is carried out.
5. The preparation method of the (111) plane orientation enrichment-based ultrafine nanoporous silver SERS substrate material according to claim 2, wherein the preparation method comprises the following steps: the concentration of the KOH aqueous solution is 0.1-1M.
6. The preparation method of the (111) plane orientation enrichment-based ultrafine nanoporous silver SERS substrate material according to claim 2, wherein the preparation method comprises the following steps: the range of the constant potential is-0.5V-0.35V, the time of constant potential polarization is more than or equal to 24h, and the cleaning times are 2-3.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285893A (en) * 2013-06-26 2013-09-11 华东理工大学 Method for preparing coralline porous silver bromiodide/silver photocatalyst
CN109137058A (en) * 2018-11-16 2019-01-04 南京工业大学 The method for preparing the dendritic cluster of Nano silver grain using cyclic voltammetry
CN109371279A (en) * 2018-10-26 2019-02-22 昆明理工大学 A kind of preparation method of porous silverskin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103285893A (en) * 2013-06-26 2013-09-11 华东理工大学 Method for preparing coralline porous silver bromiodide/silver photocatalyst
CN109371279A (en) * 2018-10-26 2019-02-22 昆明理工大学 A kind of preparation method of porous silverskin
CN109137058A (en) * 2018-11-16 2019-01-04 南京工业大学 The method for preparing the dendritic cluster of Nano silver grain using cyclic voltammetry

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Bimodal nanoporous silver fabricated from dual-phase Ag10Zn90 precursor ";jiayu luo 等，;《Microporous and Mesoporous Materials》;20200811;第308卷;第110532页 *
"电化学脱合金制备纳米多孔Ag及其甲醛检测性能";杨玉林 等，;《金属学报》;20191011;第55卷(第10期);第1302-1310页 *
jiayu luo 等，."Bimodal nanoporous silver fabricated from dual-phase Ag10Zn90 precursor ".《Microporous and Mesoporous Materials》.2020,第308卷 *

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