CN113567527A - Nano porous gold, preparation method thereof and electrochemical analysis sensor - Google Patents
Nano porous gold, preparation method thereof and electrochemical analysis sensor Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 182
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 180
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000840 electrochemical analysis Methods 0.000 title abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 28
- 150000003751 zinc Chemical class 0.000 claims abstract description 15
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- 239000000243 solution Substances 0.000 claims description 47
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- 239000011701 zinc Substances 0.000 claims description 27
- 238000002484 cyclic voltammetry Methods 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 15
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 14
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 3
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 44
- 239000011521 glass Substances 0.000 description 42
- 235000005074 zinc chloride Nutrition 0.000 description 22
- 239000011592 zinc chloride Substances 0.000 description 22
- 125000004122 cyclic group Chemical group 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XQNZLTZMXPNJQY-UHFFFAOYSA-L [Cl-].[Cl-].[Zn+2].OCC(O)CO Chemical compound [Cl-].[Cl-].[Zn+2].OCC(O)CO XQNZLTZMXPNJQY-UHFFFAOYSA-L 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
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- 239000012085 test solution Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- JAWTVJKIBRFPKC-UHFFFAOYSA-L [Cl-].[Zn+2].C(CO)O.[Cl-] Chemical compound [Cl-].[Zn+2].C(CO)O.[Cl-] JAWTVJKIBRFPKC-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention provides a nano porous gold and a preparation method thereof and an electrochemical analysis sensor, wherein the preparation method of the nano porous gold comprises the steps of placing gold in a zinc salt solution, and sequentially carrying out electrochemical deposition and electrochemical dealloying treatment to obtain the nano porous gold; wherein, the zinc salt solution is obtained by dissolving zinc salt in alcohol solvent. The nano porous gold with the three-dimensional structure is constructed by an in-situ self-alloying and dealloying method, has a cooperative sensitivity enhancement mechanism of noble metal nano particles and the porous nano structure, and can realize rapid and high-sensitivity monitoring on low-concentration life information molecules when being used as an electrode in an electrochemical analysis sensor.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to nano porous gold, a preparation method thereof and an electrochemical analysis sensor.
Background
The electrochemical analysis sensor is the most core and reliable technology of the quantitative analysis detection technology at present, and has a very prominent position. The method mainly utilizes the electrochemical oxidation reaction of a compound on a noble metal electrode to generate an oxidation current, and the intensity of the current is directly related to the concentration of the compound, so that a concentration value is obtained by utilizing the intensity of the current. Noble metal electrodes play an important role in electrochemical analysis techniques because they act as electrochemical catalysts to accelerate electron transfer and reduce reaction activation energy. For many years, researchers have been working on developing electrochemical catalysts with high catalytic activity, such as increasing specific surface area, electrochemically active sites, or regulating mass transfer diffusion of reactants at an electrode-electrolyte interface.
Compared with electrochemical catalysts of noble metals, porous metal materials with three-dimensional staggered network structures have attracted much attention in electrochemical analysis techniques due to their unique properties. The porous metal material has a better catalytic structure, and the staggered net structure can effectively promote mass transfer and diffusion of reactants; and the net-shaped internal height curve structure can expose multiple crystal faces, thereby providing diversified electrochemical active sites. Therefore, the unique properties of the porous metal material provide potential application values for the porous metal material in the fields of electrocatalysis and electroanalysis.
At present, diversified technical means are applied to the construction of porous metal materials, such as an alloy removing method, an electrochemical deposition method, a template synthesis method and the like. The dealloying method is widely applied, and a binary or ternary alloy consisting of noble metal and active metal is usually used as an initial reactant, and the active metal is dissolved in multiple steps under the strong acid or strong alkaline condition, so that a porous structure of the noble metal is formed. However, this method is usually harsh, needs strong acid and strong alkali conditions, lacks certain controllability in the construction of the ordered porous structure, and the electrochemical catalytic activity of the obtained porous metal material is also not high.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the nano porous gold, the preparation method thereof and the electrochemical analysis sensor, the nano porous gold with the three-dimensional structure is constructed by the in-situ self-alloying and alloy removing method, the nano porous gold has the cooperative sensitization mechanism of the noble metal nano particles and the porous nano structure, and when the nano porous gold is used as an electrode for the electrochemical analysis sensor, the quick and high-sensitivity monitoring on low-concentration life information molecules can be realized.
The invention provides a preparation method of nano porous gold, which comprises the following steps: placing gold in a zinc salt solution, and sequentially carrying out electrochemical deposition and electrochemical dealloying treatment to obtain the nano-porous gold;
wherein, the zinc salt solution is obtained by dissolving zinc salt in alcohol solvent.
Preferably, the alcohol solvent is ethylene glycol, benzyl alcohol, glycerol or polyethylene glycol 600, preferably ethylene glycol.
Preferably, the electrochemical deposition and electrochemical dealloying treatment specifically comprises:
gold is used as a working electrode, a zinc plate is used as a counter electrode, a zinc sheet is used as a reference electrode, a zinc salt solution is used as an electrolyte, and after the electrolyte is heated to 90-130 ℃, cyclic voltammetry scanning is carried out for 10-60 times within a working voltage range of-0.8-1.8V at a scanning rate of 8-12 mV/s.
Preferably, the concentration of the zinc salt solution is 10 to 20 wt%.
Preferably, before performing the electrochemical deposition and the electrochemical dealloying treatment, the method further comprises the following steps: and placing the gold in a sulfuric acid solution for electrochemical activation pretreatment.
Preferably, the electrochemical activation pretreatment specifically comprises:
gold is used as a working electrode, platinum is used as a counter electrode, Ag/AgCl is used as a reference electrode, sulfuric acid solution is used as electrolyte, and cyclic voltammetry scanning is carried out for 5-15 times at a scanning rate of 15-25mV/s within a working voltage range of 0-1.5V.
Preferably, the concentration of the sulfuric acid solution is 0.4-0.6 mol/L.
The invention provides nano porous gold which is prepared by the preparation method.
The invention provides an electrochemical analysis sensor, which comprises an electrochemical sensing electrode constructed by the nano-porous gold.
Preferably, the electrochemical analytical sensor can be used for detecting life information small molecules;
preferably, the vital information small molecule is nitric oxide.
Preferably, the detecting the life information small molecule specifically includes:
an electrochemical sensing electrode constructed by nano-porous gold is used as a working electrode, platinum is used as a counter electrode, Ag/AgCl is used as a reference electrode, phosphate buffer solution is used as electrolyte, and cyclic voltammetry scanning is carried out at a scanning rate of 15-25mV/s within a working voltage range of 0.2-0.8V.
The preparation method of the nano porous gold provided by the invention utilizes a cyclic voltammetry method to alloy and dealloye the surface of the gold, thereby preparing the nano porous gold. Specifically, zinc ions are electrodeposited on the surface of a gold electrode in cathode potential scanning, an AuZn alloy is formed on the surface of the gold electrode, reduced zinc is gradually oxidized to form zinc ions in anode potential scanning, the zinc ions are dissolved and diffused into an electrolyte, the migration of zinc on the surface of the electrode causes the synchronous migration of gold atoms, and the electrodeposition, migration and dissolution of the zinc ions are repeated in the subsequent cathode reduction and anode oxidation process, so that the pure gold with the three-dimensional nano-porous structure is prepared. The nano-porous gold obtained by the method greatly increases the specific surface area and the roughness of gold, has a cooperative sensitization mechanism of noble metal nano-particles and a porous nano-structure, and has very high current density and charge transfer electron speed when being used as an electrode, so that the nano-porous gold is expected to obtain excellent performance of analyzing ions with silk quantity.
Meanwhile, when the three-dimensional nano-porous gold is formed by using a cyclic voltammetry method, the invention discovers that when a zinc salt solution is used as an electrolyte, the effective reduction reaction of Au is realized due to the strong reduction effect of zinc salt and the uniform distribution of Zn in an organic solution, Zn is uniformly dispersed on the surface of Au, and the porous structure of the nano-porous gold is uniformly distributed after dealloying, so that the three-dimensional nano-porous gold with nano-pores is obtained. Among them, the present invention has found that the specific surface area of the obtained nanoporous gold can be greatly changed by controlling the solvent selection of the electrolyte. When ethylene glycol is used as a solvent, the obtained nano-porous gold has very high specific surface area and electrochemical activity, and shows the optimal electrochemical sensitive response characteristic to trace analytes (such as life information molecules). And the specific surface area of the obtained nano-porous gold can be regulated and controlled by controlling the cycle number so as to further improve the electrochemical sensitive response of the nano-porous gold to trace analytes.
The invention also provides an electrochemical analysis sensor, and a sensing electrode is constructed by the nano-porous gold. When the nano-porous gold is used for detecting the nitric oxide which is a life information molecule, compared with a sensing electrode of a bare gold electrode, the sensing electrode constructed by the nano-porous gold realizes the high-sensitivity detection of the life information molecule, and effectively solves the problems of difficult electrochemistry capture and low sensitivity of the short-life information molecule.
Drawings
FIG. 1 is an SEM image of nanoporous gold prepared in example 1 of the invention.
FIG. 2 is an SEM image of nanoporous gold prepared in example 2 of the invention.
FIG. 3 is an SEM image of nanoporous gold prepared in example 3 of the invention.
FIG. 4 is an SEM image of nanoporous gold prepared in example 4 of the invention.
FIG. 5 is an SEM image of nanoporous gold prepared at different cycle scanning times in example 1 of the present invention: (a) is SEM picture of the nano-porous gold prepared under 10 times of scanning in the embodiment 1 of the invention; (b) is SEM picture of the nano-porous gold prepared under 20 times of scanning in the embodiment 1 of the invention; (c) is SEM picture of the nano-porous gold prepared under 30 times of scanning in the embodiment 1 of the invention; (d) is SEM picture of the nano-porous gold prepared under 40 times of scanning in the embodiment 1 of the invention; (e) is SEM picture of the nano-porous gold prepared under 50 times of scanning in the embodiment 1 of the invention; (f) is an SEM image of the nanoporous gold prepared in example 1 of the present invention at 60 scan times.
FIG. 6 is an SEM image of nanoporous gold prepared at different cycle scanning times for example 4 of the present invention: (a) is SEM picture of the nano-porous gold prepared under 10 times of scanning in the embodiment 4 of the invention; (b) is SEM picture of the nano-porous gold prepared under 20 times of scanning in the embodiment 4 of the invention; (c) is SEM picture of the nano-porous gold prepared under 30 times of scanning in the embodiment 4 of the invention; (d) is the SEM image of the nanoporous gold prepared by the method of example 4 in the invention under the condition of 40 times of scanning.
Fig. 7 is an SEM image of nanoporous gold prepared in comparative example 1 of the present invention.
FIG. 8 is a cyclic voltammogram of the electrode made of nanoporous gold in different cyclic scanning times in 0.1M sulfuric acid according to example 1 of the present invention.
FIG. 9 is a cyclic voltammogram of the nanoporous gold and bare gold electrodes prepared in example 4 of the present invention as electrodes in 0.1M sulfuric acid.
FIG. 10 is a cyclic voltammogram of nanoporous gold as an electrode prepared in different organic solvents according to test example 1 of the present invention in 0.1M sulfuric acid.
Fig. 11 is a graph of cyclic voltammetry response of the nanoporous gold and bare gold electrodes prepared in example 1 of the present invention as an electrode to nitric oxide.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of benzyl alcohol, and performing ultrasonic dissolution to obtain a transparent and clear zinc chloride benzyl alcohol solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating a zinc chloride benzyl alcohol solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride benzyl alcohol solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of initial voltage of 0.2V, lowest voltage of-0.8V, highest voltage of 1.8V and scanning speed of 10mV/s, taking out the working electrode, and washing with absolute ethyl alcohol to obtain the nano porous gold, wherein the surface of the gold working electrode which is smooth and bright yellow is changed into tan after the circular scanning is performed for 50 times.
Scanning electron microscope detection is carried out on the nanoporous gold prepared in example 1, and the result is shown in fig. 1. Fig. 1 is an SEM image of nanoporous gold prepared in this example. Referring to fig. 1, after the electrochemical deposition/dealloying treatment, a uniform nano-porous structure is formed on the surface of the bare gold electrode, and the porous structure shows uniformly distributed orientation.
And (3) repeating the steps (1) to (3), except that in the cyclic scanning, only 10, 20, 30, 40 and 60 times of cyclic scanning are carried out, and the nanoporous gold obtained after 10, 20, 30, 40, 50 and 60 times of cyclic scanning is obtained respectively. Scanning electron microscope detection is carried out on the nanoporous gold respectively, and the results are shown in fig. 5. Fig. 5 is an SEM image of nanoporous gold prepared in example 1 at different cycle scan times. Referring to fig. 5, after 10 times of cyclic scanning, a porous structure appears on the surface of the nano-porous gold, and the porous structure gradually becomes obvious and forms a three-dimensional structure with the increase of the scanning times, and after 60 times of cyclic scanning, a macroporous structure is formed on the surface of the nano-porous gold and pores are dispersed.
Respectively using the nano-porous gold prepared after the cyclic scanning for 10, 20, 30, 40, 50 and 60 times as electrodes, in a 0.1M sulfuric acid solution, using the nano-porous gold as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, connecting an electrochemical workstation, and setting the initial voltage to be 0V and the final voltage to beThe sweep rate was 20mV/s at 1.5V, and the sweep was cycled until a stable cyclic voltammogram was obtained, as shown in FIG. 8. FIG. 8 is a cyclic voltammogram of the electrode made of nanoporous gold in different cyclic scanning times in 0.1M sulfuric acid according to example 1 of the present invention. Referring to fig. 8, the characteristic reduction peak of the metal oxide is at +0.90V, and the characteristic reduction peak gradually increases with the increase of the number of the cyclic scans; when the scanning times are 50 times, the characteristic reduction peak reaches the maximum value; when the number of scanning times is 60, the reduction peak begins to decrease, and the result is consistent with the SEM characterization result. In addition, the characteristic reduction peaks of the nanoporous gold prepared by different cycle scanning times were integrated, and the electrochemical active area and the roughness thereof compared to the bare gold electrode having a smooth surface were calculated, and the results are shown in table 1. Referring to Table 1, when the number of scanning cycles was 50, the electrochemical active area of the nanoporous gold was the largest, and was 25.00mm2The roughness reaches 29.48.
TABLE 1
| Electrode for electrochemical cell | Integral electric quantity (mu C) | Active area (mm)2) | Roughness of |
| Bare | 3.869 | 0.99 | |
| NPAu(10) | 23.61 | 6.054 | 7.14 |
| NPAu(20) | 49.64 | 11.68 | 13.65 |
| NPAu(30) | 57.34 | 14.70 | 17.34 |
| NPAu(40) | 73.13 | 18.75 | 22.11 |
| NPAu(50) | 97.51 | 25.00 | 29.48 |
| NPAu(60) | 63.61 | 16.31 | 19.23 |
Example 2
The preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of polyethylene glycol-600, and performing ultrasonic dissolution to obtain a transparent and clear zinc chloride polyethylene glycol-600 solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating the zinc chloride polyethylene glycol-600 solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride polyethylene glycol-600 solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of initial voltage of 0.2V, lowest voltage of-0.8V, highest voltage of 1.8V and scanning rate of 10mV/s, taking out the working electrode, and washing with absolute ethyl alcohol to obtain the nano porous gold, wherein the surface of the gold working electrode which is smooth and bright yellow is changed into tan after 50 times of circular scanning.
Scanning electron microscope detection is performed on the nanoporous gold prepared in example 2, and the result is shown in fig. 2. Fig. 2 is an SEM image of the nanoporous gold prepared in this example. Referring to fig. 2, it can be known that nanoporous gold has the existence of a nanoporous structure, and the porous structure exhibits uniformly distributed orientation.
Example 3
The preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of glycerol, and performing ultrasonic dissolution to obtain a transparent and clear zinc chloride glycerol solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating a zinc chloride glycerol solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride glycerol solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of initial voltage of 0.2V, lowest voltage of-0.8V, highest voltage of 1.8V and scanning speed of 10mV/s, taking out the working electrode, and washing with absolute ethyl alcohol to obtain the nano porous gold, wherein the surface of the gold working electrode which is smooth and bright yellow is changed into tan after the circular scanning is performed for 50 times.
Scanning electron microscope detection is performed on the nanoporous gold prepared in example 3, and the result is shown in fig. 3, and fig. 3 is an SEM image of the nanoporous gold prepared in this example. Referring to fig. 3, it can be known that nanoporous gold has the existence of a nanoporous structure, and the porous structure exhibits uniformly distributed orientation.
Example 4
The preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of ethylene glycol, and performing ultrasonic dissolution to obtain a transparent and clear zinc chloride ethylene glycol solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating a zinc chloride glycol solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride glycol solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of initial voltage of 0.2V, lowest voltage of-0.8V, highest voltage of 1.8V and scanning speed of 10mV/s, taking out the working electrode, and washing with absolute ethyl alcohol to obtain the nano porous gold, wherein the surface of the gold working electrode which is smooth and bright yellow is changed into tan after the circular scanning is performed for 20 times.
Scanning electron microscope detection is performed on the nanoporous gold prepared in example 4, and the result is shown in fig. 4, and fig. 4 is an SEM image of the nanoporous gold prepared in this example. Referring to fig. 4, it can be known that nanoporous gold has the existence of a nanoporous structure, and the porous structure exhibits uniformly distributed orientation.
And (4) repeating the steps (1) to (3), except that in the cyclic scanning, only 10, 30 and 40 times of cyclic scanning are carried out, and the nanoporous gold obtained after 10, 20, 30 and 40 times of cyclic scanning is obtained respectively. Scanning electron microscope detection is carried out on the nanoporous gold respectively, and the result is shown in fig. 6. Fig. 6 is an SEM image of nanoporous gold prepared in example 4 at different cycle scan times. Referring to fig. 6, after 10 cycles of scanning, a three-dimensional porous structure appears clearly on the surface of the nano-porous gold, and the porous structure becomes more obvious as the number of scanning times increases.
The nanoporous gold and bare gold electrodes (after activation treatment) prepared after the above cyclic scanning for 20 times are respectively used as electrodes, in a 0.1M sulfuric acid solution, the nanoporous gold or bare gold electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, an electrochemical workstation is connected, and cyclic scanning is performed under the conditions that the initial voltage is 0V, the final voltage is 1.5V, and the scanning rate is 20mV/s until a stable cyclic voltammetry curve is obtained, and the result is shown in FIG. 9. FIG. 9 is a cyclic voltammogram of the nanoporous gold and bare gold electrodes prepared in example 4 of the present invention as electrodes in 0.1M sulfuric acid. Referring to fig. 9, the characteristic reduction peak of the metal oxide is +0.89V, and the characteristic reduction peak of the metal oxide corresponding to the nanoporous gold is significantly increased compared to the bare gold electrode. In addition, the characteristic reduction peak of the nanoporous gold was integrated, and the electrochemical active area and the roughness thereof compared to the bare gold electrode having a smooth surface were calculated, and as a result, the nanoporous gold prepared in example 4 had an electrochemical active area of 34.88mm2The roughness reaches 40.74. From this, it is understood that the nanoporous gold according to example 4 has the largest electrochemical active area and also has the optimal electrochemical sensitive response effect, compared to the nanoporous gold prepared in example 1.
Comparative example 1
The preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of N, N-Dimethylformamide (DMF) and carrying out ultrasonic dissolution completely to obtain a transparent and clear zinc chloride DMF solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating a zinc chloride DMF solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride DMF solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of an initial voltage of 0.2V, a lowest voltage of-0.8V, a highest voltage of 1.8V and a scanning rate of 10mV/s, taking out the working electrode, and washing with absolute ethyl alcohol to obtain the nano porous gold, wherein the surface of the gold working electrode which is smooth and bright yellow is changed into tan after the circular scanning is performed for 20 times.
The result of the scanning electron microscope examination of the nano-porous gold prepared in comparative example 1 is shown in fig. 7, and fig. 7 is an SEM image of the nano-porous gold prepared in the comparative example. Referring to fig. 7, it can be seen that a large amount of non-dealloyed zinc remained on the nanoporous gold obtained in this comparative example, and when used as an electrode active material, the activity thereof was much lower than that of the nanoporous gold obtained in examples 1 to 4.
Test example 1:
the preparation method of the nano-porous gold comprises the following steps:
(1) taking a gold wire with the diameter of 0.127mm and the length of 30mm, placing the gold wire at one port of a glass tube, taking another copper wire and wrapping one end of the copper wire with silver paste, penetrating the end wrapped with the silver paste into the glass tube, connecting the glass tube with the gold wire, placing the glass tube in an oven for drying, taking out the glass tube after drying, measuring whether the glass tube is conductive by using a universal meter, and sealing two ends of the glass tube by using AB glue after measuring good conductivity to obtain the required bare gold electrode;
(2) introducing nitrogen into 5mL of 0.1M sulfuric acid solution for 15min, and discharging air in the sulfuric acid solution to obtain degassed sulfuric acid; taking the bare gold electrode prepared in the step (1) as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, placing the three electrodes in the degassed sulfuric acid, connecting the three electrodes to an electrochemical workstation, activating by adopting a three-electrode cyclic voltammetry method, circularly scanning under the conditions of an initial voltage of 0V, a termination voltage of 1.5V and a scanning rate of 20mV/s, and obtaining the activated bare gold electrode after cyclic scanning for 10 times;
(3) adding 1.022g of zinc chloride into 5mL of organic solvent (benzyl alcohol, polyethylene glycol 600, glycerol and ethylene glycol) and completely dissolving by ultrasonic wave to obtain a transparent and clear zinc chloride solution; polishing the zinc sheet and the zinc wire to be bright respectively to remove an oxide film on the surface, soaking in ethanol, and ultrasonically cleaning for 5min to obtain the zinc sheet and the zinc wire after cleaning and impurity removal; heating a zinc chloride solution to 110 ℃, then using the bare gold electrode subjected to activation treatment in the step (2) as a working electrode, using a zinc wire as a counter electrode, using a zinc sheet as a reference electrode, placing the three electrodes in the zinc chloride solution, connecting the three electrodes to an electrochemical workstation, circularly scanning under the conditions of an initial voltage of 0.2V, a lowest voltage of-0.8V, a highest voltage of 1.8V and a scanning rate of 10mV/s, taking out the working electrode after circularly scanning for 20 times, and washing the working electrode with absolute ethyl alcohol to obtain the nano-porous gold.
Taking the nano-porous gold respectively prepared in benzyl alcohol, polyethylene glycol 600, glycerol and glycol organic solvents as electrodes, taking the nano-porous gold as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode in a 0.1M sulfuric acid solution, connecting an electrochemical workstation, and carrying out initial electroanalysisThe pressure was 0V, the stop voltage was 1.5V, and the sweep rate was 20mV/s, and the results are shown in FIG. 10. FIG. 10 is a cyclic voltammogram of nanoporous gold prepared in different organic solvents of test example 1 as an electrode in 0.1M sulfuric acid. Referring to FIG. 10, the characteristic reduction peak of the MOS is mostly concentrated at + 0.89V. Moreover, after electrochemical treatment of a zinc chloride glycol solution, the characteristic reduction peak of the metal oxide is the largest; after electrochemical treatment by a zinc chloride polyethylene glycol solution, the characteristic reduction peak of the metal oxide is minimum. Integrating the characteristic reduction peaks of the nanoporous gold prepared by electrochemical treatment under different organic solvent conditions, and calculating the electrochemical active area and the roughness of the nanoporous gold compared with a bare gold electrode, so as to obtain that the electrochemical active areas of the nanoporous gold are respectively 11.68mm under the conditions of benzyl alcohol, polyethylene glycol 600, glycerol and glycol solution2、7.01mm2、13.66mm2And 34.88mm2The roughness corresponds to 13.65, 8.19, 15.61 and 40.74, respectively. The results show that the nanoporous gold prepared using ethylene glycol as solvent has the highest electrochemical active area and the largest roughness under the same number of scans.
Test example 2
The nanoporous gold or bare gold electrodes (after activation treatment) prepared in example 1 were used as working electrodes for electrochemical analysis and testing, and a three-electrode test system was composed of Ag/AgCl as a reference electrode and a platinum wire as a counter electrode, 0.1M phosphate buffer (pH 7.2) as an electrolyte, and Nitric Oxide (NO) as a life information molecule to be analyzed.
Before testing, introducing inert argon into the electrolyte for 20min to remove dissolved oxygen, taking cyclic voltammetry as an analysis method, circularly scanning a substrate solution (blank sample) under the conditions that the initial voltage is 0.2V, the termination voltage is 0.8V and the scanning rate is 20mV/s, and recording the electrochemical behavior; then, NO solution was added to the electrolyte and stirred uniformly to obtain a test solution, the concentration was controlled to 5 μ M, the test solution (NO sample) was cyclically scanned again under the same conditions by cyclic voltammetry, and the electrochemical behavior was recorded, the result being shown in fig. 11. Fig. 11 is a graph of cyclic voltammetry response of the nanoporous gold and bare gold electrodes prepared in example 1 of the present invention as an electrode to nitric oxide, and referring to fig. 11, it can be seen that the nanoporous gold prepared in example 1 shows a strong electrochemical oxidation behavior for NO at + 0.75V. Compared with a bare gold electrode with a smooth surface as an electrode, when the nano-porous gold is used as the electrode, the electrochemical response to NO is improved by 6.3 times, and the oxidation potential is lower than that of the bare gold electrode (+0.84V), which shows that NO is easier to generate oxidation reaction on the surface of the nano-porous gold and has higher electrocatalytic activity.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing nano-porous gold is characterized by comprising the following steps: placing gold in a zinc salt solution, and sequentially carrying out electrochemical deposition and electrochemical dealloying treatment to obtain the nano-porous gold;
wherein, the zinc salt solution is obtained by dissolving zinc salt in alcohol solvent.
2. The method for preparing nanoporous gold according to claim 1, wherein the alcohol solvent is ethylene glycol, benzyl alcohol, glycerol or polyethylene glycol 600, preferably ethylene glycol;
preferably, the concentration of the zinc salt solution is 10 to 20 wt%.
3. The method for preparing nanoporous gold according to claim 1 or 2, wherein the electrochemical deposition and electrochemical dealloying treatment specifically comprises:
gold is used as a working electrode, a zinc plate is used as a counter electrode, a zinc sheet is used as a reference electrode, a zinc salt solution is used as an electrolyte, and after the electrolyte is heated to 90-130 ℃, cyclic voltammetry scanning is carried out for 10-60 times within a working voltage range of-0.8-1.8V at a scanning rate of 8-12 mV/s.
4. The method for preparing nanoporous gold according to any one of claims 1-3, further comprising, prior to the electrochemical deposition and electrochemical dealloying treatment: and placing the gold in a sulfuric acid solution for electrochemical activation pretreatment.
5. The method for preparing nanoporous gold according to claim 4, wherein the electrochemical activation pre-treatment specifically comprises:
gold is used as a working electrode, platinum is used as a counter electrode, Ag/AgCl is used as a reference electrode, sulfuric acid solution is used as electrolyte, and cyclic voltammetry scanning is carried out for 5-15 times at a scanning rate of 15-25mV/s within a working voltage range of 0-1.5V.
6. The method for preparing nanoporous gold according to claim 5, wherein the concentration of the sulfuric acid solution is 0.4-0.6 mol/L.
7. Nanoporous gold, which is prepared by the preparation method according to any one of claims 1 to 6.
8. An electrochemical analytical sensor comprising a sensing electrode constructed from nanoporous gold according to claim 7.
9. The electrochemical analytical sensor of claim 8, which is for detecting a life information small molecule;
preferably, the vital information small molecule is nitric oxide.
10. The electrochemical analytical sensor of claim 9, wherein the detection of the life information small molecule specifically includes:
a sensing electrode constructed by nano-porous gold is used as a working electrode, platinum is used as a counter electrode, Ag/AgCl is used as a reference electrode, phosphate buffer solution is used as electrolyte, and cyclic voltammetry scanning is performed at a scanning rate of 15-25mV/s within a working voltage range of 0.2-0.8V.
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