CN110767913B - Single silver-palladium alloy nanowire electrode and preparation method and application thereof - Google Patents
Single silver-palladium alloy nanowire electrode and preparation method and application thereof Download PDFInfo
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- 230000007774 longterm Effects 0.000 abstract description 4
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a single silver-palladium alloy nanowire electrode and a preparation method and application thereof. Moreover, the single silver-palladium alloy nanowire electrode prepared by the method is used for catalyzing methanol, the catalytic performance of the single nanowire can be observed from the perspective of the single nanowire, which is not possessed by most other methods, and the current density generated by the single silver-palladium alloy nanowire electrode prepared by the method is high. In addition, the single silver-palladium alloy nanowire electrode prepared by the invention has excellent catalytic performance, long-term stability, catalytic stability and carbon monoxide removal capability on methanol.
Description
Technical Field
The invention belongs to the field of nano electrode preparation, and particularly relates to a single silver-palladium alloy nano line electrode as well as a preparation method and application thereof.
Background
As one of the most promising clean energy sources in the future, the direct methanol fuel cell has attracted attention in the past decades due to its advantages of high energy density, easy storage, low operating temperature, and low environmental pollution. However, since the electrochemical activity of methanol is at least 3 orders of magnitude lower than that of hydrogen, one of the key technologies to be solved by the direct methanol fuel cell is to find an efficient electrocatalyst for electrocatalytic oxidation of the methanol anode, increase the speed of anodic oxidation of methanol, and reduce the polarization loss of the anode.
Although the platinum-based catalyst is considered to be the most effective methanol catalyst, when platinum is used as the anode electrocatalyst, carbon monoxide intermediates generated during the oxidation of methanol are easily adsorbed on the surface of the catalyst, thereby causing the catalyst to be poisoned. And the high cost of use of platinum-based catalysts makes them a great challenge for large-scale commercial production. There is therefore a need to develop a better catalyst to replace the platinum based catalyst.
Many studies have shown that palladium-based catalysts have good catalytic effects on methanol in alkaline medium. However, the wide use of palladium-based catalysts has relatively low catalytic performance and poor durability for direct catalysis of methanol.
In addition, the metal one-dimensional nanostructure plays an important role in the manufacture of electronic devices due to its special electrochemical, thermal and optical properties. Among them, silver nanowires are attracting much attention and widely used in the fields of solar cells, flexible photoelectrons, electrocatalysis, surface enhanced raman scattering and the like.
The current synthesis methods of silver nanowires include hydrothermal synthesis, wet chemical synthesis, polyol reduction and the like. Although these methods have been very successful, most of the prepared silver nanowires have irregular shapes, poor conductivity and low aspect ratio, and a template is always required to guide the growth of the silver nanowires in the synthesis process, and the catalytic performance of the silver nanowires cannot be inspected from the perspective of a single nanowire.
Disclosure of Invention
The invention aims to provide a preparation method of a single silver-palladium alloy nanowire electrode.
It is yet another object of the present invention to provide a single silver-palladium alloy nanowire electrode.
The final purpose of the invention is to provide the application of the single silver-palladium alloy nanowire electrode in catalysis of methanol in an alkaline medium.
The specific technical scheme of the invention is as follows:
the preparation method of the single silver-palladium alloy nanowire electrode comprises the following steps:
1) preparing a silver nanowire electrode;
2) soaking the silver nanowire electrode prepared in the step 1) in a palladium nitrate solution to obtain a single silver-palladium alloy nanowire electrode.
Step 1) the preparation of the silver nanowire electrode comprises the following steps:
1-1) plugging silver wires into an aluminosilicate capillary tube, and sealing one end of the capillary tube by using epoxy resin adhesive;
1-2) after the epoxy resin glue is completely dried, drawing the capillary processed in the step 1-1) into two probes with nano-scale tips by using a laser drawing instrument;
1-3) connecting the tungsten wire with the silver wire by using silver conductive adhesive;
1-4) grinding and polishing the tip by using metallographic abrasive paper to obtain the nanodisk electrode.
1-5) etching the nanodisk electrode obtained in the step 1-4) by using an HF solution to obtain the silver nanowire electrode.
Further, in the step 1-1), the diameter of the silver wire is 25 μm, and the length of the silver wire is 2-3 cm; the outer diameter of the aluminosilicate capillary is 1.0 mm; the inner diameter is 0.64 mm.
In the step 1-1), one end of the capillary is sealed by using epoxy resin glue, so that the tube is in a vacuum state in the drawing process;
the method for drawing by the laser drawing instrument in the step 1-2) comprises the following steps: setting heating program parameters: temperature 440 ℃, rate 5, pull 5; the heating program was run for 40s and then cooled for 20s, and 4 cycles were repeated; then 2 probes with two nanometer-sized tips are obtained by drawing under the drawing program, wherein the parameters of the drawing program are as follows: temperature 445 ℃, rate 30, pull force 118.
And (3) respectively polishing the tip by using 400-mesh, 800-mesh and 2000-mesh metallographic abrasive paper in sequence in the step 1-3) to obtain the nanodisk electrode.
The preparation method of the HF solution in the steps 1-5) comprises the following steps: preparing a hydrofluoric acid solution with the mass concentration of 40% and water according to the volume ratio of 1: 4; etching in the step 1-5) for 5-20 seconds; according to experimental requirements, the etching time of each electrode is different, and the length of the nanowire is longer and longer along with the increase of the etching time.
The preparation method of the palladium nitrate solution in the step 2) comprises the following steps: 0.0133g of palladium nitrate dihydrate and 33.3 mu L of 15mol/L of analytically pure nitric acid solution are placed in deionized water and mixed uniformly to obtain 10ml of solution, wherein the concentration of nitric acid in the solution is 50mM, and the concentration of palladium nitrate in the solution is 5 mM. The purpose of the nitric acid is to dissolve the palladium nitrate more quickly and obtain a palladium nitrate solution.
Further, the soaking time in the step 2) is 10-40 min.
The single silver-palladium alloy nanowire electrode provided by the invention is prepared by the method.
The single silver-palladium alloy nanowire electrode provided by the invention is applied to catalysis of methanol.
The specific catalysis method comprises the following steps: the single silver-palladium alloy nanowire electrode prepared by the invention is saturated by nitrogen and contains 0.2MKOH and 1.0MCH3CV scanning is carried out in OH solution, the potential is-0.8 v-0.4 v, and the scanning speed is 50 mV/s.
After the replacement soaking, the EDS diagram of the electrode shows that Pd successfully replaces Ag, the electrode contains silver and palladium elements, and the silver-palladium alloy nanowire electrode is successfully prepared. According to the d-band center theory, due to Pd
Has a lattice constant less than Ag
And therefore the structure of the Pd surface will produce tensile strain when alloyed with Ag. The d-band center of Pd moves upward, resulting in stronger adsorption capacity of hydroxyl groups (OHads) and promoting methanol oxidation reaction on the metal surface. In alkaline medium, the rate determining step of MOR (methanol oxidation) is the removal of methoxy intermediates from the catalyst surface by adsorption of Olads groups. Thus, a stronger hydroxyl (OHads) adsorption capacity can remove intermediates faster and release more active sites, resulting in faster MOR with better intermediate tolerance. According to the theory of bi-functional mechanism, the water activation potential is lower due to the presence of Ag in the Ag-Pd alloy compared to pure Pd, and more active sites on Pd are released because the activated water can oxidize CO or other poisoning intermediates. Single silver nanowireThe electrode has no catalytic performance on methanol, and has good catalytic performance on methanol due to the special synergistic effect of the electrode and palladium and the exposure of more active sites when the electrode and the palladium form a silver-palladium alloy through a displacement reaction.
Compared with the prior art, the single silver-palladium alloy nanowire electrode is successfully prepared by preparing the single silver nanowire electrode and then carrying out the current displacement reaction, and a nanowire material is not required to be synthesized, so that the problems of irregular shape, poor conductivity, low aspect ratio and the like of the synthesized nanowire are avoided, and a template is not required to guide the growth of the nanowire. Moreover, the single silver-palladium alloy nanowire electrode prepared by the method is used for catalyzing methanol, the catalytic performance of the single nanowire can be observed from the perspective of the single nanowire, which is not possessed by most other methods, and the current density generated by the single silver-palladium alloy nanowire electrode prepared by the method is high. In addition, the single silver-palladium alloy nanowire electrode prepared by the invention has excellent catalytic performance, long-term stability, catalytic stability and carbon monoxide removal capability on methanol.
Drawings
FIG. 1 is a schematic diagram of the preparation of a single silver-palladium alloy nanowire electrode according to the present invention;
FIG. 2 shows the electrode of silver nanowire of different lengths prepared by the present invention in the presence of 5mM Ru (NH)6)Cl3And 0.2KNO3CV plot in solution;
FIG. 3 is a simulation diagram of COMSOL of silver electrodes of different lengths;
FIG. 4 is an electrochemical characterization of single silver-palladium alloy nanowire electrodes with different silver-palladium contents in a 0.2M KOH solution;
FIG. 5 shows a single Ag-Pd alloy nanowire electrode with different Ag-Pd contents and a commercial Pd-C catalyst in the presence of 0.2MKOH and 1.0MCH3Performance diagram of catalytic methanol in OH solution;
FIG. 6 is a graph comparing the performance of different displacement times for electrodes with commercial palladium on carbon catalysts; in the figure, Onset potential refers to the initial potential of methanol oxidation, If：IbIs the ratio of the peak current of the front scan to the peak current of the back scan;
FIG. 7 substitution time 30minSingle silver-palladium alloy nanowire electrode and glassy carbon electrode loaded with commercial palladium carbon catalyst and saturated with nitrogen and containing 0.2MKOH and 1.0MCH3Testing the long-term stability performance of the OH solution to methanol oxidation;
fig. 8 is a comparison of CV curves of the first catalytic methanol and the fifth hundred times of the single silver-palladium alloy nanowire electrode with a displacement time of 30 min;
FIG. 9 is an LSV curve of the capacity of a single silver-palladium alloy nanowire electrode to remove carbon monoxide with a glassy carbon electrode loaded with a commercial palladium-carbon catalyst for a displacement time of 30 min;
figure 10 is an EDS plot of a single silver-palladium alloy nanowire electrode with a displacement time of 10 min.
Detailed Description
The conditions of the electrodes are shown as parameters, other experiments are carried out at room temperature, and all solutions in the invention are reused in a nitrogen saturated state after being filled with nitrogen and deoxidized for thirty minutes.
Example 1
The preparation method of the single silver-palladium alloy nanowire electrode comprises the following steps:
1) preparing a silver nanowire electrode:
1-1) filling silver wires with the diameter of 25 mu m and the length of 3cm into an aluminosilicate capillary tube, and sealing one end of the capillary tube by using epoxy resin glue;
1-2) after the epoxy resin glue is completely dried, drawing the capillary processed in the step 1) into two probes with nano-scale tips by using a laser drawing instrument; the drawing method by using the laser drawing instrument comprises the following steps: setting heating program parameters: temperature 440 ℃, rate 5, pull 5; after the heating program is operated for 40s, cooling for 20s, operating for 40s according to the heating program, cooling for 20s, and operating for 40s according to the heating program, cooling for 20 s; then 2 probes with two nanometer-sized tips are obtained by drawing under the drawing program, wherein the parameters of the drawing program are as follows: temperature 445 ℃, rate 30, pull force 118.
1-3) connecting a tungsten wire with the diameter of 250 mu m and the length of 8cm with the silver wire at the other end of the probe drawn in the step 2) by using silver conductive adhesive;
1-4) sequentially and respectively polishing the tip by using 400-mesh, 800-mesh and 2000-mesh metallographic abrasive paper for 10s to obtain the nanodisk electrode.
1-5) etching the nano-disk electrode obtained in the step 1-5) by using an HF solution for 5s, 8s, 14s and 18s respectively to obtain the silver nano-wire electrode. The preparation method of the HF solution comprises the following steps: preparing a hydrofluoric acid solution with the concentration of 40% and water according to the volume ratio of 1: 4;
2) 0.0133g of palladium nitrate dihydrate and 33.3 mu L of 15mol/L analytically pure nitric acid solution are placed in deionized water and mixed uniformly to obtain 10ml of palladium nitrate solution, the silver nanowire electrode prepared in the step 1) is placed in the obtained palladium nitrate solution to be soaked for 0min, 10min, 20min, 30min and 40min, and in the soaking process, a replacement reaction is carried out to obtain a single silver-palladium alloy nanowire electrode. And the single silver-palladium alloy nanowire electrodes with different contents are obtained by different soaking times and different replacement degrees.
Etching for different time in the step 1-5), placing the prepared silver nanowire electrodes with different lengths in a container containing 5mM Ru (NH)6)Cl3And 0.2KNO3Performing electrochemical characterization in the solution, and performing cyclic voltammetry scanning at a potential of 0.1 to-0.4V at a scanning speed of 50mV/s, wherein the result is shown in FIG. 2, and the length of 0nm in the graph refers to the silver nanowire electrode without etching, namely the silver nanodisk electrode. As can be seen from fig. 2, the CV curve exhibits an ideal sigmoid shape, and the positive and negative sweeps coincide well, indicating that the charging current is small, which is consistent with the previously reported phenomenon. And as the length of the silver nanowire increases, the limiting diffusion current of cyclic voltammetry also increases. The radius of the electrode can be controlled by the formula (I) id ═ 4nFDCb r0To calculate idIs the limiting diffusion current of the electrode, n is the electron transfer number, F is the Faraday constant, CbIs the concentration of the redox species, D is the diffusion coefficient, r0Is the radius of the electrode. The radius of the silver electrode before etching is 34nm according to the formula. Knowing the radius of the electrode, the length of the etched line of the silver nanoelectrode can be calculated in combination with the following equation (2).
Wherein iqssIs the steady state limiting diffusion current of the line electrode, n is the electron transfer number, F is the Faraday constant, A is the geometric area of the electrode, r0Is the radius of the electrode (same as a in the publication I, all are equal), D is the diffusion coefficient, CbIs the concentration of the redox species, τ (τ ═ 4Dt/r0 2) The expression (III) can be obtained from the expression (IV) of the time component T (T ═ RT/Fv), where T is the time component, D is the diffusion coefficient, R is the gas constant, T is the temperature, F is the faraday constant, and v is the sweep rate. Therefore, by combining the two formulas, the lengths of the silver nanowires can be calculated to be 35nm (etching 5s), 76nm (etching 8s), 143nm (etching 14s) and 197nm (etching 18s), respectively. From the steady state limiting diffusion current obtained from the electrode in hexammoniales solution, the radius r can be calculated according to formula (I)0Then, the radius r is adjusted0Substituting equation (II) allows the length of the electrode (geometric electrode area through radius r) to be calculated0And length), the rest are known except for the steady state limiting diffusion current, the radius and the length, so that the diffusion current obtained from the graph can be combined with a formula to calculate the radius and the length. From fig. 3 it can be seen that the plots simulated by COMSOL software substantially correspond to the experimentally obtained plots.
A silver nanowire electrode was prepared according to the parameters of example 1, except that the etching time in step 1-5) was controlled to 15s, and the silver nanowire electrode obtained under the same conditions as above was used. Respectively placing the mixture in a container containing 50mM HNO3And 5mMPd (NO)3)2Soaking the solution for 0min, 10min, 20min, 30min and 40min respectively to obtain electrodes with different silver and palladium contents; the CV diagram of these electrodes in a 0.2M KOH solution saturated with nitrogen is shown in FIG. 4, with a potential window of-0.8 v to 0.4v and a scanning speed of 50 mV/s. And obtaining the single silver-palladium alloy nanowire electrode with different silver-palladium contents. As can be seen from the CV diagram (FIG. 4) of the electrode in the alkaline medium, the peak of reduction of silver is at-0.2V and the peak of reduction of palladium oxide is at-0.2V. As the soaking time increased, it was found that the reduction peak of silver was gradually decreased and palladium oxide was formedThe reduction peak of (a) gradually increases, which indicates that the metal palladium is successfully modified to the surface of the silver nanowire through a current displacement reaction.
An EDS diagram of the single silver-palladium alloy nanowire electrode with the replacement time of 10min is shown in FIG. 10, which shows that after immersion replacement, Ag is successfully replaced by Pd, the electrode contains elements of silver and palladium, and the silver-palladium alloy nanowire electrode is successfully prepared.
FIG. 5 is a diagram showing the catalytic performance of a single silver-palladium alloy nanowire electrode with different contents and a palladium-carbon supported glassy carbon electrode obtained by replacing the soaking time on methanol in an alkaline medium, wherein the potential window is-0.8 v-0.4 v, and the scanning speed is 50 mV/s. As can be seen from the figure, an oxidation peak occurs at-0.1 v during the forward sweep due to methanol oxidation, and a smaller oxidation peak occurs during the flyback sweep due to the intermediate (carbon monoxide) produced during methanol oxidation. The three main indicators for evaluating the performance of catalytic methanol are initial potential, current density, ratio I of forward sweep peak current to flyback peak currentf/Ib. As can be seen from FIG. 6, when the silver nanowire electrode displacement time is 30min, the catalytic methanol has the lowest initial potential and the largest If/IbAnd at the same time, the current density is also larger. And comprehensively comparing, wherein the optimal time for soaking the electrode is 30 min. Meanwhile, the invention also compares the catalytic effect of the glassy carbon electrode loaded with commercial palladium-carbon catalyst and the prepared single silver-palladium alloy nanowire electrode on methanol, and the figure shows that the catalytic effect is no matter whether the current density, the initial potential or I is current density, initial potential or If/IbAnd single silver palladium nanowire electrodes with different contents are superior to palladium carbon supported glassy carbon electrodes. Therefore, the single silver-palladium alloy nanowire electrode has excellent performance of catalyzing methanol oxidation.
FIG. 7 is a single Ag-Pd alloy nanowire electrode obtained by soaking Ag nanowire electrode for 30min at-0.2 v potential by chronoamperometry, and a glassy carbon electrode loaded with commercial Pd-C catalyst and saturated in nitrogen and containing 0.2MKOH and 1.0MCH3Long-term stability performance test on methanol oxidation in OH solution. As can be seen from the figure, the catalytic current of the single silver-palladium alloy nanowire electrode decays rapidly within the first 100S and then slows downSlowly reaching steady state current. However, the current of the glassy carbon electrode loaded with the palladium-carbon catalyst is basically reduced to the steady-state current in the first 20S, and the current of the single silver-palladium alloy nanowire electrode is always higher than that of the glassy carbon electrode, which shows that the single silver-palladium alloy nanowire electrode prepared by the invention has good long-term stability in the capability of catalyzing methanol.
FIG. 8 shows single Ag-Pd alloy nanowire electrodes (soaked for 30min) saturated in nitrogen at 0.2MKOH and 1.0MCH3Stability test of catalytic methanol in OH solution. The potential window is-0.8 v-0.4 v, and the scanning speed is 50 mV/s. As can be seen from the CV curves, the CV curves of the first circle and the fifth circle are basically overlapped, the oxidation peak current of the methanol of the fifth circle is reduced by 7.3 percent relative to that of the first circle, and the oxidation peak current of the carbon monoxide generated in the methanol catalysis process is basically unchanged, which shows that the single silver-palladium alloy nanowire electrode prepared by the method has excellent stability.
Fig. 9 is an LSV curve for examining the ability of a single silver-palladium alloy nanowire electrode obtained by soaking for 30min to remove carbon monoxide with a glassy carbon electrode loaded with a commercial palladium carbon catalyst. The potential window is-0.8 v-0.4 v, and the scanning speed is 50 mV/s. As can be seen from the figure, both catalysts showed an oxidation peak of carbon monoxide. However, the initial potential (-0.35v) for carbon monoxide oxidation by a single silver-palladium alloy nanowire electrode was more negative than that of a commercial palladium-carbon catalyst modified glassy carbon electrode (-0.14v), indicating that the former has a stronger carbon monoxide removal capability than the latter.
Claims (4)
1. The preparation method of the single silver-palladium alloy nanowire electrode is characterized by comprising the following steps of:
1) preparing a silver nanowire electrode:
1-1) inserting silver wires into an aluminosilicate capillary tube, and sealing one end of the capillary tube by using epoxy resin glue;
1-2) after the epoxy resin glue is completely dried, drawing the capillary processed in the step 1-1) into two probes with nano-scale tips by using a laser drawing instrument;
1-3) connecting the tungsten wire with the silver wire by using silver conductive adhesive;
1-4) grinding and polishing the tip by using metallographic abrasive paper to obtain a nanodisk electrode;
1-5) etching the nanodisk electrode obtained in the step 1-4) by using an HF solution to obtain a silver nanowire electrode;
2) soaking the silver nanowire electrode prepared in the step 1) in a palladium nitrate solution for 10-40min to obtain the single silver-palladium alloy nanowire electrode.
2. The method according to claim 1, wherein the etching in the step 1-5) is performed for 5-20 seconds.
3. A single silver-palladium alloy nanowire electrode prepared according to the method of claim 1 or 2.
4. Use of single silver palladium alloy nanowire electrodes prepared according to the method of claim 1 or 2 for catalysis of methanol.
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