METHOD FOR MANUFACTURING COPPER COMPOSITE ELECTRODE WITH A FLAKE STRUCTURE ON THE SURFACE

Abstract

A method for manufacturing a copper composite electrode, including contacting a conductive substrate including copper with a phosphate solution for oxidation to produce a copper phosphate structure on a surface of the conductive substrate, thus acquiring a copper phosphate composite electrode.

Claims

1. A method for manufacturing a copper composite electrode with a flake structure on the surface, the method comprising: a) preparing a conductive substrate comprising a copper surface; b) placing the conductive substrate comprising the copper surface in a phosphate solution having pH values of 4.06.0 allows copper to contact with the phosphate solution for oxidation, wherein: the oxidation adopts electro-oxidation, chemical oxidation, or a combination thereof, when chemical oxidation is adopted, an oxidant is added and when electro-oxidation is adopted, voltages of 0.1 V0.1 V are applied; and c) forming a copper phosphate having a flake structure on the surface of the conductive substrate to acquire a copper phosphate composite electrode.

2. The method of claim 1, further comprising a1) before a): collecting a non-copper conductive substrate, and depositing copper on a surface of the non-copper conductive substrate.

3. The method of claim 2, wherein in a1), the non-copper conductive substrate is placed in a solution comprising the copper ions to nucleate the copper ions on the surface of the non-copper conductive substrate.

4. The method of claim 1, wherein the conductive substrate is a screen-printed carbon electrode or carbon.

5. The method of claim 1, wherein the oxidant is selected from the group consisting of hydrogen peroxide, potassium ferrite, potassium permanganate, and potassium dichromate.

6. The method of claim 1, wherein the oxidant is hydrogen peroxide, and a molar concentration of hydrogen peroxide is between 0.001 and 10 M.

7. The method of claim 1, wherein a molar concentration of a phosphate of the phosphate solution in b) is between 0.001 and 5 M.

8. The method of claim 1, further comprising d) after c): modifying a surface of the copper phosphate composite electrode by at least one modifier, wherein the at least one modifier is a negatively charged polymer film or an ionic liquid.

9. The method of claim 8, wherein the negatively charged polymer film is selected from the group consisting of Nafion, a sulfonated polyaniline, a sulfonated polystyrene ether, and a sulfonated polystyrene.

10. The method of claim 8, wherein in d), a thickness of a modified layer formed by the negatively charged polymer film on the surface of the copper phosphate composite electrode is between 0.25 m and 1.0 mm.

11. The method of claim 9, wherein in d), a thickness of a modified layer formed by the ionic liquid on the surface of the copper phosphate composite electrode is between 0.1 m and 1.0 mm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The invention is described hereinbelow with reference to the accompanying drawings, in which:

[0019] FIG. 1A is a first picture illustrating a surface of Cu/SPCE observed under scanning electron microscope (SEM) in accordance with one embodiment of the invention;

[0020] FIG. 1B is a second picture illustrating a surface of Cu/SPCE observed under SEM in accordance with one embodiment of the invention;

[0021] FIG. 1C is a picture illustrating a surface of Cu/SPCE treated by electrooxidation observed under SEM in accordance with one embodiment of the invention;

[0022] FIG. 1D is a picture illustrating a surface of Cu/SPCE treated by chemical oxidation observed under SEM in accordance with one embodiment of the invention;

[0023] FIG. 1E is a picture illustrating a surface of Cu/SPCE treated by electrooxidation followed with chemical oxidation observed under SEM in accordance with one embodiment of the invention;

[0024] FIG. 1F is a picture illustrating a surface of Cu/SPCE treated by chemical oxidation followed with electro-oxidation observed under SEM in accordance with one embodiment of the invention;

[0025] FIG. 2A is X-ray photoelectron spectroscopy (XPS) deconvolution peaks of Cu 2p3 of Cu/SPCE after electro-oxidation in accordance with one embodiment of the invention.

[0026] FIG. 2B is XPS deconvolution peaks of Cu 2p3 of Cu/SPCE after chemical oxidation in accordance with one embodiment of the invention.

[0027] FIG. 3 is the LSV scanning result of the copper foil electrodes putting in 100 mM and 1.0 M NaH.sub.2PO.sub.4 solutions (pH 5.0) by using 10 mV/s between 0.3 V0.2 V

[0028] FIG. 4A is SEM morphological images the Cu electrodes electro-oxidized at E.sub.pa2 (about 0 V) for 900 s in the 0.1 M NaH.sub.2PO.sub.4 solutions of pH 5.0.

[0029] FIG. 4B is SEM morphological images the Cu electrodes electro-oxidized at E.sub.pa2 (about 0 V) for 900 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 5.0.

[0030] FIG. 5 is the LSV scanning result of the copper foil electrodes putting in the 1.0 M NaH.sub.2PO.sub.4 solutions with different pH values by using 10 mV/s between 0.3 V0.2 V.

[0031] FIG. 6A is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa1 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 3.0.

[0032] FIG. 6B is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa1 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 4.0.

[0033] FIG. 6C is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa1 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 5.0.

[0034] FIG. 7A is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa2 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 3.0.

[0035] FIG. 7B is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa2 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 4.0.

[0036] FIG. 7C is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa2 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 5.0.

[0037] FIG. 7D is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa2 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 6.0.

[0038] FIG. 7E is SEM morphological images of the Cu electrodes electro-oxidized at E.sub.pa2 for 600 s in the 1.0 M NaH.sub.2PO.sub.4 solutions of pH 7.0.

[0039] FIG. 8 is cyclic voltammograms of 1.0 M NaH.sub.2PO.sub.4 in different pH in accordance with one embodiment of the invention.

[0040] FIG. 9 is cyclic voltammograms of copper phosphate composite electrodes obtained by different oxidations in accordance with one embodiment of the invention; and

[0041] FIG. 10 is cyclic voltammograms of Nafion/BMPy-TFSI/Cu.sub.3(PO.sub.4).sub.2/SPCE in different solutions in accordance with one embodiment of the invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] For further illustrating the invention, experiments detailing a method for manufacturing a copper composite electrode are described below. It should be noted that the following examples are intended to describe and not to limit the invention.

[0043] The method for manufacturing the copper composite electrode comprises:

[0044] placing a conductive substrate in a phosphate solution, and allowing copper to react with the phosphate solution by oxidation to produce a copper phosphate structure on a surface of the conductive substrate, thus acquiring a copper phosphate composite electrode. The conductive substrate is optionally made of any conductive materials. When the conductive material is a non-copper material, the conductive substrate is placed in a solution comprising copper ions to deposit a copper structure on the surface of the non-copper conductive substrate by deposition.

[0045] The phosphate solution refers to a solution comprising phosphate-related ions, for example, NaHP.sub.2O.sub.4, Na.sub.2HPO.sub.4, K.sub.2HPO.sub.4, KH.sub.2PO.sub.4, or the like. Preferably, a pH value of the phosphate solution is between 4.0 and 6.0.

[0046] The deposition herein is also called copper structure deposition and includes chemical deposition and electrochemical deposition. In one embodiment of the invention, the non-copper conductive substrate is placed in the solution comprising copper ions with a molar concentration of between 0.001 and 5 M, and applied with a first voltage and scanned, so that the copper ions are nucleated on the surface of the non-copper conductive substrate, in which, the voltage is between 0.6 V and +0.05 V, and a scanning cycle is at least 5 cycles. In order to distribute the copper on the whole surface of the conductive substrate, a second voltage is further applied, and preferably, the second voltage is between 0.321 V and 0.072 V, and an applying time of the voltage is between 100 s and 300 s.

[0047] The oxidation herein is electro-oxidation, chemical oxidation, or a combination of alternate use thereof. The electro-oxidation comprises: placing the conductive substrate comprising copper in a phosphate solution having a set concentration, applying a set voltage on the phosphate solution to carry out reaction, therefore producing a copper phosphate structure on the surface of the conductive material and acquiring the copper phosphate composite electrode. The chemical oxidation comprises: placing the conductive substrate comprising copper in a mixed solution comprising a phosphate and hydrogen peroxide with set concentrations for reaction for a relatively long period to acquire a copper phosphate composite electrode.

[0048] According to embodiments of the invention, operation processes are different when using different oxidation methods, taken the following as examples:

[0049] First, the conductive substrate comprising copper is placed in a 0.001 M-5 M phosphate solution, and applied with a voltage of 0.025 V0.1 V for 300-3600 s to acquire the copper phosphate composite electrode.

[0050] Wherein, the pH value is between 4.06.0, and particularly preferably is about 5.0.

[0051] Second, the conductive substrate comprising copper is placed in a 0.001 M-5 M phosphate solution added with 0.001 M-10 M hydrogen peroxide, after 5-120 min of treatment, the copper phosphate composite electrode is acquired.

[0052] Third, the conductive substrate comprising copper is placed in the 0.001 M-5 M phosphate solution, and applied with the voltage of 0.025 V0.1 V for 300-3600 s; thereafter, the conductive substrate comprising copper is transferred to the 0.001 M-5 M phosphate solution added with 0.001 M-10 M hydrogen peroxide, after 5-120 min of treatment, the copper phosphate composite electrode is acquired.

[0053] Fourth, the conductive substrate comprising copper is placed in the 0.001 M-5 M phosphate solution added with the 0.001 M-10 M hydrogen peroxide, after 5-120 min of treatment, the conductive substrate comprising copper is transferred to the 0.001 M-5 M phosphate solution, and applied with the voltage of 0.025 V0.1 V for 300-3600 s to yield the copper phosphate composite electrode.

[0054] The surface modification herein refers to modify the surface of the copper phosphate composite electrode by a modifier, such as an ionic liquid or a polymer film. The modifier is coated on the surface of the copper phosphate composite electrode for a thickness of between 0.25 m and 1.0 mm to improve the stability and sensibility of the electrode. In embodiments of the invention, the ionic liquid is preferably a bis (trifluoromethanesulfonyl) imide (TFSI)-series. The polymer film is preferably negatively charged, such as Nafion, a sulfonated polyaniline, a sulfonated polystyrene ether, a sulfonated polystyrene, or the like.

[0055] In the following examples, disposable SPCE adopted as the non-copper conductive substrate was taken as an example, which was used to explain the invention but was not intended to limit the scope of the invention.

Example 1: Preparation of Electrode

[0056] The disposable SPCE was used as a working electrode and a working area thereof was 3.14 mm.sup.2, Ag/AgCl and platinum wire were respectively used a reference electrodes and an auxiliary electrode. The electrochemical experiment in this example was carried out in the form of three electrodes.

[0057] The SPCE was firstly placed in a 100 mM phosphate solution, applied with a voltage of between 0.2 V and +1.3 V by a potentiostat and scanned for 10 cycles to clean the surface of the SPCE. After that, the SPCE was transferred to a 100 mM sodium hydrate solution and applied with a voltage of +2.0 V for 300 s to produce hydrophilic groups on the surface of the SPCE. The SPCE was then immersed in a 50 mM copper nitrate solution prepared by deionized water and having a pH value of 4.71. Copper was thereafter electrodeposited on the SPCE via the following two steps:

[0058] step 1): 50 mM Cu(NO.sub.3).sub.2 solution was applied with a voltage of between 0.381 V and +0.05 V and scanned for 10 cycles to nucleate copper on carbon; and

[0059] step 2): a voltage of 0.321 V was applied for 300 s to distribute copper on the whole working region.

[0060] SPEC (also referring to Cu/SPCE hereinbelow) with a large quantity of copper deposited on the surface thereof was acquired from the above operations. Thereafter, Cu.sub.3(PO.sub.4).sub.2 composite material (also referring to Cu.sub.3(PO.sub.4).sub.2/SPCE hereinbelow) was prepared by adopting any of the following means:

[0061] Electrooxidation: the Cu/SPCE was transferred to a 1.0 M sodium phosphate solution having a pH value of 5.0, and applied with a voltage of 0.025 V for 1200 s to yield the Cu.sub.3(PO.sub.4).sub.2/SPCE.

[0062] Chemical oxidation: the Cu/SPCE was directly immersed in a solution comprising 1.0 M hydrogen peroxide and 1.0 M sodium phosphate, after 20 min chemical oxidation, the Cu.sub.3(PO.sub.4).sub.2/SPCE was yielded.

[0063] Comprehensive oxidation: the electrooxidation and chemical oxidation were alternately used to yield the Cu.sub.3(PO.sub.4).sub.2/SPCE.

[0064] The Cu.sub.3(PO.sub.4).sub.2/SPCE was then modified by the ionic liquid (IL) and a 0.5% Nafion membrane, and dried at room temperature for 1 hr to yield a Nafion/IL/Cu.sub.3(PO.sub.4).sub.2/SPCE.

Example 2: Observation of Surface Structures of Cu.SUB.3.(PO.SUB.4.).SUB.2./SPCE

[0065] Materials during the preparation of the Cu.sub.3(PO.sub.4).sub.2/SPCE were detected by a scanning electron microscope (EOL JSM-7401F, Japan) to observe surface structures thereof, and results were shown in FIGS. 1A-1F.

[0066] As shown in FIGS. 1A-1B, in step 1), copper was deposited on the carbon substrate by the nucleation. In step 2), the nucleated copper began to grow so that copper particles completely covered a sensing region of the SPCE. As shown in FIG. 1C, the Cu/SPCE was treated by the electro-oxidation and the copper particle structure was totally transformed into relatively large flakes of copper phosphate structure. As shown in FIG. D, the Cu/SPCE was treated by the chemical oxidation for 20 min, and relatively small flakes of copper phosphate structure were formed on a surface of each copper particle. As indicated in FIG. E, by treating the Cu/SPCE with the electro-oxidation followed with the chemical oxidation, relatively large flake structures were formed on the surface, which was similar to that treated by the electro-oxidation. As indicated in FIG. F, by treating the Cu/SPCE with the chemical oxidation followed with the electro-oxidation, relatively small flake structures were formed on the surface.

[0067] It was demonstrated from FIGS. 1A-1F that any non-copper conductive substrate after treated by the method of according to embodiments of the invention was able to yield the Cu.sub.3(PO.sub.4).sub.2 structure.

Example 3: Detection of Chemical Compositions of Cu.SUB.3.(PO.SUB.4.).SUB.2./SPCE

[0068] The chemical compositions of the Cu.sub.3(PO.sub.4).sub.2/SPCE were analyzed by an XPS (type: PHI 5000 VersaProbe, provided by ULVAC-PHI corporation), and results were listed in FIGS. 2A-2B.

TABLE-US-00001 TABLE 1 Composition analysis of Cu 2p3 in Cu.sub.3(PO.sub.4).sub.2/SPCE in different forms Cu 2p3 composition (%) Cu, CuH.sub.2PO.sub.4/ CuCl Cu.sub.2O CuO Cu(OH).sub.2 Cu.sub.3(PO.sub.4).sub.2 CuHPO.sub.4 Electrode 930.9 932.5 933.55 934.65 935.1 936 treatment (eV) (eV) (eV) (eV) (eV) (eV) Pristine 1.3 48.7 18.7 31.3 0 0 Chemical 3.7 36.5 31.9 6.5 17.3 4.0 oxidation Electro- 0 9.1 13.6 16.1 33.3 27.9 oxidation

[0069] Table 1 was known from the results of this example that in the Cu.sub.3(PO.sub.4).sub.22/SPCE prepared by either the electro-oxidation or the chemical oxidation, the Cu.sub.3(PO.sub.4).sub.2 and CuH.sub.2PO.sub.4/CuHPO.sub.4 were produced, and the contents of Cu/Cu.sub.2O, CuO and Cu(OH).sub.2 were reduced. In another word, a large quantity of copper oxide and cuprous oxide produced on the Cu/SPCE were transformed into copper phosphate.

Example 4: Observation of Surface Structures of Cu.SUB.3.(PO.SUB.4.).SUB.2./SPCE by Using Different Concentrations of Phosphate Solutions

[0070] The FIG. 3 shows that the LSV (linear sweep voltammetry) scan results using 10 mV/s between 0.3 V0.2 V for the copper foil electrodes putting in 100 mM and 1.0 M NaH.sub.2PO.sub.4 solutions (pH 5.0), respectively. The FIG. 4 shown that the morphology of the electro-oxidized electrodes was observed by SEM, wherein the electro-oxidized electrode are made by using 0.1 M and 1.0M NaH.sub.2PO.sub.4 solutions, respectively.

[0071] According to the result of FIGS. 3 and 4, it shown that when the concentration of NaH.sub.2PO.sub.4 solution is 0.1 M, the flake structure can not be produced on the surface of the copper foil electrode; but when the concentration of NaH.sub.2PO.sub.4 solution is 1.0 M, the flake structure can be produced on the surface of the copper foil electrode.

Example 5: Observation of Surface Structures of Cu.SUB.3.(PO.SUB.4.).SUB.2./SPCE by Using 1.0 M Phosphate Solutions of Different pH Values of Phosphate Solutions

[0072] The copper foil electrodes put in 1.0 M NaH.sub.2PO.sub.4 solutions with different pH values: 3.0, 4.0, 5.0, 6.0, 7.0 for LSV scan, and the results are in FIG. 5 and Table.2.

TABLE-US-00002 TABLE 2 The concentration of each phosphate ion in 1.0M phosphoric acid solutions with different pH values pH [H.sub.2PO.sub.4.sup.] [HPO.sub.4.sup.2] [PO.sub.4.sup.3] 3.0 1.000M 6.20 10.sup.5M 2.89 10.sup.14M 4.0 0.999M 6.16 10.sup.4M 2.88 10.sup.12M 5.0 0.994M 6.13 10.sup.3M 2.87 10.sup.10M 6.0 0.942M 0.058M .sup.2.71 10.sup.8M 7.0 0.619M 0.381M .sup.1.78 10.sup.6M

[0073] Furthermore, the FIGS. 6-7 shown the morphology of the electro-oxidized electrodes was observed by SEM, wherein the electro-oxidized electrode are made by using pH 3.0, 4.0, 5.0, 6.0, 7.0 of NaH.sub.2PO.sub.4 solutions at E.sub.pa1 (0.09V) and E.sub.pa2 (about 0V), respectively.

[0074] After electro-oxidation at E.sub.pa1/E.sub.pa2 for 600 s in the pH 3.0 solution, curved flake structures were observed with a length of 1-3 m and a thickness of about 100 nm (FIGS. 6A and 7A). Electro-oxidation in the pH 4.0 solution (FIGS. 6B and 7B) resulted in the curved flake structures having a denser distribution on the electrode surface than those produced in the pH 3.0 solution. Electro-oxidation in the pH 7.0 solution (FIG. 7E) resulted in almost no flake structure produced. Moreover, the length of the curved flak structures increased with the solution pH from 3.0 to 5.0.

[0075] When the pH value of electro-oxidation solutions increased from 3.0 to 5.0, the Cu/Cu.sub.2O percentage of the electrodes increased from 24.1% to 40.4%, the Cu(OH).sub.2 percentage decreased from 9.7% to 5.6%, and the percentage of total copper-phosphate complexes (Cu.sub.3(PO.sub.4).sub.2, CuH.sub.2PO.sub.4 and CuHPO.sub.4) decreased from 53.3% to 40.5%. These results imply that the electro-oxidative reactions of Cu.sub.2O to form the CuO/Cu(OH).sub.2 and the copper-phosphate complexes are faster in more acidic solutions. Although the electrodes electro-oxidized in the pH 3.0 solution had a higher percentage of copper-phosphate complexes than those electro-oxidized in the pH 5.0 solution, the kinetics-controlled behavior of the electrodes is unfavorable for use in an amperometric sensor. Furthermore, the pH 5.0-electrooxidation electrodes exhibited a greater percentage of Cu.sub.3(PO.sub.4).sub.2 than that of CuH.sub.2PO.sub.4/CuHPO.sub.4 in the Cu 2p3 composition and the largest PO.sub.4.sup.3 percentage (52.9%) in the P 2p composition, indicating that these electrodes are Cu.sub.3(PO.sub.4).sub.2 dominated. The results demonstrate that the electro-oxidizing process of E.sub.pa1 and the pH 5.0 solution provides a Cu electrode to form a stable Cu.sub.3(PO.sub.4).sub.2 electrode in 10 min.

[0076] Furthermore, the FIG. 8 shown that the electrooxidized electrode is made by using pH 5.0 of H.sub.2PO.sub.4 solution is more stable than others and has good electrochemical properties after dipping in H.sub.2PO.sub.4.sup.1 solution for 1 h.

Example 6: Electrochemical Properties of Nafion/BMPy-TFSI/Cu.SUB.3.(PO.SUB.4.).SUB.2./SPCE

[0077] As shown in FIG. 9, electrochemical properties of the copper phosphate electrodes prepared by different methods were compared. The copper phosphate electrodes were respectively prepared by the electro-oxidation, the chemical oxidation, and the comprehensive oxidation which were illustrated in Example 1, and the dissolution/precipitation method in the prior art.

[0078] It was known from the scanning in a 20 mM sodium phosphate solution having a pH value of 5.0 that the copper phosphate electrodes prepared by the four methods were different in current due to the difference of the surface areas. However, all the copper phosphate electrodes had obvious oxidation waves at the potential of +0.1 V, which meant that the four methods were able to form copper phosphate quickly.

[0079] As disclosed in the prior research, the ionic liquid comprising the TFSI anions was able to be stably coated on a copper foil of a Cu.sub.3(PO.sub.4).sub.2 composite material in a solution having a pH value of between 5 and 11 and the electrochemical stability of the resulting product was demonstrated to be good. Thus, the ionic liquid comprising N-propyl-N-methylpyrrolidinium (BMPy)-TFSI was further taken as an example, and Nafion was used to modify the BMPy-TFSI-modified Cu.sub.3(PO.sub.4).sub.2/SPCE to yield the Nafion/BMPy-TFSI/Cu.sub.3(PO.sub.4).sub.2/SPCE, which was placed in the 20 mM phosphate solution having a pH value of 8.5 to detect whether 1 mM histamine was contained in the solution, and the cyclic voltammograms were shown in FIG. 10.

[0080] When histamine was contained in the solution, I.sub.P (I.sub.Pa-histamine-I.sub.Pa.sub.-blank) was increased by 253.8%, which indicated that the oxidation of histamine was related to the Cu.sup.IH.sub.2PO.sub.4/Cu.sup.IIHPO.sub.4, and the histamine-Cu.sup.IIHPO.sub.4 composite was formed under the electrochemical-chemical mechanics. The result demonstrates that the copper phosphate electrodes have an electrocatalytic property.

[0081] It was demonstrated from the above results that the method according to embodiments of the invention was able to prepare the copper composite electrode.

[0082] Unless otherwise indicated, the numerical ranges involved in the invention include the end values. While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention.