CN109811341A - An erasable precious metal substrate and its application - Google Patents
An erasable precious metal substrate and its application Download PDFInfo
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- CN109811341A CN109811341A CN201910025441.XA CN201910025441A CN109811341A CN 109811341 A CN109811341 A CN 109811341A CN 201910025441 A CN201910025441 A CN 201910025441A CN 109811341 A CN109811341 A CN 109811341A
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- substrate
- noble metal
- erasable
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- 239000000758 substrate Substances 0.000 title claims abstract description 109
- 239000010970 precious metal Substances 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 238000004064 recycling Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 50
- 235000019441 ethanol Nutrition 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 235000013824 polyphenols Nutrition 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 11
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
- 238000007540 photo-reduction reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002198 insoluble material Substances 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 21
- 239000010931 gold Substances 0.000 description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 13
- 229910052737 gold Inorganic materials 0.000 description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 description 2
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940074360 caffeic acid Drugs 0.000 description 1
- 235000004883 caffeic acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Chemically Coating (AREA)
Abstract
本发明公开了一种可擦除贵金属的基底及其应用，该基底为两层结构，其下层为衬底(a)，上层的聚多酚类物质涂层(b)修饰在衬底上。该基底应用于擦除回收贵金属，包括以下步骤：1)在可擦除贵金属的基底表面制备贵金属涂层(c)；2)将具有贵金属涂层(c)的基底浸泡到回收溶液中，反应一段时间后，贵金属涂层(c)可自发擦除；3)在反应后的回收溶液中回收贵金属。上述基底可在常温常压、无添加酸碱的情况下实现对贵金属涂层的擦除，实现对贵金属的回收；该应用方法反应条件温和，可用于任意不溶于水的材料表面，扩展了该方法的通用性，很好的解决了涉及到界面上贵金属擦除的工作，尤其是对电子电路中的贵金属回收具有重大应用价值。
The invention discloses an erasable precious metal substrate and its application. The substrate has a two-layer structure, the lower layer is a substrate (a), and the upper layer is a polyphenolic substance coating (b) decorated on the substrate. The substrate is used for erasing and recovering precious metals, including the following steps: 1) preparing a precious metal coating (c) on the surface of a substrate capable of erasing precious metals; 2) immersing the substrate with the precious metal coating (c) into a recycling solution, and reacting After a period of time, the precious metal coating (c) can be erased spontaneously; 3) the precious metal is recovered in the recovery solution after the reaction. The above-mentioned substrate can realize the erasing of the precious metal coating and the recovery of the precious metal without adding acid and alkali at normal temperature and pressure; the application method has mild reaction conditions and can be used on the surface of any water-insoluble material. The versatility of the method solves the work involving the erasing of precious metals on the interface, and has great application value especially for the recovery of precious metals in electronic circuits.
Description
Technical field
The present invention relates to the substrates and its application of a kind of erasable noble metal, belong to technical field of material chemistry.
Background technique
So that life, the production of the mankind all be unable to do without electric power, the application of electric power brings for us for the emergence of the industrial revolution
Be difficult to the convenience quantified and efficiently.Wherein, the use of the either transmission of electric power or device terminal all be unable to do without metal, almost
Each inside of electronic component includes metal, this is because either considering from electric conductivity or economic cost, metal is
The highest electric power medium of cost performance at present.It is therein however while the mankind discard on a large scale every year, replace electronic device
Metal especially noble metal is similarly largely discarded, and discarded noble metal a part enters soil, ocean, river, for ecology
Environment brings fearful heavy metal pollution；Another part is brought huge because improperly recovery measure is wasted
Economic loss.
For the recycling of noble metal, currently used method mainly includes physical method and chemical method.Physical method is main
Using the method for broken sorting, this method complex steps, screening accuracy are low, rely on large scale equipment；Chemical method is mainly
Referring in the way of heat treatment method and strong acid treatment that high temperature incinerates etc., the former causes serious pollution to the environment, and energy consumption is big, after
Person's operation is extremely dangerous.
Just allowing for that annual large-scale noble metal is discarded and the noble metal way of recycling of subsequent difficulty, we are general
Solved these problems from the preparation source of noble metal products, propose a kind of erasable noble metal substrate and one answer
With.Under conditions of extremely mild the efficient erasing to noble metal in the substrate may be implemented, by noble metal with metal in the substrate
The form of cation is effectively recycled.This method is simple, mild, has a possibility that large-scale industrial application, for circuit
In precious metal material recycling with major application be worth.
Summary of the invention
Technical problem: the object of the present invention is to provide the substrate and its application of a kind of erasable noble metal, which can be
Room temperature, normal pressure, without strong acid and strong base, without large scale equipment in the case where realize effective recycling to noble metal, be it is a kind of it is economical, can
By the method for recovering precious metals of large-scale application；This method is also equipped with excellent space controlling, it can be achieved that special in substrate simultaneously
The noble metal erasing set is positioned, there are comparable potentiality for the research and development of advanced function material.
Technical solution: the present invention provides a kind of substrate of erasable noble metal, which is double-layer structure, and lower layer is
Substrate, the poly- polyphenols coating modification on upper layer is on substrate.
Wherein:
The substrate is any material not soluble in water with interface, including two dimension or three-dimensional material, including glass
Glass, silicon, quartz, plastics, metal, woven fabric or PE piece.
The poly- polyphenols is the polymer that Small Phenolic Molecule substance is formed after aoxidizing, wherein Small Phenolic Molecule
Substance includes Dopamine hydrochloride, tannic acid, caffeic acid or gallic acid and their derivative.
The substrate of the erasable noble metal the preparation method comprises the following steps: substrate material to be dipped into the solution of Small Phenolic Molecule substance
In, stand or 1~72h of stirring after take out, alternately cleaned, and drying at room temperature, obtained described erasable using ethyl alcohol and pure water
Except the substrate of noble metal.
The configuration method of polyphenols solution is that the polyphenol substances such as Dopamine hydrochloride are dissolved in 10mM Tris-HCl to delay
In fliud flushing (pH=8.5), the concentration of polyphenols is 0.01~10mg/mL.
The present invention also provides a kind of application of the substrate of erasable noble metal, which is applied to your gold erasing recycles
Belong to, comprising the following steps:
1) noble coatings are prepared in the substrate surface of erasable noble metal；
2) substrate with noble coatings is dipped into recycling solution, after reacting a period of time, noble coatings can
Spontaneous erasing；
3) noble metal is recycled in recycling solution after the reaction.
Wherein:
The noble metal is metal Ag or metal Au.
It is prepared in noble coatings described in step 1) in the substrate surface of erasable noble metal, to the system of noble coatings
With no restrictions for mode, including but not limited to magnetron sputtering, plasma beam vapor deposition, atomic layer deposition, chemical method reduction, photo-reduction
Method or galvanoplastic.
The substrate with noble coatings is dipped into recycling solution described in step 2), recycling solution is the water of ethyl alcohol
Solution, KI solution or hypo solution.
1~100vol% of concentration of alcohol in the aqueous solution of the ethyl alcohol；KI concentration in the KI solution is 10~
200mg/mL, solvent are the mixed solution of ethyl alcohol, water or ethyl alcohol and water；Thio sulphur in the solution of the sodium thiosulfate
The concentration of sour sodium is 1~100mmol/L, and solvent is the mixed solution of ethyl alcohol, water or ethyl alcohol and water.
After reaction a period of time described in step 2), when reaction a length of 10s~120min.
After reaction a period of time described in step 2), which carries out under ultraviolet light.
During the reaction process carries out under ultraviolet light, the wavelength of ultraviolet light is less than 365nm, and UV Light is strong
Degree is 0.1~1000mW/cm-2, light application time is 10s~120min.
The utility model has the advantages that compared with prior art, present invention has the advantage that
1, a kind of substrate of erasable noble metal proposed by the present invention has versatility, which does not have substrate material
Selectivity, any materials, such as glass, silicon, quartz, plastics, metal, woven fabric etc. can be used for that your erasable gold prepared
The substrate of category；
2, effective wiping to noble coatings can be achieved in a kind of application of the substrate of erasable noble metal proposed by the present invention
It removes, reaction condition is mild, and no soda acid addition, normal temperature and pressure can occur, and not depend on large scale equipment, and the reaction time is short, has big
The basis of sizable application；
3, a kind of substrate of erasable noble metal proposed by the present invention and its application can be achieved to the metal of specific region
Coating carries out specific aim erasing, has good space controllability.
Detailed description of the invention
Fig. 1 is the preparation method schematic diagram of erasable noble metal substrate provided by the invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the metal coating in erasable noble metal substrate provided by the invention；
Fig. 3 is the scanning electron microscope (SEM) photograph after the metal coating in erasable noble metal substrate prepared by the present invention is erased；
Wherein: substrate a, poly- polyphenols coating b and noble coatings c.
Specific embodiment
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, and the present embodiment is with technical solution of the present invention
Premised under implemented, it should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Embodiment 1
A kind of substrate of erasable noble metal, the substrate are double-layer structure, and lower layer is substrate slide a, the hydrochloric acid on upper layer
Dopamine coating b modify on substrate, preparation method is as follows: by slide a be dipped into Dopamine hydrochloride solution (2mg/mL,
10mM tris-HCl buffer, pH=8.5) in, after impregnating for 24 hours, material is taken out, is alternately cleaned using ethyl alcohol and pure water, and room
Temperature is dry, has obtained the substrate with Dopamine hydrochloride coating b, i.e., the substrate of erasable noble metal.
A kind of application of the substrate of erasable noble metal, the substrate are applied to erasing recycling noble metal, comprising the following steps:
1) substrate of erasable noble metal is dipped into the silver nitrate solution of 0.1mol/mL (solvent is water), then made
The ultraviolet light for being 365nm with wavelength this be soaked in the substrate in silver nitrate solution, exposure intensity 5mW/cm2, when irradiation
Between be that 30min takes out substrate after completing illumination from solution, alternately cleaned using ethyl alcohol and pure water, and drying at room temperature, just
It completes and prepares silver coating c, such as Fig. 2 on the surface of the material；
2) substrate with silver coating c is dipped into dehydrated alcohol, is placed in the ultraviolet light (5mW/cm of 254nm wavelength2)
Lower irradiation 1h, silver coating c spontaneous can be wiped；After completing illumination, substrate is taken out from solution, is replaced using ethyl alcohol and pure water clear
It washes, and drying at room temperature, has just obtained the substrate for erasing silver coating c, such as Fig. 3；
3) recycle noble metal in recycling solution after the reaction: silver is deposited in the recycling solution after reaction in the form of cation
In the reducing agents progress secondary reduction recycling such as addition ascorbic acid, sodium citrate, hydroxylamine hydrochloride.
Embodiment 2
A kind of substrate of erasable noble metal, the substrate are double-layer structure, and lower layer is substrate fabric a, the coffee on upper layer
On substrate, preparation method is as follows: fabric a is dipped into coffee acid solution (1mg/mL, 10mMtris- for acid coated b modification
HCl buffer, pH=8.5) in, after impregnating for 24 hours, fabric a is taken out, is alternately cleaned, and drying at room temperature, is obtained using ethyl alcohol and pure water
The substrate with the acid coated b of coffee, i.e., the substrate of erasable noble metal are arrived.
A kind of application of the substrate of erasable noble metal, the substrate are applied to erasing recycling noble metal, comprising the following steps:
1) physical vapour deposition (PVD) silver coating c is carried out to the substrate of erasable noble metal in a manner of vapor deposition, vapor deposition finishes it
Afterwards, material is taken out out of vacuum chamber, is alternately cleaned, and drying at room temperature, is just completed on the surface of the material using ethyl alcohol and pure water
Prepare silver coating c；
2) by the substrate with silver coating c be dipped into sodium thiosulfate solution (concentration of sodium thiosulfate 18mmol/L,
Solvent is the mixed solution of ethyl alcohol and water, wherein the concentration of ethyl alcohol later takes material to stay overnight in 50vol%) from solution
Out, it is alternately cleaned using ethyl alcohol and pure water, and drying at room temperature, has just obtained the substrate for erasing silver coating c；
3) recycle noble metal in recycling solution after the reaction: silver is deposited in the recycling solution after reaction in the form of cation
, by the above-mentioned resulting substrate for erasing silver coating c, or be prepared for poly- polyphenols coating substrate be soaked in should
Solution is recycled, the secondary deposition for carrying out ultraviolet lighting (wavelength 365nm) acquisition silver is recycled.
Embodiment 3
A kind of substrate of erasable noble metal, the substrate are double-layer structure, and lower layer is silicon substrate a, the tannin on upper layer
On substrate, preparation method is as follows: 1) silicon wafer a being dipped into tannic acid solution (0.2mg/mL, 10mM for acid coated b modification
Tris-HCl buffer, pH=8.5) in, after stirring for 24 hours, silicon wafer a is taken out, is alternately cleaned using ethyl alcohol and pure water, and room temperature is dry
It is dry, obtain the substrate with the acid coated b of tannin, i.e., the substrate of erasable noble metal.
A kind of application of the substrate of erasable noble metal, the substrate are applied to erasing recycling noble metal, comprising the following steps:
1) substrate of erasable noble metal is carried out to physical vapour deposition (PVD) gold plating c in a manner of being deposited, vapor deposition finishes it
Afterwards, substrate is taken out out of vacuum chamber, is alternately cleaned, and drying at room temperature, is just completed on the surface of the material using ethyl alcohol and pure water
Prepare gold plating c；
2) substrate with gold plating c is dipped into and is placed in KI solution (KI concentration is 100mg/mL, solvent be ethyl alcohol with
The mixed solution of water, wherein the concentration of ethyl alcohol is 50vol%), in the ultraviolet light (10mW/cm of 254nm wavelength2) under irradiate 1h,
After completing illumination, material is taken out from solution, is alternately cleaned using ethyl alcohol and pure water, and drying at room temperature, just wiped
The substrate of gold plating c；
3) recycle noble metal in recycling solution after the reaction: the recycling GOLD FROM PLATING SOLUTION after reaction is deposited in the form of cation
In the reducing agents progress secondary reduction recycling such as addition sodium borohydride, sodium citrate.
Embodiment 4
A kind of substrate of erasable noble metal, the substrate are double-layer structure, and lower layer is substrate PE piece a, and upper layer is not eaten
On substrate, preparation method is as follows: 1) PE piece a being dipped into gallic acid solution (2mg/mL, 10mM for the acid coated b modification of son
Tris-HCl buffer, pH=8.5) in, after impregnating for 24 hours, PE piece is taken out, is alternately cleaned using ethyl alcohol and pure water, and room temperature is dry
It is dry, obtain the substrate with gallic acid coating b, i.e., the substrate of erasable noble metal.
A kind of application of the substrate of erasable noble metal, the substrate are applied to erasing recycling noble metal, comprising the following steps:
1) substrate of erasable noble metal is dipped into the chlorauric acid solution of 10mmol/mL to (solvent is water, uses hydrogen-oxygen
Change sodium and adjust PH=7), then using the ultraviolet light that wavelength is 365nm, this is soaked in the substrate in chlorauric acid solution, irradiates
Intensity is 5mW/cm2, irradiation time 10min taken out from solution after completing illumination, alternately cleaned using ethyl alcohol and pure water,
And drying at room temperature, just complete the preparation of material surface gold plating c；
2) substrate with gold plating c is placed in KI solution to (KI concentration is 50mg/mL, and solvent is the mixed of ethyl alcohol and water
Close solution, wherein the concentration of ethyl alcohol is 50vol%) overnight, it takes out from solution, is alternately cleaned using ethyl alcohol and pure water later,
And drying at room temperature, just obtain the substrate for erasing gold plating c.
3) recycle noble metal in recycling solution after the reaction: the recycling GOLD FROM PLATING SOLUTION after reaction is deposited in the form of cation
, by the above-mentioned resulting substrate for erasing gold plating c, or be prepared for poly- polyphenols coating substrate be soaked in should
Solution is recycled, the secondary deposition for carrying out ultraviolet lighting (wavelength 365nm) acquisition gold is recycled.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
Several improvements and modifications can also be made, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (10)
1. a kind of substrate of erasable noble metal, it is characterised in that: the substrate is double-layer structure, and lower layer is substrate (a), upper layer
Poly- polyphenols coating (b) modification on substrate.
2. a kind of substrate of erasable noble metal as described in claim 1, it is characterised in that: the substrate (a) is any
Material not soluble in water with interface, including two dimension or three-dimensional material, material be glass, silicon, quartz, plastics, metal,
Woven fabric or PE piece.
3. a kind of substrate of erasable noble metal as described in claim 1, it is characterised in that: the poly- polyphenols is
The polymer that Small Phenolic Molecule substance is formed after aoxidizing, wherein Small Phenolic Molecule substance includes Dopamine hydrochloride, tannic acid, coffee
Coffee acid or gallic acid and their derivative.
4. a kind of application of the substrate of erasable noble metal as described in claim 1, it is characterised in that: the substrate is applied to wipe
Except recycling noble metal, comprising the following steps:
1) noble coatings (c) are prepared in the upper surface of the substrate of erasable noble metal；
2) substrate with noble coatings (c) is dipped into recycling solution, after reacting a period of time, noble coatings (c)
It spontaneous can wipe；
3) noble metal is recycled in recycling solution after the reaction.
5. a kind of application of the substrate of erasable noble metal as claimed in claim 4, it is characterised in that: the noble metal is
Metal Ag or metal Au.
6. a kind of application of the substrate of erasable noble metal as claimed in claim 4, it is characterised in that: described in step 1)
The upper surface of the substrate of erasable noble metal prepares in noble coatings (c), and preparation method includes magnetron sputtering, plasma beam steaming
Plating, atomic layer deposition, chemical method reduction, photo-reduction method or galvanoplastic.
7. a kind of application of the substrate of erasable noble metal as claimed in claim 4, it is characterised in that: described in step 2) general
Substrate with noble coatings (c) is dipped into recycling solution, and recycling solution is aqueous solution, the KI solution or thio of ethyl alcohol
Metabisulfite solution.
8. a kind of application of the substrate of erasable noble metal as claimed in claim 7, it is characterised in that: the water of the ethyl alcohol
1~100vol% of concentration of alcohol in solution；KI concentration in the KI solution is 10~200mg/mL, solvent be ethyl alcohol,
The mixed solution of water or ethyl alcohol and water；In the solution of the sodium thiosulfate concentration of sodium thiosulfate be 1~
100mmol/L, solvent are the mixed solution of ethyl alcohol, water or ethyl alcohol and water.
9. a kind of application of the substrate of erasable noble metal as claimed in claim 4, it is characterised in that: anti-described in step 2)
After answering a period of time, when reaction a length of 10s~120min.
10. a kind of application of the substrate of erasable noble metal as claimed in claim 4, it is characterised in that: described in step 2)
After reacting a period of time, which carries out under ultraviolet light, and wherein the wavelength of ultraviolet light is less than 365nm, ultraviolet light
Intensity of illumination is 0.1~1000mW/cm-2, light application time is 10s~120min.
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