TWI856576B - Metal schiff base electrode material and the preparing method thereof - Google Patents
Metal schiff base electrode material and the preparing method thereof Download PDFInfo
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 136
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 136
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 134
- 239000002184 metal Substances 0.000 title claims abstract description 134
- 239000007772 electrode material Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims description 17
- 239000000758 substrate Substances 0.000 claims abstract description 83
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- -1 transition metal salts Chemical class 0.000 claims description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 39
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 229920003023 plastic Polymers 0.000 claims description 26
- 239000004033 plastic Substances 0.000 claims description 26
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 26
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 25
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000006262 metallic foam Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 26
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- 238000001962 electrophoresis Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000005516 engineering process Methods 0.000 description 21
- 238000005868 electrolysis reaction Methods 0.000 description 18
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
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- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 4
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XYNZKHQSHVOGHB-UHFFFAOYSA-N copper(3+) Chemical compound [Cu+3] XYNZKHQSHVOGHB-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
本發明涉及一種金屬希夫鹼複合物合成技術，特別是有關於一種以電泳沉積技術將金屬希夫鹼沉積在泡沫金屬上以形成金屬希夫鹼電極材料。 The present invention relates to a metal Schiff base complex synthesis technology, and in particular to a method of depositing metal Schiff base on foam metal using electrophoretic deposition technology to form a metal Schiff base electrode material.
希夫鹼(Schiff base)也稱為亞胺或是亞胺取代物(例如腙)。希夫鹼可以在路易士酸(Lewis acid)的催化下以含羰基的化合物與含氨基的有機物反應脫水得到。希夫鹼雜化軌道中的N原子上具有孤對電子，可以引入各類功能基團使其衍生物化，具有一定的藥理學和生理學活性。在合成、催化、生化以及生物學等都具有重要應用價值。 Schiff base is also called imine or imine substituted (such as hydrazone). Schiff base can be obtained by dehydration of carbonyl-containing compounds and amino-containing organic substances under the catalysis of Lewis acid. The N atom in the hybridization orbit of Schiff base has a lone pair of electrons, and various functional groups can be introduced to make it derivatized, with certain pharmacological and physiological activities. It has important application value in synthesis, catalysis, biochemistry and biology.
傳統希夫鹼的合成需要在加熱攪拌回流下才能形成產物，反應的副產物是水。在反應的過程中需要脫水，較高的溫度同時還容易引起一些活潑芳香環氧化，導致副產物增多，產率降低，使得整個反應操作不便，耗能耗時較多，難以分離提純等缺點。在現有技術中，也有揭露直接使用苄胺合成希夫鹼的合成方法，但是這些反應都要使用到金屬催化劑、氧化劑，且反應條件劇烈，需要高溫才能完成。導致產品過度氧化生成多種副產物，後處理過程繁瑣。這些方法在實際生產過程中對設備要求高，也不符合現在節能減碳、友善環境的趨勢。 The traditional synthesis of Schiff bases requires heating, stirring and reflux to form products, and the byproduct of the reaction is water. Dehydration is required during the reaction process, and the higher temperature is also prone to cause some active aromatic ring oxidation, resulting in an increase in byproducts and a decrease in yield, making the entire reaction operation inconvenient, energy-consuming and time-consuming, and difficult to separate and purify. In the prior art, there are also methods for synthesizing Schiff bases directly using benzylamine, but these reactions all require metal catalysts and oxidants, and the reaction conditions are severe and require high temperatures to complete. This results in excessive oxidation of the product to generate a variety of byproducts, and the post-treatment process is cumbersome. These methods have high requirements for equipment in the actual production process, and are not in line with the current trend of energy saving, carbon reduction, and environmental friendliness.
根據現有技術的缺點，本發明的主要目的在於將含有聚對苯二甲酸乙二酯(PET，poly(ethyl benzene-1,4-dicarboxylate))的塑膠與乙二醇(EG，ethylene glycol)製備形成對苯二甲酸，並以此對苯二甲酸上的甲酸官能基的羰基與胺基化合物的胺基進行縮合反應製備形成希夫鹼，此希夫鹼可作為形成複合材料的成分之一，據此，可以提高含有聚對苯二甲酸乙二酯的塑膠製品的再利用性以及降低處理含有聚對苯二甲酸乙二酯的寶特瓶及面罩等相關塑膠製品的處理成本。 According to the shortcomings of the prior art, the main purpose of the present invention is to prepare terephthalic acid from plastic containing polyethylene terephthalate (PET, poly (ethyl benzene-1,4-dicarboxylate)) and ethylene glycol (EG, ethylene glycol), and to condense the carbonyl group of the formic acid functional group on the terephthalic acid with the amine group of the amino compound to prepare Schiff base. The Schiff base can be used as one of the components of the composite material. Thus, the recyclability of plastic products containing polyethylene terephthalate can be improved and the processing cost of related plastic products such as PET bottles and masks containing polyethylene terephthalate can be reduced.
本發明的另一目的在於利用胺基化合物與含有羰基或甲酸官能基的化合物例如苯甲酸、聚對苯二甲酸乙二酯、均苯三甲酸、1，2，3，4-苯四甲酸等形成希夫鹼(Schiff base)，並與過渡金屬鹽類混合利用電泳技術在金屬基材上沉積形成金屬希夫鹼電極材料。 Another purpose of the present invention is to use amino compounds and compounds containing carbonyl or formic acid functional groups such as benzoic acid, polyethylene terephthalate, trimesic acid, 1,2,3,4-benzenetetracarboxylic acid, etc. to form Schiff bases, and mix them with transition metal salts to form metal Schiff base electrode materials by electrophoresis technology.
根據上述目的，本發明提供一種金屬希夫鹼電極材料，由金屬基材及覆蓋於金屬基材的表面上的金屬希夫鹼構成。 According to the above purpose, the present invention provides a metal Schiff base electrode material, which is composed of a metal substrate and a metal Schiff base covering the surface of the metal substrate.
根據上述目的，本發明還提供一種金屬希夫鹼電極材料的製備方法，其步驟包括；由提供含有羰基或甲酸官能基的化合物；提供希夫鹼，希夫鹼由含有羰基或甲酸官能基的化合物與胺基化合物反應形成；以及執行電泳沉積步驟以形成金屬希夫鹼電極材料，其步驟包括：提供陽極基板及陰極基板；將希夫鹼與過渡金屬鹽類溶液混合以形成混合溶液；將不銹鋼板及金屬基材浸泡於混合溶液中；以及分別對陰極基板及陽極基板同時施加電壓，使得希夫鹼與過渡金屬鹽類溶液沉積在陰極基板的表面上以形成金屬希夫鹼電極材料。 According to the above purpose, the present invention also provides a method for preparing a metal Schiff base electrode material, the steps of which include: providing a compound containing a carbonyl or formic acid functional group; providing a Schiff base, which is formed by reacting a compound containing a carbonyl or formic acid functional group with an amino compound; and performing an electrophoretic deposition step to form a metal Schiff base electrode material, the steps of which include: providing an anode substrate and a cathode substrate; mixing the Schiff base with a transition metal salt solution to form a mixed solution; immersing a stainless steel plate and a metal substrate in the mixed solution; and applying voltage to the cathode substrate and the anode substrate at the same time, respectively, so that the Schiff base and the transition metal salt solution are deposited on the surface of the cathode substrate to form the metal Schiff base electrode material.
1:金屬希夫鹼複合物材料 1: Metal Schiff base complex material
10:金屬基材 10: Metal substrate
20:金屬希夫鹼 20:Metallic Schiff bases
30:電泳槽 30: Electrophoresis tank
32:電源 32: Power supply
40:陽極基板 40: Anode substrate
42:陰極基板 42: Cathode substrate
50:電泳液 50: Electrophoresis fluid
S10-S20:金屬希夫鹼電極材料的製備步驟流程 S10-S20: Preparation process of metal Schiff base electrode materials
S30-S38:金屬希夫鹼電極材料的製備步驟流程 S30-S38: Preparation process of metal Schiff base electrode materials
圖1是根據本發明所揭露的技術，表示金屬希夫鹼電極材料的示意圖。 FIG1 is a schematic diagram showing a metal Schiff base electrode material according to the technology disclosed in the present invention.
圖2是根據本發明所揭露的技術，表示於實施例一中，金屬希夫鹼電極材料的製備流程步驟示意圖。 FIG2 is a schematic diagram of the steps of preparing the metal Schiff base electrode material in Embodiment 1 according to the technology disclosed in the present invention.
圖3是根據本發明所揭露的技術，表示電泳槽的裝置示意圖。 Figure 3 is a schematic diagram of an electrophoresis tank device according to the technology disclosed in the present invention.
圖4是根據本發明所揭露的技術，表示由具有不同胺基化合物的希夫鹼進行電泳沉積之後形成金屬希夫鹼電極材料的SEM圖。 FIG4 is a SEM image of a metal Schiff base electrode material formed by electrophoretic deposition of Schiff bases with different amino compounds according to the technology disclosed in the present invention.
圖5是根據本發明所揭露的技術，表示各種金屬希夫鹼電極材料在鹼性電解水電解時，進行電化學析氧反應(OER)的電位(potential)與電流密度(Current density)的關係圖及塔弗曲線。 FIG. 5 is a diagram and Tafel curve showing the relationship between potential and current density of various metal Schiff base electrode materials during electrochemical oxygen evolution reaction (OER) in alkaline electrolysis of water according to the technology disclosed in the present invention.
圖6是根據本發明所揭露的技術，表示各種金屬希夫鹼電極材料在鹼性電解水電解時，進行析氫反應(HER)的電位(potential)與電流密度(Current density)的關係圖及塔弗曲線。 FIG6 is a diagram and Tafel curve showing the relationship between the potential and current density of various metal Schiff base electrode materials during the electrolysis of alkaline water during the hydrogen evolution reaction (HER) according to the technology disclosed in the present invention.
圖7是根據本發明所揭露的技術，表示金屬希夫鹼電極材料當作鹼性電解水電解時的陰極及陽極電極材料時的析氫與析氧量。 Figure 7 shows the amount of hydrogen and oxygen released when the metal Schiff base electrode material is used as the cathode and anode electrode materials for electrolysis of alkaline electrolyzed water according to the technology disclosed in the present invention.
圖8是根據本發明所揭露的技術，表示以金屬希夫鹼電極材料構成鹼性電解水單電解池組的示意圖。 FIG8 is a schematic diagram showing a single electrolytic cell group for alkaline water electrolysis formed by metal Schiff base electrode materials according to the technology disclosed in the present invention.
圖9是根據本發明所揭露的技術，表示將圖8中的單電解池組施加電流之後獲得平均能量效率的時間與能量密度的關係圖。 FIG. 9 is a graph showing the relationship between the time and energy density for obtaining average energy efficiency after applying current to the single electrolytic cell group in FIG. 8 according to the technology disclosed in the present invention.
圖10是根據本發明所揭露的技術，表示以含有羰基或甲酸官能基的化合物製備金屬希夫鹼電極材料的製備流程步驟示意圖。 Figure 10 is a schematic diagram showing the steps of preparing a metal Schiff base electrode material using a compound containing a carbonyl or formic acid functional group according to the technology disclosed in the present invention.
圖11是根據本發明所揭露的技術，表示由含有羰基或甲酸官能基的化合物與胺基化合物反應形成具有不同胺基化合物的希夫鹼進行電泳沉積之後形成金屬希夫鹼電極材料的SEM圖。 FIG. 11 is a SEM image of a metal Schiff base electrode material formed by electrophoretic deposition of Schiff bases with different amino compounds formed by the reaction of a compound containing a carbonyl or formic acid functional group with an amino compound according to the technology disclosed in the present invention.
圖12是根據本發明所揭露的技術，表示以含有羰基或甲酸官能基的化合物製備的各種金屬希夫鹼電極材料在鹼性電解水電解時，進行電化學析氧反應(OER)的電位(potential)與電流密度(Current density)的關係圖及塔弗曲線。 FIG. 12 is a graph and Tafel curve showing the relationship between potential and current density of various metal Schiff base electrode materials prepared from compounds containing carbonyl or formic acid functional groups during electrochemical oxygen evolution reaction (OER) in alkaline electrolyzed water according to the technology disclosed in the present invention.
圖13是根據本發明所揭露的技術，表示以含有羰基或甲酸官能基的化合物製備的各種金屬希夫鹼電極材料在鹼性電解水電解時，進行析氫反應(HER)的電位(potential)與電流密度(Current density)的關係圖及塔弗曲線。 FIG. 13 is a diagram and Tafel curve showing the relationship between the potential and current density of various metal Schiff base electrode materials prepared from compounds containing carbonyl or formic acid functional groups during the electrolysis of alkaline electrolyzed water in the hydrogen evolution reaction (HER) according to the technology disclosed in the present invention.
首先請參考圖1。圖1是根據本發明所揭露的技術，表示金屬希夫鹼電極材料的截面示意圖。在圖1中，金屬希夫鹼電極材料1由金屬基材10及金屬希夫鹼配合物20所構成，其中金屬基材10為泡沫金屬(metal-foam)，金屬希夫鹼配合物20是由希夫鹼(Schiff base)及過渡金屬鹽類所構成，其相關的製備流程在後續說明。 First, please refer to Figure 1. Figure 1 is a cross-sectional schematic diagram of a metal Schiff base electrode material according to the technology disclosed in the present invention. In Figure 1, the metal Schiff base electrode material 1 is composed of a metal substrate 10 and a metal Schiff base complex 20, wherein the metal substrate 10 is a metal-foam, and the metal Schiff base complex 20 is composed of a Schiff base and a transition metal salt. The relevant preparation process will be described later.
請參考圖2。圖2是表示金屬希夫鹼電極材料的製備流程步驟示意圖。在圖2中，步驟S10：將含有聚對苯二甲酸乙二酯(PET，poly(ethyl benzene-1,4-dicarboxylate))的塑膠進行粉碎以形成塑膠顆粒(後續稱為PET塑膠顆粒)。在此步驟中，PET塑膠顆粒可以是寶特瓶或是塑膠面罩，這些PET塑膠顆粒都是容易取得，且回收洗淨之後，進行破碎或是粉碎至顆粒狀。步驟S12：將PET塑膠顆粒與乙二醇(EG，ethylene glycol)混合後在反應釜中進行反應，反應結束後得到 對苯二甲酸，冷卻後備用。步驟S14：將對苯二甲酸與胺基化合物，並且在氫氧化鉀(KOH)溶液的環境下進行縮合反應以得到希夫鹼(Schiff base)。步驟S16：提供電泳槽、陽極基板及陰極基板。在此步驟中，陽極基板為不銹鋼板(stainless plate)及陰極基板為金屬基材。步驟S18：將希夫鹼與過渡金屬鹽類溶液混合形成具有金屬希夫鹼的電泳液。步驟S20：將電泳液倒入電泳槽中，並分別對陽極基板及陰極基板施加電壓，使得電泳液中的金屬希夫鹼沉積在陰極基板的表面上以形成金屬希夫鹼電極材料。 Please refer to Figure 2. Figure 2 is a schematic diagram showing the steps of the preparation process of the metal Schiff base electrode material. In Figure 2, step S10: crushing the plastic containing polyethylene terephthalate (PET, poly (ethyl benzene-1,4-dicarboxylate)) to form plastic particles (hereinafter referred to as PET plastic particles). In this step, the PET plastic particles can be plastic bottles or plastic masks. These PET plastic particles are easy to obtain, and after recycling and washing, they are crushed or crushed into particles. Step S12: Mix the PET plastic particles with ethylene glycol (EG) and react in a reactor. After the reaction is completed, terephthalic acid is obtained, which is cooled and set aside. Step S14: terephthalic acid and an amino compound are subjected to a condensation reaction in a potassium hydroxide (KOH) solution environment to obtain a Schiff base. Step S16: Provide an electrophoresis tank, an anode substrate, and a cathode substrate. In this step, the anode substrate is a stainless steel plate and the cathode substrate is a metal substrate. Step S18: Mix the Schiff base with a transition metal salt solution to form an electrophoresis solution having a metal Schiff base. Step S20: Pour the electrophoresis liquid into the electrophoresis tank, and apply voltage to the anode substrate and the cathode substrate respectively, so that the metal Schiff base in the electrophoresis liquid is deposited on the surface of the cathode substrate to form a metal Schiff base electrode material.
以下是根據上述圖2的金屬希夫鹼電極材料的製備流程步驟，對金屬希夫鹼電極材料的製備流程詳細說明。 The following is a detailed description of the preparation process of the metal Schiff base electrode material based on the preparation process steps of the metal Schiff base electrode material in Figure 2 above.
合成對苯二甲酸： Synthetic terephthalic acid:
首先，利用含有聚對苯二甲酸乙二酯成分的廢棄塑膠製品例如寶特瓶、塑膠面罩合成對苯二甲酸。將寶特瓶、塑膠面罩這些塑膠製品回收後洗淨，並且進行粉碎，以得到塑膠顆粒(以下稱PET塑膠顆粒)。接著，取3g-5g的PET塑膠顆粒與體積為3ml-5ml的乙二醇及體積為50ml-70ml的去離子水均勻混合後，將混合溶液置於容積為250ml的反應釜。 First, terephthalic acid is synthesized from waste plastic products containing polyethylene terephthalate, such as PET bottles and plastic masks. Plastic products such as PET bottles and plastic masks are recovered, washed, and crushed to obtain plastic particles (hereinafter referred to as PET plastic particles). Then, 3g-5g of PET plastic particles are mixed evenly with 3ml-5ml of ethylene glycol and 50ml-70ml of deionized water, and the mixed solution is placed in a reactor with a volume of 250ml.
對反應釜進行升溫加熱至180℃-220℃，並且在此溫度範圍條件下持溫至少16-20小時。反應結束之後，待反應釜降溫後取出產物，並且對此產物進行過濾及利用去離子水清洗，直到過濾水呈現澄清為止。再將清洗後的產物於真空條件下、溫度為50℃-70℃進行真空乾燥，其真空乾燥時間至少24小時。待真空乾燥結束之後，降溫，可以得到對苯二甲酸。在本發明中，直接利用含有聚對苯二甲酸乙二酯成分的回收塑膠製品例如寶特瓶、塑膠面罩來合成對苯二甲酸可以增加這些回收塑膠製品再利用率。 The reactor is heated to 180℃-220℃ and maintained at this temperature for at least 16-20 hours. After the reaction is completed, the product is taken out after the reactor cools down, and the product is filtered and washed with deionized water until the filtered water is clear. The washed product is then vacuum dried at a temperature of 50℃-70℃ under vacuum conditions for at least 24 hours. After the vacuum drying is completed, the temperature is lowered to obtain terephthalic acid. In the present invention, directly using recycled plastic products containing polyethylene terephthalate components such as plastic bottles and plastic masks to synthesize terephthalic acid can increase the reuse rate of these recycled plastic products.
製備希夫鹼： Preparation of Schiff Base:
以莫耳比(molar ratio)1：1的比例，將前述製備得到的對苯二甲酸與胺基化合物充分混合，再加入100ml-150ml，濃度為0.1M的氫氧化鉀(KOH)進行縮合反應，於反應的同時進行攪拌至少2小時，待反應結束，在溫度範圍為50℃-70℃進行乾燥，冷卻後得到希夫鹼。在本發明中，胺基化合物可以是脂肪胺、脂環胺、芳香胺或是聚醯胺。具體來說，本發明是使用乙二胺(EDA，ethylenediamine)、二乙烯三胺(DETA，diethylenetriamine)、三乙烯四胺(TETA，triethylenetetramine)、四乙烯五胺(TEPA，tetraethylenepentamine)、五乙烯六胺(PTHA，pentaethylenehexamine)或是雙氰胺(DICY，Dicyandiamide)來製備希夫鹼。 The terephthalic acid prepared above and the amino compound are mixed thoroughly at a molar ratio of 1:1, and then 100ml-150ml of 0.1M potassium hydroxide (KOH) is added to carry out condensation reaction, and the mixture is stirred for at least 2 hours during the reaction. After the reaction is completed, the mixture is dried at a temperature range of 50°C-70°C, and cooled to obtain Schiff base. In the present invention, the amino compound can be a fatty amine, a cycloaliphatic amine, an aromatic amine or a polyamide. Specifically, the present invention uses ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PTHA) or dicyandiamide (DICY) to prepare schiff base.
電泳沉積形成金屬希夫鹼電極材料： Electrophoretic deposition to form metal Schiff base electrode materials:
如圖3所示，提供電泳裝置其包括電泳槽30、陽極基板40及陰極基板42，其中，陽極基板40為不銹鋼板(ASTM 316L)，陰極基板42為金屬基材，以相互平行方式且間隔一段距離設置在電泳槽30中。在本發明的較佳實施例中，金屬基材42為泡沫金屬(metal-foam)，例如可以是泡沫鎳、泡沫鈦、泡沫鐵、泡沫銅、泡沫鐵鎳、泡沫鋁及泡沫銀。於本發明中則是採用泡沫鎳作為金屬基材42。要說明的是，泡沫金屬42在使用之前，預先浸泡在清洗溶液(未在圖中表示)一段時間，以除去在泡沫金屬42表面上的氧化物(oxide)，清洗後乾燥備用。上述的清洗溶液是由酸液、乙醇及去離子水混合而成，酸液較佳的是鹽酸，特別是濃度為3M的鹽酸。此外，於另一實施例中，將泡沫金屬42浸泡在清洗溶液時，可同時進行超音波震盪以加速泡沫金屬42表面氧化物的去除。 As shown in FIG3 , an electrophoresis device is provided, which includes an electrophoresis tank 30, an anode substrate 40 and a cathode substrate 42, wherein the anode substrate 40 is a stainless steel plate (ASTM 316L), and the cathode substrate 42 is a metal substrate, which are arranged in parallel with each other and at a distance in the electrophoresis tank 30. In a preferred embodiment of the present invention, the metal substrate 42 is a foam metal (metal-foam), for example, it can be foam nickel, foam titanium, foam iron, foam copper, foam iron nickel, foam aluminum and foam silver. In the present invention, foam nickel is used as the metal substrate 42. It should be noted that before use, the foam metal 42 is pre-soaked in a cleaning solution (not shown in the figure) for a period of time to remove the oxide on the surface of the foam metal 42, and then dried for use after cleaning. The cleaning solution is a mixture of acid, ethanol and deionized water. The acid is preferably hydrochloric acid, especially hydrochloric acid with a concentration of 3M. In addition, in another embodiment, when the foam metal 42 is immersed in the cleaning solution, ultrasonic vibration can be performed at the same time to accelerate the removal of oxides on the surface of the foam metal 42.
製備電泳液： Prepare electrophoresis fluid:
將希夫鹼與氯化鐵溶液(FeCl3)(Iron(III)，chloride anhydrous)、乙酸銅溶液(Cu(C2H3O2)2．H2O)(Copper(III)，acetate monohydrate)及鉬酸銨溶液((NH4)6Mo7O24．H2O)(Ammonium molybdate tetrahydrate)以莫耳比1：1：1：1的比例混合，再加入體積為5000μl-5500μl．濃度為0.02M的硝酸鎳(Ni(NO3)2．6H2O)的充電試劑(charging agent)均勻混合後形成電泳液50，並將此電泳液50倒進電泳槽30裡，且陽極基板40和陰極基板42可以浸泡在電泳液50中。 Schiff's base is mixed with ferric chloride solution (FeCl 3 ) (Iron(III), chloride anhydrous), copper acetate solution (Cu(C 2 H 3 O 2 ) 2 ．H 2 O) (Copper(III), acetate monohydrate) and ammonium molybdate solution ((NH 4 ) 6 Mo 7 O 24 ．H 2 O) (Ammonium molybdate tetrahydrate) in a molar ratio of 1:1:1:1, and then added in a volume of 5000μl-5500μl. A charging agent of 0.02M nickel nitrate (Ni(NO 3 ) 2 .6H 2 O) is uniformly mixed to form an electrophoretic solution 50 , and the electrophoretic solution 50 is poured into the electrophoretic tank 30 , and the anode substrate 40 and the cathode substrate 42 can be immersed in the electrophoretic solution 50 .
同樣的，將陽極基板40與陰極基板42分別與電源32連接，電源32的陽極電壓與陽極基板40連接及電源32的陰極電壓與陰極基板42連接．電源32提供的電壓範圍為8-15伏特，為了避免電壓供應不均勻，進而影響電泳沉積速率的均勻性，電源32提供陽極電壓與陰極電壓的電壓值是相同的。當開啟電源32之後，即開始進行電泳沉積，電泳沉積的執行時間範圍為20-40分鐘。在電泳沉積的過程中，電泳液50中的過渡金屬離子，鐵(Fe3+)、銅(Cu3+)及鉬(Mo3+)與希夫鹼會形成金屬希夫鹼(metal Schiff base)然後沉積在作為陰極基板42的金屬基材的表面上，直到電泳沉積結束之後，將陰極基板42從電泳槽30取出，並且以去離子水清洗並且烘乾，此陰極基板42的表面即被金屬希夫鹼20(如圖1所示)覆蓋．以得到如前述圖1中的金屬希夫鹼電極材料1。根據上述，表1則是將胺基化合物與對苯二甲酸縮合反應形成的希夫鹼的化學結構及與希夫鹼與過渡金屬鹽類(M)形成的金屬希夫鹼的化學結構列出：
圖4是表示利用具有不同胺基化合物的希夫鹼進行電泳沉積之後的金屬希夫鹼電極材料的SEM圖。在圖4中的(a)-(b)的胺基化合物為乙二胺、(c)-(d)的胺基化合物為二乙烯三胺、(e)-(f)的胺基化合物為三乙烯四胺、(g)-(h)的胺 基化合物為四乙烯五胺、(i)-(j)的胺基化合物為五乙烯六胺以及(k)-(l)的胺基化合物為雙氰胺。由圖4中(a)-(l)可以得到不同胺基化合物的希夫鹼進行電泳沉積之後所形成的金屬希夫鹼電極材料的表面形貌不同。 FIG4 is a SEM image of a metal Schiff base electrode material after electrophoretic deposition using Schiff bases with different amine compounds. In FIG4, the amine compounds (a)-(b) are ethylenediamine, (c)-(d) are diethylenetriamine, (e)-(f) are triethylenetetramine, (g)-(h) are tetraethylenepentamine, (i)-(j) are pentaethylenehexamine, and (k)-(l) are dicyandiamide. From FIG4 (a)-(l), it can be seen that the surface morphology of the metal Schiff base electrode material formed after electrophoretic deposition of Schiff bases with different amine compounds is different.
圖5是根據本發明所揭露的技術，表示各種金屬希夫鹼電極材料在鹼性電解水電解時，進行電化學析氧反應(OER)的電位(potential)與電流密度(Current density)的關係圖及塔弗曲線。圖5(a)是表示各種金屬希夫鹼電極材料進行電化學析氧反應(OER)的線性掃描伏安曲線，電位(potential)與電流密度(Current density)的關係圖。從圖5(a)中可以獲得利用不同胺基化合物製成的金屬希夫鹼電極材料，其在10mA/cm2電流密度獲得的過電壓，皆低於商用貴金屬氧化物RuO2製成的電極，顯見其析氧反應優於RuO2之電極。在鹼性電解水電解過程中，獲得最佳的析氧反應特性，以四乙烯五胺(TEPA)製成的金屬希夫鹼電極材料為主。同時可以獲得最小的塔弗斜率，如圖5(b)所示。 FIG5 is a graph and Tafel plot showing the relationship between potential and current density of various metal Schiff base electrode materials during electrochemical oxygen evolution reaction (OER) in alkaline electrolysis of water according to the technology disclosed in the present invention. FIG5(a) is a linear sweep voltammetric curve showing the relationship between potential and current density of various metal Schiff base electrode materials during electrochemical oxygen evolution reaction (OER). From Figure 5(a), we can see that the overvoltage obtained by the metal Schiff base electrode materials made of different amine compounds at a current density of 10mA/ cm2 is lower than that of the electrode made of commercial precious metal oxide RuO2 , which shows that its oxygen evolution reaction is better than that of RuO2 . In the alkaline electrolysis process, the best oxygen evolution reaction characteristics are obtained, mainly by the metal Schiff base electrode material made of tetraethylenepentamine (TEPA). At the same time, the smallest Tafel slope can be obtained, as shown in Figure 5(b).
圖6是表示各種金屬希夫鹼電極材料進行析氫反應(HER)的線性掃描伏安曲線，電位(potential)與電流密度(Current density)的關係圖。從圖6(a)中可以獲得利用不同胺基化合物製成的金屬希夫鹼電極材料，其在10mA/cm2電流密度獲得的過電壓，雖皆大於商用貴金屬氧化物Pt/C製成的電極，然而當電流密度大於133mA/cm2以上，時以四乙烯五胺(TEPA)製成的金屬希夫鹼電極材料其電壓小於Pt/C電極，在此條件下，其析氫反應優於Pt/C之電極。同時可以獲得最小的塔弗斜率，如圖6(b)所示。在鹼性電解水電解過程中，獲得最佳的析氫反應特性，以四乙烯五胺(TEPA)製成的金屬希夫鹼電極材料為主。 FIG6 is a linear sweep voltammogram showing the relationship between potential and current density for various metal Schiff base electrode materials in the hydrogen evolution reaction (HER). FIG6(a) shows that the overvoltages obtained by the metal Schiff base electrode materials made of different amine compounds at a current density of 10 mA/ cm2 are greater than those of the electrodes made of commercial precious metal oxide Pt/C. However, when the current density is greater than 133 mA/ cm2 , the voltage of the metal Schiff base electrode material made of tetraethylenepentamine (TEPA) is less than that of the Pt/C electrode. Under this condition, its hydrogen evolution reaction is better than that of the Pt/C electrode. At the same time, the minimum Tafel slope can be obtained, as shown in Figure 6(b). In the alkaline electrolysis process, the best hydrogen evolution reaction characteristics are obtained, mainly using the metal Schiff base electrode material made of tetraethylenepentamine (TEPA).
圖7是將鹼性電解水中的陽極及陰極電極使用四乙烯五胺(TEPA)製成的金屬希夫鹼材料，可以獲得析氫及析氧量皆優於商用使用的陰極Pt/C及陽極RuO2。 Figure 7 shows that the metal Schiff base material made of tetraethylenepentamine (TEPA) is used as the anode and cathode electrodes in alkaline electrolysis of water, and the hydrogen and oxygen evolution rates are better than those of commercial cathode Pt/C and anode RuO 2 .
圖8是表示以金屬希夫鹼電極材料構成鹼性電解水單電解池組的示意圖。於圖8(a)是鹼性電解水單電解池組中的陽極鈦金屬板，陰極也是由相同的鈦金屬板所組成，將所製備的長5公分及寬5公分的25cm2面積的四乙烯五胺(TEPA)製成的金屬希夫鹼電極材料，如圖8(b)所示，放在陽極及陰極鈦金屬板上，附上矽膠墊片如圖8(c)，並使用Fumasep FAA-3-50的隔離膜，組成鹼性電解水單電解池組如圖8(d)。使用濃度1M的KOH電解液，利用蠕動泵使電解液在陽極及陰極個別循環。在室溫下，施加電流密度200mA/cm2，獲得單電解池組電解水的操作電壓為2.5V，能量效率(energy efficiency)為70.4%，產氫量約為2484cm3/h及產氧量約為1242cm3/h，單位耗能量(specific energy consumption)為56kWh/kg。 FIG8 is a schematic diagram showing a single electrolytic cell set for alkaline water electrolysis using a metal Schiff base electrode material. FIG8(a) shows an anode titanium metal plate in the single electrolytic cell set for alkaline water electrolysis, and the cathode is also composed of the same titanium metal plate. The prepared metal Schiff base electrode material made of tetraethylenepentamine (TEPA) with a length of 5 cm and a width of 5 cm and an area of 25 cm2 is placed on the anode and cathode titanium metal plates as shown in FIG8(b), and a silicone gasket is attached as shown in FIG8(c), and a Fumasep FAA-3-50 isolation membrane is used to form a single electrolytic cell set for alkaline water electrolysis as shown in FIG8(d). Using 1M KOH electrolyte, a peristaltic pump was used to circulate the electrolyte in the anode and cathode separately. At room temperature, a current density of 200mA/cm 2 was applied, and the operating voltage of the single electrolytic cell group for water electrolysis was 2.5V, the energy efficiency was 70.4%, the hydrogen production was about 2484cm 3 /h and the oxygen production was about 1242cm 3 /h, and the specific energy consumption was 56kWh/kg.
圖9是表示將圖8中的單電解池組施加電流之後獲得平均能量效率的時間與能量密度的關係圖。在圖9中，將圖8(d)的單電解池組施加電流密度為200mA/cm2持續100小時後，所獲得的平均能量效率(energy efficiency)為70.2%，顯示由四乙烯五胺(TEPA)製成的金屬希夫鹼電極材料的陽極及陰極，可以在長時間電解下獲得穩定的能量效率。 FIG9 is a graph showing the relationship between the time and energy density of the average energy efficiency obtained after applying current to the single electrolytic cell group in FIG8. In FIG9, after applying a current density of 200 mA/ cm2 to the single electrolytic cell group in FIG8(d) for 100 hours, the average energy efficiency obtained is 70.2%, indicating that the anode and cathode of the metal Schiff base electrode material made of tetraethylenepentamine (TEPA) can obtain stable energy efficiency under long-term electrolysis.
在上述是將含有聚對苯二甲酸乙二酯(PET，poly(ethyl benzene-1,4-dicarboxylate))的塑膠與乙二醇(EG，ethylene glycol)形成對苯二甲酸之後，以合成的對苯二甲酸上的甲酸官能基的羰基與胺基化合物的胺基進行縮合反應製備形成希夫鹼，而在本發明中進一步揭露利用含有羰基或甲酸官能基的商用的苯 甲酸、對苯二甲酸、聚對苯二甲酸乙二酯或是均苯三甲酸、1，2，3，4-苯四甲酸與胺基化合物並在氫氧化鉀溶液的環境下進行縮合反應以得到希夫鹼來作為對照組並進行比較。 In the above, after the plastic containing polyethylene terephthalate (PET, poly (ethyl benzene-1,4-dicarboxylate)) and ethylene glycol (EG, ethylene glycol) form terephthalic acid, the carbonyl group of the formic acid functional group on the synthesized terephthalic acid and the amino group of the amino compound are subjected to condensation reaction to prepare Schiff base. In the present invention, commercial benzoic acid, terephthalic acid, polyethylene terephthalate or trimesic acid, 1,2,3,4-pyromellitic acid and amino compounds containing carbonyl or formic acid functional groups are further disclosed to be used as a control group for comparison.
接著請參考圖10。圖10是表示以含有羰基或甲酸官能基的化合物製備金屬希夫鹼電極材料的製備流程步驟示意圖。在圖10中，步驟S30：將含有羰基或甲酸官能基的化合物與胺基化合物並在氫氧化鉀溶液的環境下進行縮合反應以得到希夫鹼(Schiff base)。步驟S32：提供電泳槽、陽極基板及陰極基板。在此步驟中，陽極基板為不銹鋼板(stainless plate)及陰極基板為金屬基材。步驟S34：將希夫鹼與過渡金屬鹽類溶液混合行成具有金屬希夫鹼的電泳液。步驟S36：將電泳液倒入電泳槽中，並分別對陽極基板及陰極基板施加電壓，使得電泳液中的金屬希夫鹼沉積在陰極基板的表面上以形成金屬希夫鹼電及材料。 Please refer to Figure 10. Figure 10 is a schematic diagram showing the steps of the preparation process of preparing a metal Schiff base electrode material using a compound containing a carbonyl or formic acid functional group. In Figure 10, step S30: a compound containing a carbonyl or formic acid functional group and an amino compound are subjected to a condensation reaction in an environment of a potassium hydroxide solution to obtain a Schiff base. Step S32: an electrophoresis tank, an anode substrate, and a cathode substrate are provided. In this step, the anode substrate is a stainless steel plate and the cathode substrate is a metal substrate. Step S34: the Schiff base is mixed with a transition metal salt solution to form an electrophoresis solution containing a metal Schiff base. Step S36: Pour the electrophoretic liquid into the electrophoretic tank, and apply voltage to the anode substrate and the cathode substrate respectively, so that the metal Schiff base in the electrophoretic liquid is deposited on the surface of the cathode substrate to form a metal Schiff base electrode material.
根據上述圖10的金屬希夫鹼電極材料的製備流程步驟，以下針對金屬希夫鹼電極材料的製備流程進行詳細說明。 According to the steps of the preparation process of the metal Schiff base electrode material in Figure 10 above, the preparation process of the metal Schiff base electrode material is described in detail below.
以含有羰基或甲酸官能基的化合物製備希夫鹼： Preparation of Schiff bases from compounds containing carbonyl or formate functional groups:
以莫耳比(molar ratio)1：1的比例，將含有羰基或甲酸官能基的化合物與胺基化合物充分混合，再加入100ml-150ml，濃度為0.1M的氫氧化鉀(KOH)進行縮合反應，於反應的同時進行攪拌至少2小時，待反應結束，在溫度範圍為50℃-70℃進行乾燥，冷卻後得到希夫鹼。在本發明中，含有羰基或甲酸官能基的化合物是由商用的苯甲酸、對苯二甲酸、聚對苯二甲酸乙二酯或是均苯三甲酸、1，2，3，4-苯四甲酸所提供。胺基化合物如同前述，可以是脂肪胺、脂環胺、芳香胺或是聚醯胺。具體來說，在本發明中所使用的胺基化合物例如可以是乙二胺(EDA，ethylenediamine)、二乙烯三胺(DETA，diethylenetriamine)、三乙烯 四胺(TETA，triethylenetetramine)、四乙烯五胺(TEPA，tetraethylenepentamine)、五乙烯六胺(PTHA，pentaethylenehexamine)或是雙氰胺(DICY，Dicyandiamide)來製備希夫鹼。 A compound containing a carbonyl or formic acid functional group and an amino compound are mixed at a molar ratio of 1:1, and then 100ml-150ml of potassium hydroxide (KOH) with a concentration of 0.1M is added to carry out a condensation reaction. The mixture is stirred for at least 2 hours during the reaction. After the reaction is completed, the mixture is dried at a temperature range of 50°C-70°C and cooled to obtain a Schiff base. In the present invention, the compound containing a carbonyl or formic acid functional group is provided by commercial benzoic acid, terephthalic acid, polyethylene terephthalate or trimesic acid, 1,2,3,4-pyromellitic acid. The amino compound can be a fatty amine, alicyclic amine, aromatic amine or polyamide as described above. Specifically, the amino compound used in the present invention can be, for example, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PTHA) or dicyandiamide (DICY) to prepare schiff base.
電泳沉積形成金屬希夫鹼電極材料： Electrophoretic deposition to form metal Schiff base electrode materials:
如同前述圖3所示，提供電泳裝置及電泳液。要說明的是，在對照組中，電泳裝置的操作及電泳液的配置都與前述相同。電泳裝置包含電泳槽30、陽極基板40及陰極基板42，其中，陽極基板40為不銹鋼板(ASTM 316L)，陰極基板42為金屬基材，以相互平行方式且間隔一段距離設置在電泳槽30中。在本發明的較佳實施例中，金屬基材42為泡沫金屬(metal-foam)，例如可以是泡沫鎳、泡沫鈦、泡沫鐵、泡沫銅、泡沫鐵鎳、泡沫鋁及泡沫銀。於本發明中則是採用泡沫鎳作為金屬基材42。要說明的是，泡沫金屬42在使用之前，預先浸泡在清洗溶液(未在圖中表示)一段時間，以除去在泡沫金屬42表面上的氧化物(oxide)，清洗後乾燥備用。上述的清洗溶液是由酸液、乙醇及去離子水混合而成，酸液較佳的是鹽酸，特別是濃度為3M的鹽酸。此外，於另一實施例中，將泡沫金屬42浸泡在清洗溶液時，可同時進行超音波震盪以加速泡沫金屬42表面氧化物的去除。 As shown in FIG. 3 above, an electrophoresis device and an electrophoresis solution are provided. It should be noted that in the control group, the operation of the electrophoresis device and the configuration of the electrophoresis solution are the same as those described above. The electrophoresis device includes an electrophoresis tank 30, an anode substrate 40 and a cathode substrate 42, wherein the anode substrate 40 is a stainless steel plate (ASTM 316L), and the cathode substrate 42 is a metal substrate, which are arranged in the electrophoresis tank 30 in a parallel manner and at a distance. In a preferred embodiment of the present invention, the metal substrate 42 is a foam metal (metal-foam), for example, it can be foamed nickel, foamed titanium, foamed iron, foamed copper, foamed iron-nickel, foamed aluminum and foamed silver. In the present invention, foamed nickel is used as the metal substrate 42. It should be noted that the foam metal 42 is soaked in a cleaning solution (not shown in the figure) for a period of time before use to remove the oxide on the surface of the foam metal 42, and then dried for use after cleaning. The above cleaning solution is a mixture of acid, ethanol and deionized water, and the acid is preferably hydrochloric acid, especially hydrochloric acid with a concentration of 3M. In addition, in another embodiment, when the foam metal 42 is soaked in the cleaning solution, ultrasonic vibration can be performed at the same time to accelerate the removal of oxide on the surface of the foam metal 42.
製備電泳液： Prepare electrophoresis fluid:
將希夫鹼與氯化鐵溶液(FeCl3)(Iron(III)，chloride anhydrous)、乙酸銅溶液(Cu(C2H3O2)2．H2O)(Copper(III)，acetate monohydrate)及鉬酸銨溶液((NH4)6Mo7O24．H2O)(Ammonium molybdate tetrahydrate)以莫耳比1：1：1：1的比例混合，再加入體積為5000μl-5500μl．濃度為0.02M的硝酸鎳(Ni(NO3)2．6H2O)的充電試劑(charging agent)均勻混合後形成電泳液50，並將此電泳液50倒進電泳槽30裡，且陽極基板40和陰極基板42可以浸泡在電泳液50中。 Schiff's base is mixed with ferric chloride solution (FeCl 3 ) (Iron(III), chloride anhydrous), copper acetate solution (Cu(C 2 H 3 O 2 ) 2 ．H 2 O) (Copper(III), acetate monohydrate) and ammonium molybdate solution ((NH 4 ) 6 Mo 7 O 24 ．H 2 O) (Ammonium molybdate tetrahydrate) in a molar ratio of 1:1:1:1, and then added in a volume of 5000μl-5500μl. A charging agent of 0.02M nickel nitrate (Ni(NO 3 ) 2 .6H 2 O) is uniformly mixed to form an electrophoretic solution 50 , and the electrophoretic solution 50 is poured into the electrophoretic tank 30 , and the anode substrate 40 and the cathode substrate 42 can be immersed in the electrophoretic solution 50 .
接著，將陽極基板40與陰極基板42分別與電源32連接，電源32的陽極電壓與陽極基板40連接及電源32的陰極電壓與陰極基板42連接．電源32提供的電壓範圍為8-15伏特，為了避免電壓供應不均勻，進而影響電泳沉積速率的均勻性，電源32提供陽極電壓與陰極電壓的電壓值是相同的。當開啟電源32之後，即開始進行電泳沉積，電泳沉積的執行時間範圍為20-40分鐘。在電泳沉積的過程中，電泳液50中的過渡金屬離子，鐵(Fe3+)、銅(Cu3+)及鉬(Mo3+)與希夫鹼會形成金屬希夫鹼(metal Schiff base)然後沉積在作為陰極基板42的金屬基材的表面上，直到電泳沉積結束之後，將陰極基板42從電泳槽30取出，並且以去離子水清洗並且烘乾，此陰極基板42的表面即被金屬希夫鹼20(如圖1所示)覆蓋．以得到如前述圖1中的金屬希夫鹼電極材料1。根據上述，胺基化合物與含有羰基或甲酸官能基的化合物縮合反應形成的希夫鹼的化學結構及與希夫鹼與過渡金屬鹽類(M)形成的金屬希夫鹼的化學結構如下表示：
圖11是根據本發明所揭露的技術，表示由含有羰基或甲酸官能基的商用對苯二甲酸化合物與四乙烯五胺的胺基化合物反應形成希夫鹼，與金屬鹽溶液進行電泳沉積之後形成金屬希夫鹼電極材料的SEM圖，此結果證明此組成之製程方法製備金屬希夫鹼電極材料是可行的。 Figure 11 is a SEM image of a metal Schiff base electrode material formed by the reaction of a commercial terephthalic acid compound containing a carbonyl or formic acid functional group with an amino compound of tetraethylenepentamine according to the technology disclosed in the present invention, and after electrophoretic deposition with a metal salt solution, this result proves that the process method of this composition is feasible for preparing a metal Schiff base electrode material.
圖12是根據本發明所揭露的技術，表示具有不同的羰基或甲酸官能基的化合物所形成的各種金屬希夫鹼電極材料進行電化學析氧反應(OER)的線性掃描伏安曲線，電位(potential)與電流密度(Current density)的關係圖。從圖12結果獲得各種金屬希夫鹼電極材料在電流密度10mA/cm2的過電壓皆低於貴重金屬RuO2，表示在鹼性電解水電解過程中其析氧反應優於RuO2。 FIG12 is a linear sweep voltammogram showing the relationship between potential and current density of various metal Schiff base electrode materials formed by compounds with different carbonyl or formic acid functional groups in electrochemical oxygen evolution reaction (OER) according to the technology disclosed in the present invention. From the results of FIG12, it is obtained that the overvoltage of various metal Schiff base electrode materials at a current density of 10 mA/cm 2 is lower than that of the precious metal RuO 2 , indicating that its oxygen evolution reaction is better than RuO 2 in the alkaline electrolysis process of water electrolysis.
圖13是根據本發明所揭露的技術，表示具有不同的羰基或甲酸官能基的化合物所形成的各種金屬希夫鹼電極材料進行電化學析氫反應(HER)的線性掃描伏安曲線，電位(potential)與電流密度(Current density)的關係圖。從圖13可以獲得利用不同的羰基或甲酸官能基的化合物的金屬希夫鹼電極材料，其在10mA/cm2電流密度獲得的過電壓，雖皆大於商用貴金屬氧化物Pt/C製成的電極，然而當電流密度大於133mA/cm2以上，時以對苯二甲酸及均苯三甲酸製成的金 屬希夫鹼電極材料其電壓小於Pt/C電極，在此條件下，在鹼性電解水電解過程中其析氫反應優於Pt/C之電極。 FIG. 13 is a linear sweep voltammogram showing the relationship between potential and current density of various metal Schiff base electrode materials formed by compounds with different carbonyl or formic acid functional groups for electrochemical hydrogen evolution reaction (HER) according to the technology disclosed in the present invention. From Figure 13, we can see that the overvoltages obtained by the metal Schiff base electrode materials using compounds with different carbonyl or formic acid functional groups at a current density of 10 mA/ cm2 are all greater than those of the electrodes made of commercial precious metal oxide Pt/C. However, when the current density is greater than 133 mA/ cm2 , the voltage of the metal Schiff base electrode materials made of terephthalic acid and trimesic acid is less than that of the Pt/C electrode. Under this condition, its hydrogen evolution reaction is better than that of the Pt/C electrode during the electrolysis of alkaline water.
綜上所述，本發明所揭露的金屬希夫鹼電極材料除了可以利用含有羰基或甲酸官能基的商用苯甲酸、對苯二甲酸、聚對苯二甲酸乙二酯或是均苯三甲酸、1，2，3，4-苯四甲酸與胺基化合物形成希夫鹼，進行電泳沉積來製備得到之外，亦可以將含有PET的塑膠製品回收製備成含有甲酸官能基的對苯二甲酸，與胺基化合物形成希夫鹼，進行電泳沉積來製備得到金屬希夫鹼電極材料，相對於含有羰基或甲酸官能基的化合物所形成的金屬希夫鹼電極材料，同樣有良好的析氧及析氫反應，在長時間電解下獲得穩定的能量效率。因此，可以透過本發明所揭露的製備方法，來對廢棄的PET塑膠製品進行再生利用，以達到節能省碳、友善環境的目的。 In summary, the metal Schiff base electrode material disclosed in the present invention can be prepared by using commercial benzoic acid, terephthalic acid, polyethylene terephthalate or trimesic acid, 1,2,3,4-pyromellitic acid and amino compounds to form Schiff bases, and then electrophoresis deposition to obtain the metal Schiff base electrode material. In addition, the metal Schiff base electrode material can also be prepared by recycling plastic products containing PET to prepare terephthalic acid containing formic acid functional groups, and then reacting with amino compounds to form Schiff bases, and then electrophoresis deposition to obtain the metal Schiff base electrode material. Compared with the metal Schiff base electrode material formed by compounds containing carbonyl or formic acid functional groups, the metal Schiff base electrode material also has good oxygen evolution and hydrogen evolution reactions, and obtains stable energy efficiency under long-term electrolysis. Therefore, the preparation method disclosed in the present invention can be used to recycle discarded PET plastic products to achieve the goals of energy saving, carbon saving and environmental friendliness.
1:金屬希夫鹼電極材料 1:Metal Schiff base electrode material
10:金屬基材 10: Metal substrate
20:金屬希夫鹼 20:Metallic Schiff bases
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| TW112110949A TWI856576B (en) | 2023-03-23 | 2023-03-23 | Metal schiff base electrode material and the preparing method thereof |
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| TW (1) | TWI856576B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219957A (en) * | 1996-03-22 | 1999-06-16 | 普罗格特-甘布尔公司 | Delivery system containing zeolite loaded release inhibitor and method of making same |
| CN1737002A (en) * | 2005-07-29 | 2006-02-22 | 南开大学 | Quaternary ammonium group modified water-soluble chiral Schiff base metal complex and its synthesis method |
| WO2008126426A1 (en) * | 2007-03-30 | 2008-10-23 | Fujifilm Corporation | Conductive-substance-adsorbing resin film, process for producing conductive-substance-adsorbing resin film, metal-layer-coated resin film made from the same, and process for producing metal-layer-coated resin film |
| EP1500151B1 (en) * | 2002-01-25 | 2014-04-30 | Engen Group Inc. | Polymer-modified electrode for energy storage devices and electrochemical supercapacitor based on said polymer-modified electrode |
-
2023
- 2023-03-23 TW TW112110949A patent/TWI856576B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219957A (en) * | 1996-03-22 | 1999-06-16 | 普罗格特-甘布尔公司 | Delivery system containing zeolite loaded release inhibitor and method of making same |
| EP1500151B1 (en) * | 2002-01-25 | 2014-04-30 | Engen Group Inc. | Polymer-modified electrode for energy storage devices and electrochemical supercapacitor based on said polymer-modified electrode |
| CN1737002A (en) * | 2005-07-29 | 2006-02-22 | 南开大学 | Quaternary ammonium group modified water-soluble chiral Schiff base metal complex and its synthesis method |
| WO2008126426A1 (en) * | 2007-03-30 | 2008-10-23 | Fujifilm Corporation | Conductive-substance-adsorbing resin film, process for producing conductive-substance-adsorbing resin film, metal-layer-coated resin film made from the same, and process for producing metal-layer-coated resin film |
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| Publication number | Publication date |
|---|---|
| TW202439660A (en) | 2024-10-01 |
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