KR101378201B1 - Preparation method of titanium oxide nanostructure for dsa electrode by one-step anodization - Google Patents
Preparation method of titanium oxide nanostructure for dsa electrode by one-step anodization Download PDFInfo
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- KR101378201B1 KR101378201B1 KR1020120157463A KR20120157463A KR101378201B1 KR 101378201 B1 KR101378201 B1 KR 101378201B1 KR 1020120157463 A KR1020120157463 A KR 1020120157463A KR 20120157463 A KR20120157463 A KR 20120157463A KR 101378201 B1 KR101378201 B1 KR 101378201B1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 27
- 238000002048 anodisation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 12
- 150000002602 lanthanoids Chemical class 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000000576 coating method Methods 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000007743 anodising Methods 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- -1 4 − Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B82—NANOTECHNOLOGY
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- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Description
본 발명은 양극산화 공정과 촉매코팅 공정을 각각 별도로 수행하는 기존의 2단계 티타늄 옥사이드 나노구조 제조방법을 개선하여 양극산화 시 촉매코팅도 동시에 수행할 수 있는 단일공정의 DSA 전극용 티타늄 옥사이드 나노구조 제조방법에 관한 것이다.The present invention improves the conventional two-step titanium oxide nanostructure manufacturing method to perform the anodization process and the catalyst coating process separately, to prepare a titanium oxide nanostructure for a single process DSA electrode that can also be carried out at the same time catalyst coating during anodization It is about a method.
현재 알려진 청정에너지원 중에 수소는 저장과 이동이 용이한 화학연료라는 점에서 화석연료를 대체할 수 있는 가장 유망한 에너지원이다. 수소를 생산하기 위한 물분해용 전극으로 티타늄 금속을 양극산화하여 산화티타늄(TiO2) 모제를 만들고 물분해 활성을 높이기 위해 루테늄, 이리듐이나 탄탈륨과 같은 촉매를 코팅시켜 DSA(Dimensonally Stable Anode) 전극을 제조하는 방식이 잘 알려져 있다.Among the currently known clean energy sources, hydrogen is the most promising energy source to replace fossil fuels in that it is easy to store and transport. As a water decomposition electrode for producing hydrogen, titanium oxide (TiO 2 ) is produced by anodizing titanium metal and a catalyst such as ruthenium, iridium or tantalum is coated to increase water decomposition activity, thereby producing DSA (Dimensonally Stable Anode) electrode. The way to do it is well known.
한편, 한국등록특허 제1067867호에서 흑연소재 활물질과 도전재 및 결착제를 혼합하여 혼합물을 만든 후 알콜류와 함께 슬러리로 제조하는 제 1단계; 상기 제 1단계에서 혼합된 슬러리를 알콜류를 증발시키고 페이스트로 제조하는 제 2단계; 상기 제 2단계에서 제조된 페이스트된 혼합물을 얇게 펴서 전극 시트로 제조하는 제 3단계; 및 DSA 전극과 함께 상기 제 3단계에서 제조된 전극 시트를 압연하여 일체화 하는 방법으로 전극을 제조하는 제 4단계를 포함하는 레독스 흐름 전지용 흑연/DSA 일체형 전극 제조 방법을 개시하고 있다.On the other hand, Korean Patent No. 1067867, the first step of preparing a mixture with an alcohol and after mixing the graphite material active material, conductive material and binder to make a mixture; A second step of preparing the slurry mixed in the first step by evaporating an alcohol and forming a paste; A third step of thinly spreading the paste mixture prepared in the second step to form an electrode sheet; And a fourth step of manufacturing the electrode by rolling and integrating the electrode sheet prepared in the third step together with the DSA electrode.
그러나, 아직까지 양극산화 공정 시 촉매코팅을 동시에 수행할 수 있는 티타늄 옥사이드 나노구조의 제조방법은 전혀 알려진 바 없다.However, there is no known method for producing titanium oxide nanostructures that can simultaneously perform catalytic coating during anodization.
이에, 본 발명은 양극산화를 진행함과 동시에 촉매를 코팅할 수 있는 단일 공정을 통한 DSA 전극용 티타늄 옥사이드 나노구조 제조방법을 제공하는 데에 있다.Accordingly, the present invention is to provide a method for producing titanium oxide nanostructures for a DSA electrode through a single process that can be coated with a catalyst while anodizing.
상기 목적을 달성하기 위하여, 본 발명은 티타늄 기판과 전해질을 이용한 양극산화 공정을 포함하는 DSA 전극 제조방법에 있어서, 상기 양극산화 공정 시 루테늄, 이리듐 및 탄탈륨으로 이루어진 군에서 선택된 란탄족 금속의 산화물 음이온을 갖는 화합물을 전해질로 사용한 것을 특징으로 하는 단일공정의 DSA 전극용 티타늄 옥사이드 나노구조 제조방법을 제공한다. In order to achieve the above object, the present invention provides a method for producing a DSA electrode comprising an anodization process using a titanium substrate and an electrolyte, the oxide anion of a lanthanide metal selected from the group consisting of ruthenium, iridium and tantalum during the anodization process It provides a method for producing a titanium oxide nanostructures for a DSA electrode in a single process, characterized in that the compound having an electrolyte as an electrolyte.
상기 란탄족 금속의 산화물 음이온을 갖는 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다:The compound having an oxide anion of the lanthanide metal may be a compound represented by Formula 1 below:
[화학식 1][Formula 1]
AMOxAMOx
A는 알칼리금속 또는 알칼리토금속에서 선택되고, M은 루테늄, 이리듐 및 탄탈륨으로 이루어진 군에서 선택된 란탄족 금속이며, x는 1 ≤ x ≤ 4의 정수일 수 있다. A is selected from alkali metals or alkaline earth metals, M is a lanthanide metal selected from the group consisting of ruthenium, iridium and tantalum, and x may be an integer of 1 ≦ x ≦ 4.
특히, 상기 란탄족 금속의 산화물 음이온을 갖는 화합물은 KRuO4, NaRuO4, KIrO4, NaIrO4, LiTaO3, NaTaO3 및 CsTaO3에서 선택될 수 있다.In particular, the compound having an oxide anion of the lanthanide metal may be selected from KRuO 4 , NaRuO 4 , KIrO 4 , NaIrO 4 , LiTaO 3 , NaTaO 3 and CsTaO 3 .
상기 양극산화는 20V 내지 100V에서 1시간 내지 2시간 동안 수행할 수 있다.The anodization may be performed at 20V to 100V for 1 hour to 2 hours.
본 발명에 따르면, 종래 양극산화 공정 후 촉매코팅 공정을 수행하여 DSA 전극용 티타늄 옥사이드 나노구조를 제조한 방법에서 진일보하여 양극산화를 진행함과 동시에 촉매를 코팅할 수 있는 단일공정의 DSA 전극용 티타늄 옥사이드 나노구조 제조방법을 제공함으로써 단시간 내에 간단하게 DSA 전극용 티타늄 옥사이드 나노구조를 제조할 수 있어 물 분해 효율을 향상시킬 수 있다.According to the present invention, the titanium oxide for DSA electrode in a single process that can be coated with a catalyst while performing anodization in the method of producing a titanium oxide nanostructure for the DSA electrode by performing a catalyst coating process after the conventional anodization process By providing an oxide nanostructure manufacturing method, the titanium oxide nanostructures for DSA electrodes can be easily produced in a short time, thereby improving water decomposition efficiency.
도 1은 0.002M의 KRuO4 전해질 용액을 이용하고 80V를 인가하여 양극산화하여 제조한 티타늄 옥사이드 나노구조의 SEM 이미지를 나타낸 것이다(a, b: 위에서 본 이미지, c: 옆에서 본 이미지).
도 2는 본 발명에 따른 티타늄 옥사이드 나노구조의 XPS 분석 결과를 나타낸 것이다.
도 3은 본 발명에 따른 티타늄 옥사이드 나노구조의 LSV 분석 결과를 나타낸 것이다(a: 0.02M의 KRuO4로 양극산화한 모제, b: 0.002M의 KRuO4로 양극산화한 모제).
도 4는 마이크로아크산화를 통해 얻어진 티타늄 옥사이드의 SEM 이미지를 나타낸 것이다.
도 5는 본 발명에 따른 티타늄 옥사이드 나노구조의 LSV 분석 결과를 마이크로아크산화를 통해 얻어진 티타늄 옥사이드와 비교하여 나타낸 것이다(a: 1M H3PO4로 양극산화한 MAO, b: 0.002M의 KRuO4로 양극산화한 모제).Figure 1 shows a SEM image of a titanium oxide nanostructure prepared by using an 0.002M KRuO 4 electrolyte solution and anodized by applying 80V (a, b: image from above, c: image from the side).
Figure 2 shows the XPS analysis of the titanium oxide nanostructures according to the present invention.
Figure 3 shows the LSV analysis results of the titanium oxide nanostructures according to the present invention (a: a mother anodized with KRuO 4 of 0.02M, b: a mother anodized with KRuO 4 of 0.002M).
4 shows an SEM image of titanium oxide obtained through microarc oxidation.
FIG. 5 shows LSV analysis results of titanium oxide nanostructures according to the present invention in comparison with titanium oxide obtained through microarc oxidation (a: MAO anodized with 1M H 3 PO 4 , b: KRuO 4 of 0.002M). As anodized matrix).
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
일반적으로 양극산화를 수행할 때 전해질로서 인산(H3PO4)을 많이 사용하는데 이때 H+는 공기 중으로 빠져나가고, PO4 3-는 Ti에 접근하여 산화막을 만드는데 기여하는 데, 이를 착안하여 RuO4 -와 같은 음이온으로 작용할 수 있는 화합물을 이용하여 직접 양극산화를 진행한 결과, 양극산화와 동시에 촉매코팅도 가능하다는 것을 확인하여 본 발명을 완성하였다.In general, when anodizing, phosphoric acid (H 3 PO 4 ) is frequently used as an electrolyte, where H + is released into the air, and PO 4 3- contributes to Ti to form an oxide film. As a result of the direct anodization using a compound capable of acting as an anion such as 4 − , the present invention was completed by confirming that anodization and catalytic coating were also possible.
따라서, 본 발명은 티타늄 기판과 전해질을 이용한 양극산화 공정을 포함하는 DSA 전극용 티타늄 옥사이드 나노구조 제조방법에 있어서, 상기 양극산화 공정 시 루테늄, 이리듐 및 탄탈륨으로 이루어진 군에서 선택된 란탄족 금속의 산화물 음이온을 갖는 화합물을 전해질로 사용한 것을 특징으로 하는 단일공정의 DSA 전극용 티타늄 옥사이드 나노구조 제조방법을 제공한다. Accordingly, the present invention provides a method for producing a titanium oxide nanostructure for a DSA electrode including an anodization process using a titanium substrate and an electrolyte, wherein the anion oxidation process is an oxide anion of a lanthanide metal selected from the group consisting of ruthenium, iridium, and tantalum It provides a method for producing a titanium oxide nanostructures for a DSA electrode in a single process, characterized in that the compound having an electrolyte as an electrolyte.
상기 란탄족 금속의 산화물 음이온을 갖는 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다:The compound having an oxide anion of the lanthanide metal may be a compound represented by Formula 1 below:
[화학식 1][Formula 1]
AMOxAMOx
A는 알칼리금속 또는 알칼리토금속에서 선택되고, M은 루테늄, 이리듐 및 탄탈륨으로 이루어진 군에서 선택된 란탄족 금속이며, x는 1 ≤ x ≤ 4의 정수일 수 있다. A is selected from alkali metals or alkaline earth metals, M is a lanthanide metal selected from the group consisting of ruthenium, iridium and tantalum, and x may be an integer of 1 ≦ x ≦ 4.
특히, 상기 란탄족 금속의 산화물 음이온을 갖는 화합물은 KRuO4, NaRuO4, KIrO4, NaIrO4, LiTaO3, NaTaO3 및 CsTaO3에서 선택될 수 있다.In particular, the compound having an oxide anion of the lanthanide metal may be selected from KRuO 4 , NaRuO 4 , KIrO 4 , NaIrO 4 , LiTaO 3 , NaTaO 3 and CsTaO 3 .
상기 양극산화는 20V 내지 100V에서 1시간 내지 2시간 동안 수행할 수 있으며, 바람직하게는 80V에서 2시간 동안 수행할 수 있다.
The anodization may be performed at 20V to 100V for 1 hour to 2 hours, preferably at 80V for 2 hours.
이하, 하기 실시예를 통해 본 발명을 보다 상세하게 설명한다. 다만, 이러한 실시예에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.
<실시예 1> DSA 전극용 티타늄 옥사이드 나노구조 제조Example 1 Preparation of Titanium Oxide Nanostructures for DSA Electrodes
전해질 용액으로 0.02M 또는 0.002M의 KRuO4 수용액을 사용하였으며, 양극으로 티타늄을 사용하였고, 80V에서 2시간 동안 양극산화를 수행하여 DSA 전극용 티타늄 옥사이드 나노구조용 티타늄 옥사이드 나노구조를 제조하였다.A 0.02M or 0.002M KRuO 4 aqueous solution was used as an electrolyte solution, titanium was used as the anode, and anodization was performed at 80 V for 2 hours to prepare titanium oxide nanostructures for titanium oxide nanostructures for DSA electrodes.
<실험예 1> DSA 전극용 티타늄 옥사이드 나노구조의 물성 평가Experimental Example 1 Evaluation of Properties of Titanium Oxide Nanostructures for DSA Electrodes
1. SEM 이미지 분석1. SEM image analysis
실시예 1에서 제조된 나노구조의 SEM 이미지(FE-SEM, 4300S, Hitachi, Japan) 를 사용하여 분석하였으며, 그 결과, 도 1a 및 도 1b는 0.002M의 KRuO4 수용액을 전해질로 사용한 경우 위에서 본 SEM 이미지이고, 도 1c는 0.002M의 KRuO4 수용액을 전해질로 사용한 경우 옆에서 본 SEM 이미지를 나타내었다. 이러한 결과로부터 690nm 두께를 갖는 산화막이 형성되었음을 확인할 수 있었으며, F-나 Cl- 이온을 첨가하지 않았기 때문에 산화막에서 용출이 일어나지 않아 기공은 형성되지 않은 것으로 보였다.SEM images of the nanostructures prepared in Example 1 (FE-SEM, 4300S, Hitachi, Japan) were analyzed using the results. As a result, FIGS. 1A and 1B were seen from above when using 0.002M of aqueous KRuO 4 solution as an electrolyte. SEM image, Figure 1c shows a SEM image seen from the side when using a 0.002M KRuO 4 aqueous solution as an electrolyte. From these results, it was confirmed that an oxide film having a thickness of 690 nm was formed. Since no F - or Cl - ions were added, elution did not occur in the oxide film, and no pores were formed.
2. XPS 분석2. XPS Analysis
실시예 1과 같이 전해질로 KRuO4를 이용하여 양극산화를 한 후 따로 촉매를 코팅하지 않아도 루테늄이 제대로 함유되었는지를 확인하기 위해, 실시예 1에서 제조된 나노구조의 XPS(X-ray Photoelectron Spectrocopy) 분석을 Electron Spectroscopy For Chemical Analysis, K-Alpha 를 사용하여 수행하였다.After anodizing with KRuO 4 as an electrolyte as in Example 1, in order to check whether ruthenium is properly contained even without coating the catalyst, the nanostructured XPS (X-ray Photoelectron Spectrocopy) prepared in Example 1 was used. Analysis was performed using Electron Spectroscopy For Chemical Analysis, K-Alpha.
그 결과, 도 2와 같이 KRuO4를 이용하여 양극산화를 한 후 따로 촉매를 입히지 않고도 33.19 원자%의 루테늄이 함유된 것을 확인할 수 있었다.As a result, after anodizing with KRuO 4 as shown in FIG. 2, it was confirmed that ruthenium contained 33.19 atomic% without applying a catalyst.
3. LSV 분석3. LSV Analysis
실시예 1과 같이 전해질로 KRuO4를 이용하여 양극산화를 한 모제를 이용하여 일정속도 전위 훑음법(linear sweep voltammetry; LSV; Autolab, PGSTAT 302N, AUTOLAB, Netherlands)을 측정하여 물 분해 효율을 분석하였다. 그 결과, 도 3(b)와 같이 0.002M의 KRuO4로 양극산화한 모제의 개시 전위(onset potential)이 도 3(a)의 0.02M의 KRuO4로 양극산화한 모제의 그것보다 훨씬 좋음을 육안으로 관측할 수 있었다. 따라서 본 연구에서는 농도 조건을 0.002M로 맞추어 실험을 진행하였다. As in Example 1, a linear sweep voltammetry (LSV; Autolab, PGSTAT 302N, AUTOLAB, Netherlands) was measured using an anodized mother using KRuO 4 as an electrolyte to analyze water decomposition efficiency. . As a result, the onset potential of the mother anodized with 0.002M KRuO 4 as shown in FIG. 3 (b) is much better than that of the mother anodized with KRuO 4 of 0.02M in FIG. 3 (a). It could be observed with the naked eye. Therefore, the experiment was conducted by adjusting the concentration condition to 0.002M.
4. 마이크로아크산화를 통한 TiO4. TiO through Microarc Oxidation 22 모제와의 비교 Comparison with Mother
일반적으로 양극산화를 통해 얻을 수 있는 TiO2 모제와의 물 분해 효율을 비교하기 위해, 고전압을 인가하여 다양한 직경의 포어를 갖는 마이크로아크산화를 통한 TiO2 모제를 제조하였다. 이때, 전해질로서 1M H3PO4와 0.5 중량% HF를 사용하여 200V에서 2시간 동안 마이크로아크산화를 수행하였다. In order to compare the water decomposition efficiency with TiO 2 mothers generally obtained through anodization, TiO 2 mothers were prepared through microarc oxidation having pores of various diameters by applying a high voltage. At this time, microarc oxidation was performed at 200V for 2 hours using 1M H 3 PO 4 and 0.5 wt% HF as the electrolyte.
도 4는 마이크로아크산화한 TiO2 모제의 SEM 이미지로서, 고전압을 인가하였기 때문에 붕괴가 일어나 많은 기공이 형성된 것을 확인할 수 있었으며, 직경은 300nm~1㎛로 다양한 크기로 형성되었다. FIG. 4 is an SEM image of the microarcated TiO 2 mother material, and it was confirmed that many pores were formed due to collapse due to the application of a high voltage, and the diameters were formed in various sizes ranging from 300 nm to 1 μm.
그리고, 도 5에서는 (a) 1M H3PO4로 마이크로아크산화한 TiO2 모제와, (b) 0.002M의 KRuO4로 양극산화한 TiO2 모제의 LSV를 분석하였다.And in Figure 5 (a) it was analyzed 1M H 3 PO 4 micro-arc and a TiO 2 moje, LSV of (b) 0.002M TiO 2 moje by anodizing a KRuO 4 of oxidized to.
이러한 결과로부터, 촉매를 코팅하지 않고 양극산화만 한 MAO와 비교하였을 때, KRuO4를 이용하여 양극산화한 모제의 개시전압과 전류 모두 효율이 훨씬 높음을 확인할 수 있었다. MAO의 SEM 이미지를 통해 MAO 구조가 상대적으로 큰 표면적을 가지므로 물 분해 효율이 더 좋을 것이라 예상되지만, 보통 물 분해 전극으로 쓰이는 티타늄 옥사이드 전극은 안정하지만 과전압이 높아 별도의 촉매를 첨가해 주어야 물 분해 효율이 향상된다. 따라서 양극산화 후 촉매를 첨가해 주는 2-step 과정으로 전극을 제조하는데 반면, 본 발명에서는 KRuO4를 가지고 직접 양극산화를 진행함으로써 1-step으로 물 분해 효율을 향상시킬 수 있었다.
From these results, it can be seen that the efficiency of both the starting voltage and the current of the mother anodized using KRuO 4 was much higher than that of MAO which was only anodized without coating the catalyst. The SEM image of MAO suggests that the MAO structure has a relatively large surface area, so that the water decomposition efficiency will be better.However, the titanium oxide electrode, which is usually used as a water decomposition electrode, is stable but has a high overvoltage. The efficiency is improved. Therefore, the electrode is manufactured by a two-step process of adding a catalyst after anodization, whereas in the present invention, by directly anodizing with KRuO 4 , water decomposition efficiency can be improved in one-step.
본 발명은 한정된 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며, 본 기술 분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 다른 실시예가 가능하다는 점을 이해할 것이다. 따라서, 본 발명의 진정한 기술적 보호 범위는 첨부된 특허청구범위의 기술적 사상에 의하여 정해져야 할 것이다.
While the invention has been described with reference to a limited number of embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.
Claims (4)
[화학식 1]
AMOx
A는 알칼리금속 또는 알칼리토금속에서 선택되고, M은 루테늄, 이리듐 및 탄탈륨으로 이루어진 군에서 선택된 란탄족 금속이며, x는 1 ≤ x ≤ 4의 정수임. The method of claim 1, wherein the compound having an oxide anion of the lanthanide metal is a compound represented by Formula 1 below.
[Chemical Formula 1]
AMOx
A is selected from alkali metals or alkaline earth metals, M is a lanthanide metal selected from the group consisting of ruthenium, iridium and tantalum, and x is an integer of 1 ≦ x ≦ 4.
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| KR101609947B1 (en) * | 2014-09-30 | 2016-04-07 | 인하대학교 산학협력단 | Preparing method of electrodes using a potential shock |
| KR101784092B1 (en) * | 2016-01-29 | 2017-10-10 | 인하대학교 산학협력단 | Method of Manufacturing Titanium oxide structure for Type of Microcone |
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| KR101609947B1 (en) * | 2014-09-30 | 2016-04-07 | 인하대학교 산학협력단 | Preparing method of electrodes using a potential shock |
| KR101784092B1 (en) * | 2016-01-29 | 2017-10-10 | 인하대학교 산학협력단 | Method of Manufacturing Titanium oxide structure for Type of Microcone |
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