EP4524290A1 - Catalyseur poreux à champ électrique contrôlé pour réaction de génération de chlore électrochimique dans un état salin extrêmement bas, et électrode catalytique poreuse l'utilisant - Google Patents

Catalyseur poreux à champ électrique contrôlé pour réaction de génération de chlore électrochimique dans un état salin extrêmement bas, et électrode catalytique poreuse l'utilisant Download PDF

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Publication number
EP4524290A1
EP4524290A1 EP23803868.1A EP23803868A EP4524290A1 EP 4524290 A1 EP4524290 A1 EP 4524290A1 EP 23803868 A EP23803868 A EP 23803868A EP 4524290 A1 EP4524290 A1 EP 4524290A1
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EP
European Patent Office
Prior art keywords
porous catalyst
catalyst
porous
electrode
platinum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23803868.1A
Other languages
German (de)
English (en)
Other versions
EP4524290A4 (fr
Inventor
Myeongsoo Chang
Byung Soo Oh
Chang Hyun Lee
Kang Hee Cho
Ki Tae Nam
Seungwoo Choi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Electronics Inc
SNU R&DB Foundation
Original Assignee
LG Electronics Inc
Seoul National University R&DB Foundation
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Publication date
Application filed by LG Electronics Inc, Seoul National University R&DB Foundation filed Critical LG Electronics Inc
Publication of EP4524290A1 publication Critical patent/EP4524290A1/fr
Publication of EP4524290A4 publication Critical patent/EP4524290A4/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Definitions

  • the present disclosure relates to a porous catalyst for electrochemical chlorine generation reaction under an extremely low salt condition and a porous catalyst electrode using the same.
  • Hypochlorous acid and sodium hypochlorite generated by electrolysis are excellent substances with sterilizing power, organic matter decomposition ability, bleaching, etc. Since they are almost harmless to the human body, they are widely used for sterilizing ship ballast water, restaurants and food materials, swimming pools, medical care, livestock, etc. In addition, they may be obtained by electrolyzing salt water or tap water. Since such hypochlorous acid or sodium hypochlorite may be easily obtained by electrolysis using an insoluble electrode, the electrolysis scheme is widely used.
  • a method of improving the life of the electrode by coating an electrode base with platinum or a platinum-group metal compound is mainly used.
  • a certain amount or greater of expensive platinum-group metal compound should be used and a uniform coating layer should be formed via multiple coatings.
  • reduced economic feasibility occurs due to the use of the significant amount of Expensive material.
  • a purpose of the present disclosure is to provide a novel catalyst for electrochemical chlorine generation under an extremely low salt condition and a catalyst electrode using the same.
  • a purpose of the present disclosure is to provide a novel catalyst having a reduced used amount of an expensive catalyst material and a catalyst electrode using the same.
  • a purpose of the present disclosure is to provide a novel catalyst that has excellent chlorine generation efficiency under an extremely low salt condition even when the used amount of Expensive catalyst material is reduced, and a catalyst electrode using the same.
  • the porous catalyst according to the present disclosure has excellent electrochemical chlorine generation effect under an extremely low salt condition.
  • a mono-atomic or sub-nanometer-sized platinum-group metal-based catalyst included in the catalyst of the present disclosure has high atomic utilization efficiency compared to a bulk metal catalyst, so that high chlorine generation efficiency may be obtained with a small amount of metal.
  • the catalyst electrode of the present disclosure not only may suggest a novel composition of the catalyst but also may exhibit high chlorine generation efficiency under an extremely low salt condition via control of the overall shape of the electrode.
  • FIG. 1 is a SEM photograph showing a porous catalyst according to the present disclosure.
  • the porous catalyst according to the present disclosure has a structure in which a platinum-group metal catalyst is supported on a porous support including a conductive metal oxide.
  • the porous catalyst of the present disclosure has the structure as described above, it has excellent chlorine generation efficiency, especially under an extremely low salt condition smaller than 1 mM.
  • the catalyst of the present disclosure since the catalyst of the present disclosure has the structure as described above, it may stably generate chlorine under an extremely low salt condition even when using a very small amount of expensive catalyst material. Therefore, the catalyst of the present disclosure may improve economic efficiency and exhibit an effect equivalent to or superior to that of a conventional catalyst using a large amount of a platinum-group metal.
  • the conductive metal oxide may include oxides of various metals such as niobium (Nb), tin (Sn), manganese (Mn), zirconium (Zr), molybdenum (Mo), ruthenium (Ru), osmium (Os), rhodium (Rh), palladium (Pd), tantalum (Ta), titanium (Ti), and cobalt (Co).
  • the conductive metal oxide may preferably include tin oxide, niobium oxide, or a mixture thereof.
  • the platinum-group metal catalyst may include platinum (Pt), iridium (Ir), ruthenium (Ru), osmium (Os), rhodium (Rh), and palladium (Pd) as a platinum-group metal.
  • the platinum-group metal catalyst may include platinum, iridium, or a mixture thereof.
  • the porous catalyst of the present disclosure may contain the platinum-group metal catalyst at 0.3 atomic % or smaller based on 100 atomic % of the porous catalyst.
  • the porous catalyst of the present disclosure may have a composition of a following Chemical Formula 1.
  • Chemical Formula 1 Ir a Pt b Sn c Nb d Ti e O f (a and b satisfy 0 ⁇ a ⁇ 0.3, 0 ⁇ b ⁇ 0.3, and 0 ⁇ a+b ⁇ 0.3, 0.7 ⁇ c+d+e ⁇ 0.95, and f is 2).
  • FIG. 2 is a cross-sectional view schematically showing a porous catalyst electrode 100 of the present disclosure.
  • the porous catalyst electrode 100 of the present disclosure includes an electrode base 10; and a porous catalyst coating layer 20 formed on at least a portion of a top surface of the electrode base, wherein the porous catalyst coating layer 20 has a structure in which a metal catalyst including at least one of platinum and iridium is supported on a porous support including a conductive metal oxide. Accordingly, the electrode of the present disclosure has excellent chlorine generation efficiency under an extremely low salt condition smaller than 1 mM.
  • the conductive metal oxide may include oxides of various metals such as niobium (Nb), tin (Sn), manganese (Mn), zirconium (Zr), molybdenum (Mo), ruthenium (Ru), osmium (Os), rhodium (Rh), palladium (Pd), tantalum (Ta), titanium (Ti), and cobalt (Co).
  • the conductive metal oxide may preferably include tin oxide, niobium oxide, or a mixture thereof.
  • the platinum-group metal catalyst may include platinum (Pt), iridium (Ir), ruthenium (Ru), osmium (Os), rhodium (Rh), and palladium (Pd) as a platinum-group metal.
  • the platinum-group metal catalyst may include platinum, iridium, or a mixture thereof.
  • the porous catalyst of the present disclosure may contain the platinum-group metal catalyst at 0.3 atomic % or smaller based on 100 atomic % of the porous catalyst.
  • the porous catalyst of the present disclosure may have a composition of a following Chemical Formula 1.
  • Chemical Formula 1 Ir a Pt b Sn c Nb d Ti e O f (a and b satisfy 0 ⁇ a ⁇ 0.3, 0 ⁇ b ⁇ 0.3, and 0 ⁇ a+b ⁇ 0.3, 0.7 ⁇ c+d+e ⁇ 0.95, and f is 2).
  • the conductive metal oxide support included in the porous catalyst electrode of the present disclosure may be synthesized using a thermal decomposition method or a hydrothermal synthesis method of a metal precursor.
  • a catalyst structure in which a platinum-group metal catalyst is stabilized in a conductive metal oxide framework may be realized using polystyrene beads having a size of about 100 nm or smaller.
  • the structure of the porous network may be controlled by changing a content ratio of the noble metal precursor and the polystyrene beads.
  • the surface shape of the porous structure changes depending on the content ratio of the noble metal precursor and the polystyrene beads.
  • the porous network structure formed in the above manner may easily increase a total catalyst surface area of the electrode.
  • the stabilized metal and/or metal oxide catalyst may be present in a sub-nanometer size within the porous catalyst.
  • the porous catalyst electrode of the present disclosure may have a Faradaic efficiency of 4.5% or greater, preferably 6% or greater, for the chlorine generation reaction under an extremely low salt condition where a chlorine concentration is 1 mM or smaller.
  • porous catalyst electrode as described above may be applied particularly for the purpose of generating chlorine under an extremely low salt condition such as tap water, and may also be applied to other similar fields.
  • a 1 mm thick titanium (Ti) electrode base was cut into a size of 10 ⁇ 63 mm 2 .
  • the electrode base was soaked in ethyl alcohol, ultrasonically washed, and then washed with pure water using a brush.
  • a washing time was 1 minute per time, and foreign substances that were not removed from a surface of the electrode base were removed using a brush.
  • porous electrode catalyst according to an embodiment of the present disclosure may be identified as having a Faradaic efficiency of at least 4.5% or greater under the extremely low salt condition.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP23803868.1A 2022-05-12 2023-05-11 Catalyseur poreux à champ électrique contrôlé pour réaction de génération de chlore électrochimique dans un état salin extrêmement bas, et électrode catalytique poreuse l'utilisant Pending EP4524290A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020220058547A KR102886302B1 (ko) 2022-05-12 2022-05-12 극저염 조건에서의 전기화학적 염소 발생 반응을 위한 전기장이 제어된 다공성 촉매 및 이를 이용한 다공성 촉매 전극
PCT/KR2023/006431 WO2023219445A1 (fr) 2022-05-12 2023-05-11 Catalyseur poreux à champ électrique contrôlé pour réaction de génération de chlore électrochimique dans un état salin extrêmement bas, et électrode catalytique poreuse l'utilisant

Publications (2)

Publication Number Publication Date
EP4524290A1 true EP4524290A1 (fr) 2025-03-19
EP4524290A4 EP4524290A4 (fr) 2025-09-17

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EP23803868.1A Pending EP4524290A4 (fr) 2022-05-12 2023-05-11 Catalyseur poreux à champ électrique contrôlé pour réaction de génération de chlore électrochimique dans un état salin extrêmement bas, et électrode catalytique poreuse l'utilisant

Country Status (4)

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US (1) US20250313972A1 (fr)
EP (1) EP4524290A4 (fr)
KR (1) KR102886302B1 (fr)
WO (1) WO2023219445A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL73536A (en) * 1984-09-13 1987-12-20 Eltech Systems Corp Composite catalytic material particularly for electrolysis electrodes,its manufacture and its use in electrolysis
JP2505563B2 (ja) * 1989-01-30 1996-06-12 石福金属興業株式会社 電解用電極
DE102013202144A1 (de) * 2013-02-08 2014-08-14 Bayer Materialscience Ag Elektrokatalysator, Elektrodenbeschichtung und Elektrode zur Herstellung von Chlor
KR101854737B1 (ko) * 2017-04-07 2018-05-04 서울대학교 산학협력단 촉매 및 촉매 제조 방법
JP6588816B2 (ja) * 2015-12-22 2019-10-09 石福金属興業株式会社 塩素発生用電極
KR101812008B1 (ko) * 2016-03-15 2017-12-27 (주)엘켐텍 3차원 다공성 단극 전극체를 구비한 전기살균 필터 및 이를 이용한 수처리 방법
JP7097042B2 (ja) * 2017-12-27 2022-07-07 石福金属興業株式会社 塩素発生用電極
IT201800003533A1 (it) * 2018-03-14 2019-09-14 Industrie De Nora Spa Elettrodo per processi di elettroclorazione
KR20190129369A (ko) * 2018-05-10 2019-11-20 엘지전자 주식회사 담지체와 촉매를 포함한 전극

Also Published As

Publication number Publication date
KR102886302B9 (ko) 2026-01-09
KR20230158885A (ko) 2023-11-21
US20250313972A1 (en) 2025-10-09
EP4524290A4 (fr) 2025-09-17
KR102886302B1 (ko) 2025-11-13
WO2023219445A1 (fr) 2023-11-16

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