WO2010146475A1 - Catalyseurs supportés - Google Patents

Catalyseurs supportés Download PDF

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Publication number
WO2010146475A1
WO2010146475A1 PCT/IB2010/051372 IB2010051372W WO2010146475A1 WO 2010146475 A1 WO2010146475 A1 WO 2010146475A1 IB 2010051372 W IB2010051372 W IB 2010051372W WO 2010146475 A1 WO2010146475 A1 WO 2010146475A1
Authority
WO
WIPO (PCT)
Prior art keywords
supported catalyst
catalysts
nanoparticles
supported
spe
Prior art date
Application number
PCT/IB2010/051372
Other languages
English (en)
Inventor
Shan Ji
Sivakumar Pasupathi
Bernard Jan Bladergroen
Vladimir Mikhailovich Linkov
Xolelwa Ralam
Original Assignee
University Of The Western Cape
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University Of The Western Cape filed Critical University Of The Western Cape
Priority to EP10789089.9A priority Critical patent/EP2446494A4/fr
Publication of WO2010146475A1 publication Critical patent/WO2010146475A1/fr
Priority to ZA2011/06273A priority patent/ZA201106273B/en

Links

Classifications

    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • C25B11/097—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 comprising two or more noble metals or noble metal alloys

Definitions

  • the present invention relates to supported catalysts.
  • the present invention relates to supported catalysts for solid polymer electrolyte electrolysers.
  • a SPE (solid polymer electrolyte) electrolyser system is potentially the best to produce hydrogen using renewable energy and is seen as the best electrolyser candidate for the sustainable energy future.
  • electricity is applied to the electrode assembly and water is split at the anode into oxygen and protons. The protons diffuse through the conducting membrane to the cathode to form hydrogen.
  • a renewable source of energy e.g. wind or solar
  • SPE electrolysers can be coupled to distributed, intermittent renewable electricity sources (e.g. wind generators or solar panels), in order to store energy generated from excess electricity as hydrogen in gas cylinders or in metal hydrides.
  • the stored hydrogen can later be used in hydrogen fuel cells to generate electricity at one's convenience (like a battery).
  • electrolyser systems can also be used to store energy generated by electrical turbines during low demand periods or off peak times in order to reduce peak electricity costs.
  • hydrogen mixed with air or oxygen
  • a supported catalyst for SPE electrolyser applications includes
  • a method to produce a supported catalyst for SPE electrolyser applications which includes the steps of
  • the supported catalyst may be used as anode catalysts for SPE electrolysers.
  • the support for may include carbon nanotubes, carbon nanofibers, titanium nanotubes, titanium nanofibres and TiB 2 .
  • the supported catalysts may be prepared by means of wet impregnation and autoclave methods.
  • the supported catalysts may be stable up to 1.7V vs standard hydrogen electrode for oxygen evolution reaction.
  • the mass specific activities of the supported catalysts may be better than unsupported catalysts.
  • the stability of the support may be improved through pre-treatment by heating under controlled atmosphere or by acid treatment.
  • the stability and activity of the supported catalysts may be improved by tailoring their preparation conditions.
  • the nanoparticles may include be Pt, Ir, Ru, Ta, Sn or Pd or oxides of the same.
  • the nanoparticles may include binary mixtures of Pt, Ir, Ru, Ta, Sn and Pd and their oxides.
  • the supported catalyst may include highly dispersed and homogeneously distributed nanoparticles on the CNT support.
  • the supported catalyst may include highly dispersed IrO 2 nanoparticles over the CNT support.
  • Figure 1 Stability of supported nanoparticles at various potentials
  • Figure 2 Activity and stability of supported nanoparticles prepared at various PH
  • Figure 3 Activity and stability of supported nanoparticles prepared at various temperatures
  • Figure 4 Mass specific activity of supported catalyst as compared to commercial unsupported catalyst
  • Figure 5 TEM image of CNT supported IrO2 nanoparticles.
  • a supported catalyst includes supported nanoparticles as oxygen evolution catalysts for SPE electrolyser applications.
  • Carbon nanotubes were selected as supports due to their unique physical and thermal properties.
  • the CNT supported catalysts were developed by impregnation reduction method and evaluated for its stability and performance as SPE electrolyser anodes. Also, the preparation conditions of the supported catalyst were optimized with respect to pH, reducing temperature and loading of Ir on the support. An alternative synthesis method was also investigated, where highly dispersed and homogeneously distributed nanoparticles on the CNT support was achieved.
  • the supported nanoparticles were characterised electrochemically using chronoamperometric technique to study the stability of catalysts under SPE electrolyser operating conditions i.e., up to 1.8V.
  • CNT supported catalysts when electrochemically evaluated were found to be stable up to 1.7V, which is considered to be the maximum operating potential for the electrolyser to produce hydrogen at economically feasible power consumption.
  • the effect of synthesis conditions on the activity of catalysts was also studied.
  • the mass specific activity of the prepared catalysts was then compared with that of commercial IrO 2 (Alfa Aesar) and was found to be better than twice the activity of the commercial catalyst.
  • An alternative preparation method for the supported catalysts was also studied, where highly dispersed IrO 2 nanoparticles over the CNT support was achieved.
  • the supported catalysts were prepared using a wet impregnation method.
  • the catalyst precursor solution was prepared beforehand by weighing a required amount of hexachloroiridic acid and dissolving it in hydrochloric acid.
  • the required amount of carbon nanotubes were weighed into beaker and ultra pure water was added and the CNTs were ultrasonically dispersed for three minutes. Then, additional amount of ultrapure water was added and the solution was further ultrasonically dispersed for half an hour.
  • the dispersion was then mechanically stirred and a catalyst precursor solution was added drop wise from a burette to form a heterogeneous mixture.
  • the precursor solution was prepared by dissolving H 2 IrCI 6 -SH 2 O in HCI.
  • the pH of the suspension was adjusted to the required value by adding NaOH and a required volume of formaldehyde was then gradually added drop wise into the mixture with a burette and was left to stir over night.
  • the suspension was then filtered, washed copiously with water and dried in an oven for two hours at 8O 0 C.
  • the catalysts were then oxidized in a furnace at 200 0 C to obtain IrO 2 ZCNT and was then stored in an air tight container for characterization.
  • the electrochemical measurements were carried out with Eco-Chemie Autolab PGSTAT30 using a three electrode setup.
  • a glassy carbon electrode coated with the catalyst layer was used as the working electrode.
  • a platinum mesh was used as the counter electrode and Ag/ AgCI was used as the reference electrode. All the potentials referred herein are with respect to the standard hydrogen electrode.
  • the catalyst ink was prepared by ultrasonically blending the required amount of catalyst with ultra pure water and nafion (perflourinated ion-exchange resin) in the ultrasonic water bath for 3-20 minutes.
  • the working electrode was prepared by pipetting the required amount of the catalyst ink onto the glassy carbon electrode and then dried in an oven at 8O 0 C.
  • FIG. 1 shows the chronoamperometric graphs of CNT supported IrO 2 at different potentials ranging from 1.4 to 1.8V. The results show that no noticeable current was produced at 1.4V but above 1.4V the OER activity was noted, which increased with the potential. The figure also reveals that the oxidized CNT supported catalysts are stable up to 1.7V. Above 1.7V, the stability of the supported catalysts dropped significantly with time and finally dropped to zero within 1200 seconds of operation. The results indicate that the support is oxidised above 1.7V. It is evident from Figure 1 that the catalyst is stable up to 1.7V, which is a feasible operating voltage for electrolysis. This study proves that CNTs can be used as supports for SPE electrolyser anodes. The activity of supported catalysts can be further improved by tailoring their preparation conditions.
  • the method for preparing the catalysts was similar to the one described above but during the pH adjusting step, it was varied from 1.8 - 9.
  • the catalysts were prepared at pH ranging from acidic to basic conditions and its effect on the catalyst activity was studied.
  • Figure 2 shows the chronoamperometric graphs of catalysts prepared at various pH.
  • the catalyst prepared at pH 6 showed the best performance.
  • the conditions for synthesizing the catalysts were the same as described earlier in the detailed description section.
  • the pH was fixed at 6 and the temperature was varied from O 0 C to 8O 0 C while the reducing agent was added to the suspension.
  • the activities of the catalysts are shown in Figure 3.
  • the catalyst prepared at 8O 0 C was found have the highest activity of those tested.
  • the mass specific activity of the supported catalyst was found to be twice better than that of the commercial unsupported catalyst ( Figure 4).
  • the supported catalysts were prepared in a different way than described above.
  • H 2 IrCl6»6H2 ⁇ and sodium citrate (1-50: 1 weight ratio) were dissolved in ethylene glycol and stirred for 0.5-10 h to obtain the precursor solution.
  • CNTs were added into H 2 O/ethylene glycol mixture containing 1-90% H 2 O and mechanically stirred for 30 min and were then dispersed in an ultrasonic bath for 30 min.
  • the H 2 IrCU solution was added to the CNT slurry under stirring and then treated in an ultrasonic bath for 10-600 min. At the end of the reaction, the pH was adjusted within the range 6-14 using NaOH/ethylene glycol solution.
  • the CNT/ H 2 IrCU mixture was then kept in an autoclave and heated at the temperature range from 100 to 200 0 C in a furnace and the temperature was programmed with a rate on increase of l-50°C/min.
  • the autoclave was cooled down slowly to room temperature and the pH adjusted to 1-7 using 10% HNO 3 in ethylene glycol.
  • the sample was recovered by filtering, and washed with de-ionized water until all Cl " ions are completely removed.
  • the black precipitate was dried in oven at 6O 0 C for 1-8 h. After that, the sample was heated in the temperature range from 150-350 0 C to oxidize Ir.
  • the TEM image of synthesized IrO 2 /CNTs was shown in Figure 5.
  • the present invention thus relates to the development of supported IrO 2 nanoparticles as electrocatalysts for SPE electrolyser anodes.
  • the support allows the dispersion of particles leading to a greater utilization of the active surfaces and thereby is expected to reduce the catalyst loading considerably.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Catalysts (AREA)

Abstract

La présente invention a trait à un catalyseur supporté pour applications d'électrolyseur SPE, lequel catalyseur est pourvu d'un support portant des nanoparticules en tant que catalyseurs de dégagement d'oxygène.
PCT/IB2010/051372 2009-06-18 2010-03-30 Catalyseurs supportés WO2010146475A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP10789089.9A EP2446494A4 (fr) 2009-06-18 2010-03-30 Catalyseurs supportés
ZA2011/06273A ZA201106273B (en) 2009-06-18 2011-08-26 Supported catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA200904250 2009-06-18
ZA2009/04250 2009-06-18

Publications (1)

Publication Number Publication Date
WO2010146475A1 true WO2010146475A1 (fr) 2010-12-23

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EP (1) EP2446494A4 (fr)
WO (1) WO2010146475A1 (fr)
ZA (1) ZA201106273B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2634290A1 (fr) * 2012-02-28 2013-09-04 Fritz Haber Institute of the Max Planck Society Department of Inorganic Chemistry Hydrolyse électrolytique utilisant un composé MnOx sur support de carbone
WO2017091858A1 (fr) * 2015-11-30 2017-06-08 Newsouth Innovations Pty Limited Procédé d'amélioration de l'activité catalytique
CN109589974A (zh) * 2018-11-05 2019-04-09 中国科学院广州能源研究所 一种用于水电解器的低贵金属载量的析氧催化剂

Citations (6)

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JP2000342965A (ja) * 1999-06-09 2000-12-12 Agency Of Ind Science & Technol 一体化再生型固体高分子型燃料電池の酸素極用触媒
US20050106449A1 (en) * 2002-02-27 2005-05-19 Qun Fan Fuel cell electrocatalyst of pt-mn-co
US7087341B2 (en) * 1998-02-24 2006-08-08 Cabot Corporation Metal-air battery components and methods for making same
US20070082255A1 (en) * 2005-10-06 2007-04-12 Gongquan Sun Fuel cells and fuel cell catalysts incorporating a nanoring support
US20080138696A1 (en) * 2006-12-08 2008-06-12 Eveready Battery Company, Inc. Electrochemical cell having a deposited gas electrode
WO2008085472A1 (fr) * 2006-12-27 2008-07-17 Eveready Battery Company, Inc. Cellule électrochimique à électrode catalytique et procédé de fabrication de l'électrode et de la cellule

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EP1254712B1 (fr) * 2001-05-05 2005-07-20 Umicore AG & Co. KG Catalyseur supporté à base de métal noble et son procédé de préparation
US20090250353A1 (en) * 2006-05-26 2009-10-08 Aicheng Chen Nanoporous Material
WO2008040222A1 (fr) * 2006-09-22 2008-04-10 Ocean University Of China Catalyseur en poudre d'ordre de grandeur nanométrique, et son procédé de préparation

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US7087341B2 (en) * 1998-02-24 2006-08-08 Cabot Corporation Metal-air battery components and methods for making same
JP2000342965A (ja) * 1999-06-09 2000-12-12 Agency Of Ind Science & Technol 一体化再生型固体高分子型燃料電池の酸素極用触媒
US20050106449A1 (en) * 2002-02-27 2005-05-19 Qun Fan Fuel cell electrocatalyst of pt-mn-co
US20070082255A1 (en) * 2005-10-06 2007-04-12 Gongquan Sun Fuel cells and fuel cell catalysts incorporating a nanoring support
US20080138696A1 (en) * 2006-12-08 2008-06-12 Eveready Battery Company, Inc. Electrochemical cell having a deposited gas electrode
WO2008085472A1 (fr) * 2006-12-27 2008-07-17 Eveready Battery Company, Inc. Cellule électrochimique à électrode catalytique et procédé de fabrication de l'électrode et de la cellule

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2634290A1 (fr) * 2012-02-28 2013-09-04 Fritz Haber Institute of the Max Planck Society Department of Inorganic Chemistry Hydrolyse électrolytique utilisant un composé MnOx sur support de carbone
WO2013127920A1 (fr) * 2012-02-28 2013-09-06 Fritz Haber Institut Der Max Planck Gesellschaft Department Of Inorganic Chemistry Séparation électrolytique de l'eau à l'aide d'un composite mnox support sur du carbone
CN104136661A (zh) * 2012-02-28 2014-11-05 德国马普弗利兹-哈伯无机化学研究所 使用碳负载MnOX的复合材料电解分解水
US9797052B2 (en) 2012-02-28 2017-10-24 Fritz Haber Institut Der Max Planck Gesellschaft Electrolytic water splitting using a carbon-supported MnOx-composite
WO2017091858A1 (fr) * 2015-11-30 2017-06-08 Newsouth Innovations Pty Limited Procédé d'amélioration de l'activité catalytique
CN108291320A (zh) * 2015-11-30 2018-07-17 新南创新私人有限公司 用于改进催化活性的方法
JP2019505361A (ja) * 2015-11-30 2019-02-28 ニューサウス イノベーションズ ピーティーワイ リミテッド 触媒活性を向上させる方法
US11141723B2 (en) 2015-11-30 2021-10-12 Newsouth Innovations Pty Limited Method for improving catalytic activity
AU2016363676B2 (en) * 2015-11-30 2022-08-18 Newsouth Innovations Pty Limited Method for improving catalytic activity
CN109589974A (zh) * 2018-11-05 2019-04-09 中国科学院广州能源研究所 一种用于水电解器的低贵金属载量的析氧催化剂

Also Published As

Publication number Publication date
EP2446494A1 (fr) 2012-05-02
ZA201106273B (en) 2012-11-28
EP2446494A4 (fr) 2014-08-27

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