Chorkendorff, Ib

Frydendal, Rasmus

Hernandez-Fernandez, Patricia

Paoli, Elisa Antares

Rossmeisl, Jan

Stephens, Ifan

Online Research Database In Technology

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Downloaded from orbit.dtu.dk on: Dec 20, 2017Development of new catalysts for water electrolysisHernandez-Fernandez, Patricia; Paoli, Elisa Antares; Frydendal, Rasmus; Stephens, Ifan; Rossmeisl,Jan; Chorkendorff, IbPublication date:2013Link back to DTU OrbitCitation (APA):Hernandez-Fernandez, P., Paoli, E. A., Frydendal, R., Stephens, I., Rossmeisl, J., & Chorkendorff, I. (2013).Development of new catalysts for water electrolysis [Sound/Visual production (digital)]. International Symposiumon Water Electrolysis and Hydrogen as part of the future Renewable Energy System, Copenhagen, Denmark,10/05/2013Development of  new catalysts for water electrolysis Patricia Hernández-Fernández1, Elisa A. Paoli1, Rasmus Frydendal1, Ifan E.L. Stephens1, Jan Rossmeisl2, Ib Chorkendorff1 1Center for Individual Nanoparticle Functionality, 2Center for Atomic-scale Materials Design Technical University of Denmark  Symposium                                                              Water electrolysis and hydrogen as part of  the future Renewable Energy System Outline  Motivation  Theoretical trends in oxygen evolution activity  Corrosion protection mechanism  Summary  Films preparation- Sputter deposition Water electrolysis and hydrogen as part of  the future Renewable Energy System  Nanoparticles- Cluster source Motivation Renewable sources Electrical energy Chemical energy H2 Electrolysers Fuel Cells H2 O2 H2O PEM Motivation anodic cathodic Marshall et al, Energy 32 (2007) 431 Ecell = E0 + anode + cathode + IR Limitations of  the efficiency of  a PEM electrolyser Perfect catalyst Parsons for a multi electron reaction    Ideal catalyst Theoretical trends in oxygen evolution activity 1.23 eV 1.23 eV 1.23 eV 1.23 eV 0Perfect catalyst Parsons for a multi electron reaction    RuO2 (110) Theoretical trends in oxygen evolution activity 0Theoretical trends in oxygen evolution activity Composition of  the earth crust O, Si, Al, Fe, Ca, Na, Mg, K, Ti → 98.8% Ru → 1E-7 % Mn → 0.095%         Ir → 3E-8 % Theoretical trends in oxygen evolution activity H2O + * → HO* + H+ + e-  G1  HO* → O* + H+ + e-    G2  O* + H2O → HOO* + H+ + e-   G3  HOO* → O2 + H+ + e-  G4   Scaling relations: 3.2 eV Descriptor of  the oxygen evolving activity: GO*-GHO* EHOO= EHO+3.2 eV Perovskites, rutiles, anatase, MnxOy, Co3O4, NiO Volcano plots GO*-GHO* Theoretical trends in oxygen evolution activity Volcano plots for oxides Garcia-Mota and col, Chem Cat Chem 3 (2011) 1159  -Theoretical /V Theoretical trends in oxygen evolution activity Manganese MnO2 →Stable from 1.1 to 1.7V at pH1 Mann I., Thesis, 2010, DTU Physics    0.61 V RuO2 → 0.37 V   IrO2 → 0.57 V How to protect MnOx from corrosion RuO2-IrO2  activity ( = 0.42V @10mA/cm2)   corrosion resistance (1.4 V at pH1)    activity ( = 0.58V @10mA/cm2)   corrosion resistance (2.1 V at pH1)   Ruthenium Iridium Mann I., Thesis, 2010, DTU Physics  Trasatti et al, Materials Chem and Phys 22 (1989) 231 Protection from corrosion  Protection from corrosion  Ir segregates to the kink sites IrO2+2H2O ↔IrO42-+4H++4e-   U0=2.057V RuO2+3H2O ↔H2RuO4+4H++4e-   U0=1.4V Rukink Irkink Mann, I. Thesis, 2011, DTU Physics Ir should be placed on the kink sites to protect Ru from corrosion -0.82 eV U=U0-0.1V U=U0+0.6V Film preparation- Sputter deposition  Gaseous plasma • MnOX-1 • 90 nm Mn at 5 mTorr Ar and 480C • 100 W • Annealed in air at 480 C (Furnace) • MnOX-2 • 1.5 nm Ti • 90 nm MnOX at 3 mTorr Ar/O2 (10sccm) and 150C • 100 W • Annealed in air at 480 C (Furnace) GC GC Mn Ti Heat MnOx Heat 1.8VRHE @ 10 mA/cm2 Jaramillo et al., JACS 132 (2010) 13612 1.66 VRHE @ 5 mA/cm2 1.73 VRHE @ 5 mA/cm2 Film preparation- Sputter deposition  1.0 1.2 1.4 1.6 1.80246810  j (mA/cm2)U(V) vs RHEOER activity in N2 sat. 0.1M KOH 1600 rpm  5mV/s MnOx-1 Film preparation- Sputter deposition  MnOx-1 MnOx electrodeposited Jaramillo et al, JACS 132 (2010) 13612 Corrosion protection → Acidic media 500 nm SEM Magnetron sputter source Nanoparticle filtering Support (GC) • Size varies from 1 atom to 10nm • Size is function on the power and gas flow Nanoparticles- Cluster source • STM • SEM • ISS • TPD • LEED • TEM • ATM Nanoparticles- Cluster source Ru NP 4nm OER activity in N2 sat. 0.1M HClO4 1600 rpm  20mV/s 0.8 1.0 1.2 1.4 1.60.000.250.500.751.001.251.501.75  j (mA/cm2)U(V) vs RHE0.07 gRu Nanoparticles- Cluster source Ru NP 4nm → 1344 mA/mgRu @1.48V Strasser et al., Electrochem Solid St Lett 13 (2010) B36 Fuentes et al., Electrochem Solid St Lett 14 (2011) E5 Ru NP 4nm → 1344 A/gRu @1.48V Corrosion protection Summary • RuO2 is the most active catalysts for OER, but we need to protect it from corrosion → Ir on the kink sites • MnO2 is a good candidate to replace RuO2 because is active and abundant • The catalytic activity of  the MnO2 films prepared by sputter deposition are comparable with the state of  the art (alkaline)  • The mass activity of  the Ru NP prepared in the cluster source is one order of  magnitude higher than the state of  the art Development of  new catalysts for water electrolysis Patricia Hernández-Fernández1, Elisa A. Paoli1, Rasmus Frydendal1, Ifan E.L. Stephens1, Jan Rossmeisl2, Ib Chorkendorff1 1Center for Individual Nanoparticle Functionality, 2Center for Atomic-scale Materials Design Technical University of Denmark  Symposium                                                              Water electrolysis and hydrogen as part of  the future Renewable Energy System Rossmeisl et al, J Phys Chem C 111 (2007) 18821 Theoretical trends in oxygen evolution activity RuO2 vs ideal catalyst Perfect catalyst Parsons for a multi electron reaction    Ideal catalyst Theoretical trends in oxygen evolution activity 0Perfect catalyst Parsons for a multi electron reaction    RuO2 (110) Theoretical trends in oxygen evolution activity 0(110)MnO2 3.11(eV) Theoretical trends in oxygen evolution activity Free energy diagram: Rossmeisl and col, Chem Cat Chem 3 (2011) 1159  Rossmeisl et al, J Electroanal Chem 607 (2007) 83  (101)RuO2,r HO* → O* + H+ + e-    G2  O* + H2O → HOO* + H+ + e-   G3  G3-G2  3 eV → O* position 2 2 3 3 ideal catalyst   0.61 V RuO2 → 0.37 V   IrO2 → 0.57 V 

Development of new catalysts for water electrolysis

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Development of new catalysts for water electrolysis

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