B1: Plasma induced nano-structuring for catalyst activation under operando conditions

Principal Investigators: B. Roldan

Team

Roldan, Beatriz (Principal Investigator)

Grosse, Philipp (PostDoc)

Öner, Sebastian (PostDoc)

Nguyen, Khanh-Ly (PhD)

Description

In this project, atmospheric plasmas will be used for the synthesis and modification of active thin films and nanoparticle catalysts. The plasma might promote controlled oxidation and stabilize active oxygen species. Furthermore, the surface roughness and the number of catalytically active defect sites might be enhanced. The performance of such plasma-synthesized and functionalized catalysts will be evaluated for energy-related electrochemical reactions. Finally, plasmas will be used under electrochemical operando reaction conditions to increase the catalyst activity via controlled generation of defects, the stabilization of a given oxidation state, via a maintained surface roughness or the generation of very high electric fields.

Publications

• Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO_{_2} electroreduction
  A. Herzog, M. L. Luna, H. S. Jeon, C. Rettenmaier, P. Grosse, A. Bergmann, B. Roldán Cuenya
  Nat Commun 15, 3986 (2024)
  
• Assessment of the Degradation Mechanisms of Cu Electrodes during the CO₂ Reduction Reaction
  R. V. Mom, L. E. Sandoval-Diaz, D. F. Gao, C. H. Chuang, E. A. Carbonio, T. E. Jones, R. Arrigo, D. Ivanov, M. Hävecker, B. Roldán Cuenya, R. Schlögl, T. Lunkenbein, A. Knop-Gericke, J. J. Velasco-Vélez
  ACS Appl. Mater. 15, 30052-30059 (2023)
  
• Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO₂ Revealed by In Situ X-Ray Spectroscopy
  J. J. Velasco-Vélez, J. Poon, D. F. Gao, C. H. Chuang, A. Bergmann, T. E. Jones, S. C. Haw, J. M. Chen, E. Carbonio, R. V. Mom, D. Ivanov, R. Arrigo, B. Roldán Cuenya, A. Knop-Gericke, R. Schlögl
  Adv. Sustainable Syst. 7, 2200453 (2023)
  
• Plasma Functionalization of Silica Bilayer Polymorphs
  M. J. Prieto, T. Mullan, W. Wan, L. C. Tǎnase, L. De Souza Caldas, S. Shaikhutdinov, J. Sauer, D. Usvyat, T. Schmidt, B. Roldán Cuenya
  ACS Appl. Mater. 14, 48609-48618 (2022)
  
• Highly Stable and Reactive Platinum Single Atoms on Oxygen Plasma-Functionalized CeO₂ Surfaces: Nanostructuring and Peroxo Effects
  W. Wan, J. Geiger, N. Berdunov, M. Lopez Luna, S. W. Chee, N. Daelman, N. López, S. Shaikhutdinov, B. Roldán Cuenya
  Angew. Chem. Int. Ed. 61, e202112640 (2022)
  
• Identifying structure-selectivity correlations in the electrochemical reduction of CO₂: a comparison of well-ordered atomically-clean and chemically-etched Cu single crystal surfaces
  F. Scholten, K.-L. C. Nguyen, J. P. Bruce, M. Heyde, B. Roldán Cuenya
  Angew. Chem. Int. Ed. 60, 19169 (2021)
  
• Plasma-assisted oxidation of Cu(100) and Cu(111)
  S. Kunze, L. C. Tănase, M. J. Prieto, P. Grosse, F. Scholten, L. de Souza Caldas, D. van Vörden, T. Schmidt, B. Roldán Cuenya
  Chem. Sci. 12, 14241-14253 (2021)
  
• Dynamic transformation of cubic copper catalysts during CO₂ electroreduction and its impact on catalytic selectivity
  P. Grosse, A. Yoon, C. Rettenmaier, A. Herzog, S. W. Chee, B. Roldán Cuenya
  Nat. Commun. 12, 6736 (2021)
  
• Linking the Evolution of Catalytic Properties and Structural Changes in Copper-Zinc Nanocatalysts using Operando EXAFS and Neural-Networks
  J. Timoshenko, H. S. Jeon, I. Sinev, F. Haase, A. Herzog, B. Roldán Cuenya
  Chem. Sci. 11, 3727-3736 (2020)
  
• Transition metal-based catalysts for the electrochemical CO₂ reduction: from atoms and molecules to nanostructured materials
  F. Franco, C. Rettenmaier, H. S. Jeon, B. Roldán Cuenya
  Chem. Soc. Rev. 49, 6884-6946 (2020)
  
• Growth Dynamics and Processes Governing the Stability of Electrodeposited Size-controlled cubic Cu catalysts
  P. Grosse, A. Yoon, C. Rettenmaier, S.W. Chee, B. Roldán Cuenya
  J. Phys. Chem. C 124, 26908-26915 (2020)
  
• Operando NRIXS and XAFS Investigation of Segregation Phenomena in Fe-Cu and Fe-Ag nanoparticle catalysts during CO₂ electroreduction
  S. Kunze, P. Grosse, M. B. Lopez, I. Sinev, Zegkinoglou, H. Mistry, J. Timoshenko, Y. Hu, Zhao, E. Alp, S. W. Chee , B. Roldán Cuenya
  Angew. Chem. Int. Ed. 59, 22667 (2020)
  
• On the activity/selectivity and phase-stability of thermally-grown copper oxides during the electrocatalytic reduction of CO₂
  J.-J. Velasco-Vélez, C.-H. Chuang, D. Gao, Q. Zhu, D. Ivanov, H.-S. Jeon, R. Arrigo, R. Mom, E. Stotz, H.-L. Wu, T. Jones, B. Roldán Cuenya Cuenya, A. Knop-Gericke, R. Schlögl
  ACS Catalysis 10, 11510-11518 (2020)
  
• Rational catalyst and electrolyte design for CO₂ electro reduction towards multicarbon products
  D. Gao, R. M. Arán-Ais, H. S. Jeon, B. Roldán Cuenya
  Nat. Catal. 2, 198-210 (2019)
  
• Plasma-modified dendritic Cu catalyst for CO₂ electroreduction
  F. Scholten, I. Sinev, M. Bernal, B. Roldán Cuenya
  ACS Catalysis 9, 5496-5502 (2019)
  
• Operando Insights into Nanoparticle Transformations during Catalysis
  A. Bergmann, B. Roldán Cuenya
  ACS Catalysis 9, 10020-10043 (2019)
  

Thesis

• Philipp Grosse, PhD thesis - 02/2021
  Investigating Dynamic Changes in Morphology and Chemical State of Copper Catalysts for the Electrochemical Reduction of CO₂
• Claudia Khanh-Ly Nguyen, PhD thesis - 09/2024
  Electrochemical Reduction of CO₂ on UHV-Prepared Cu Single Crystals

Further reading

• Highly selective plasma-activated Cu catalysts for CO₂ reduction to ethylene
  H. Mistry, A.Varela, C. Bonifacio, I. Zegkinoglou, I. Sinev, Y. Choi, K. Kisslinger, E. A. Stach, J.C. Yang, P. Strasser, and B. Roldán Cuenya
  Nat. Commun. 7, 12123 (2016)
• Nanostructured electrocatalysts with tunable activity and selectivity
  H. Mistry, A. Varela, S. Kühl, P. Strasser, and B. Roldán Cuenya
  Nat. Rev. Mater. 1, 16009 (2016)