TY - JOUR
T1 - Block-Copolymers Enable Direct Reduction and Structuration of Noble Metal-Based Films
AU - Gayrard, Maxime
AU - Chancerel, Francois
AU - De Marco, Maria Letizia
AU - Naumenko, Denys
AU - Boissière, Cédric
AU - Rozes, Laurence
AU - Amenitsch, Heinz
AU - Peron, Jennifer
AU - Cattoni, Andrea
AU - Faustini, Marco
N1 - Funding Information:
The authors thank D. Montero and the Institut des Matériaux de Paris Centre (IMPC FR2482) for servicing FEGSEM & EDX instrumentation and Sorbonne Université, CNRS and C'Nano projects of the Région Ile‐de‐France for funding. The authors thank Sophie Nowak for in situ XRD measurements. This work was supported by French state funds managed by the National Research Agency (ANR) through the MetaFleSS project, grant no. ANR‐17‐CE09‐0027. M.L.D.M. and M.F. acknowledge funding from the European Research Council (ERC) under European Union's Horizon 2020 Programme (Grant agreement no. 803220, TEMPORE). This project also received funding from the EU‐H2020 Research and Innovation Programme under grant agreement no. 654360 having benefitted from the access provided by ELETTRA Trieste, Italy, within the framework of the NFFA‐Europe Transnational Access Activity. The IR ellipsometry was funded by the Région Ile‐de‐France in the framework of DIM ResPore and by the French state within the Investissements d'Avenir Programme under reference ANR‐11‐IDEX‐0004‐02, within the framework of the Cluster of Excellence MATISSE. The work was also partially supported by the French RENATECH network.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2022/2/3
Y1 - 2022/2/3
N2 - Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H2 generation into microfluidic reactors.
AB - Noble metal nanostructured films are of great interest for various applications including electronics, photonics, catalysis, and photocatalysis. Yet, structuring and patterning noble metals, especially those of the platinum group, is challenging by conventional nanofabrication. Herein, an approach based on solution processing to obtain metal-based films (rhodium, ruthenium (Ru) or iridium in the presence of residual organic species) with nanostructuration at the 20 nm-scale is introduced. Compared to existing approaches, the dual functionality of block-copolymers acting both as structuring and as reducing agent under inert atmosphere is exploited. A set of in situ techniques has allowed for the capturing of the carbothermal reduction mechanism occurring at the hybrid organic/inorganic interface. Differently from previous literature, a two-step reduction mechanism is unveiled with the formation of a carbonyl intermediate. From a technological point of view, the materials can be solution-processed on a large scale by dip-coating as polymers and simultaneously structured and reduced into metals without requiring expensive equipment or treatments in reducing atmosphere. Importantly, the metal-based films can be patterned directly by block-copolymer lithography or by soft-nanoimprint lithography on various substrates. As proof-of-concept of application, the authors demonstrate that nanostructured Ru films can be used as efficient catalysts for H2 generation into microfluidic reactors.
KW - block-copolymers
KW - mesoporous films
KW - metals
KW - patterning
KW - reduction
KW - small-angle X-ray scattering
UR - http://www.scopus.com/inward/record.url?scp=85120611231&partnerID=8YFLogxK
U2 - 10.1002/smll.202104204
DO - 10.1002/smll.202104204
M3 - Article
AN - SCOPUS:85120611231
SN - 1613-6810
VL - 18
JO - Small
JF - Small
IS - 5
M1 - 2104204
ER -