Carbon Thin-Film Electrodes as High-Performing Substrates for...

Single-entity electrochemistry (SEE) is an emerging area of research that aims at evaluating the electrochemical response of materials at the micro- and nanoscale. *

Several SEE studies have demonstrated how valuable this approach is toward achieving a fundamental understanding of the intrinsic electrochemical properties of nanomaterials, in particular with relevance to energy storage or energy conversion. *

Nanomaterials of interest for such applications often exhibit heterogeneity in their composition and structure that arises from population heterogeneity or from the presence of different nanoscale sub-domains within single entities. This represents a significant challenge when interpreting their electrochemical response using conventional bulk electrochemistry, given that crucial information on, e.g., the role of specific catalytic sites or of inert sub-domains can be obscured in the ensemble response of a macroscopic electrode. *

SEE in combination with complementary characterization techniques has opened the door to a new type of characterization known as correlative-SEE that holds exceptional potential toward understanding nanomaterials for energy applications. In such methods, spectroscopy and/or microscopy are used in tandem with SEE to correlate the electrochemical response to chemical and/or structural properties of probed entities. *

In the article “Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry” Marc Brunet Cabré, Christian Schröder, Filippo Pota, Maida A. Costa de Oliveira, Hugo Nolan, Lua Henderson, Laurence Brazel, Dahnan Spurling, Valeria Nicolosi, Pietro Martinuz, Mariangela Longhi, Faidra Amargianou, Peer Bärmann, Tristan Petit, Kim McKelvey and Paula E. Colavita discuss properties and demonstrate applications of graphitized carbon thin film electrodes as substrates for correlative-SECCM.*

The authors first discuss chemical and structural properties of these films and how they can be tuned through synthesis/deposition conditions to deliver several of the above-mentioned requirements of correlative-SECCM. *

Marc Brunet Cabré et al. demonstrate the capability and versatility of these substrates using three nano-entities of very distinct morphological and chemical composition, such as carbon-encapsulated nickel nanoparticles (Ni@C), carbon nanocubes (CNC), and 2D MXenes (Ti3C2Tx). Correlative-SEE of these was achieved by coupling SECCM with a range of widely accessible scanning microscopies, including scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and atomic force microscopy (AFM). *

Finally, Marc Brunet Cabré et al. demonstrate correlative-SEE applications that integrate advanced synchrotron techniques such as scanning X-ray microscopy (SXM) in transmission and total electron yield (TEY) modes. Using SXM the authors show that it is possible to obtain both nm-resolution imaging and spectroscopic chemical information from X-ray absorption spectra (XAS) on these thin films substrates to correlate against the electrochemical response of nano-entities. *

NANOSENSORS^TM PointProbe® Plus PPP-NCHR AFM probes (typical resonance frequency: 330 kHz, typical force constant: 42 N/m) were used for the atomic force microscopy (AFM) characterization in non-contact mode.

Figure 2 from Marc Brunet Cabré et al 2024 “Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry”
A) AFM image of anC:NG substrate; red section indicates the approximate region that is expanded in B); both images show a smooth and homogeneous substrate surface. C) Cross section SEM image of the anC:NG substrate: Si, SiO2 and anC:NG layers can be observed in side view, with the anC:NG layer displaying constant thickness and no evidence of inhomogeneities. D) Comparison of Raman spectra of anC, anC:NG and anC:NP displaying the characteristic D and G bands of amorphous carbons, as previously discussed.[13] E) Example of Raman mapping of the D/G intensity ratio across a typical anC:NG surface and F) summary of D/G value distributions for all carbon materials.

S15 from Marc Brunet Cabré et al 2024 “Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry”
SI-5: Morphology of isolated MXene (Ti3C2Tx) on anC by AFM
Figure S15: AFM images of two different regions of anC substrate with dropcasted MXene flakes. (A) Displays an isolated flake on anC and (B) displays multiple flakes which present partial stacking between them.

*Marc Brunet Cabré, Christian Schröder, Filippo Pota, Maida A. Costa de Oliveira, Hugo Nolan, Lua Henderson, Laurence Brazel, Dahnan Spurling, Valeria Nicolosi, Pietro Martinuz, Mariangela Longhi, Faidra Amargianou, Peer Bärmann, Tristan Petit, Kim McKelvey and Paula E. Colavita
Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry
Small Methods 2024, 2400639
DOI: https://doi.org/10.1002/smtd.202400639

The article “Carbon Thin-Film Electrodes as High-Performing Substrates for Correlative Single Entity Electrochemistry” by Marc Brunet Cabré, Christian Schröder, Filippo Pota, Maida A. Costa de Oliveira, Hugo Nolan, Lua Henderson, Laurence Brazel, Dahnan Spurling, Valeria Nicolosi, Pietro Martinuz, Mariangela Longhi, Faidra Amargianou, Peer Bärmann, Tristan Petit, Kim McKelvey and Paula E. Colavita is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.