A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
What Determines the Electrochemical Properties of Nitrogenated Amorphous Carbon Thin Films? (2021)
Etula, J., Wester, N., Liljeström, T., Sainio, S., Palomäki, T., Arstila, K., Sajavaara, T., Koskinen, J., Caro, M. A., & Laurila, T. (2021). What Determines the Electrochemical Properties of Nitrogenated Amorphous Carbon Thin Films?. Chemistry of Materials, 33(17), 6813-6824. https://doi.org/10.1021/acs.chemmater.1c01519
JYU-tekijät tai -toimittajat
Julkaisun tiedot
Julkaisun kaikki tekijät tai toimittajat: Etula, Jarkko; Wester, Niklas; Liljeström, Touko; Sainio, Sami; Palomäki, Tommi; Arstila, Kai; Sajavaara, Timo; Koskinen, Jari; Caro, Miguel A.; Laurila, Tomi
Lehti tai sarja: Chemistry of Materials
ISSN: 0897-4756
eISSN: 1520-5002
Julkaisuvuosi: 2021
Ilmestymispäivä: 23.08.2021
Volyymi: 33
Lehden numero: 17
Artikkelin sivunumerot: 6813-6824
Kustantaja: American Chemical Society (ACS)
Julkaisumaa: Yhdysvallat (USA)
Julkaisun kieli: englanti
DOI: https://doi.org/10.1021/acs.chemmater.1c01519
Julkaisun avoin saatavuus: Avoimesti saatavilla
Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava
Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/77472
Tiivistelmä
Linking structural and compositional features with the observed electrochemical performance is often ambiguous and sensitive to known and unknown impurities. Here an extensive experimental investigation augmented by computational analyses is linked to the electrochemical characterization of in situ nitrogen-doped tetrahedral amorphous carbon thin films (ta-C:N). Raman spectroscopy combined with X-ray reflectivity shows nitrogen disrupting the sp3 C–C structure of the reference ta-C, supported by the observations of graphitic nitrogen substitution in X-ray absorption spectroscopy. The surface roughness also increases, as observed in atomic force microscopy and atomic-level computational analyses. These changes are linked to significant increases in the hydrogen and oxygen content of the films by utilizing time-of-flight elastic recoil detection analysis. The conductivity of the films increases as a function of the nitrogen content, which is seen as a facile reversible outer-sphere redox reaction on ta-C:N electrodes. However, for the surface-sensitive inner-sphere redox (ISR) analytes, it is shown that the electrochemical response instead follows the oxygen and hydrogen content. We argue that the passivation of the required surface adsorption sites by hydrogen decreases the rates of all of the chemically different ISR probes investigated on nitrogenated surfaces significantly below that of the nitrogen-free reference sample. This hypothesis can be used to readily rationalize many of the contradictory electrochemical results reported in the literature.
YSO-asiasanat: sähkökemia
Liittyvät organisaatiot
OKM-raportointi: Kyllä
Raportointivuosi: 2021
JUFO-taso: 3