Electrochemical reduction of carbon dioxide to formate in a flow cell on CuSx grown by atomic layer deposition

M. Suominen; M. Mäntymäki; M. Mattinen; J. Sainio; M. Putkonen; T. Kallio

doi:10.1016/j.mtsust.2023.100575

Electrochemical reduction of carbon dioxide to formate in a flow cell on CuS_x grown by atomic layer deposition

M. Suominen^*, M. Mäntymäki, M. Mattinen, J. Sainio, M. Putkonen, T. Kallio^*

^*Tämän työn vastaava kirjoittaja

University of Helsinki

Tutkimustuotos: Lehtiartikkeli › Article › Scientific › vertaisarvioitu

14 Sitaatiot (Scopus)

92 Lataukset (Pure)

Abstrakti

Transition metal chalcogenides (TMCs) are promising pre-catalysts for tuning the selectivity of electrochemical carbon dioxide (CO₂₎ reduction (CO2R). Atomic layer deposition (ALD) enables well-controlled growth of thin TMC films on various gas diffusion electrodes. Herein, we have studied the CO2R performance of ALD-grown copper sulfide (CuS_x) in a flow cell. The effects of electrode configuration, electrolyte concentration, temperature, and electrolysis time were carefully studied, combined with pre- and post-electrolysis physico-chemical analyses of the films. The unique selectivity of sulfur-doped Cu towards formate was retained with Faradaic efficiencies between 40 and 60%, but slow selectivity changes were observed over time. Major loss of sulfur was encountered during the initial 5-min reduction period, and after that, progressive formation of nanoparticles could be observed. Comparisons to ALD-grown Cu thin film and CuS_x-modified Cu foam electrodes verified the importance of sulfur and suggested that other electrocatalyst films could be easily realized with ALD.

Alkuperäiskieli	Englanti
Artikkeli	100575
Sivumäärä	10
Julkaisu	Materials Today Sustainability
Vuosikerta	24
Varhainen verkossa julkaisun päivämäärä	2 marrask. 2023
DOI - pysyväislinkit	https://doi.org/10.1016/j.mtsust.2023.100575
Tila	Julkaistu - jouluk. 2023
OKM-julkaisutyyppi	A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Rahoitus

M.P. acknowledges funding from the Academy of Finland by the profiling action on Matter and Materials (grant no. 318913). M.S. and T.K. acknowledge funding from Jane and Aatos Erkko foundation (the USVA project). Dr. Timo Hatanpää is thanked for synthesizing the Cu(dmap)2 precursor. Mr. Chao Zhang is thanked for the ALD copper film depositions. Dr. Lilian Moumaneix is thanked for the TEM images. This work made use of Aalto University RawMatters, Bioeconomy, and OtaNano Low Temperature Laboratory and Nanomicroscopy Center facilities, and the ALD center Finland research infrastructure. M.P. acknowledges funding from the Academy of Finland by the profiling action on Matter and Materials (grant no. 318913). M.S. and T.K. acknowledge funding from Jane and Aatos Erkko foundation (the USVA project). Dr. Timo Hatanpää is thanked for synthesizing the Cu(dmap) 2 precursor. Mr. Chao Zhang is thanked for the ALD copper film depositions. Dr. Lilian Moumaneix is thanked for the TEM images. This work made use of Aalto University RawMatters, Bioeconomy, and OtaNano Low Temperature Laboratory and Nanomicroscopy Center facilities, and the ALD center Finland research infrastructure.

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@article{8e27923659f046b8a8f73940a4bdc5a2,

title = "Electrochemical reduction of carbon dioxide to formate in a flow cell on CuSx grown by atomic layer deposition",

abstract = "Transition metal chalcogenides (TMCs) are promising pre-catalysts for tuning the selectivity of electrochemical carbon dioxide (CO2) reduction (CO2R). Atomic layer deposition (ALD) enables well-controlled growth of thin TMC films on various gas diffusion electrodes. Herein, we have studied the CO2R performance of ALD-grown copper sulfide (CuSx) in a flow cell. The effects of electrode configuration, electrolyte concentration, temperature, and electrolysis time were carefully studied, combined with pre- and post-electrolysis physico-chemical analyses of the films. The unique selectivity of sulfur-doped Cu towards formate was retained with Faradaic efficiencies between 40 and 60\%, but slow selectivity changes were observed over time. Major loss of sulfur was encountered during the initial 5-min reduction period, and after that, progressive formation of nanoparticles could be observed. Comparisons to ALD-grown Cu thin film and CuSx-modified Cu foam electrodes verified the importance of sulfur and suggested that other electrocatalyst films could be easily realized with ALD.",

keywords = "ALD, Copper sulfide, Electrochemical CO reduction, Electrolyte concentration effects, Temperature effects",

author = "M. Suominen and M. M{\"a}ntym{\"a}ki and M. Mattinen and J. Sainio and M. Putkonen and T. Kallio",

note = "Funding Information: M.P. acknowledges funding from the Academy of Finland by the profiling action on Matter and Materials (grant no. 318913). M.S. and T.K. acknowledge funding from Jane and Aatos Erkko foundation (the USVA project). Dr. Timo Hatanp{\"a}{\"a} is thanked for synthesizing the Cu(dmap) 2 precursor. Mr. Chao Zhang is thanked for the ALD copper film depositions. Dr. Lilian Moumaneix is thanked for the TEM images. This work made use of Aalto University RawMatters, Bioeconomy, and OtaNano Low Temperature Laboratory and Nanomicroscopy Center facilities, and the ALD center Finland research infrastructure. Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = dec,

doi = "10.1016/j.mtsust.2023.100575",

language = "English",

volume = "24",

journal = "Materials Today Sustainability",

issn = "2589-2347",

publisher = "Elsevier",

}

TY - JOUR

T1 - Electrochemical reduction of carbon dioxide to formate in a flow cell on CuSx grown by atomic layer deposition

AU - Suominen, M.

AU - Mäntymäki, M.

AU - Mattinen, M.

AU - Sainio, J.

AU - Putkonen, M.

AU - Kallio, T.

N1 - Funding Information: M.P. acknowledges funding from the Academy of Finland by the profiling action on Matter and Materials (grant no. 318913). M.S. and T.K. acknowledge funding from Jane and Aatos Erkko foundation (the USVA project). Dr. Timo Hatanpää is thanked for synthesizing the Cu(dmap) 2 precursor. Mr. Chao Zhang is thanked for the ALD copper film depositions. Dr. Lilian Moumaneix is thanked for the TEM images. This work made use of Aalto University RawMatters, Bioeconomy, and OtaNano Low Temperature Laboratory and Nanomicroscopy Center facilities, and the ALD center Finland research infrastructure. Publisher Copyright: © 2023 The Author(s)

PY - 2023/12

Y1 - 2023/12

N2 - Transition metal chalcogenides (TMCs) are promising pre-catalysts for tuning the selectivity of electrochemical carbon dioxide (CO2) reduction (CO2R). Atomic layer deposition (ALD) enables well-controlled growth of thin TMC films on various gas diffusion electrodes. Herein, we have studied the CO2R performance of ALD-grown copper sulfide (CuSx) in a flow cell. The effects of electrode configuration, electrolyte concentration, temperature, and electrolysis time were carefully studied, combined with pre- and post-electrolysis physico-chemical analyses of the films. The unique selectivity of sulfur-doped Cu towards formate was retained with Faradaic efficiencies between 40 and 60%, but slow selectivity changes were observed over time. Major loss of sulfur was encountered during the initial 5-min reduction period, and after that, progressive formation of nanoparticles could be observed. Comparisons to ALD-grown Cu thin film and CuSx-modified Cu foam electrodes verified the importance of sulfur and suggested that other electrocatalyst films could be easily realized with ALD.

AB - Transition metal chalcogenides (TMCs) are promising pre-catalysts for tuning the selectivity of electrochemical carbon dioxide (CO2) reduction (CO2R). Atomic layer deposition (ALD) enables well-controlled growth of thin TMC films on various gas diffusion electrodes. Herein, we have studied the CO2R performance of ALD-grown copper sulfide (CuSx) in a flow cell. The effects of electrode configuration, electrolyte concentration, temperature, and electrolysis time were carefully studied, combined with pre- and post-electrolysis physico-chemical analyses of the films. The unique selectivity of sulfur-doped Cu towards formate was retained with Faradaic efficiencies between 40 and 60%, but slow selectivity changes were observed over time. Major loss of sulfur was encountered during the initial 5-min reduction period, and after that, progressive formation of nanoparticles could be observed. Comparisons to ALD-grown Cu thin film and CuSx-modified Cu foam electrodes verified the importance of sulfur and suggested that other electrocatalyst films could be easily realized with ALD.

KW - ALD

KW - Copper sulfide

KW - Electrochemical CO reduction

KW - Electrolyte concentration effects

KW - Temperature effects

UR - https://www.scopus.com/pages/publications/85175483637

U2 - 10.1016/j.mtsust.2023.100575

DO - 10.1016/j.mtsust.2023.100575

M3 - Article

AN - SCOPUS:85175483637

SN - 2589-2347

VL - 24

JO - Materials Today Sustainability

JF - Materials Today Sustainability

M1 - 100575

ER -

Electrochemical reduction of carbon dioxide to formate in a flow cell on CuSx grown by atomic layer deposition

Abstrakti

Rahoitus

YK:n kestävän kehityksen tavoitteet

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Electrochemical reduction of carbon dioxide to formate in a flow cell on CuS_x grown by atomic layer deposition