Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR?
There is an extensive but not conclusive debate about the factors determining selectivity in the competitive path to C1 vs. C2+ products in the electrocatalytic reduction of CO2 (CO2RR). While the predominant indication is that C2+ products require specific active sites and/or surface features of th...
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Elsevier
2025-10-01
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| Series: | Journal of CO2 Utilization |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2212982025001726 |
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| author | Angela Mercedes Ronsisvalle Daniele Giusi Mario Samperi Chiara Genovese Siglinda Perathoner Gabriele Centi Claudio Ampelli |
| author_facet | Angela Mercedes Ronsisvalle Daniele Giusi Mario Samperi Chiara Genovese Siglinda Perathoner Gabriele Centi Claudio Ampelli |
| author_sort | Angela Mercedes Ronsisvalle |
| collection | DOAJ |
| description | There is an extensive but not conclusive debate about the factors determining selectivity in the competitive path to C1 vs. C2+ products in the electrocatalytic reduction of CO2 (CO2RR). While the predominant indication is that C2+ products require specific active sites and/or surface features of the electrocatalyst, we prove here that selectivity can be entirely switched from C2+ to C1 products by controlling H+ accessibility. This indicates that the electrocatalytic path is determined by proton availability rather than the intrinsic presence of specific active sites. To validate this, we investigated CO2RR on CuO nanoplates with identical structural and morphological features (confirmed by XRD, SEM-EDX, TEM, HRTEM analyses) but varying wettability characteristics using different precursors (Li or Na), thereby modulating the surface H+ accessibility. The applied potential also controls this accessibility. By analysing Faradaic selectivity as a function of applied potential across CuO nanoplate samples with different wettability, we observe a transition from 100 % C2+ selectivity to 100 % C1 selectivity, with the potential threshold for this switch dependent on wettability. Our findings demonstrate that the C2+ vs. C1 product pathway in CO2RR is not an intrinsic property of the electrocatalyst but is governed by the availability of surface protons, which is a function of the operating conditions and electrode/electrocatalyst characteristics that regulate proton access to the catalyst surface. |
| format | Article |
| id | doaj-art-e39779ec20ee45f1a05eb7d6550d19e2 |
| institution | Kabale University |
| issn | 2212-9839 |
| language | English |
| publishDate | 2025-10-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Journal of CO2 Utilization |
| spelling | doaj-art-e39779ec20ee45f1a05eb7d6550d19e22025-08-20T03:47:03ZengElsevierJournal of CO2 Utilization2212-98392025-10-0110010318810.1016/j.jcou.2025.103188Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR?Angela Mercedes Ronsisvalle0Daniele Giusi1Mario Samperi2Chiara Genovese3Siglinda Perathoner4Gabriele Centi5Claudio Ampelli6Department of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, ItalyDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, Italy; Corresponding authors.Institute of Advanced for Energy Technology CNR-ITAE, Via Comunale S. Lucia 5, Messina 98126, ItalyDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, ItalyDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, ItalyDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, ItalyDepartment of Chemical, Biological, Pharmaceutical and Environmental Sciences (ChiBioFarAm), University of Messina, ERIC aisbl and CASPE/INSTM, Viale Ferdinando Stagno d′Alcontres 31, Messina 98166, Italy; Corresponding authors.There is an extensive but not conclusive debate about the factors determining selectivity in the competitive path to C1 vs. C2+ products in the electrocatalytic reduction of CO2 (CO2RR). While the predominant indication is that C2+ products require specific active sites and/or surface features of the electrocatalyst, we prove here that selectivity can be entirely switched from C2+ to C1 products by controlling H+ accessibility. This indicates that the electrocatalytic path is determined by proton availability rather than the intrinsic presence of specific active sites. To validate this, we investigated CO2RR on CuO nanoplates with identical structural and morphological features (confirmed by XRD, SEM-EDX, TEM, HRTEM analyses) but varying wettability characteristics using different precursors (Li or Na), thereby modulating the surface H+ accessibility. The applied potential also controls this accessibility. By analysing Faradaic selectivity as a function of applied potential across CuO nanoplate samples with different wettability, we observe a transition from 100 % C2+ selectivity to 100 % C1 selectivity, with the potential threshold for this switch dependent on wettability. Our findings demonstrate that the C2+ vs. C1 product pathway in CO2RR is not an intrinsic property of the electrocatalyst but is governed by the availability of surface protons, which is a function of the operating conditions and electrode/electrocatalyst characteristics that regulate proton access to the catalyst surface.http://www.sciencedirect.com/science/article/pii/S2212982025001726CO2RRCu electrocatalystsMulti-carbon productsHydrothermal synthesisProton accessibilityElectrode wettability |
| spellingShingle | Angela Mercedes Ronsisvalle Daniele Giusi Mario Samperi Chiara Genovese Siglinda Perathoner Gabriele Centi Claudio Ampelli Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? Journal of CO2 Utilization CO2RR Cu electrocatalysts Multi-carbon products Hydrothermal synthesis Proton accessibility Electrode wettability |
| title | Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? |
| title_full | Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? |
| title_fullStr | Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? |
| title_full_unstemmed | Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? |
| title_short | Does the presence of only specific active sites control the switch of selectivity from C1 to C2+ products in CO2RR? |
| title_sort | does the presence of only specific active sites control the switch of selectivity from c1 to c2 products in co2rr |
| topic | CO2RR Cu electrocatalysts Multi-carbon products Hydrothermal synthesis Proton accessibility Electrode wettability |
| url | http://www.sciencedirect.com/science/article/pii/S2212982025001726 |
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