Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate

Multi-junction copper oxide nanocomposite photocathodes formed by CuO nanowire arrays coated with Cu2O nanopyramids or stacked nanoprisms, i.e. CuO(NWA)|Cu2O(NPy), exhibit remarkable electrochemical stability toward reductive corrosion. Whilst bare CuO nanowires are extremely prone to decomposition...

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Main Authors: Tahereh Mokary Yazdely, Ricard Garcia-Valls, Alberto Puga
Format: Article
Language:English
Published: Elsevier 2025-01-01
Series:Next Nanotechnology
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Online Access:http://www.sciencedirect.com/science/article/pii/S294982952400086X
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author Tahereh Mokary Yazdely
Ricard Garcia-Valls
Alberto Puga
author_facet Tahereh Mokary Yazdely
Ricard Garcia-Valls
Alberto Puga
author_sort Tahereh Mokary Yazdely
collection DOAJ
description Multi-junction copper oxide nanocomposite photocathodes formed by CuO nanowire arrays coated with Cu2O nanopyramids or stacked nanoprisms, i.e. CuO(NWA)|Cu2O(NPy), exhibit remarkable electrochemical stability toward reductive corrosion. Whilst bare CuO nanowires are extremely prone to decomposition even at the mildest potentials applied, the core@shell morphology of CuO(NWA)|Cu2O(NPy) resists cathodic potentials up to −0.7 V (vs. AgCl/Ag). Precisely controlled electrodeposition of silver or gold nanoparticles resulted in Ag nanotrails arranged on flatter surface regions in CuO(NWA)|Cu2O(NPy)|Ag, whereas Au nanoaggregates were deposited on both flat areas and prominent apexes in CuO(NWA)|Cu2O(NPy)|Au. Photocurrent measurements demonstrated redox process activation, namely above three-fold current density increases, by light for CuO(NWA)|Cu2O(NPy). The participation of CO2 in them was also confirmed by around 70 % photocurrent increases (higher than 0.2 mA cm−2) and by sensibly milder cathodic potential onsets (≤ −0.4 V), as recorded by linear sweep voltammetry. Photoelectrochemical CO2 reduction experiments under simulated sunlight yielded oxygenated products in the liquid phase, chiefly formate, although acetate was also consistently produced, especially in the presence of noble metal co-catalysts. Specifically, acetate yields increased by 30–40 % for CuO(NWA)|Cu2O(NPy)|Ag and CuO(NWA)|Cu2O(NPy)|Au up to 56 and 54 μM, respectively. Methanol could be also formed under specific conditions. A mechanistic proposal is postulated to account for all stability and selectivity phenomena observed.
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spelling doaj-art-e3282d33f8a842c887ec2d03f22c5f3b2025-08-20T03:30:45ZengElsevierNext Nanotechnology2949-82952025-01-01710012510.1016/j.nxnano.2024.100125Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetateTahereh Mokary Yazdely0Ricard Garcia-Valls1Alberto Puga2Department of Chemical Engineering, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona 43007, SpainDepartment of Chemical Engineering, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona 43007, SpainCorresponding author.; Department of Chemical Engineering, Universitat Rovira i Virgili, Av. Països Catalans 26, Tarragona 43007, SpainMulti-junction copper oxide nanocomposite photocathodes formed by CuO nanowire arrays coated with Cu2O nanopyramids or stacked nanoprisms, i.e. CuO(NWA)|Cu2O(NPy), exhibit remarkable electrochemical stability toward reductive corrosion. Whilst bare CuO nanowires are extremely prone to decomposition even at the mildest potentials applied, the core@shell morphology of CuO(NWA)|Cu2O(NPy) resists cathodic potentials up to −0.7 V (vs. AgCl/Ag). Precisely controlled electrodeposition of silver or gold nanoparticles resulted in Ag nanotrails arranged on flatter surface regions in CuO(NWA)|Cu2O(NPy)|Ag, whereas Au nanoaggregates were deposited on both flat areas and prominent apexes in CuO(NWA)|Cu2O(NPy)|Au. Photocurrent measurements demonstrated redox process activation, namely above three-fold current density increases, by light for CuO(NWA)|Cu2O(NPy). The participation of CO2 in them was also confirmed by around 70 % photocurrent increases (higher than 0.2 mA cm−2) and by sensibly milder cathodic potential onsets (≤ −0.4 V), as recorded by linear sweep voltammetry. Photoelectrochemical CO2 reduction experiments under simulated sunlight yielded oxygenated products in the liquid phase, chiefly formate, although acetate was also consistently produced, especially in the presence of noble metal co-catalysts. Specifically, acetate yields increased by 30–40 % for CuO(NWA)|Cu2O(NPy)|Ag and CuO(NWA)|Cu2O(NPy)|Au up to 56 and 54 μM, respectively. Methanol could be also formed under specific conditions. A mechanistic proposal is postulated to account for all stability and selectivity phenomena observed.http://www.sciencedirect.com/science/article/pii/S294982952400086XCarbon dioxideMethanolAcetateHeterojunctionCopper oxidesSolar fuels
spellingShingle Tahereh Mokary Yazdely
Ricard Garcia-Valls
Alberto Puga
Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
Next Nanotechnology
Carbon dioxide
Methanol
Acetate
Heterojunction
Copper oxides
Solar fuels
title Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
title_full Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
title_fullStr Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
title_full_unstemmed Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
title_short Photoelectrochemical CO2 reduction on CuO-Cu2O nanocomposites with noble metal co-catalysts enhances the production of C1 oxygenates and acetate
title_sort photoelectrochemical co2 reduction on cuo cu2o nanocomposites with noble metal co catalysts enhances the production of c1 oxygenates and acetate
topic Carbon dioxide
Methanol
Acetate
Heterojunction
Copper oxides
Solar fuels
url http://www.sciencedirect.com/science/article/pii/S294982952400086X
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AT ricardgarciavalls photoelectrochemicalco2reductiononcuocu2onanocompositeswithnoblemetalcocatalystsenhancestheproductionofc1oxygenatesandacetate
AT albertopuga photoelectrochemicalco2reductiononcuocu2onanocompositeswithnoblemetalcocatalystsenhancestheproductionofc1oxygenatesandacetate