Role of oxide support in electrocatalytic nitrate reduction on Cu
Abstract The electrochemical nitrate reduction reaction (NO3RR) has the potential for distributed water treatment and renewable chemical synthesis. Cu is an active monometallic electrocatalyst for the NO3RR in acidic and alkaline electrolytes, where activity is limited by the reduction of adsorbed n...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2024-02-01
|
| Series: | Electrochemical Science Advances |
| Online Access: | https://doi.org/10.1002/elsa.202100201 |
| _version_ | 1797316446639882240 |
|---|---|
| author | O. Quinn Carvalho Sophia R. S. Jones Ashley E. Berninghaus Richard F. Hilliard Tyler S. Radniecki Kelsey A. Stoerzinger |
| author_facet | O. Quinn Carvalho Sophia R. S. Jones Ashley E. Berninghaus Richard F. Hilliard Tyler S. Radniecki Kelsey A. Stoerzinger |
| author_sort | O. Quinn Carvalho |
| collection | DOAJ |
| description | Abstract The electrochemical nitrate reduction reaction (NO3RR) has the potential for distributed water treatment and renewable chemical synthesis. Cu is an active monometallic electrocatalyst for the NO3RR in acidic and alkaline electrolytes, where activity is limited by the reduction of adsorbed nitrate to nitrite. Oxygen‐vacancy forming metal‐oxide supports provide sites for N‐O bond activation in thermal reduction, impacting product distribution as well. Here we compare the electrochemical NO3RR activity of Cu deposited on two metal‐oxide supports (cerium dioxide [Cu/CeO2‐δ] and fluorine‐doped tin dioxide [Cu/FTO]) to a Cu foil benchmark. Considering activity in phosphate‐buffered neutral media, nitrate and adsorbed hydrogen compete for surface sites under NO3RR conditions. The less‐cathodic overpotential on Cu/CeO2‐δ compared to Cu/FTO is attributed to stronger nitrate adsorption, similar to thermal nitrate reduction. Utilization of CeO2‐δ as an electrocatalyst support slightly shifting product distribution toward more oxidized products, either by enhancing nitrate affinity or by a more dynamic process involving the formation and healing of oxygen vacancies (𝑣O••). These results suggest supporting catalysts on metal oxides may enhance activity by promoting the adsorption of anionic reactants on cathodic electrocatalysts. |
| first_indexed | 2024-03-08T03:18:30Z |
| format | Article |
| id | doaj.art-4144252c46fc456c8bb0f8b326d22e90 |
| institution | Directory Open Access Journal |
| issn | 2698-5977 |
| language | English |
| last_indexed | 2024-03-08T03:18:30Z |
| publishDate | 2024-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | Electrochemical Science Advances |
| spelling | doaj.art-4144252c46fc456c8bb0f8b326d22e902024-02-12T11:40:07ZengWiley-VCHElectrochemical Science Advances2698-59772024-02-0141n/an/a10.1002/elsa.202100201Role of oxide support in electrocatalytic nitrate reduction on CuO. Quinn Carvalho0Sophia R. S. Jones1Ashley E. Berninghaus2Richard F. Hilliard3Tyler S. Radniecki4Kelsey A. Stoerzinger5School of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USASchool of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USASchool of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USASchool of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USASchool of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USASchool of Chemical Biological, and Environmental Engineering Oregon State University Corvallis Oregon USAAbstract The electrochemical nitrate reduction reaction (NO3RR) has the potential for distributed water treatment and renewable chemical synthesis. Cu is an active monometallic electrocatalyst for the NO3RR in acidic and alkaline electrolytes, where activity is limited by the reduction of adsorbed nitrate to nitrite. Oxygen‐vacancy forming metal‐oxide supports provide sites for N‐O bond activation in thermal reduction, impacting product distribution as well. Here we compare the electrochemical NO3RR activity of Cu deposited on two metal‐oxide supports (cerium dioxide [Cu/CeO2‐δ] and fluorine‐doped tin dioxide [Cu/FTO]) to a Cu foil benchmark. Considering activity in phosphate‐buffered neutral media, nitrate and adsorbed hydrogen compete for surface sites under NO3RR conditions. The less‐cathodic overpotential on Cu/CeO2‐δ compared to Cu/FTO is attributed to stronger nitrate adsorption, similar to thermal nitrate reduction. Utilization of CeO2‐δ as an electrocatalyst support slightly shifting product distribution toward more oxidized products, either by enhancing nitrate affinity or by a more dynamic process involving the formation and healing of oxygen vacancies (𝑣O••). These results suggest supporting catalysts on metal oxides may enhance activity by promoting the adsorption of anionic reactants on cathodic electrocatalysts.https://doi.org/10.1002/elsa.202100201 |
| spellingShingle | O. Quinn Carvalho Sophia R. S. Jones Ashley E. Berninghaus Richard F. Hilliard Tyler S. Radniecki Kelsey A. Stoerzinger Role of oxide support in electrocatalytic nitrate reduction on Cu Electrochemical Science Advances |
| title | Role of oxide support in electrocatalytic nitrate reduction on Cu |
| title_full | Role of oxide support in electrocatalytic nitrate reduction on Cu |
| title_fullStr | Role of oxide support in electrocatalytic nitrate reduction on Cu |
| title_full_unstemmed | Role of oxide support in electrocatalytic nitrate reduction on Cu |
| title_short | Role of oxide support in electrocatalytic nitrate reduction on Cu |
| title_sort | role of oxide support in electrocatalytic nitrate reduction on cu |
| url | https://doi.org/10.1002/elsa.202100201 |
| work_keys_str_mv | AT oquinncarvalho roleofoxidesupportinelectrocatalyticnitratereductiononcu AT sophiarsjones roleofoxidesupportinelectrocatalyticnitratereductiononcu AT ashleyeberninghaus roleofoxidesupportinelectrocatalyticnitratereductiononcu AT richardfhilliard roleofoxidesupportinelectrocatalyticnitratereductiononcu AT tylersradniecki roleofoxidesupportinelectrocatalyticnitratereductiononcu AT kelseyastoerzinger roleofoxidesupportinelectrocatalyticnitratereductiononcu |