Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3−
Abstract Electrochemical C−N coupling presents a promising strategy for converting abundant small molecules like CO2 and NO3− to produce low‐carbon‐intensity chemicals in a potentially more sustainable route. A prominent challenge is the limited product scope, particularly for organonitrogen chemica...
Saved in:
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2025-01-01
|
| Series: | Advanced Science |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/advs.202414431 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1841543122866143232 |
|---|---|
| author | Shuai Yan Shuai Chen Morgan McKee Alexandre Terry Ralf Weisbarth Nikolay Kornienko |
| author_facet | Shuai Yan Shuai Chen Morgan McKee Alexandre Terry Ralf Weisbarth Nikolay Kornienko |
| author_sort | Shuai Yan |
| collection | DOAJ |
| description | Abstract Electrochemical C−N coupling presents a promising strategy for converting abundant small molecules like CO2 and NO3− to produce low‐carbon‐intensity chemicals in a potentially more sustainable route. A prominent challenge is the limited product scope, particularly for organonitrogen chemicals featuring a variety of functional groups, alongside the limited understanding of plausible reaction mechanisms leading up to these products. In light of this, the total electrosynthesis method is reported for producing N, N‐dimethylformamide (DMF), a widespread solvent and commodity chemical, from NO3− and CO2. This method enabled a notable production rate of 1.24 mmol h−1 gcat−1 for DMF employing a hybrid Ag/Cu catalyst. Additionally, an impressive Faradaic efficiency (FE) of 28.6% is attained for DMF through oxidative coupling of dimethylamine using Ag/Cu catalyst. Through a distinctive retrosynthetic experimental analysis, the DMF synthesis pathway is systematically deconstructed, tracing its origins from dimethylamine to methylamine, and ultimately to CO2 and NO3−. The investigation revealed that the hydrogenation of coupled intermediates proves to be the limiting step, rather than the C−N coupling steps in the synthetic pathway. Finally, using a combination of in situ measurements and retrosynthetic analysis, the possible mechanism is elucidated underlying DMF synthesis and identified subsequent routes for system improvement. |
| format | Article |
| id | doaj-art-0247d34df1d54b11bd93b79ad64e46a5 |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj-art-0247d34df1d54b11bd93b79ad64e46a52025-01-13T15:29:43ZengWileyAdvanced Science2198-38442025-01-01122n/an/a10.1002/advs.202414431Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3−Shuai Yan0Shuai Chen1Morgan McKee2Alexandre Terry3Ralf Weisbarth4Nikolay Kornienko5Institute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyInstitute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyInstitute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyInstitute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyInstitute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyInstitute of Inorganic ChemistryUniversity of BonnGerhard‐Domagk‐Str. 153121BonnGermanyAbstract Electrochemical C−N coupling presents a promising strategy for converting abundant small molecules like CO2 and NO3− to produce low‐carbon‐intensity chemicals in a potentially more sustainable route. A prominent challenge is the limited product scope, particularly for organonitrogen chemicals featuring a variety of functional groups, alongside the limited understanding of plausible reaction mechanisms leading up to these products. In light of this, the total electrosynthesis method is reported for producing N, N‐dimethylformamide (DMF), a widespread solvent and commodity chemical, from NO3− and CO2. This method enabled a notable production rate of 1.24 mmol h−1 gcat−1 for DMF employing a hybrid Ag/Cu catalyst. Additionally, an impressive Faradaic efficiency (FE) of 28.6% is attained for DMF through oxidative coupling of dimethylamine using Ag/Cu catalyst. Through a distinctive retrosynthetic experimental analysis, the DMF synthesis pathway is systematically deconstructed, tracing its origins from dimethylamine to methylamine, and ultimately to CO2 and NO3−. The investigation revealed that the hydrogenation of coupled intermediates proves to be the limiting step, rather than the C−N coupling steps in the synthetic pathway. Finally, using a combination of in situ measurements and retrosynthetic analysis, the possible mechanism is elucidated underlying DMF synthesis and identified subsequent routes for system improvement.https://doi.org/10.1002/advs.202414431couplingelectrosynthesishydrogenationretrosynthetic analysis |
| spellingShingle | Shuai Yan Shuai Chen Morgan McKee Alexandre Terry Ralf Weisbarth Nikolay Kornienko Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− Advanced Science coupling electrosynthesis hydrogenation retrosynthetic analysis |
| title | Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− |
| title_full | Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− |
| title_fullStr | Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− |
| title_full_unstemmed | Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− |
| title_short | Total Electrosynthesis of N, N‐Dimethylformamide From CO2 and NO3− |
| title_sort | total electrosynthesis of n n dimethylformamide from co2 and no3 |
| topic | coupling electrosynthesis hydrogenation retrosynthetic analysis |
| url | https://doi.org/10.1002/advs.202414431 |
| work_keys_str_mv | AT shuaiyan totalelectrosynthesisofnndimethylformamidefromco2andno3 AT shuaichen totalelectrosynthesisofnndimethylformamidefromco2andno3 AT morganmckee totalelectrosynthesisofnndimethylformamidefromco2andno3 AT alexandreterry totalelectrosynthesisofnndimethylformamidefromco2andno3 AT ralfweisbarth totalelectrosynthesisofnndimethylformamidefromco2andno3 AT nikolaykornienko totalelectrosynthesisofnndimethylformamidefromco2andno3 |