Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation
The origin of selectivity and activity of the CO2 hydrogenation reaction on single-atom catalysts composed of three adjacent 3d transition metals (Fe, Co, and Ni) supported on N-doped graphene quantum dots were systematically investigated and compared using density functional theory (DFT) calculatio...
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Elsevier
2024-12-01
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| Series: | Carbon Trends |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S266705692400110X |
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| author | Armin Mahmoudi Siyavash Kazemi Movahed Hossein Farrokhpour |
| author_facet | Armin Mahmoudi Siyavash Kazemi Movahed Hossein Farrokhpour |
| author_sort | Armin Mahmoudi |
| collection | DOAJ |
| description | The origin of selectivity and activity of the CO2 hydrogenation reaction on single-atom catalysts composed of three adjacent 3d transition metals (Fe, Co, and Ni) supported on N-doped graphene quantum dots were systematically investigated and compared using density functional theory (DFT) calculations, natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM) analysis. This study reveals that π-backbonding between the metal and CO2* does not occur and [CO2]δ+ species drive the reaction. The CO2* reacts with H2 via the Eley-Rideal (ER) mechanism by using the synergistic effects of the N site. The higher the partial positive charge on the C atom, the lower the Ea of the reaction. Subsequently, a tautomerization reaction, which is facilitated by hydrogen bonding, occurs and hydrogen is transferred to HCOO* resulting in the formation of CHOOH*. This study shows the selective formation of formic acid from CO2 is accessible on these SACs and Fe-SAC is the best one between these three catalysts. Although CO2 is more inert than formic acid the H2 molecule reacts with the adsorbed formic acid more difficult than the adsorbed CO2. It is because the hydrogenation of formic acid causes C-H bond formation resulting in failure of the coordinated O atom's octet and the unstable H2COOH* is formed. This step is the rate-determining step of HOCH2OH formation from CO2, with Ea of 1.94, 2.03, and 2.23 eV for Fe, Co, and Ni, respectively. Finally, the system undergoes another tautomerization reaction resulting in the formation of HOCH2OH (formaldehyde monohydrate). |
| format | Article |
| id | doaj-art-a7b27398cd9640e7a5a1b78b1718fa38 |
| institution | Kabale University |
| issn | 2667-0569 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Elsevier |
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| series | Carbon Trends |
| spelling | doaj-art-a7b27398cd9640e7a5a1b78b1718fa382024-12-15T06:17:39ZengElsevierCarbon Trends2667-05692024-12-0117100430Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenationArmin Mahmoudi0Siyavash Kazemi Movahed1Hossein Farrokhpour2Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, IranCorrespondence authors at: Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, Iran.; Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, IranCorrespondence authors at: Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, Iran.; Department of Chemistry, Isfahan University of Technology, Isfahan 8415683111, IranThe origin of selectivity and activity of the CO2 hydrogenation reaction on single-atom catalysts composed of three adjacent 3d transition metals (Fe, Co, and Ni) supported on N-doped graphene quantum dots were systematically investigated and compared using density functional theory (DFT) calculations, natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM) analysis. This study reveals that π-backbonding between the metal and CO2* does not occur and [CO2]δ+ species drive the reaction. The CO2* reacts with H2 via the Eley-Rideal (ER) mechanism by using the synergistic effects of the N site. The higher the partial positive charge on the C atom, the lower the Ea of the reaction. Subsequently, a tautomerization reaction, which is facilitated by hydrogen bonding, occurs and hydrogen is transferred to HCOO* resulting in the formation of CHOOH*. This study shows the selective formation of formic acid from CO2 is accessible on these SACs and Fe-SAC is the best one between these three catalysts. Although CO2 is more inert than formic acid the H2 molecule reacts with the adsorbed formic acid more difficult than the adsorbed CO2. It is because the hydrogenation of formic acid causes C-H bond formation resulting in failure of the coordinated O atom's octet and the unstable H2COOH* is formed. This step is the rate-determining step of HOCH2OH formation from CO2, with Ea of 1.94, 2.03, and 2.23 eV for Fe, Co, and Ni, respectively. Finally, the system undergoes another tautomerization reaction resulting in the formation of HOCH2OH (formaldehyde monohydrate).http://www.sciencedirect.com/science/article/pii/S266705692400110XCO2 hydrogenationNitrogen dopingSingle-atom catalystDensity functional theory: Graphene quantum dotSynergistic activation |
| spellingShingle | Armin Mahmoudi Siyavash Kazemi Movahed Hossein Farrokhpour Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation Carbon Trends CO2 hydrogenation Nitrogen doping Single-atom catalyst Density functional theory: Graphene quantum dot Synergistic activation |
| title | Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation |
| title_full | Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation |
| title_fullStr | Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation |
| title_full_unstemmed | Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation |
| title_short | Mechanistic insight into the catalytic activities of metallic sites on nitrogen-doped graphene quantum dots for CO2 hydrogenation |
| title_sort | mechanistic insight into the catalytic activities of metallic sites on nitrogen doped graphene quantum dots for co2 hydrogenation |
| topic | CO2 hydrogenation Nitrogen doping Single-atom catalyst Density functional theory: Graphene quantum dot Synergistic activation |
| url | http://www.sciencedirect.com/science/article/pii/S266705692400110X |
| work_keys_str_mv | AT arminmahmoudi mechanisticinsightintothecatalyticactivitiesofmetallicsitesonnitrogendopedgraphenequantumdotsforco2hydrogenation AT siyavashkazemimovahed mechanisticinsightintothecatalyticactivitiesofmetallicsitesonnitrogendopedgraphenequantumdotsforco2hydrogenation AT hosseinfarrokhpour mechanisticinsightintothecatalyticactivitiesofmetallicsitesonnitrogendopedgraphenequantumdotsforco2hydrogenation |