Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction
Defective electrocatalysts, especially for intrinsic defective carbon, have aroused a wide concern owing to high spin and charge densities. However, the designated nitrogen species favorable for creating defects by the removal of nitrogen, and the influence of defects for the coordination structure...
| Main Authors: | , , , , , , , , , , , , |
|---|---|
| Format: | Journal Article |
| Language: | English |
| Published: |
TSINGHUA UNIV PRESS
2021
|
| Subjects: | |
| Online Access: | http://purl.org/au-research/grants/arc/DP180100568 http://hdl.handle.net/20.500.11937/90806 |
| _version_ | 1848765433506693120 |
|---|---|
| author | Su, P. Huang, W. Zhang, J. Guharoy, U. Du, Q. Sun, Q. Jiang, Q. Cheng, Yi Yang, J. Zhang, X. Liu, Y. Jiang, San Ping Liu, Jian |
| author_facet | Su, P. Huang, W. Zhang, J. Guharoy, U. Du, Q. Sun, Q. Jiang, Q. Cheng, Yi Yang, J. Zhang, X. Liu, Y. Jiang, San Ping Liu, Jian |
| author_sort | Su, P. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Defective electrocatalysts, especially for intrinsic defective carbon, have aroused a wide concern owing to high spin and charge densities. However, the designated nitrogen species favorable for creating defects by the removal of nitrogen, and the influence of defects for the coordination structure of active site and oxygen reduction reaction (ORR) activity have not been elucidated. Herein, we designed and synthesized a pair of electrocatalysts, denoted as Fe-N/C and Fe-ND/C for coordination sites of atomic iron-nitrogen and iron-nitrogen/defect configuration embedded in hollow carbon spheres, respectively, through direct pyrolysis of their corresponding hollow carbon spheres adsorbed with Fe(acac)3. The nitrogen defects were fabricated via the evaporation of pyrrolic-N on nitrogen doped hollow carbon spheres. Results of comparative experiments between Fe-N/C and Fe-ND/C reveal that Fe-ND/C shows superior ORR activity with an onset potential of 30 mV higher than that of Fe-N/C. Fe-ND sites are more favorable for the enhancement of ORR activity. Density functional theory (DFT) calculation demonstrates that Fe-ND/C with proposed coordination structure of FeN4−x (0<x<4) anchored by OH as axial ligand during ORR, weakens the strong binding of OH* intermediate and promotes the desorption of OH* as rate-determining step for ORR in alkaline electrolyte. Thus, Fe-ND/C electrocatalysts present much better ORR activity compared with that of Fe-N/C with proposed coordination structure of FeN4. [Figure not available: see fulltext.] |
| first_indexed | 2025-11-14T11:35:10Z |
| format | Journal Article |
| id | curtin-20.500.11937-90806 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T11:35:10Z |
| publishDate | 2021 |
| publisher | TSINGHUA UNIV PRESS |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-908062023-04-20T07:51:03Z Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction Su, P. Huang, W. Zhang, J. Guharoy, U. Du, Q. Sun, Q. Jiang, Q. Cheng, Yi Yang, J. Zhang, X. Liu, Y. Jiang, San Ping Liu, Jian Science & Technology Physical Sciences Technology Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Physics, Applied Chemistry Science & Technology - Other Topics Materials Science Physics atomic iron nitrogen defect coordination environment hollow carbon spheres oxygen reduction reaction MESOPOROUS CARBON METAL-CATALYSTS POROUS CARBON ACTIVE-SITES GRAPHENE NANOPARTICLES COBALT Defective electrocatalysts, especially for intrinsic defective carbon, have aroused a wide concern owing to high spin and charge densities. However, the designated nitrogen species favorable for creating defects by the removal of nitrogen, and the influence of defects for the coordination structure of active site and oxygen reduction reaction (ORR) activity have not been elucidated. Herein, we designed and synthesized a pair of electrocatalysts, denoted as Fe-N/C and Fe-ND/C for coordination sites of atomic iron-nitrogen and iron-nitrogen/defect configuration embedded in hollow carbon spheres, respectively, through direct pyrolysis of their corresponding hollow carbon spheres adsorbed with Fe(acac)3. The nitrogen defects were fabricated via the evaporation of pyrrolic-N on nitrogen doped hollow carbon spheres. Results of comparative experiments between Fe-N/C and Fe-ND/C reveal that Fe-ND/C shows superior ORR activity with an onset potential of 30 mV higher than that of Fe-N/C. Fe-ND sites are more favorable for the enhancement of ORR activity. Density functional theory (DFT) calculation demonstrates that Fe-ND/C with proposed coordination structure of FeN4−x (0<x<4) anchored by OH as axial ligand during ORR, weakens the strong binding of OH* intermediate and promotes the desorption of OH* as rate-determining step for ORR in alkaline electrolyte. Thus, Fe-ND/C electrocatalysts present much better ORR activity compared with that of Fe-N/C with proposed coordination structure of FeN4. [Figure not available: see fulltext.] 2021 Journal Article http://hdl.handle.net/20.500.11937/90806 10.1007/s12274-020-3151-8 English http://purl.org/au-research/grants/arc/DP180100568 http://creativecommons.org/licenses/by/4.0/ TSINGHUA UNIV PRESS fulltext |
| spellingShingle | Science & Technology Physical Sciences Technology Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Physics, Applied Chemistry Science & Technology - Other Topics Materials Science Physics atomic iron nitrogen defect coordination environment hollow carbon spheres oxygen reduction reaction MESOPOROUS CARBON METAL-CATALYSTS POROUS CARBON ACTIVE-SITES GRAPHENE NANOPARTICLES COBALT Su, P. Huang, W. Zhang, J. Guharoy, U. Du, Q. Sun, Q. Jiang, Q. Cheng, Yi Yang, J. Zhang, X. Liu, Y. Jiang, San Ping Liu, Jian Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title | Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title_full | Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title_fullStr | Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title_full_unstemmed | Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title_short | Fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| title_sort | fe atoms anchored on defective nitrogen doped hollow carbon spheres as efficient electrocatalysts for oxygen reduction reaction |
| topic | Science & Technology Physical Sciences Technology Chemistry, Physical Nanoscience & Nanotechnology Materials Science, Multidisciplinary Physics, Applied Chemistry Science & Technology - Other Topics Materials Science Physics atomic iron nitrogen defect coordination environment hollow carbon spheres oxygen reduction reaction MESOPOROUS CARBON METAL-CATALYSTS POROUS CARBON ACTIVE-SITES GRAPHENE NANOPARTICLES COBALT |
| url | http://purl.org/au-research/grants/arc/DP180100568 http://hdl.handle.net/20.500.11937/90806 |