Saved in:
| Main Authors: | , , , , , , , , , , |
|---|---|
| Format: | Preprint |
| Published: |
2024
|
| Subjects: | |
| Online Access: | https://arxiv.org/abs/2409.14116 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866909692204154880 |
|---|---|
| author | Liang, Lecheng Li, Hengyu Li, Peng Liang, Jinhui Ye, Shao Zeng, Binwen Xie, Yanhong Wang, Yucheng Ozaki, Taisuke Chen, Shengli Cui, Zhiming |
| author_facet | Liang, Lecheng Li, Hengyu Li, Peng Liang, Jinhui Ye, Shao Zeng, Binwen Xie, Yanhong Wang, Yucheng Ozaki, Taisuke Chen, Shengli Cui, Zhiming |
| contents | A long-standing puzzle for methanol electrooxidation is how to achieve a CO-free pathway and accurately understand the origin of electrocatalytic selectivity. Herein, we unequivocally demonstrate that the Bi-modified Pt/C follows a CO-free dominated pathway during alkaline methanol electrooxidation, and unveil the formaldehyde (HCHO) intermediate as a critical factor influencing pathway selectivity. These findings are substantiated by kinetic isotope effects, formate Faradaic efficiency, in situ spectroscopy, ab initio molecular dynamic simulations, and density functional theory calculations. Bi modification significantly increases the HCHO dehydrogenation barrier, which facilitates its desorption and subsequent conversion to the H2COOH- anion at the alkaline interface, intrinsically avoiding CO formation. More specifically, the formation of ensemble sites featuring V-shaped Bi-Pt-Bi configuration inhibits the cleavage of C-H bond, and the weak OH binding energy at Bi adatoms effectively prevents blockage of oxygenated species, allowing such ensemble sites to fulfill their functional role. Our study opens up a novel dimension for designing advanced CO-free catalysts. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2409_14116 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Unveiling High Selectivity Origin of Pt-Bi Catalysts for Alkaline Methanol Electrooxidation via CO-free pathway Liang, Lecheng Li, Hengyu Li, Peng Liang, Jinhui Ye, Shao Zeng, Binwen Xie, Yanhong Wang, Yucheng Ozaki, Taisuke Chen, Shengli Cui, Zhiming Chemical Physics A long-standing puzzle for methanol electrooxidation is how to achieve a CO-free pathway and accurately understand the origin of electrocatalytic selectivity. Herein, we unequivocally demonstrate that the Bi-modified Pt/C follows a CO-free dominated pathway during alkaline methanol electrooxidation, and unveil the formaldehyde (HCHO) intermediate as a critical factor influencing pathway selectivity. These findings are substantiated by kinetic isotope effects, formate Faradaic efficiency, in situ spectroscopy, ab initio molecular dynamic simulations, and density functional theory calculations. Bi modification significantly increases the HCHO dehydrogenation barrier, which facilitates its desorption and subsequent conversion to the H2COOH- anion at the alkaline interface, intrinsically avoiding CO formation. More specifically, the formation of ensemble sites featuring V-shaped Bi-Pt-Bi configuration inhibits the cleavage of C-H bond, and the weak OH binding energy at Bi adatoms effectively prevents blockage of oxygenated species, allowing such ensemble sites to fulfill their functional role. Our study opens up a novel dimension for designing advanced CO-free catalysts. |
| title | Unveiling High Selectivity Origin of Pt-Bi Catalysts for Alkaline Methanol Electrooxidation via CO-free pathway |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2409.14116 |