Abstract
The low-energy electrochemical production of hydrogen peroxide (H2O2) has garnered significant attention as a viable alternative to traditional industrial routes, with the goal of achieving carbon neutrality. For their H2O2 selectivity in the two-electron oxygen reduction reaction (ORR), the coordination environment of tungsten (W)-based materials is critical. In this study, atomically dispersed W single atoms were immobilized on N-doped carbon substrates by a facile pyrolysis method to obtain a W single-atom catalyst (W-SAC). The coordination environment of an isolated W single atom with a tetra-coordinated porphyrin-like structure in W-SAC was determined by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy analysis. Notably, the as-prepared W-SAC showed superior two-electron ORR activity in 0.1 M KOH solution, including high onset potential (0.89 V), high H2O2 selectivity (82.5%), and excellent stability. By using differential phase contrast-scanning transmission electron microscopy and density functional theory calculations, it is revealed that the charge symmetry-breaking of W atoms changes the adsorption behavior of the intermediates, leading to enhanced reactivity and selectivity for two-electron ORR. This work broadens the avenue for understanding the charge transfer of W-based electrocatalytic materials and the in-depth reaction mechanism of SACs in two-electron ORR.
| Original language | English |
|---|---|
| Article number | e581 |
| Journal | Carbon Energy |
| Volume | 6 |
| Issue number | 10 |
| DOIs | |
| State | Published - Oct 2024 |
| Externally published | Yes |
Funding
This work was financially supported by the National Natural Science Foundation of China (51971157), the Science and Technology Commission of Shanghai Municipality (22ZR1415700), the Shanghai Rising-star Program (20QA1402400), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, the Fundamental Research Funds for the Central Universities, and the Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ20210324122803009, ZDSYS20210813095534001, J10M00172307180001, and JCYJ20210324123202008). Additional support was provided by the Frontiers Science Center for Materiobiology and Dynamic Chemistry and the Feringa Nobel Prize Scientist Joint Research Center at East China University of Science and Technology. This work was financially supported by the National Natural Science Foundation of China (51971157), the Science and Technology Commission of Shanghai Municipality (22ZR1415700), the Shanghai Rising\u2010star Program (20QA1402400), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning, the Fundamental Research Funds for the Central Universities, and the Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ20210324122803009, ZDSYS20210813095534001, J10M00172307180001, and JCYJ20210324123202008). Additional support was provided by the Frontiers Science Center for Materiobiology and Dynamic Chemistry and the Feringa Nobel Prize Scientist Joint Research Center at East China University of Science and Technology.
Keywords
- charge symmetry-breaking
- density functional theory
- scanning transmission electron microscopy
- tungsten single-atom catalyst
- two-electron oxygen reduction reaction