Abstract
Solar-driven CO2 reduction reaction (CO2RR) with water into carbon-neutral fuels is of great significance but remains challenging due to thermodynamic stability and kinetic inertness of CO2. Biomass-derived nitrogen-doped carbon (N-Cb) have been considered as promising earth-abundant photocatalysts for CO2RR, although their activities are not ideal and the reaction mechanism is still unclear. Herein, an efficient catalyst is developed for CO2-to-CO conversion realized on diverse N-Cb materials with hierarchical pore structures. It is demonstrated that the CO2-to-CO conversion preferentially takes place on positively charged carbon atoms next to pyridinic-N using two representatives treated pollens with the largest difference in pyridinic-N density and N content as model photocatalysts. Systematic experimental results indicate that surface local electric field originating from charge separation can be boosted by hierarchical pore structures, doped N, as well as pyridinic-N. Mechanistic studies reveal that positively charged carbon atoms next to pyridinic-N serve as active sites for CO2RR, reduce the energy barrier on the formation of CO*, and facilitate the CO2RR performance. All these benefits cooperatively contribute to treated chrysanthemum pollen catalyst exhibiting excellent CO formation rate of 203.2 µmol h−1 g−1 with 97.2% selectivity in pure water vapor. These results provide a new perspective into CO2RR on N-Cb, which shall guide the design of nature-based photocatalysts for high-performance solar-fuel generation. © 2023 Wiley-VCH GmbH.
| Original language | English |
|---|---|
| Article number | 2301785 |
| Journal | Advanced Functional Materials |
| Volume | 33 |
| Issue number | 29 |
| Online published | 18 Apr 2023 |
| DOIs | |
| Publication status | Published - 18 Jul 2023 |
Research Keywords
- carbon-based materials
- metal-free catalysts
- nitrogen doping
- photocatalytic CO 2 reduction
Publisher's Copyright Statement
- COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: This is the peer reviewed version of the following article: Jiang, Z., Zhang, Z., Liang, J., Zhou, M., Liu, D., Mao, D., Zhang, Q., Zhang, W., Li, H., Song, L., An, T., Wong, P. K., & Lee, C-S. (2023). Understanding Boosted Selective CO2-to-CO Photoreduction with Pure Water Vapor over Hierarchical Biomass-Derived Carbon Matrix. Advanced Functional Materials, 33(29), Article 2301785, which has been published in final form at https://doi.org/10.1002/adfm.202301785.
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