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Oxidation State Modulation of Bismuth for Efficient Electrocatalytic Nitrogen Reduction to Ammonia |
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| Authors: | Yuchi Wan Hongjiang Zhou Muyun Zheng Zheng-Hong Huang Feiyu Kang Jia Li Ruitao Lv |
| Affiliation: | 1. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084 China;2. Guangdong Provincial Key Laboratory of Thermal Management Engineering and Materials and Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055 China;3. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084 China
Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing, 100084 China;4. Guangdong Provincial Key Laboratory of Thermal Management Engineering and Materials and Institute of Materials Research, Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, 518055 China Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing, 100084 China |
| Abstract: | Electrocatalytic nitrogen reduction reaction (NRR) is a promising strategy for ammonia (NH3) production under ambient conditions. However, it is severely impeded by the challenging activation of the NN bond and the competing hydrogen evolution reaction (HER), which makes it crucial to design electrocatalysts rationally for efficient NRR. Herein, the rational design of bismuth (Bi) nanoparticles with different oxidation states embedded in carbon nanosheets (Bi@C) as efficient NRR electrocatalysts is reported. The NRR performance of Bi@C improves with the increase of Bi0/Bi3+ atomic ratios, indicating that the oxidation state of Bi plays a significant role in electrochemical ammonia synthesis. As a result, the Bi@C nanosheets annealed at 900 ° C with the optimal oxidation state of Bi demonstrate the best NRR performance with a high NH3 yield rate and remarkable Faradaic efficiency of 15.10 ± 0.43% at − 0.4 V versus RHE. Density functional theory calculations reveal that the effective modulation of the oxidation state of Bi can tune the p-filling of active Bi sites and strengthen adsorption of *NNH, which boost the potential-determining step and facilitate the electrocatalytic NRR under ambient conditions. This work may offer valuable insights into the rational material design by modulating oxidation states for efficient electrocatalysis. |
| Keywords: | ammonia synthesis bismuth electrocatalysis nitrogen reduction reaction oxidation state modulation |