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Electronic structure regulation and built-in electric field synergistically strengthen photocatalytic nitrogen fixation performance on Ti-BiOBr/TiO2 heterostructure

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Abstract

At present, industrial synthetic ammonia was still obtained through the Hubble-Bosch process, with large energy consumption. It is a research hotspot to realize green synthetic ammonia by using solar energy. The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N. In this study, Ti was doped into BiOBr by one-step hydrothermal method, which was oxidized into TiO2 when the doping amount reaches the maximum, in situ forming Ti0.31B0.69OB/TiO2 composites. Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction, the synthetic ammonia efficiency of Ti0.31B0.69OB/TiO2-11.96 reached 1.643 mmol·g−1cat at mild conditions and without hole scavenger for up to 7 h, the efficiency of synthetic ammonia is 115 times, 10.5 times and 3.3 times of that of BiOBr, Ti0.31B0.69OB and TiO2, respectively. Specifically, DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr, facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier, thus accelerating the reaction kinetics of photocatalytic nitrogen reduction (NRR). Meanwhile, constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron–hole pairs, improving the reduction ability of electrons in the conduction band of TiO2 and the oxidation ability of holes in the valence band of Ti0.31B0.69OB.

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摘要

工业合成氨采用Haber–Bosch工艺，需要在高温(300–500 ℃)、高压(15–25 MPa)下进行，能耗高且会产生大量的温室气体。与Haber–Bosch法相比，光催化合成氨可在常温、常压下进行，是一种能耗低、操作安全，且无CO2排放的绿色工艺。光催化固氮技术已成为当前催化领域的研究热点，是一种有望替代传统的哈伯法的新兴固氮技术。在本研究中，我们通过一步水热法将Ti掺杂取代BiOBr结构中的Bi原子，进一步增加Ti元素的掺杂量原位形成Ti0.31B0.69OB/TiO2异质结。Ti掺杂和构建异质界面的协同作用下，在不添加牺牲剂的情况下光照7小时，Ti0.31B0.69OB/TiO2的合成氨效率高达1.643 mmol·g−1cat，分别是BiOBr、Ti0.31B0.69OB和TiO2合成氨效率的115倍、10.5倍和3.3倍。DFT计算证实，Ti掺杂精准可调控BiOBr的电子结构，从而有效增强Bi位点对氮气（N2）在催化剂表面的吸附活化、降低活化氮分子（·N2）氢化反应的能垒，加速光催化氮还原（NRR）的反应动力学。同时，构建S-型异质结构可降低光生电子-空穴重组、促进电子-空穴的分离和转移，从而提高TiO2导带电子的还原能力和Ti0.31B0.69OB价带空穴的氧化能力。

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Nos. 22168040 and 22162025) and the Project of Science & Technology Office of Shannxi Province (No. 2022JM-062).

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  1. Ru-Qi Li and Yu-Jie Bian have equally contributed to this work.

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  1. College of Chemistry and Chemical Engineering, Yan’an University, Yan’an Key Laboratory of Green Catalysis and Quality Improvement and Utilization of Low Rank Coal, Yan’an, 716000, China

    Ru-Qi Li, Yu-Jie Bian, Chun-Ming Yang, Li Guo, Tao-Xia Ma, Chuan-Tao Wang, Feng Fu & Dan-Jun Wang

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Li, RQ., Bian, YJ., Yang, CM. et al. Electronic structure regulation and built-in electric field synergistically strengthen photocatalytic nitrogen fixation performance on Ti-BiOBr/TiO2 heterostructure. Rare Met. 43, 1125–1138 (2024). https://doi.org/10.1007/s12598-023-02471-1

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