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Direct Z-scheme photocatalytic nitrogen reduction to ammonia with water in metal-free BC4N/aza-CMP heterobilayer

具有直接Z型光催化机制的非金属BC4N/aza-CMP异质双层的光催化固氮性能

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Abstract

Photocatalytic ammonia (NH3) synthesis from air and water without external energy input or sacrificial agents is an attractive approach for nitrogen fixation. However, finding a suitable photocatalyst with strong optical absorption, efficient photogenerated carrier separation, and adequate driving force (potentials of photoinduced carriers) to trigger the nitrogen reduction reactions (NRRs) and oxygen evolution reactions (OERs) simultaneously is challenging. Herein, we propose a direct Z-scheme photocatalytic system based on a two-dimensional metal-free BC4N/aza-CMP heterobilayer. The results of density functional theory and time-dependent ab initio nonadiabatic molecular dynamics reveal that the photoexcited carriers in the BC4N/aza-CMP heterobilayer follow a Z-scheme migration route, leading to the efficient charge carrier separation and spatially separated reaction sites for NRR (BC4N layer) and OER (aza-CMP layer). Moreover, the appropriate band gaps and energy levels of the BC4N/aza-CMP heterobilayer enable efficient solar energy capture and provide sufficient driving force (1.01 V for NRR and 2.11 V for OER) to initiate the redox reactions. Additionally, the activation of the N≡N bond by B atoms in the BC4N layer promotes the sequential hydrogenation of N atoms and reduces the overpotential of NRR. Consequently, the NRR and OER can proceed spontaneously, driven by photogenerated carriers with no need for sacrificial agents. The predicted maximum value of solar-to-chemical efficiency is 7.59%. This work will be an important reference for the rational design of direct Z-scheme photocatalysts for NRR and promote the development of solar-driven NH3 synthesis.

摘要

我们设计了一种不含金属的二维双层异质结构BC4N/aza-CMP, 该体系可在水溶液中将N2分子通过光催化作用还原为氨. 通过密度泛函理论和非绝热分子动力学方法, 我们发现该异质结构中的光生载流子遵循直接Z型迁移机制. 这将有效分离光生电荷并使氮还原反应和氧发生反应分别在BC4N层和aza-CMP层上进行, 实现反应位点的空间分离. 值得一提的是, BC4N上的B原子可以有效吸附N2分子并激活N≡N键, 这将降低氮还原反应的过电势并促进随后的质子化进程, 且该异质双层具有适宜的带隙和带边位置, 能够有效吸收太阳光并提供充足的驱动力来触发氧化还原反应, 实现无任何牺牲剂辅助的光催化氨合成. 本工作将为直接Z型固氮光催化剂的设计提供重要借鉴, 并促进太阳能驱动的氨合成的发展.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21833004), Taishan Scholar Program of Shandong Province, and the Natural Science Foundation of Shandong Province (ZR2020QA055).

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Authors and Affiliations

  1. School of Information and Electronic Engineering, Shandong Technology and Business University, Yantai, 264005, China

    Yingcai Fan  (范英才)

  2. School of Physics and State Key Laboratory of Crystal Materials, Shandong University, **an, 250100, China

    Zhihua Zhang  (张志华), Juan Wang  (王娟), **kui Ma  (马西奎) & Mingwen Zhao  (赵明文)

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  1. Yingcai Fan  (范英才)
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  2. Zhihua Zhang  (张志华)
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  3. Juan Wang  (王娟)
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  5. Mingwen Zhao  (赵明文)
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Contributions

Author contributions Fan Y performed DFT calculations and contributed to the data analysis and writing of the manuscript. Zhang Z, Wang J and Ma X contributed to the data interpretation. Zhao M designed the study and contributed to the data interpretation and writing of the manuscript. All authors have given approval to the final version of the manuscript.

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Correspondence to Yingcai Fan  (范英才) or Mingwen Zhao  (赵明文).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Yingcai Fan received his BSc (2007), MSc (2011) and PhD (2021) degrees in physics from Shandong University. He is currently working at the School of Information and Electronic Engineering, Shandong Technology and Business University. His research mainly focuses on photocatalytic properties of 2D materials by first-principles calculations and nonadiabatic molecular dynamics method.

Mingwen Zhao received his PhD degree in 2001 from Shandong University. He is currently a professor of the School of Physics, Shandong University. His research interests are focused on the theoretical design of electronic structures of nanomaterials based on first principles, which are closely related to applications in spintronics devices and energy generation.

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Fan, Y., Zhang, Z., Wang, J. et al. Direct Z-scheme photocatalytic nitrogen reduction to ammonia with water in metal-free BC4N/aza-CMP heterobilayer. Sci. China Mater. 66, 4377–4386 (2023). https://doi.org/10.1007/s40843-023-2587-7

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