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Black phosphorus-hosted single-atom catalyst for electrocatalytic nitrogen reduction

黑磷负载的单原子催化剂用于电催化N2还原

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Abstract

Designing highly selective and efficient single-atom electrocatalysts is essential for ammonia production under ambient conditions. This paper describes a density functional theory study on exploring the performance trends of transition metal complexes with P-based ligands in nitrogen reduction reaction (NRR) and further develops a design principle for high-performance single-atom catalysts (SACs) of NRR. Among the explored catalysts, W@BP (0.40 eV), Ta@BP (0.47 eV), and Nb@BP (0.53 eV) are identified as remarkable candidates with low free energy change in the potential-limiting step, high stability and high electrical conductivity for NRR. It is worth noting that almost all SACs with P-based ligands exhibit high NRR selectivity, due to the fact that they adsorb *N2 more strongly than *H. The adsorption free energy of *N2H can be considered as a descriptor for the intrinsic activity trends in NRR. Furthermore, by constructing a volcano plot of the activity against the electronic charge on metal centers, it is demonstrated that the metal center with a moderate amount of positive charge can promote the catalytic performance of NRR.

摘要

设计和开发高选择性、高活性的单原子电催化剂是实现在 常规环境条件下合成氨的关键. 本论文利用密度泛函理论对P配体 在N2还原反应(NRR)中的应用前景进行了预测, 并且提出了一种高 性能NRR单原子催化剂的设计准则. 理论计算结果显示, W@BP (0.40 eV)、Ta@BP(0.47 eV)和Nb@BP(0.53 eV)由于具有低反应自 由能、高稳定性和导电性, 在高效电催化NRR中潜力巨大. 特别是, 几乎所有金属中心对*N2中间体的吸附能力都比*H更强, 这表明以 P为配体的单原子催化剂具有较强的NRR选择性, 且*N2H中间体的 吸附自由能可作为描述符, 反映这一系列催化剂的催化活性. 此外, 计算结果显示, 金属中心向P配体转移的电子数目与NRR活性存在 着火山关系, 带有适度正电荷的金属中心具有优异的电催化NRR 活性. 该发现为高性能单原子催化剂的设计提供了理论指导.

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Acknowledgements

We thank Prof. Dr. Lyudmila Moskaleva for her valuable comments on the revision. This work was supported by the National Natural Science Foundation of China (21525626 and 21761132023), and the Program of Introducing Talents of Discipline to Universities (BP0618007).

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Authors and Affiliations

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, China

    Xiaoyun Lin  (林晓韵), Lulu Li  (李璐璐), Xin Chang  (常鑫), Chunlei Pei  (裴春雷), Zhi-Jian Zhao  (赵志坚) & Jinlong Gong  (巩金龙)

  2. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300350, China

    Chunlei Pei  (裴春雷), Zhi-Jian Zhao  (赵志坚) & Jinlong Gong  (巩金龙)

  3. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, 350207, China

    Jinlong Gong  (巩金龙)

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  1. Xiaoyun Lin  (林晓韵)
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  2. Lulu Li  (李璐璐)
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Contributions

Zhao ZJ conceived and coordinated the research. Lin X designed the models and performed the calculations. Lin X and Zhao ZJ wrote the manuscript. All authors participated in the discussions of the research and the revision of manuscript.

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Correspondence to Zhi-Jian Zhao  (赵志坚).

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The authors declare no conflict of interest.

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Supporting data are available in the online version of the paper.

Xiaoyun Lin is currently a MSc candidate at the School of Chemical Engineering and Technology, Tianjin University. She received her BSc degree from Beijing University of Chemical Technology in 2018. Her current interest lies in the molecular level understanding of electrocatalytic reactions.

Zhi-Jian Zhao received his BSc and MSc degrees in chemistry from Zhejiang University and his PhD degree from Technische Universität München in 2012. After working as a Postdoc with Prof. Greeley in Purdue University and with Dr. Studt and Prof. Nørskov at Stanford University, now he is a professor at Tianjin University. His current research focuses on mechanistic studies on heterogeneous catalysts using multi-scaling simulation methods.

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Lin, X., Li, L., Chang, X. et al. Black phosphorus-hosted single-atom catalyst for electrocatalytic nitrogen reduction. Sci. China Mater. 64, 1173–1181 (2021). https://doi.org/10.1007/s40843-020-1522-y

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