Design Principles for Transition Metal Nitride Stability and Ammonia Generation in Acid
Meeting abstracts(2023)
摘要
Transition metal nitrides have shown great promise for reducing or eliminating the use of expensive precious-metal-based catalysts (e.g., Pt) in proton exchange membrane fuel cells and electrolyzers, but the use of these nitrides in such technologies is severely hindered by their dissolution at acidic pHs [1-2]. More importantly, the decomposition of transition metal nitrides in acid generates ammonia from the protonation of lattice nitrogen, giving rise to many false positives in previous reports of nitride catalysts for electrochemical nitrogen reduction to ammonia. For example, while nitrides such as VN [3], NbN [4], and Mo 2 N [5] have been computationally predicted to catalyze the reduction of nitrogen to ammonia, the experimentally observed ammonia has been attributed to the decomposition of nitrides in acid [6-8]. To tackle this challenge, motivated by our previous work [9-12] on the design principles of transition-metal-oxide-based catalysts, we established the stability descriptors of transition metal nitrides in acid. Such stability descriptors not only offer a fundamental understanding of nitride dissolution but also provide new guiding principles to optimize the intrinsic stability of nitrides for diverse acidic applications. In this work [13], combining ab initio calculations with synchrotron X-ray spectroscopies, we identified electronic-structure-based design principles governing the extent and kinetics of nitride dissolution and ammonia production in acid. We found that lowering the nitrogen 2p band center of transition metal nitrides with respect to the Fermi level leads to weakened metal-nitrogen bonds, increased labile metallic character, and a reduced barrier for the protonation of lattice nitrogen to produce ammonia, correlating with faster dissolution kinetics of nitrides in acid. Moreover, increasing the solubility of dissolved metal ions in acid was found to be critical in preventing surface oxide passivation to ensure the complete conversion from transition metal nitrides to ammonia. Based on these observations, a new mechanistic picture was formulated, where the initial protonation step of lattice nitrogen is critical to trigger nitride dissolution, and this proposed reaction scheme was supported by the pH-dependent dissolution kinetics of nitrides in acid. These design principles and mechanistic insights for producing ammonia and dissolving metal cations from the decomposition of nitrides in acid are essential for a variety of clean energy applications. For instance, such design principles can be leveraged to boost the stability of nitride catalysts for proton-exchange membrane fuel cells and electrochemical ammonia synthesis, where the dissolution of nitrides in acid has hindered their functions. Moreover, these descriptors for nitride dissolution and ammonia formation in acid provide emerging opportunities for designing novel nitride chemistries for distributed, on-demand ammonia generation. As nitrides represent an exciting, yet markedly unexplored chemical space, this work provides a blueprint to design multinary nitrides in such a vast materials space for various acidic applications, including electrocatalysis and beyond. References: [1] D. Göhl, et al. Nat. Mater. 19, 287 (2020). [2] M.E. Kreider, et al. ACS Appl. Mater. Interfaces 11, 26863 (2019). [3] Y. Abghoui, et al. ACS Catal. 6, 635 (2016). [4] Y. Abghoui and E. Skúlason, J. Phys. Chem. C 121, 6141 (2017). [5] I. Matanović, et al. Phys. Chem. Chem. Phys. 16, 3014 (2014). [6] B. Hu, et al. ACS Energy Lett. 4, 1053 (2019). [7] H.L. Du, et al. ACS Sustain. Chem. Eng. 7, 6839 (2019). [8] R. Manjunatha, et al. ChemCatChem 12, 438 (2020). [9] D.A. Kuznetsov†, J. Peng†, et al. J. Phys. Chem. C 124, 6562 (2020). († denotes equal contribution) [10] S. Yuan†, J. Peng†, B. Cai†, et al. Nat. Mater. 21, 673 (2022). († denotes equal contribution) [11] J. Peng, et al. Chem. Mater. 34, 7774 (2022). [12] J. Peng, et al. Nat. Rev. Mater. (2022) doi: 10.1038/s41578-022-00466-5. [13] J. Peng, et al. Joule (2022) accepted.
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关键词
transition metal nitride stability,ammonia generation
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