Regulating the d-Band Center of Metal–Organic Frameworks for Efficient Nitrate Reduction Reaction and Zinc-Nitrate Battery

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2024-10-18 DOI:10.1021/acscatal.4c04340

Yuanhui Yao, Xiaofei Wei, Haiqiao Zhou, Kai Wei, Bin Kui, Fangfang Wu, Liang Chen, Wei Wang, Fangna Dai, Peng Gao, Nana Wang, Wei Ye

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Abstract

The electrochemical reduction of nitrate ions to valuable ammonia enables the recovery of nitrate pollutants from industrial wastewater, thereby synchronously balancing the nitrogen cycle and achieving NH₃ production. However, the currently reported electrocatalysts still suffer from the low NH₃ yield rate, NH₃ Faradaic inefficiency, and NH₃ partial current density. Herein, a strategy based on the regulation of the d-band center by Ru doping is presented to boost ammonia production. Theoretical calculations unravel that the Ru dopant in Ni metal–organic framework shifts the d-band center of the neighboring Ni sites upward, optimizing the adsorption strength of the N-intermediates, resulting in greatly enhanced nitrate reduction reaction performance. The synthesized Ru-doped Ni metal–organic framework rod array electrode delivers a NH₃ yield rate of 1.31 mmol h^–1 cm^–2 and NH₃ Faradaic efficiency of 91.5% at −0.6 V versus reversible hydrogen electrode, as well as good cycling stability. In view of the multielectron transfer in nitrate reduction and electrocatalytic activity, the Zn-NO₃^– battery is assembled by this electrode and Zn anode, which delivers a high open-circuit voltage of 1.421 V and the maximum output power density of 4.99 mW cm^–2, demonstrating potential application value.

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调节金属有机框架的 d 波段中心以实现高效硝酸盐还原反应和硝酸锌电池

通过电化学方法将硝酸根离子还原成有价值的氨，可以回收工业废水中的硝酸盐污染物，从而同步平衡氮循环并实现 NH3 生产。然而，目前报道的电催化剂仍存在 NH3 产率低、NH3 法拉第效率低和 NH3 部分电流密度低等问题。本文提出了一种通过掺杂 Ru 来调节 d 波段中心以提高氨生产的策略。理论计算表明，掺杂在镍金属有机框架中的 Ru 会使邻近镍位点的 d 带中心上移，从而优化 N 中间体的吸附强度，从而大大提高硝酸盐还原反应的性能。合成的 Ru 掺杂镍金属有机框架棒阵列电极的 NH3 产率为 1.31 mmol h-1 cm-2，在 -0.6 V 电压下与可逆氢电极相比，NH3 法拉第效率为 91.5%，并且具有良好的循环稳定性。鉴于硝酸盐还原过程中的多电子转移和电催化活性，该电极与锌阳极组装成 Zn-NO3- 电池，可提供 1.421 V 的高开路电压和 4.99 mW cm-2 的最大输出功率密度，具有潜在的应用价值。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.