Atomic vacancy engineering of Co(OH)F nanoarray toward high-performance ammonia electrosynthesis with waste plastics upgrading

IF 13.1 1区化学 Q1 Energy

Journal of Energy Chemistry Pub Date : 2025-06-14 DOI:10.1016/j.jechem.2025.06.012

Mingdan Wang , Qianyu Zhang , Kun Chen , Cong Lin , Huigang Wang , Yanying Zhao , Pengzuo Chen

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引用次数: 0

Abstract

Developing energy-efficient nitrite-to-ammonia (NO₂RR) conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate (PET) plastics into high-value-added chemicals is of great significance. Herein, an atomic oxygen vacancy (V_o) engineering is developed to optimize the catalytic performance of V_o2-Co(OH)F nanoarray towards the NO₂RR and PET-derived ethylene glycol oxidation reaction (EGOR). The optimal V_o2-Co(OH)F achieves an ultralow operating potential of −0.03 V vs. RHE at −100 mA cm⁻² and a remarkable NH₃ Faradaic efficiency (FE) of 98.4% at −0.2 V vs. RHE for NO₂RR, and a high formate FE of 98.03% for EGOR. Operando spectroscopic analysis and theoretical calculations revealed that oxygen vacancies play a crucial role in optimizing the electronic structure of V_o2-Co(OH)F, modulating the adsorption free energies of key reaction intermediates, and lowering the reaction energy barrier, thereby enhancing its overall catalytic performance. Remarkably, the V_o2-Co(OH)F-based NO₂RR||EGOR electrolyzer realized high NH₃ and formate yield rates of 33.9 and 44.9 mg h⁻¹ cm⁻² at 1.7 V, respectively, while demonstrating outstanding long-term stability over 100 h. This work provides valuable insights into the rational design of advanced electrocatalysts for co-electrolysis systems.

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Co(OH)F纳米阵列的原子空位工程及其在高性能氨电合成中的应用

开发高能效亚硝酸盐制氨（NO2RR）转化技术，同时实现废旧聚对苯二甲酸乙二醇酯（PET）塑料的电化学升级回收，使其成为高附加值化学品具有重要意义。本文采用原子氧空位（Vo）工程优化了Vo2-Co(OH)F纳米阵列对NO2RR和pet衍生乙二醇氧化反应（EGOR）的催化性能。最佳的Vo2-Co(OH)F在−100 mA cm−2条件下的工作电位为−0.03 V vs. RHE， NO2RR在−0.2 V vs. RHE条件下的NH3法拉第效率（FE）为98.4%，EGOR的FE为98.03%。Operando光谱分析和理论计算表明，氧空位在优化Vo2-Co(OH)F的电子结构，调节关键反应中间体的吸附自由能，降低反应能垒，从而提高其整体催化性能方面起着至关重要的作用。值得注意的是，基于Vo2-Co(OH) f的NO2RR||EGOR电解槽在1.7 V下分别实现了33.9 mg h - 1 cm - 2和44.9 mg h - 1 cm - 2的高NH3和甲酸产率，同时在100 h以上表现出出色的长期稳定性。这项工作为合理设计先进的电催化剂提供了有价值的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Energy Chemistry CHEMISTRY, APPLIED-CHEMISTRY, PHYSICAL

CiteScore

19.10

自引率

8.40%

发文量

3631

审稿时长

15 days

期刊介绍： The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies. This journal focuses on original research papers covering various topics within energy chemistry worldwide, including: Optimized utilization of fossil energy Hydrogen energy Conversion and storage of electrochemical energy Capture, storage, and chemical conversion of carbon dioxide Materials and nanotechnologies for energy conversion and storage Chemistry in biomass conversion Chemistry in the utilization of solar energy