整流异质界面促进 C-N 耦合动力学实现超低电位下的高效尿素电合成

IF 19.3 1区材料科学 Q1 CHEMISTRY, PHYSICAL

ACS Energy Letters Pub Date : 2024-09-25 DOI:10.1002/anie.202413534

Mingyu Cheng, Shao Wang, Zechuan Dai, Jing Xia, Bocheng Zhang, Pingyi Feng, Yin Zhu, Yangyang Zhang, Genqiang Zhang

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引用次数: 0

摘要

以二氧化碳（CO2）和硝酸盐（NO3-）为原料合成尿素的电催化 C-N 偶联法为传统的 Bosch-Meiser 方法提供了一种可持续的替代方法。然而，共还原过程中中间产物的复杂性阻碍了尿素产量和法拉第效率（FE）的同步提高。在此，我们通过对 Cu2O 纳米线进行精确可控的原位电还原，开发出了一种具有纳米级整流异质界面的 Cu/Cu2O Mott-Schottky 催化剂，在广泛的超低应用电位（0 至 -0.3 V 对 RHE）范围内实现了显著的 FE（32.6-47.0%）和可观的产率（6.08-30.4 μmol h-1 cm-2）。操作同步辐射-傅立叶变换红外光谱（SR-FTIR）证实了*CO中间体和C-N键的形成，随后的密度泛函理论（DFT）计算破译了Cu/Cu2O整流异质表面对*CO吸附的调节作用，显著增强了随后*CO和*NOH中间体之间的C-N耦合动力学。这项工作不仅为 C-N 偶联提供了一种开创性的先进途径，还为铜基异质界面催化剂在尿素合成中的应用提供了深刻的见解。

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Rectifying Heterointerface Facilitated C-N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials

Electrocatalytic C-N coupling for urea synthesis from carbon dioxide (CO2) and nitrate (NO3-) offers a sustainable alternative to the traditional Bosch-Meiser method. However, the complexity of intermediates in co-reduction hampers simultaneous improvement in urea yield and Faradaic efficiency (FE). Herein, we developed a Cu/Cu2O Mott-Schottky catalyst with nanoscale rectifying heterointerfaces through precise controllable in-situ electroreduction of Cu2O nanowires, achieving notable FE (32.6-47.0%) and substantial yields (6.08-30.4 μmol h-1 cm-2) across a broad range of ultralow applied potentials (0 to -0.3 V vs. RHE). Operando synchrotron radiation-Fourier transform infrared spectroscopy (SR-FTIR) confirmed the formation of *CO intermediates and C-N bonds, subsequently density functional theory (DFT) calculations deciphered that the Cu/Cu2O rectifying heterointerface modulated *CO adsorption, significantly enhancing subsequent C-N coupling dynamics between *CO and *NOH intermediates. This work not only provides a groundbreaking and advanced pathway for C-N coupling, but also offers deep insights into copper-based heterointerface catalysts for urea synthesis.

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来源期刊

ACS Energy Letters Energy-Renewable Energy, Sustainability and the Environment

CiteScore

31.20

自引率

5.00%

发文量

469

审稿时长

1 months

期刊介绍： ACS Energy Letters is a monthly journal that publishes papers reporting new scientific advances in energy research. The journal focuses on topics that are of interest to scientists working in the fundamental and applied sciences. Rapid publication is a central criterion for acceptance, and the journal is known for its quick publication times, with an average of 4-6 weeks from submission to web publication in As Soon As Publishable format. ACS Energy Letters is ranked as the number one journal in the Web of Science Electrochemistry category. It also ranks within the top 10 journals for Physical Chemistry, Energy & Fuels, and Nanoscience & Nanotechnology. The journal offers several types of articles, including Letters, Energy Express, Perspectives, Reviews, Editorials, Viewpoints and Energy Focus. Additionally, authors have the option to submit videos that summarize or support the information presented in a Perspective or Review article, which can be highlighted on the journal's website. ACS Energy Letters is abstracted and indexed in Chemical Abstracts Service/SciFinder, EBSCO-summon, PubMed, Web of Science, Scopus and Portico.