电催化二氧化碳和硝酸根共还原合成尿素研究进展

doi:10.16085/j.issn.1000-6613.2024-1800

摘要/Abstract

摘要：

尿素是一种关键的农业氮肥，是作物生长不可或缺的原料。电催化CO₂和NO₃^-共还原的C-N偶联反应制尿素被认为是实现清洁和可持续生产的一种有前途的策略，引起了广泛关注。相比于传统的Bosch-Meiser工艺，C-N偶联反应具有降低能耗和减少碳排放的潜力。本文综述了电催化CO₂和NO₃^-共还原合成尿素的最新研究进展，深入探讨了该反应的机理，结合原位表征和密度泛函理论计算，揭示了促进C-N偶联和提升尿素合成效率的微观机制。本文还总结了提高尿素产率的关键催化剂设计策略，包括杂原子掺杂、缺陷工程、异质结构构建、合金化和原子尺度等调控策略。最后，本文提出了未来研究及工业化应用的挑战与展望，特别关注如何在大规模生产中实现高效、低能耗的尿素合成，同时分析了催化剂的结构设计和精细调控，为实现可持续尿素生产提供理论和实践支持。

关键词: 电化学, 催化剂, 可持续性, NO₃^-还原反应, CO₂还原反应, 尿素电合成

Abstract:

Urea is a critical agricultural nitrogen fertilizer and an essential component for crop growth. Electrocatalytic co-reduction of CO₂ and NO₃^-via C-N coupling to synthesize urea has emerged as a promising strategy for achieving clean and sustainable urea production, and has attracted considerable attentions. Compared to the traditional Bosch-Meiser process, the C-N coupling reaction offers potential for reduced energy consumption and lower carbon emissions. This review summarizes recent research progress in electrocatalytic co-reduction of CO₂ and NO₃^- for urea synthesis, providing an in-depth discussion of the reaction mechanisms. By integrating in-situ characterization techniques and density functional theory calculations, this paper reveals the micro-level mechanisms that promote C-N coupling and enhance urea synthesis efficiency. Key catalyst design strategies to improve urea yields are also outlined, including heteroatom doping, defect engineering, heterostructure construction, alloying, and atomic-scale modulation. Finally, the challenges and prospects for future research and industrial applications are addressed, with a focus on achieving efficient, low energy consumption urea synthesis at large scale. It also analyzes the structural design and precise regulation of catalysts, providing theoretical and practical support for sustainable urea production.

Key words: electrochemistry, catalyst, sustainability, nitrate reduction reaction, carbon dioxide reduction reaction, urea electrosynthesis

中图分类号:

TQ032.4

范晓娅, 赵镇, 彭强. 电催化二氧化碳和硝酸根共还原合成尿素研究进展[J]. 化工进展, 2025, 44(5): 2856-2869.

FAN Xiaoya, ZHAO Zhen, PENG Qiang. Review on electrocatalytic co-reduction of carbon dioxide and nitrate for urea synthesis[J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2856-2869.

图/表 8

参考文献 78

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催化剂	电解质	过电位（vs. RHE）/V	尿素产率	法拉第效率/%	参考文献
Bi:10%In/C NPs（铟掺杂铋纳米颗粒）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.45	606.38μg/(h·mg)	20.31	[64]
VB₁₂-CNTs（维生素B负载碳纳米管）	0.1mol/L KNO₃	-0.5	164.04μg/(h·mg)	26.04	[65]
Ru-Cu₉Bi/CNT（钌掺杂铜铋碳纳米管）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.4	2928μg/(h·mg)	65.7	[10]
CuSiO _x （硅酸铜）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.2	1606.1μg/(h·mg)	79.01	[66]
V_o-In-TiO₂（富氧空位铟掺杂二氧化钛）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.65	759.8μg/(h·mg)	9.06	[67]
Co-O-C（氧配位钴单原子）	0.1mol/L KHCO₃+0.05mol/L KNO₃	-1.5	2704.2μg/(h·mg)	31.4	[68]
Ti-DHTP（钛基MOF）	0.5mol/L K₂SO₄+0.1mol/L KNO₃	-0.6	696.0μg/(h·mg)	21.75	[69]
Cu₁Au₈@CeO₂（氧化铈负载铜金单原子）	0.1mol/L KNO₃	-0.74	813.6μg/(h·mg)	45.2	[70]
Co@C（碳负载钴金属催化剂）	0.2mol/L NaHCO₃+0.05mol/L NaNO₃	-0.5	2217.5μg/(h·mg)	54.3	[71]
Mo-PCN-222(Co)（钼钴串联催化剂）	0.1mol/L KHCO₃+0.05mol/L KNO₃	-0.4	844.11μg/(h·mg)	33.9	[72]
CoPc-COF@TiO₂（二氧化钛复合钴酞菁）	0.3mol/L KHCO₃+0.2mol/L KNO₃	-0.6	753.1μg/(h·mg)	49	[73]
CuWO₄（钨酸铜）	0.1mol/L KNO₃	-0.2	98.5μg/(h·mg)	70.1	[32]
F-doped CNTs（氟掺杂碳纳米管）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.65	381.6μg/(h·mg)	18	[40]
6Å-Cu₂O（原子级间距氧化亚铜）	1mol/L KOH+0.1mol/L KNO₃	-0.53	7541.9μg/(h·mg)	51.97	[74]
Cu@Zn（铜锌核壳纳米线）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-1.02	7.29μmol/(h·cm²)	9.28	[75]
O-PdZn/C（有序金属间钯锌催化剂）	0.2mol/L KHCO₃+0.1mol/L KNO₃	-0.4	1274.42μg/(h·mg)	62.78	[76]
Cu₉₇In₃-C（碳负载铜铟催化剂）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-1.4	786μg/(h·mg)	—	[77]
Bi₂Se₃（硒化铋纳米片）	0.1mol/L KNO₃	-0.4	276000μg/(h·mg)	32	[78]

催化剂	电解质	过电位（vs. RHE）/V	尿素产率	法拉第效率/%	参考文献
Bi:10%In/C NPs（铟掺杂铋纳米颗粒）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.45	606.38μg/(h·mg)	20.31	[64]
VB₁₂-CNTs（维生素B负载碳纳米管）	0.1mol/L KNO₃	-0.5	164.04μg/(h·mg)	26.04	[65]
Ru-Cu₉Bi/CNT（钌掺杂铜铋碳纳米管）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.4	2928μg/(h·mg)	65.7	[10]
CuSiO _x （硅酸铜）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.2	1606.1μg/(h·mg)	79.01	[66]
V_o-In-TiO₂（富氧空位铟掺杂二氧化钛）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.65	759.8μg/(h·mg)	9.06	[67]
Co-O-C（氧配位钴单原子）	0.1mol/L KHCO₃+0.05mol/L KNO₃	-1.5	2704.2μg/(h·mg)	31.4	[68]
Ti-DHTP（钛基MOF）	0.5mol/L K₂SO₄+0.1mol/L KNO₃	-0.6	696.0μg/(h·mg)	21.75	[69]
Cu₁Au₈@CeO₂（氧化铈负载铜金单原子）	0.1mol/L KNO₃	-0.74	813.6μg/(h·mg)	45.2	[70]
Co@C（碳负载钴金属催化剂）	0.2mol/L NaHCO₃+0.05mol/L NaNO₃	-0.5	2217.5μg/(h·mg)	54.3	[71]
Mo-PCN-222(Co)（钼钴串联催化剂）	0.1mol/L KHCO₃+0.05mol/L KNO₃	-0.4	844.11μg/(h·mg)	33.9	[72]
CoPc-COF@TiO₂（二氧化钛复合钴酞菁）	0.3mol/L KHCO₃+0.2mol/L KNO₃	-0.6	753.1μg/(h·mg)	49	[73]
CuWO₄（钨酸铜）	0.1mol/L KNO₃	-0.2	98.5μg/(h·mg)	70.1	[32]
F-doped CNTs（氟掺杂碳纳米管）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-0.65	381.6μg/(h·mg)	18	[40]
6Å-Cu₂O（原子级间距氧化亚铜）	1mol/L KOH+0.1mol/L KNO₃	-0.53	7541.9μg/(h·mg)	51.97	[74]
Cu@Zn（铜锌核壳纳米线）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-1.02	7.29μmol/(h·cm²)	9.28	[75]
O-PdZn/C（有序金属间钯锌催化剂）	0.2mol/L KHCO₃+0.1mol/L KNO₃	-0.4	1274.42μg/(h·mg)	62.78	[76]
Cu₉₇In₃-C（碳负载铜铟催化剂）	0.1mol/L KHCO₃+0.1mol/L KNO₃	-1.4	786μg/(h·mg)	—	[77]
Bi₂Se₃（硒化铋纳米片）	0.1mol/L KNO₃	-0.4	276000μg/(h·mg)	32	[78]

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