利用不同氢源及氮源电化学合成氨研究进展与挑战

doi:10.16085/j.issn.1000-6613.2021-2178

摘要/Abstract

摘要：

氨是基本有机化学工业及化肥生产的主要原料。工业上利用哈伯法合成氨，该工艺不仅耗能大且转化率仅有10%~15%。相比传统合成氨工艺，电化学合成氨有着清洁环保、反应条件温和等优点。本文综述了氮气、硝酸盐及一氧化氮作为氮源时电化学合成氨的特点与优势，并依据不同氮源的特点，剖析了电化学合成氨的反应机制。文中针对不同的氮源，分析总结了多种氢源方案与氢化机理，系统地概述了反应催化剂的研究进展。分别讨论了氮气在水中溶解度较差、硝酸盐在反应过程中元素价态跨度大而生成诸多中间产物、氮氧化物体系不稳定、电解体系中存在析氢竞争反应等问题，提出了通过改变氢源的组成或结构抑制析氢反应、开发新型高活性位点及氧空位的催化剂体系强化反应选择性、研制非水电解质体系提高反应速率及合成效率等解决思路。

关键词: 电化学, 合成, 催化剂, 还原, 电解质, 氨

Abstract:

Ammonia is a primary chemical for the synthesis of basic organic chemicals and fertilizers. The Haber-Bosch process is employed in industry to synthesize ammonia, which not only uses a lot of energy but also has a low conversion of only 10% to 15%. Electrochemical ammonia synthesis has the advantages of clean production and gentle reaction conditions as compared to the Haber-Bosch process. The features and benefits of electrochemical ammonia synthesis using nitrogen, nitrate, and nitric oxide as nitrogen sources are discussed, and the reaction mechanisms are studied based on the properties of these nitrogen sources. Different hydrogen supply schemes and hydrogenation methods are described and evaluated based on the diverse nitrogen sources, and the research development of reaction catalysts is systematically summarized. Problems of the electrolytic systems such as poor solubility of nitrogen in water, nitrates with too many valence states, excessive intermediates, instable nitrogen oxide system, and competing hydrogen evolution reaction, are discussed in detail. Some suggestions for them are proposed which include altering the composition or structure of the hydrogen source to prevent hydrogen evolution, developing new catalyst systems with high active sites and oxygen vacancies to improve reaction selectivity, and developing non-aqueous electrolyte systems to improve reaction rate and synthesis efficiency.

Key words: electrochemistry, synthesis, catalyst, reduction, electrolytes, ammonia

中图分类号:

TQ113.2

关浩然, 朱丽娜, 朱凌岳, 苑丹丹, 张雨晴, 王宝辉. 利用不同氢源及氮源电化学合成氨研究进展与挑战[J]. 化工进展, 2022, 41(8): 4098-4110.

GUAN Haoran, ZHU Lina, ZHU Lingyue, YUAN Dandan, ZHANG Yuqing, WANG Baohui. Progress and challenges of electrochemical synthesis of ammonia from different hydrogen and nitrogen sources[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4098-4110.

图/表 6

图1 N2还原解离机制与缔合机制合成氨反应机理[21]

图2 NO3RR反应机理[13]

图3 一氧化氮还原反应合成氨机理[20]

图4 电化学实验装置示意图

表1 以水为氢源电化学合成氨（表中均为NRR反应）

温度/℃	阴极/催化剂	阳极	还原电位(vs.RHE)/V	电解质	/mol·s^-1·cm^-2	FE/%	参考文献
贵金属
RT	THH Au NRs	石墨棒	-0.2	0.1mol/L KOH	2.7×10^-11	3.9	［32］
AT	pAu/NF	Ag/AgCl（饱和KCl溶液）	-0.2	0.1mol/L Na₂SO₄	1.54×10^-10	13.36	［33］
AT	TA-Au NW	—	-0.3	0.1mol/L Na₂SO₄	4.36×10^-9g·s^-1· $m g c a t - 1$	14.83	［34］
AT	NCM-Au NPs	Pt	-0.3	0.1mol/L HCl	5.88×10^-10	22	［35］
AT	Rh NNs	碳棒	-0.2	0.1mol/L KOH	6.63×10^-9g·s^-1· $m g c a t - 1$	0.7	［36］
AT	Pd/C	Pt	0.1	0.05mol/L H₂SO₄	1.25×10^-9g·s^-1· $m g c a t - 1$	8.2	［37］
过渡金属（铁基）
65	γ-Fe₂O₃/CP	石墨棒	-0.4	0.1mol/L KOH	1.64×10^-11	1.96	［38］
AT	磁性Fe₃O₄	石墨片	-0.15	0.1mol/L Na₂SO₄	3.36×10^-9g·s^-1· $m g c a t - 1$	16.9	［39］
250	Fe₂O₃/AC	Ni	1.55	熔融NaOH-KOH	8.27×10^-9	13.7	［40］
RT	Fe₂O₃/CNT	Pt	-2.0(vs.Ag/AgCl)	KHCO₃	3.59×10^-12	95.1	［41］
25	o-Fe₂O₃-CNT/CP	石墨棒	-0.9(vs.Ag/AgCl)	0.1mol/L KOH	2.37×10^-11	8.28	［42］
90	MOF（Fe）	Pt	1.2	2mol/L KOH	2.12×10^-9	1.43	［43］
AT	α-Fe/Fe₃O₄	Pt	0.15	［C₄mpyr］［eFAP］	2.35×10^-11	32	［44］
AT	Fe-SS	Pt	-0.8(vs.NHE)	［C₄mpyr］［eFAP］	2.2×10^-11	35	［45］
AT	Fe-FTO	Pt	-0.8(vs.NHE)	［P_{6，6，6，14}］［eFAP］	6.5×10^-12	60	［45］
过渡金属（钼基）
RT	Mo-D-R-5h	Pt	-0.49	0.01mol/L H₂SO₄	3.09×10^-11	0.72	［46］
RT	MoS₂/CC	石墨棒	-0.5	0.1mol/L HCl	8.08×10^-11	1.17	［47］
AT	Mo₂C/C	Pt	-0.3	0.5mol/L Li₂SO₄	3.14×10^-9g·s^-1· $m g c a t - 1$	7.8	［48］
过渡金属（钒基）
RT	VN/CC	石墨棒	-0.3	0.1mol/L HCl	2.48×10^-10	3.58	［49］
25	VN/钛网	石墨棒	-0.5	0.1mol/L HCl	1.21×10^-8g·s^-1· $m g c a t - 1$	2.25	［50］
AT	VO₂（空心微球）	Ag/AgCl（饱和KCl溶液）	-0.7	0.1mol/L Na₂SO₄	4.13×10^-9g·s^-1· $m g c a t - 1$	3.97	［51］
AT	V2CTx MXene	—	-0.7	0.1mol/L Na₂SO₄	3.5×10^-9g·s^-1· $m g c a t - 1$	4	［52］
过渡金属（钴基）
RT	CoP HNC	Pt	-0.4	1.0mol/L KOH	8.8×10^-11	7.36	［53］
AT	CMO-NR	—	-0.1	0.1mol/L Na₂SO₄ 或0.1mol/L KOH	1.31×10^-9g·s^-1· $m g c a t - 1$	22.76	［54］
AT	Co₄N/Co₂C@rGO	石墨棒	-0.1	0.1mol/L HCl	6.7×10^-9g·s^-1· $m g c a t - 1$	24.97	［55］
90	MOF（Co）	Pt	1.2	2mol/L KOH	1.64×10^-9	1.06	［43］
其他过渡金属
RT	Sn(Ⅱ)肽菁碳箔电极	Pt	-0.3	1mol/L KOH	1.4×10^-11	2	［56］
AT	Nb₂O₅	石墨棒	-0.55	0.1mol/L HCl	6.8×10^-11	9.26	［57］
AT	Nb₂O₅ NA/CC	石墨棒	-0.6	0.1mol/L Na₂SO₄	1.58×10^-10	2.26	［58］
AT	Ni-MOF-74	Pt	-0.7(vs.Ag/AgCl)	0.1mol/L Na₂SO₄	6.68×10^-11	23.69	［59］
90	MOF（Cu）	Pt	1.2	2mol/L KOH	1.24×10^-9	0.96	［42］
非金属
RT	B₄C/CP	石墨棒	-0.75	0.1mol/L HCl	4.34×10^-11	15.95	［60］
AT	NPC-750	Pt	0.9	0.05mol/L H₂SO₄	2.33×10^-10	1.42	［61］
AT	CNS	Pt	-1.19	0.25mol/L LiClO₄	(1.59±0.12)×10^-9	11.56	［62］
复合材料
25	Li⁺/PEBCD	Pt	-0.6	0.5mol/L Li₂SO₄	3.28×10^-11	0.42	［63］
RT	Au/C₃N₄	Pt	-0.1	0.05mol/L H₂SO₄	3.63×10^-7g·s^-1· $m g A u - 1$	11.1	［64］
AT	Au/TiO₂	Pt	-0.2	0.05mol/L H₂SO₄	3.5×10^-10	8.11	［65］
60	Au/TiO₂	Pt	-0.2	0.05mol/L H₂SO₄	5×10^-10	13.5	［65］
RT	Ag-Au/ZIF	Pt	-2.9	THF	1×10^-11	18±4	［66］
AT	NiS@MoS₂	碳棒	-0.1	0.1mol/L Na₂SO₄	N/A	14.8	［67］
AT	NiS@MoS₂	碳棒	-0.3	0.1mol/L Na₂SO₄	2.68×10^-9g·s^-1· $m g c a t - 1$	N/A	［67］
AT	非晶型Au/CeO _x -rGO	Pt	-0.2	0.1mol/L HCl	2.7×10^-8	10.1	［68］
200~250	Ru/Cs⁺/MgO\|Pd-Ag	Pt	—	CsH₂PO₄/SiP₂O₇ 复合材料	9×10^-9	2.6	［69］

表1 以水为氢源电化学合成氨（表中均为NRR反应）

温度/℃	阴极/催化剂	阳极	还原电位(vs.RHE)/V	电解质	/mol·s^-1·cm^-2	FE/%	参考文献
贵金属
RT	THH Au NRs	石墨棒	-0.2	0.1mol/L KOH	2.7×10^-11	3.9	［32］
AT	pAu/NF	Ag/AgCl（饱和KCl溶液）	-0.2	0.1mol/L Na₂SO₄	1.54×10^-10	13.36	［33］
AT	TA-Au NW	—	-0.3	0.1mol/L Na₂SO₄	4.36×10^-9g·s^-1· $m g c a t - 1$	14.83	［34］
AT	NCM-Au NPs	Pt	-0.3	0.1mol/L HCl	5.88×10^-10	22	［35］
AT	Rh NNs	碳棒	-0.2	0.1mol/L KOH	6.63×10^-9g·s^-1· $m g c a t - 1$	0.7	［36］
AT	Pd/C	Pt	0.1	0.05mol/L H₂SO₄	1.25×10^-9g·s^-1· $m g c a t - 1$	8.2	［37］
过渡金属（铁基）
65	γ-Fe₂O₃/CP	石墨棒	-0.4	0.1mol/L KOH	1.64×10^-11	1.96	［38］
AT	磁性Fe₃O₄	石墨片	-0.15	0.1mol/L Na₂SO₄	3.36×10^-9g·s^-1· $m g c a t - 1$	16.9	［39］
250	Fe₂O₃/AC	Ni	1.55	熔融NaOH-KOH	8.27×10^-9	13.7	［40］
RT	Fe₂O₃/CNT	Pt	-2.0(vs.Ag/AgCl)	KHCO₃	3.59×10^-12	95.1	［41］
25	o-Fe₂O₃-CNT/CP	石墨棒	-0.9(vs.Ag/AgCl)	0.1mol/L KOH	2.37×10^-11	8.28	［42］
90	MOF（Fe）	Pt	1.2	2mol/L KOH	2.12×10^-9	1.43	［43］
AT	α-Fe/Fe₃O₄	Pt	0.15	［C₄mpyr］［eFAP］	2.35×10^-11	32	［44］
AT	Fe-SS	Pt	-0.8(vs.NHE)	［C₄mpyr］［eFAP］	2.2×10^-11	35	［45］
AT	Fe-FTO	Pt	-0.8(vs.NHE)	［P_{6，6，6，14}］［eFAP］	6.5×10^-12	60	［45］
过渡金属（钼基）
RT	Mo-D-R-5h	Pt	-0.49	0.01mol/L H₂SO₄	3.09×10^-11	0.72	［46］
RT	MoS₂/CC	石墨棒	-0.5	0.1mol/L HCl	8.08×10^-11	1.17	［47］
AT	Mo₂C/C	Pt	-0.3	0.5mol/L Li₂SO₄	3.14×10^-9g·s^-1· $m g c a t - 1$	7.8	［48］
过渡金属（钒基）
RT	VN/CC	石墨棒	-0.3	0.1mol/L HCl	2.48×10^-10	3.58	［49］
25	VN/钛网	石墨棒	-0.5	0.1mol/L HCl	1.21×10^-8g·s^-1· $m g c a t - 1$	2.25	［50］
AT	VO₂（空心微球）	Ag/AgCl（饱和KCl溶液）	-0.7	0.1mol/L Na₂SO₄	4.13×10^-9g·s^-1· $m g c a t - 1$	3.97	［51］
AT	V2CTx MXene	—	-0.7	0.1mol/L Na₂SO₄	3.5×10^-9g·s^-1· $m g c a t - 1$	4	［52］
过渡金属（钴基）
RT	CoP HNC	Pt	-0.4	1.0mol/L KOH	8.8×10^-11	7.36	［53］
AT	CMO-NR	—	-0.1	0.1mol/L Na₂SO₄ 或0.1mol/L KOH	1.31×10^-9g·s^-1· $m g c a t - 1$	22.76	［54］
AT	Co₄N/Co₂C@rGO	石墨棒	-0.1	0.1mol/L HCl	6.7×10^-9g·s^-1· $m g c a t - 1$	24.97	［55］
90	MOF（Co）	Pt	1.2	2mol/L KOH	1.64×10^-9	1.06	［43］
其他过渡金属
RT	Sn(Ⅱ)肽菁碳箔电极	Pt	-0.3	1mol/L KOH	1.4×10^-11	2	［56］
AT	Nb₂O₅	石墨棒	-0.55	0.1mol/L HCl	6.8×10^-11	9.26	［57］
AT	Nb₂O₅ NA/CC	石墨棒	-0.6	0.1mol/L Na₂SO₄	1.58×10^-10	2.26	［58］
AT	Ni-MOF-74	Pt	-0.7(vs.Ag/AgCl)	0.1mol/L Na₂SO₄	6.68×10^-11	23.69	［59］
90	MOF（Cu）	Pt	1.2	2mol/L KOH	1.24×10^-9	0.96	［42］
非金属
RT	B₄C/CP	石墨棒	-0.75	0.1mol/L HCl	4.34×10^-11	15.95	［60］
AT	NPC-750	Pt	0.9	0.05mol/L H₂SO₄	2.33×10^-10	1.42	［61］
AT	CNS	Pt	-1.19	0.25mol/L LiClO₄	(1.59±0.12)×10^-9	11.56	［62］
复合材料
25	Li⁺/PEBCD	Pt	-0.6	0.5mol/L Li₂SO₄	3.28×10^-11	0.42	［63］
RT	Au/C₃N₄	Pt	-0.1	0.05mol/L H₂SO₄	3.63×10^-7g·s^-1· $m g A u - 1$	11.1	［64］
AT	Au/TiO₂	Pt	-0.2	0.05mol/L H₂SO₄	3.5×10^-10	8.11	［65］
60	Au/TiO₂	Pt	-0.2	0.05mol/L H₂SO₄	5×10^-10	13.5	［65］
RT	Ag-Au/ZIF	Pt	-2.9	THF	1×10^-11	18±4	［66］
AT	NiS@MoS₂	碳棒	-0.1	0.1mol/L Na₂SO₄	N/A	14.8	［67］
AT	NiS@MoS₂	碳棒	-0.3	0.1mol/L Na₂SO₄	2.68×10^-9g·s^-1· $m g c a t - 1$	N/A	［67］
AT	非晶型Au/CeO _x -rGO	Pt	-0.2	0.1mol/L HCl	2.7×10^-8	10.1	［68］
200~250	Ru/Cs⁺/MgO\|Pd-Ag	Pt	—	CsH₂PO₄/SiP₂O₇ 复合材料	9×10^-9	2.6	［69］

图5 以[P6,6,6,14][eFAP]作为质子导体合成氨机理

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