载体对单原子电催化剂合成氨性能的影响与调控策略

doi:10.11949/0438-1157.20240659

摘要/Abstract

摘要：

电催化氮还原制氨（e-NRR）是一种低碳绿色的氨合成方法，高效电催化剂的开发是打破e-NRR热力学限制，推动该技术走向工业化的关键。单原子催化剂原子利用率高，有望用于e-NRR并实现高的法拉第效率和氨产率，但受限于单原子的高表面能，需要选择合适的载体以稳定单原子位点，并利用载体-金属强相互作用（SMSI）进一步提高催化活性。以e-NRR机理为基础，系统总结了单原子催化剂的合成与表征方法以及不同载体负载的单原子催化剂在e-NRR中的应用，归纳了单原子催化剂的优化与调控策略，分析了单原子催化剂在e-NRR领域的发展趋势。研究发现碳基材料负载的单原子催化剂应用最为广泛，而以氧化物、硫族化合物、MXenes为载体的单原子催化剂以及单原子合金催化剂在e-NRR领域的研究更多停留在理论，具有广阔的研发空间。在载体中构建缺陷以增强SMSI，或构建双单原子以实现协同催化是进一步提高e-NRR性能的有效策略。

关键词: 电化学, 催化剂, 合成氨, 载体, 单原子, 载体-金属强相互作用

Abstract:

Electrocatalytic nitrogen reduction to ammonia (e-NRR) is a low-carbon and green ammonia synthesis method. The development of efficient electrocatalysts is the key to break the thermodynamic limitation of e-NRR and promote the technology to industrialization. The single atom catalyst has high atomic utilization and is expected to be used for e-NRR and achieve high Faradaic efficiency and ammonia yield. However, due to the high surface energy of the single atom, it is necessary to select a suitable support to stabilize the single atom site and further improve the catalytic activity by using the support metal strong interaction (SMSI). Based on the mechanism of e-NRR, this review summarizes the current synthesis methods and characterization of single atom catalysts and the application of single atom catalysts supported by different support in e-NRR. In addition, this review also concludes the optimal regulation strategy of single atom catalysts, and future analyzes the development trend of single atom catalyst in e-NRR. It is found that carbon based material loaded single atom catalysts are the most widely used, while single atom catalysts based on oxides, sulfur compounds, MXenes, and single atom alloy catalysts in the field of e-NRR are more theoretical, and there is a vast space for research and development. Building defects in the support to enhance SMSI, or building double single atoms to achieve synergistic catalysis is an effective strategy to further improve the performance of e-NRR.

Key words: electrochemistry, catalyst, synthetic ammonia, support, single atom, support-metal strong interaction

中图分类号:

TQ 150

纪之骄, 张晓方, 甘汶, 薛云鹏. 载体对单原子电催化剂合成氨性能的影响与调控策略[J]. 化工学报, 2025, 76(1): 18-39.

Zhijiao JI, Xiaofang ZHANG, Wen GAN, Yunpeng XUE. Influence of support on the performance of single atom electrocatalyst for ammonia synthesis and the control strategy[J]. CIESC Journal, 2025, 76(1): 18-39.

图/表 17

图1 e-NRR中Dissociative机理和Associative机理示意图

Fig.1 Schematic diagram of Dissociative mechanisms and Associative mechanisms in e-NRR

图2 Mars-van Krevelen机理和表面氢化机理示意图

Fig.2 Schematic diagram of Mars-van Krevelen mechanism and surface hydrogenation mechanism

图3 合成SACs的常用策略

Fig.3 Common strategies for synthesizing SACs

图4 “自底向上”的SACs合成法实例

Fig.4 Example of “bottom-up” SACs synthesis

图5 “自顶向下”的SACs合成法实例

Fig.5 Example of “top-down” SACs synthesis

图6 SACs常用的表征手段

Fig.6 Common characterization methods of SACs

图7 FT-IR用于表征单原子材料以及原位电化学FT-IR和Raman光谱

Fig.7 FT-IR for characterization of single atom materials and in situ electrochemical FT-IR and Raman spectra

图8 Pt1/N-C的变电位XANES表征以及对应的k2加权傅里叶变换光谱[55]

Fig.8 XANES spectra of Pt1/N-C at different applied voltages and corresponding k2-weighted Fourier transform spectra[55]

图9 用于光增强固氮的Cu SAs/TiO2机理示意图[65]

Fig.9 Schematic diagram of Cu SAs/TiO2 mechanism for photoenhanced nitrogen fixation[65]

图10 CoTA、AsTA、GaTA、ZnTA和N2吸附在Mo-CoTA、Mo-AsTA、Mo-GaTA、Mo-ZnTA表面的差分电荷图[5]

Fig.10 Differential charge diagram of CoTA, AsTA, GaTA, ZnTA and N2 adsorbed on Mo-CoTA, Mo-AsTA, Mo-GaTA, Mo-ZnTA surfaces[5]

图11 Fe-N3S和Fe-N4活化N2的配位结构（负电荷和正电荷的变化分别显示为黄色和绿色）[72]

Fig.11 N2 activation on Fe-N3S and Fe-N4 coordination structure （negative and positive charge changes are displayed in yellow and green, respectively）[72]

图12 非金属元素掺杂碳纤维载体负载的单原子催化剂催化机理示意图

Fig.12 Schematic diagram of catalytic mechanism of non-metallic element-doped carbon fiber carrier-loaded single-atom catalysts

图13 Ru SAs/Ti3C2O催化氮还原制氨不同路径下的能量谱[91]

Fig.13 Energy spectra of Ru SAs/Ti3C2O catalyzed nitrogen reduction to ammonia under different pathways[91]

图14 SA Ru-Mo2CT x 纳米片催化剂制备流程、电荷密度差分图以及N2在Ru单原子上的还原过程示意图[6](蓝色、紫色、棕色、红色、灰色、粉色球体分别代表Ru、Mo、C、O、N和H)

Fig.14 Preparation process of SA Ru-Mo2CT x nanosheet, charge density difference diagram, and the diagram of reduction process of N2 on Ru single atom[6]

图15 过渡金属硫族化合物负载的SACs实例

Fig.15 Example of SACs loaded on transition metal chalcogenides

图16 PdFe1的STEM图和PTA中引入Bi单原子的结构示意图

Fig.16 STEM image of PdFe1 and the structure diagram of Bi single atom introduced into PTA

表1 不同载体负载单原子催化剂的e-NRR性能

Table 1 e-NRR performance of single atom catalysts supported by different support

序号	催化剂		电解液	最高氨产率/	最高FE/%	负载量/	文献
序号	载体	组成	电解液	（µg·h^-1·mg ^-1）	最高FE/%	%(质量分数)	文献
1	金属氧化物	Nb-TiO₂(110)	0.1 mol·L^-1 Na₂SO₄	21.3	9.2	3.36	[64]
2		Cu SAs/TiO₂	0.5 mol·L^-1 K₂SO₄	6.3	12.9	1.44	[65]
3		Cd/In₂O₃(V_O)	0.1 mol·L^-1 KOH	57.5	4.5	0.098	[32]
4		Fe_SA-NO-C	0.1 mol·L^-1 HCl	31.9	11.8	0.78	[114]
5		D-FeN/C	0.1 mol·L^-1 KOH	24.8	15.8	0.50	[81]
6		Fe-N₃S	0.1 mol·L^-1 KOH	28.9	23.7	0.94	[72]
7		FeMo/CN	0.1 mol·L^-1 Na₂SO₄	26.8	11.8	—	[115]
8		FeRu-CNS	0.1 mol·L^-1 Na₂SO₄	43.9	29.3	1.00	[2]
9		Co-SA/N-SCF	0.01 mol·L^-1 HCl	67.6	56.9	4.66	[80]
10		Zn₁N-C	0.1 mol·L^-1 KOH	16.1	11.8	1.64	[116]
11		Mo_SA/ CMF-S	0.1 mol·L^-1 HCl	46.6	28.9	0.83	[82]
12		W-NO/NC	0.5 mol·L^-1 LiClO₄	12.6	8.4	10.20	[117]
13		Fe-B/N-C	0.1 mol·L^-1 HCl	100.1	23.0	—	[118]
14	MXenes	Ru SAs/Ti₃C₂O	0.1 mol·L^-1 HCl	27.6	23.3	0.43	[91]
15		SA Ru-Mo₂CT _x	0.5 mol·L^-1 K₂SO₄	40.57	25.8	1.41	[6]
16		Sb SA/N-Ti₃C₂T _x	0.5 mol·L^-1 K₂SO₄	108.3	41.2	2.20	[95]
17	硒化物	Au_SA/npMoSe₂	0.1 mol·L^-1 Na₂SO₄	30.8	37.8	3.80	[101]
18	单原子合金	PdFe₁	0.5 mol·L^-1 LiClO₄	111.9	37.8	—	[109]
19	单原子合金	PdFe₃	0.1 mol·L^-1 KOH	29.07	22.8	—	[108]
20	钙钛矿	LaFeO-Ru	0.1 mol·L^-1 K₂SO₄	约137.5	约56.9	—	[111]

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