Ru基氮还原电催化剂性能调控策略

doi:10.11949/0438-1157.20230048

化工学报 ›› 2023, Vol. 74 ›› Issue (6): 2264-2280.DOI: 10.11949/0438-1157.20230048

Ru基氮还原电催化剂性能调控策略

张谭¹^,²^,³(), 刘光¹(), 李晋平¹^,²^,³(), 孙予罕²^,⁴

^1.太原理工大学化学工程与技术学院，气体能源高效清洁利用山西省重点实验室，山西太原 030024
^2.怀柔实验室山西研究院，山西太原 030000
^3.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
^4.上海科技大学2060研究院，上海 201210

收稿日期:2023-01-19 修回日期:2023-06-01 出版日期:2023-06-05 发布日期:2023-07-27
通讯作者: 刘光,李晋平
作者简介:张谭（1995—），男，博士研究生，zhangtan1206@126.com
基金资助:
国家自然科学基金项目(22075196)

Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts

Tan ZHANG¹^,²^,³(), Guang LIU¹(), Jinping LI¹^,²^,³(), Yuhan SUN²^,⁴

^1.Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Shanxi Research Institute of Huairou Laboratory, Taiyuan 030000, Shanxi, China
^3.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^4.2060 Research Institute, Shanghai Tech University, Shanghai 201210, China

Received:2023-01-19 Revised:2023-06-01 Online:2023-06-05 Published:2023-07-27
Contact: Guang LIU, Jinping LI

摘要/Abstract

摘要：

氨是重要的化学品以及理想的能源载体，人工合成氨主要来源于高能耗的Haber-Bosch（H-B）工艺。相比而言，电催化合成氨以N₂和H₂O为原料，实现了温和条件下产氨。Ru基催化剂在氮还原（NRR）过程中表现出优异的催化活性，但由于较为稀缺限制了其发展。基于此，首先概述了NRR的反应机制并对现有的Ru基合成氨电催化剂进行了系统的介绍；详细分析了性能提升策略（结构调控、表/界面工程、缺陷工程），如何调控活性组分或电子结构，进而提升催化剂的性能；最后分析了Ru基催化剂所面临的挑战。旨在通过Ru基催化剂性能提升策略，实现贵金属Ru的高效利用，并为其他NRR催化剂的开发设计提供指导。

关键词: 催化剂, 催化, 电化学, 合成氨, 氮还原反应, 性能提升策略

Abstract:

Ammonia is an important chemical and ideal energy vector. Artificial ammonia synthesis through the Haber-Bosch (H-B) process is energy-intensive. In contrast, ammonia is generated from N₂ and H₂O under mild conditions through the electrocatalytic ammonia synthesis. Ru-based catalyst performs superior activities during the nitrogen reduction reaction (NRR), which has attracted extensive attention. However, its development is limited owing to its scarcity. Therefore, the NRR reaction mechanisms are briefly outlined and a systematic summary of Ru-based electrocatalysts for ammonia synthesis is introduced firstly. Subsequently, it is methodically discussed how the strategies for performance enhancement (structural optimization, surface/interface engineering, defect engineering) of catalysts regulate the active sites or electronic structure and then promote the activity of catalysts. Finally, the remaining challenges of Ru-based electrocatalysts in future are highlighted. This review aims to achieve the usage of the Ru metal effectively through the performance-improving strategies of Ru-based electrocatalysts and provides the theory guidance for the design of the other NRR catalysts.

Key words: catalyst, catalysis, electrochemistry, ammonia synthesis, nitrogen reduction reaction, performance-improving strategies

中图分类号:

O 643.36

张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.

Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts[J]. CIESC Journal, 2023, 74(6): 2264-2280.

图/表 11

图1 以氨为能源载体通过氨合成和分解的路线图[1]

Fig.1 Roadmap of ammonia as energy carrier via ammonia synthesis and decomposition[1]

图2 Ru基电催化剂的提升策略

Fig.2 Strategies to improve the performance of Ru-based electrocatalysts

图3 非均相催化剂上的NRR反应机制[23]

Fig.3 Reaction mechanisms for NRR on heterogeneous catalysts[23]

图4 不同饱和N2溶液中Ru薄膜上的傅里叶红外光谱图[28]

Fig.4 FTIR spectra on the Ru thin film in the different N2-saturated solutions[28]

表1 性能提升策略指导的部分Ru催化剂性能总结

Table 1 Summary of performance of partial Ru-based catalysts guided by performance-improving strategies

序号	催化剂	产氨率	FE/%	电解液	电位/V(vs RHE)	文献	调控策略
1	LaFeO₃-Ru	137.5 μg·h^-1·mg^-1	56.9	0.1 mol·L^-1 K₂SO₄	-0.7	[36]	单原子策略
2	Ru SAs/g-C₃N₄	23.0 μg·h^-1·mg^-1	8.3	0.5 mol·L^-1 NaOH	0.05	[40]
3	Ru SAs/N-C	120.9 μg·h^-1·mg^-1	29.6	均可	-0.2	[45]
4	SA Ru-Mo₂CT _x	40.57 μg·h^-1·mg^-1	25.77	0.5 mol·L^-1 K₂SO₄	-0.3	[55]
5	Ru SAs/Ti₃C₂O	27.56 μg·h^-1·mg^-1	23.3	0.1 mol·L^-1 HCl	-0.2	[56]
6	PdRu TPs	37.23 μg·h^-1·mg^-1	1.85	0.1 mol·L^-1 KOH	-0.2	[80]	形貌/晶体调控策略
7	PdRu BPNs	25.92 μg·h^-1·mg^-1	1.53	0.1 mol·L^-1 HCl	-0.1	[24]
8	mRhRu/NF	30.28 μg·h^-1·mg^-1	28.33	0.1 mol·L^-1 Na₂SO₄	-0.05	[84]
9	a₁-Ru/CNTs	10.49 μg·h^-1·mg^-1	17.48	5 mmol·L^-1 Cs₂CO₃	-0.2	[34]
10	Ru/rGO-C12	50 μg·h^-1·mg^-1	11	0.05 mol·L^-1 H₂SO₄	-0.1	[93]	表/界面工程
11	RuCu-FNs	53.6 μg·h^-1·mg^-1	7.2	0.1 mol·L^-1 HCl	-0.1	[103]	表/界面工程
12	Ru₈₈Pt₁₂	47.4 μg·h^-1·mg^-1	8.9	0.1 mol·L^-1 KOH	-0.2	[111]	杂原子掺杂
13	Rh_0.6Ru_0.4 NAs/CP	57.75 μg·h^-1·mg^-1	3.39	0.1 mol·L^-1 Na₂SO₄	-0.2	[112]
14	Ru-Cu NPs	73 μg·h^-1·cm^-2	30.95	0.1 mol·L^-1 HCl	-0.1	[114]
15	Ru₂P-rGO	32.8 μg·h^-1·mg^-1	13.04	0.1 mol·L^-1 HCl	-0.05	[117]
16	Ru/CeO₂-Vo	9.87×10^-8 mmol·s^-1·cm^-2	11.7	0.05 mol·L^-1 H₂SO₄	-0.25	[125]	空位调控
17	Ru/2H-MoS₂	1.14×10^-10 mmol·s^-1·cm^-2	17.6	10 mmol·L^-1 HCl	-0.15	[127]	空位调控

图5 (a) Ru@ZrO2/NC的形貌及结构表征；(b) 电化学氮还原活性；(c) NRR的计算模型以及自由能曲线 [44]

Fig.5 (a) Morphology and structure characterization of Ru@ZrO2/NC; (b) Electrochemical nitrogen reduction activities; (c) Calculation models and free energy diagrams for NRR [44]

图6 (a) PdRu TP的相关元素分布图；(b) 特定电位下PdRu TPs的产氨率和FE；(c) -0.2 V(vs RHE)下不同催化剂的产氨率；(d) PdRu TPs上的电催化NRR过程示意图[80]

Fig.6 (a) The corresponding elemental mapping images of a single PdRu TP; (b) NH3 yield rates and FE of PdRu TPs at selected potentials; (c) NH3 yield rates of different catalysts at -0.2 V(vs RHE); (d) Schematic diagram of electrocatalytic NRR process on the PdRu TPs[80]

图7 (a) 脂肪族硫醇用于Ru/rGO合成及改性；(b) TEM图像；(c) HR-TEM图像；(d) Ru/rGO-C12的FE及产氨率；(e) Ru/rGO-C12的循环性能以及(f) 长时间稳定性；(g) 15N2氛围下通过1H NMR 定量测试NH3；(h) 优化后的原子构型；(i) Bader电荷分布；(j) Ru/rGO-C12上的NRR Gibbs自由能曲线 [93]

Fig.7 (a) Illustration of synthesis and modification of Ru/rGO with aliphatic thiols; (b) TEM images; (c) HR-TEM images; (d) FE and rate of NH3 production for Ru/rGO-C12; (e) Recyclability and (f) long-term stability of Ru/rGO-C12; (g) NH3 quantification by 1H NMR in 15N2 environment; (h) The optimized atomic configuration; (i) Bader charge distribution; (j) Gibbs free energy profile of NRR on Ru/rGO-C12 [93]

图8 (a) Ru88Pt12纳米线的结构示意图；(b) Ru88Pt12纳米线的TEM图像以及(c) HAADF图像；(d) 不同电位下的产氨率以及(e) 对应的FE；(f) 电催化剂的循环性能以及(g) 长期稳定性；(h) 原子模型；(i) 计算所得吸附能；(j) 分态密度[111]

Fig.8 (a) A schematic diagram of the structure of a Ru88Pt12 nanowire; (b) TEM images and (c) HAADF images of Ru88Pt12 nanowires; (d) NH3 production rates and (e) corresponding FE at different potentials; (f) Recyclability and (g) long-term stability of electrocatalysis; (h) Atomic models; (i) Calculated adsorption energies; (j) Projected density of states[111]

图9 (a) Ru-Cu NPs的结构以及制备示意图；(b) Ru-Cu NPs的元素分布图；(c) FE和产氨率；(d) 1H NMR谱图；(e) 电催化剂NRR过程的DFT计算[114]

Fig.9 (a) Schematic diagram of the structure and fabrication of Ru-Cu NPs; (b) Mapping images of Ru-Cu NPs; (c) FE and NH3 formation rates; (d) 1H NMR spectra; (e) DFT calculations of the NRR process on the electrocatalysts[114]

图10 (a) EPR谱图；(b) O 1s 的XPS谱图；(c) 价带；(d) Ru/2H-MoS2材料电催化将N2转化为NH3的最小能量示意图[125, 127]

Fig.10 (a) EPR spectra; (b) XPS spectra of O 1s; (c) Valance bands; (d) Schematic diagram of minimum-energy pathway for electrochemical N2 conversion into NH3 catalyzed by Ru/2H-MoS2 material[125, 127]

参考文献 132

1	Fang H H, Liu D, Luo Y, et al. Challenges and opportunities of Ru-based catalysts toward the synthesis and utilization of ammonia[J]. ACS Catalysis, 2022, 12(7): 3938-3954.
2	Petitpas G. Simulation of boil-off losses during transfer at a LH₂ based hydrogen refueling station[J]. International Journal of Hydrogen Energy, 2018, 43(46): 21451-21463.
3	Metkemeijer R, Achard P. Comparison of ammonia and methanol applied indirectly in a hydrogen fuel cell[J]. International Journal of Hydrogen Energy, 1994, 19(6): 535-542.
4	Wan Z J, Tao Y K, Shao J, et al. Ammonia as an effective hydrogen carrier and a clean fuel for solid oxide fuel cells[J]. Energy Conversion and Management, 2021, 228: 113729.
5	Luo Y, Liang S J, Wang X Y, et al. Facile synthesis and high-value utilization of ammonia[J]. Chinese Journal of Chemistry, 2022, 40(8): 953-964.
6	Yang S, Zhang T, Yang Y Y, et al. Molybdenum-based nitrogen carrier for ammonia production via a chemical looping route[J]. Applied Catalysis B: Environmental, 2022, 312: 121404.
7	Zhang T, Yu Z L, Yu J Q, et al. Chemical looping ammonia synthesis with high performance supported molybdenum-based nitrogen carrier[J]. Acta Chimica Sinica, 2022, 80(6): 788.
8	Zhao R B, Xie H T, Chang L, et al. Recent progress in the electrochemical ammonia synthesis under ambient conditions[J]. EnergyChem, 2019, 1(2): 100011.
9	Wu T T, Fan W J, Zhang Y, et al. Electrochemical synthesis of ammonia: progress and challenges[J]. Materials Today Physics, 2021, 16: 100310.
10	Rod T H, Logadottir A, Nørskov J K. Ammonia synthesis at low temperatures[J]. The Journal of Chemical Physics, 2000, 112(12): 5343-5347.
11	Deng J, Iñiguez J A, Liu C. Electrocatalytic nitrogen reduction at low temperature[J]. Joule, 2018, 2(5): 846-856.
12	Ma W C, He X Y, Wang W, et al. Electrocatalytic reduction of CO₂ and CO to multi-carbon compounds over Cu-based catalysts[J]. Chemical Society Reviews, 2021, 50(23): 12897-12914.
13	Ren Y W, Yu C, Tan X Y, et al. Strategies to suppress hydrogen evolution for highly selective electrocatalytic nitrogen reduction: challenges and perspectives[J]. Energy & Environmental Science, 2021, 14(3): 1176-1193.
14	Wang Z C, Zhao H, Liu J, et al. The PdH _x metallene with vacancies for synergistically enhancing electrocatalytic N₂ fixation[J]. Chemical Engineering Journal, 2022, 450: 137951.
15	Hu L, Khaniya A, Wang J, et al. Ambient electrochemical ammonia synthesis with high selectivity on Fe/Fe oxide catalyst[J]. ACS Catalysis, 2018, 8(10): 9312-9319.
16	Xue Z H, Zhang S N, Lin Y X, et al. Electrochemical reduction of N₂ into NH₃ by donor-acceptor couples of Ni and Au nanoparticles with a 67.8% Faradaic efficiency[J]. Journal of the American Chemical Society, 2019, 141(38): 14976-14980.
17	Zhu X J, Mou S Y, Peng Q L, et al. Aqueous electrocatalytic N₂ reduction for ambient NH₃ synthesis: recent advances in catalyst development and performance improvement[J]. Journal of Materials Chemistry A, 2020, 8(4): 1545-1556.
18	Lv C D, Qian Y M, Yan C S, et al. Defect engineering metal-free polymeric carbon nitride electrocatalyst for effective nitrogen fixation under ambient conditions[J]. Angewandte Chemie International Edition, 2018, 57(32): 10246-10250.
19	Singh A R, Rohr B A, Schwalbe J A, et al. Electrochemical ammonia synthesis—the selectivity challenge[J]. ACS Catalysis, 2017, 7(1): 706-709.
20	Skúlason E, Bligaard T, Gudmundsdóttir S, et al. A theoretical evaluation of possible transition metal electro-catalysts for N₂ reduction[J]. Phys. Chem. Chem. Phys., 2012, 14(3): 1235-1245.
21	Wan Y C, Xu J C, Lv R T. Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions[J]. Materials Today, 2019, 27: 69-90.
22	Yang B, Ding W L, Zhang H H, et al. Recent progress in electrochemical synthesis of ammonia from nitrogen: strategies to improve the catalytic activity and selectivity[J]. Energy & Environmental Science, 2021, 14(2): 672-687.
23	Khalil I E, Xue C, Liu W J, et al. The role of defects in metal-organic frameworks for nitrogen reduction reaction: when defects switch to features[J]. Advanced Functional Materials, 2021, 31(17): 2010052.
24	Wang Z Q, Li C J, Deng K, et al. Ambient nitrogen reduction to ammonia electrocatalyzed by bimetallic PdRu porous nanostructures[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(2): 2400-2405.
25	Tayyebi E, Abghoui Y, Skúlason E. Elucidating the mechanism of electrochemical N₂ reduction at the Ru(0001) electrode[J]. ACS Catalysis, 2019, 9(12): 11137-11145.
26	Ma X G, Hu J S, Zheng M K, et al. N₂ reduction using single transition-metal atom supported on defective WS₂ monolayer as promising catalysts: a DFT study[J]. Applied Surface Science, 2019, 489: 684-692.
27	Fang Q J, Gao Y J, Zhang W, et al. Oxygen groups enhancing the mechanism of nitrogen reduction reaction properties on Ru- or Fe-supported Nb₂C MXene[J]. The Journal of Physical Chemistry C, 2021, 125(27): 14636-14645.
28	Yao Y, Wang H J, Yuan X Z, et al. Electrochemical nitrogen reduction reaction on ruthenium[J]. ACS Energy Letters, 2019, 4(6): 1336-1341.
29	Peng Y H, Geng Z G, Zhao S T, et al. Pt single atoms embedded in the surface of Ni nanocrystals as highly active catalysts for selective hydrogenation of nitro compounds[J]. Nano Letters, 2018, 18(6): 3785-3791.
30	Zhu Y Q, Sun W M, Chen W X, et al. Scale-up biomass pathway to cobalt single-site catalysts anchored on N-doped porous carbon nanobelt with ultrahigh surface area[J]. Advanced Functional Materials, 2018, 28(37): 1802167.
31	Zhao L, Zhao J, Zhao J X, et al. Artificial N₂ fixation to NH₃ by electrocatalytic Ru NPs at low overpotential[J]. Nanotechnology, 2020, 31(29): 29LT01.
32	Wang D B, Azofra L M, Harb M, et al. Energy-efficient nitrogen reduction to ammonia at low overpotential in aqueous electrolyte under ambient conditions[J]. ChemSusChem, 2018, 11(19): 3356.
33	Zhang S, Zhao Y X, Shi R, et al. Sub-3 nm ultrafine Cu₂O for visible light driven nitrogen fixation[J]. Angewandte Chemie International Edition, 2021, 60(5): 2554-2560.
34	Jiang M H, Tao A Y, Hu Y, et al. Crystalline modulation engineering of Ru nanoclusters for boosting ammonia electrosynthesis from dinitrogen or nitrate[J]. ACS Applied Materials & Interfaces, 2022, 14(15): 17470-17478.
35	Shi M M, Bao D, Wulan B R, et al. Au sub-nanoclusters on TiO₂ toward highly efficient and selective electrocatalyst for N₂ conversion to NH₃ at ambient conditions[J]. Advanced Materials, 2017, 29(17): 1606550.
36	Han Z Y, Tranca D, Rodríguez-Hernández F, et al. Embedding Ru clusters and single atoms into perovskite oxide boosts nitrogen fixation and affords ultrahigh ammonia yield rate[J]. Small, 2023, 19(17): 2208102.
37	Han J X, Meng X Y, Lu L, et al. Single-atom Fe-N _x -C as an efficient electrocatalyst for zinc-air batteries[J]. Advanced Functional Materials, 2019, 29(41): 1808872.
38	Zhuang Z C, Li Y, Li Z L, et al. MoB/g-C₃N₄ interface materials as a Schottky catalyst to boost hydrogen evolution[J]. Angewandte Chemie International Edition, 2018, 57(2): 496-500.
39	Zheng Y, Jiao Y, Zhu Y H, et al. Molecule-level g-C₃N₄ coordinated transition metals as a new class of electrocatalysts for oxygen electrode reactions[J]. Journal of the American Chemical Society, 2017, 139(9): 3336-3339.
40	Yu B, Li H, White J, et al. Tuning the catalytic preference of ruthenium catalysts for nitrogen reduction by atomic dispersion[J]. Advanced Functional Materials, 2020, 30(6): 1905665.
41	Chen X Z, Zhao X J, Kong Z Z, et al. Unravelling the electrochemical mechanisms for nitrogen fixation on single transition metal atoms embedded in defective graphitic carbon nitride[J]. Journal of Materials Chemistry A, 2018, 6(44): 21941-21948.
42	Liu X, Jiao Y, Zheng Y, et al. Building up a picture of the electrocatalytic nitrogen reduction activity of transition metal single-atom catalysts[J]. Journal of the American Chemical Society, 2019, 141(24): 9664-9672.
43	Zhang L F, Zhao W H, Zhang W H, et al. gt-C₃N₄ coordinated single atom as an efficient electrocatalyst for nitrogen reduction reaction[J]. Nano Research, 2019, 12(5): 1181-1186.
44	Tao H C, Choi C, Ding L X, et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction[J]. Chem, 2019, 5(1): 204-214.
45	Geng Z G, Liu Y, Kong X D, et al. N₂ electrochemical reduction: achieving a record-high yield rate of 120.9 μ g N H 3 ·mg_cat. ^-1·h^-1 for N₂ electrochemical reduction over Ru single-atom catalysts[J]. Advanced Materials, 2018, 30(40): 1870301.
46	Ji Y J, Li Y F, Dong H L, et al. Ruthenium single-atom catalysis for electrocatalytic nitrogen reduction unveiled by grand canonical density functional theory[J]. Journal of Materials Chemistry A, 2020, 8(39): 20402-20407.
47	Naguib M, Kurtoglu M, Presser V, et al. Two-dimensional nanocrystals produced by exfoliation of Ti₃AlC₂ [J]. Advanced Materials, 2011, 23(37): 4248-4253.
48	Zhao J X, Zhang L, Xie X Y, et al. Ti₃C₂T _x (T = F, OH) MXene nanosheets: conductive 2D catalysts for ambient electrohydrogenation of N₂ to NH₃ [J]. Journal of Materials Chemistry A, 2018, 6(47): 24031-24035.
49	Luo Y R, Chen G F, Ding L, et al. Efficient electrocatalytic N₂ fixation with MXene under ambient conditions[J]. Joule, 2019, 3(1): 279-289.
50	Zhang J Q, Zhao Y F, Guo X, et al. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction[J]. Nature Catalysis, 2018, 1(12): 985-992.
51	Li Z, Yu L, Milligan C, et al. Two-dimensional transition metal carbides as supports for tuning the chemistry of catalytic nanoparticles[J]. Nature Communications, 2018, 9(1): 1-8.
52	Gao Y J, Cao Y Y, Zhuo H, et al. Mo₂TiC₂ MXene: a promising catalyst for electrocatalytic ammonia synthesis[J]. Catalysis Today, 2020, 339: 120-126.
53	Azofra L M, Li N, MacFarlane D R, et al. Promising prospects for 2D d²—d⁴ M₃C₂ transition metal carbides (MXenes) in N₂ capture and conversion into ammonia[J]. Energy & Environmental Science, 2016, 9(8): 2545-2549.
54	Ni J, Shi S Y, Zhang C F, et al. Enhanced catalytic performance of the carbon-supported Ru ammonia synthesis catalyst by an introduction of oxygen functional groups via gas-phase oxidation[J]. Journal of Catalysis, 2022, 409: 78-86.
55	Peng W, Luo M, Xu X D, et al. Spontaneous atomic ruthenium doping in Mo₂CT _x MXene defects enhances electrocatalytic activity for the nitrogen reduction reaction[J]. Advanced Energy Materials, 2020, 10(25): 2001364.
56	Chen G, Ding M M, Zhang K, et al. Single-atomic ruthenium active sites on Ti₃C₂ MXene with oxygen-terminated surface synchronize enhanced activity and selectivity for electrocatalytic nitrogen reduction to ammonia[J]. ChemSusChem, 2022, 15(3): e202102352.
57	Er S, de Wijs G A, Brocks G. DFT study of planar boron sheets: a new template for hydrogen storage[J]. The Journal of Physical Chemistry C, 2009, 113(43): 18962-18967.
58	Liu C W, Li Q Y, Zhang J, et al. Conversion of dinitrogen to ammonia on Ru atoms supported on boron sheets: a DFT study[J]. Journal of Materials Chemistry A, 2019, 7(9): 4771-4776.
59	Dinh K N, Zhang Y, Zhu J X, et al. Phosphorene-based electrocatalysts[J]. Chemistry: A European Journal, 2020, 26(29): 6437-6446.
60	Zhang L L, Ding L X, Chen G F, et al. Ammonia synthesis under ambient conditions: selective electroreduction of dinitrogen to ammonia on black phosphorus nanosheets[J]. Angewandte Chemie International Edition, 2019, 58(9): 2612-2616.
61	Wang M Y, Xu Z W, Zhang X Z, et al. B-modified phosphorene for N₂ fixation: a highly efficient metal-free photocatalyst[J]. Applied Surface Science, 2021, 554: 149614.
62	Liu J D, Wei Z X, Dou Y H, et al. Ru-doped phosphorene for electrochemical ammonia synthesis[J]. Rare Metals, 2020, 39(8): 874-880.
63	Xu G R, Li H, Bati A S R, et al. Nitrogen-doped phosphorene for electrocatalytic ammonia synthesis[J]. Journal of Materials Chemistry A, 2020, 8(31): 15875-15883.
64	Zhang B, Asakura H, Zhang J, et al. Stabilizing a Platinum1 single-atom catalyst on supported phosphomolybdic acid without compromising hydrogenation activity[J]. Angewandte Chemie International Edition, 2016, 55(29): 8319-8323.
65	Liao W R, Liu H X, Qi L, et al. Lithium/bismuth co-functionalized phosphotungstic acid catalyst for promoting dinitrogen electroreduction with high Faradaic efficiency[J]. Cell Reports Physical Science, 2021, 2(9): 100557.
66	Gao L Y, Wang F T, Yu M G, et al. A novel phosphotungstic acid-supported single metal atom catalyst with high activity and selectivity for the synthesis of NH₃ from electrochemical N₂ reduction: a DFT prediction[J]. Journal of Materials Chemistry A, 2019, 7(34): 19838-19845.
67	Ying Y R, Luo X, Qiao J L, et al. “More is different”: synergistic effect and structural engineering in double-atom catalysts[J]. Advanced Functional Materials, 2021, 31(3): 2007423.
68	Deng T, Cen C, Shen H J, et al. Atom-pair catalysts supported by N-doped graphene for the nitrogen reduction reaction: d-band center-based descriptor[J]. The Journal of Physical Chemistry Letters, 2020, 11(15): 6320-6329.
69	Wang M Y, Song R F, Zhang Q, et al. Synergy effect of Cu-Ru dual atoms anchored to N-doped phosphorene for nitrogen reduction reaction[J]. Fuel, 2022, 321: 124101.
70	He T W, Santiago A R P, Du A J. Atomically embedded asymmetrical dual-metal dimers on N-doped graphene for ultra-efficient nitrogen reduction reaction[J]. Journal of Catalysis, 2020, 388: 77-83.
71	Schlögl R. Catalytic synthesis of ammonia—a “never-ending story”?[J]. Angewandte Chemie International Edition, 2003, 42(18): 2004-2008.
72	Li J, Gao X, Zhu L, et al. Graphdiyne for crucial gas involved catalytic reactions in energy conversion applications[J]. Energy & Environmental Science, 2020, 13(5): 1326-1346.
73	Zhang L L, Cong M Y, Ding X, et al. A Janus Fe-SnO₂ catalyst that enables bifunctional electrochemical nitrogen fixation[J]. Angewandte Chemie International Edition, 2020, 59(27): 10888-10893.
74	Cheng N C, Zhang L, Doyle-Davis K, et al. Single-atom catalysts: from design to application[J]. Electrochemical Energy Reviews, 2019, 2(4): 539-573.
75	Sato K, Imamura K, Kawano Y, et al. A low-crystalline ruthenium nano-layer supported on praseodymium oxide as an active catalyst for ammonia synthesis[J]. Chemical Science, 2017, 8(1): 674-679.
76	Wan J W, Chen W X, Jia C Y, et al. Defect effects on TiO₂ nanosheets: stabilizing single atomic site Au and promoting catalytic properties[J]. Advanced Materials, 2018, 30(11): 1705369.
77	Cai X Y, Yang F, An L, et al. Evaluation of electrocatalytic activity of noble metal catalysts toward nitrogen reduction reaction in aqueous solutions under ambient conditions[J]. ChemSusChem, 2022, 15(1): e202102234.
78	Andersen S Z, Čolić V, Yang S, et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements[J]. Nature, 2019, 570(7762): 504-508.
79	Shi L, Yin Y, Wang S B, et al. Rational catalyst design for N₂ reduction under ambient conditions: strategies toward enhanced conversion efficiency[J]. ACS Catalysis, 2020, 10(12): 6870-6899.
80	Wang H J, Li Y H, Li C J, et al. One-pot synthesis of bi-metallic PdRu tripods as an efficient catalyst for electrocatalytic nitrogen reduction to ammonia[J]. Journal of Materials Chemistry A, 2019, 7(2): 801-805.
81	Bu L Z, Shao Q, Pi Y C, et al. Coupled s-p-d exchange in facet-controlled Pd₃Pb tripods enhances oxygen reduction catalysis[J]. Chem, 2018, 4(2): 359-371.
82	Wang H J, Li Y H, Yang D D, et al. Direct fabrication of bi-metallic PdRu nanorod assemblies for electrochemical ammonia synthesis[J]. Nanoscale, 2019, 11(12): 5499-5505.
83	Lu Q, Hutchings G S, Yu W T, et al. Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution[J]. Nature Communications, 2015, 6(1): 1-8.
84	Wang Z Q, Tian W J, Dai Z C, et al. Bimetallic mesoporous RhRu film for electrocatalytic nitrogen reduction to ammonia[J]. Inorganic Chemistry Frontiers, 2021, 8(18): 4276-4281.
85	Li Y H, Yu H J, Wang Z Q, et al. One-step synthesis of self-standing porous palladium-ruthenium nanosheet array on Ni foam for ambient electrosynthesis of ammonia[J]. International Journal of Hydrogen Energy, 2020, 45(11): 5997-6005.
86	Liu A M, Gao M F, Ren X F, et al. A two-dimensional Ru@MXene catalyst for highly selective ambient electrocatalytic nitrogen reduction[J]. Nanoscale, 2020, 12(20): 10933-10938.
87	Smith R D L, Prévot M S, Fagan R D, et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis[J]. Science, 2013, 340(6128): 60-63.
88	Lv C D, Yan C S, Chen G, et al. An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions[J]. Angewandte Chemie International Edition, 2018, 57(21): 6073-6076.
89	Fang Z W, Wu P, Qian Y M, et al. Gel-derived amorphous bismuth-nickel alloy promotes electrocatalytic nitrogen fixation via optimizing nitrogen adsorption and activation[J]. Angewandte Chemie International Edition, 2021, 60(8): 4275-4281.
90	Liao W R, Qi L, Wang Y L, et al. Interfacial engineering promoting electrosynthesis of ammonia over Mo/phosphotungstic acid with high performance[J]. Advanced Functional Materials, 2021, 31(22): 2009151.
91	Back S, Jung Y. On the mechanism of electrochemical ammonia synthesis on the Ru catalyst[J]. Physical Chemistry Chemical Physics, 2016, 18(13): 9161-9166.
92	Wakerley D, Lamaison S, Ozanam F, et al. Bio-inspired hydrophobicity promotes CO₂ reduction on a Cu surface[J]. Nature Materials, 2019, 18(11): 1222-1227.
93	Ahmed M I, Liu C W, Zhao Y, et al. Metal-sulfur linkages achieved by organic tethering of ruthenium nanocrystals for enhanced electrochemical nitrogen reduction[J]. Angewandte Chemie International Edition, 2020, 59(48): 21465-21469.
94	Yang Y J, Wang S Q, Wen H M, et al. Nanoporous gold embedded ZIF composite for enhanced electrochemical nitrogen fixation[J]. Angewandte Chemie International Edition, 2019, 58(43): 15362-15366.
95	Li F W, Thevenon A, Rosas-Hernández A, et al. Molecular tuning of CO₂-to-ethylene conversion[J]. Nature, 2020, 577(7791): 509-513.
96	Xu G R, Batmunkh M, Donne S, et al. Ruthenium(Ⅲ) polyethyleneimine complexes for bifunctional ammonia production and biomass upgrading[J]. Journal of Materials Chemistry A, 2019, 7(44): 25433-25440.
97	Li R Y, He K Y, Xu P W, et al. Synthesis of a ruthenium-graphene quantum dot-graphene hybrid as a promising single-atom catalyst for electrochemical nitrogen reduction with ultrahigh yield rate and selectivity[J]. Journal of Materials Chemistry A, 2021, 9(43): 24582-24589.
98	Zhao S L, Wang Y, Dong J C, et al. Ultrathin metal-organic framework nanosheets for electrocatalytic oxygen evolution[J]. Nature Energy, 2016, 1(12): 16184.
99	Zhang Z Q, Yao K D, Cong L C, et al. Facile synthesis of a Ru-dispersed N-doped carbon framework catalyst for electrochemical nitrogen reduction[J]. Catalysis Science & Technology, 2020, 10(5): 1336-1342.
100	Zhao J, Liu L J, Yang Y, et al. Insights into electrocatalytic nitrate reduction to ammonia via Cu-based bimetallic catalysts[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(6): 2468-2475.
101	Zhang T H, Zhu J, Wang J J, et al. Ru alloying with La or Y for ammonia synthesis via integrated dissociative and associative mechanism with superior operational stability[J]. Chemical Engineering Science, 2022, 252: 117255.
102	Rao X F, Liu M M, Chien M F, et al. Recent progress in noble metal electrocatalysts for nitrogen-to-ammonia conversion[J]. Renewable and Sustainable Energy Reviews, 2022, 168: 112845.
103	Jin Y, Ding X, Zhang L L, et al. Boosting electrocatalytic reduction of nitrogen to ammonia under ambient conditions by alloy engineering[J]. Chemical Communications, 2020, 56(77): 11477-11480.
104	Liu A M, Liang X Y, Gao M F, et al. Ru and Fe alloying on a two-dimensional MXene support for enhanced electrochemical synthesis of ammonia[J]. ChemCatChem, 2022, 14(7): e202101775.
105	Kour G, Mao X, Du A J. Computational screening of single-atom alloys TM@Ru(0001) for enhanced electrochemical nitrogen reduction reaction[J]. Journal of Materials Chemistry A, 2022, 10(11): 6204-6215.
106	Montoya J H, Tsai C, Vojvodic A, et al. The challenge of electrochemical ammonia synthesis: a new perspective on the role of nitrogen scaling relations[J]. ChemSusChem, 2015, 8(13): 2180-2186.
107	Zhang J M, Tao H B, Kuang M, et al. Advances in thermodynamic-kinetic model for analyzing the oxygen evolution reaction[J]. ACS Catalysis, 2020, 10(15): 8597-8610.
108	Mahmood J, Li F, Jung S M, et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction[J]. Nature Nanotechnology, 2017, 12(5): 441-446.
109	Tong Y Y, Guo H P, Liu D L, et al. Vacancy engineering of iron-doped W₁₈O₄₉ nanoreactors for low-barrier electrochemical nitrogen reduction[J]. Angewandte Chemie International Edition, 2020, 59(19): 7356-7361.
110	Mavrikakis M, Hammer B, Nørskov J K. Effect of strain on the reactivity of metal surfaces[J]. Physical Review Letters, 1998, 81(13): 2819-2822.
111	Zhang W Q, Yang L T, An C H, et al. Enhancing electrochemical nitrogen reduction with Ru nanowires via the atomic decoration of Pt[J]. Journal of Materials Chemistry A, 2020, 8(47): 25142-25147.
112	Zhao L, Liu X J, Zhang S, et al. Rational design of bimetallic Rh_0.6Ru_0.4 nanoalloys for enhanced nitrogen reduction electrocatalysis under mild conditions[J]. Journal of Materials Chemistry A, 2021, 9(1): 259-263.
113	Manjunatha R, Schechter A. Electrochemical synthesis of ammonia using ruthenium-platinum alloy at ambient pressure and low temperature[J]. Electrochemistry Communications, 2018, 90: 96-100.
114	Kim C, Song J Y, Choi C, et al. Atomic-scale homogeneous Ru-Cu alloy nanoparticles for highly efficient electrocatalytic nitrogen reduction[J]. Advanced Materials, 2022, 34(40): 2205270.
115	Du X H, Li W P, Chang H T, et al. Dual heterogeneous structures lead to ultrahigh strength and uniform ductility in a Co-Cr-Ni medium-entropy alloy[J]. Nature Communications, 2020, 11: 2390.
116	Yin H Q, Du A J. Revealing the potential of ternary medium-entropy alloys as exceptional electrocatalysts toward nitrogen reduction: an example of heusler alloys[J]. ACS Applied Materials & Interfaces, 2022, 14(13): 15235-15242.
117	Zhao R, Liu C, Zhang X, et al. An ultrasmall Ru₂P nanoparticles-reduced graphene oxide hybrid: an efficient electrocatalyst for NH₃ synthesis under ambient conditions[J]. Journal of Materials Chemistry A, 2020, 8(1): 77-81.
118	Abghoui Y, Skúlason E. Computational predictions of catalytic activity of zincblende (110) surfaces of metal nitrides for electrochemical ammonia synthesis[J]. The Journal of Physical Chemistry C, 2017, 121(11): 6141-6151.
119	Gao Q, Huang C Q, Ju Y M, et al. Phase-selective syntheses of cobalt telluride nanofleeces for efficient oxygen evolution catalysts[J]. Angewandte Chemie International Edition, 2017, 56(27): 7769-7773.
120	Wang J, Huang B L, Ji Y J, et al. A general strategy to glassy M-Te (M = Ru, Rh, Ir) porous nanorods for efficient electrochemical N₂ fixation[J]. Advanced Materials, 2020, 32(11): 1907112.
121	Liao W R, Xie K, Liu L J, et al. Triggering in-plane defect cluster on MoS₂ for accelerated dinitrogen electroreduction to ammonia[J]. Journal of Energy Chemistry, 2021, 62: 359-366.
122	Guo D X, Wang S, Xu J, et al. Defect and interface engineering for electrochemical nitrogen reduction reaction under ambient conditions[J]. Journal of Energy Chemistry, 2022, 65: 448-468.
123	Liu Y T, Li D, Yu J Y, et al. Stable confinement of black phosphorus quantum dots on black tin oxide nanotubes: a robust, double-active electrocatalyst toward efficient nitrogen fixation[J]. Angewandte Chemie, 2019, 131(46): 16591-16596.
124	Montini T, Melchionna M, Monai M, et al. Fundamentals and catalytic applications of CeO₂-based materials[J]. Chemical Reviews, 2016, 116(10): 5987-6041.
125	Ding Y, Huang L S, Zhang J B, et al. Ru-doped, oxygen-vacancy-containing CeO₂ nanorods toward N₂ electroreduction[J]. Journal of Materials Chemistry A, 2020, 8(15): 7229-7234.
126	Cheng S, Gao Y J, Yan Y L, et al. Oxygen vacancy enhancing mechanism of nitrogen reduction reaction property in Ru/TiO₂ [J]. Journal of Energy Chemistry, 2019, 39: 144-151.
127	Suryanto B H R, Wang D B, Azofra L M, et al. MoS₂ polymorphic engineering enhances selectivity in the electrochemical reduction of nitrogen to ammonia[J]. ACS Energy Letters, 2019, 4(2): 430-435.
128	Li X, Li T, Ma Y, et al. Boosted electrocatalytic N₂ reduction to NH₃ by defect-rich MoS₂ nanoflower[J]. Advanced Energy Materials, 2018, 8(30): 1801357.
129	Zhao J, Wang X, Xu Z C, et al. Hybrid catalysts for photoelectrochemical reduction of carbon dioxide: a prospective review on semiconductor/metal complex co-catalyst systems[J]. Journal of Materials Chemistry A, 2014, 2(37): 15228.
130	Tang X R, Tian X Q, Zhou L, et al. Connection of Ru nanoparticles with rich defects enables the enhanced electrochemical reduction of nitrogen[J]. Physical Chemistry Chemical Physics, 2022, 24(19): 11491-11495.
131	刘恒源, 王海辉, 徐建鸿. 电催化氮还原合成氨电化学系统研究进展[J]. 化工学报, 2022, 73(1): 32-45.
	Liu H Y, Wang H H, Xu J H. Advances in electrochemical systems for ammonia synthesis by electrocatalytic reduction of nitrogen[J]. CIESC Journal, 2022, 73(1): 32-45.
132	郑沐云, 万宇驰, 吕瑞涛. 电催化氮气还原合成氨催化材料研究进展[J]. 化工学报, 2020, 71(6): 2481-2491.
	Zheng M Y, Wan Y C, Lyu R T. Research progress on electrocatalytic nitrogen reduction reaction catalysts for ammonia synthesis[J]. CIESC Journal, 2020, 71(6): 2481-2491.

[1]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[2]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[3]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[4]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[5]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[6]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[7]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[8]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[9]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[10]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[11]	涂玉明, 邵高燕, 陈健杰, 刘凤, 田世超, 周智勇, 任钟旗. 钙基催化剂的设计合成及应用研究进展[J]. 化工学报, 2023, 74(7): 2717-2734.
[12]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[13]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[14]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[15]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.

Ru基氮还原电催化剂性能调控策略

Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 132

相关文章 15

编辑推荐

Metrics

本文评价