A round-trip journey of electrons: Electron catalyzed direct fixation of N2 to azos

doi:10.1016/S1872-2067(24)60179-8

Abstract

Abstract:

The triple bond in N₂ has an extremely high bond energy and is thus difficult to break. N₂ is commonly converted into NH₃ artificially via the Haber-Bosch process, and NH₃ can be utilized to produce other nitrogen-containing chemicals. Here, we developed an electron catalyzed method to directly fix N₂ into azos, by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method. The round-trip journey of electron can successfully weaken the triple bond in N₂ through the electron pushing-induced aryl radical via a “brick trowel” transition state, and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate. Different azos can be synthesized with this developed electron catalyzed approach. This approach provides a novel concept and practical route for the fixation of N₂ at atmospheric pressure into chemical products valuable for industrial and commercial applications.

Key words: Fixed N₂, Azo, Electron catalyzed strategy, “Brick trowel” transition state, Aryl radicals

Baijing Wu, Jinrui Li, Xiaoxue Luo, Jingtian Ni, Yiting Lu, Minhua Shao, Cunpu Li, Zidong Wei. A round-trip journey of electrons: Electron catalyzed direct fixation of N₂ to azos[J]. Chinese Journal of Catalysis, 2025, 68: 386-393.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60179-8

https://www.cjcatal.com/EN/Y2025/V68/I1/386

Figures/Tables 7

Scheme 1. Production of azos. (a) Conventional route. N2 molecules are reduced and oxidized to obtain different nitrogen-containing products. This route is complex and energy-consuming. (b) This work. Electron catalyzed strategy to fix N2 to directly generate the azo. The electrons are pushed in and pulled out to obtain diazonium ions and then to form an azo directly under mild conditions.

Table 1 Optimization of the reaction conditions for 4-hydroxyazobenzenea.

Entry	Variation	Content^b (mg mL⁻¹)
1	0.02 V s^‒1	2.28
2	0.05 V s^‒1	1.00
3	0.1 V s^‒1	1.46
4	0.2 V s^‒1	2.99
5	−2.0−2.0 V	n.d.
6	−2.8−2.5 V	1.25
7	−3.0−3.0 V	2.46
8	3.5 V	2.92
9	−3.5 V	0.95
10	1 mL TEA	1.63
12	1.5 mL TEA	0.90
12	2.5 mL TEA	2.71
13	1 mL of 1 mol L⁻¹ PhOH	1.86
14	1.5 mL of 1 mol L⁻¹ PhOH	2.83
15	2.5 mL of 1 mol L⁻¹ PhOH	3.39

Scheme 2. Designed mechanism of the electron catalyzed strategy to directly fix N2 to azo. The electrons are firstly pushed in to the aromatic halide to obtain the aromatic radicals Ar●, after the Ar● coupled with N2, the electrons will be pull out to obtain the [Ar-N2]+. Azo can be obtained after the [Ar-N2]+ react with nucleophilic aromatic compounds.

Fig. 1. Activation of N2 molecule. (a) Schematic diagram of the molecular formation of the “brick trowel” TS. (b) Different orbitals of the aryl radicals, N2 and the “brick trowel” TS, where ArSOMO (ArSOMO-1) correspond to the frontier orbitals of the aryl radical; π1*, and π2* are the unoccupied frontier orbitals of the N2 molecules; Ar-N2 and Ar-N2-1 are the SOMO and SOMO-1 of the TS. (c) Molecular orbital energy level diagrams of the “brick trowel” TS. (d?f) Plots of charge density difference for the organic species adsorption with carbon paper. (d) Iodobenzene, (e) Ar●, (f) Diazo radical intermediate ([Ar?N2]●). The yellow and blue contours represent electron density accumulations and depressions, respectively. Pink, H; Blue, N; Brown, C; Purple, I. (g) Calculated free energy diagram for the direct reaction of iodobenzene with N2 via a non-catalyzed pathway. (h) Calculated free energy diagram for the reaction via an electron catalyzed pathway.

Fig. 2. (a) The GC-MS spectrum of the reaction system in 15N2 atmosphere after reaction. Azo of m/z = 200 can be detected, indicating that nitrogen is successfully fixed. (b) In-situ attenuated total reflectance FTIR (ATR-FTIR) spectra at different reaction times. The absorption peak at 2257 cm?1 corresponds to the N≡N bond of the [Ar-N2]+; 1441 cm?1 corresponds to the vibrational absorption peak of Ar●; 1411 cm?1 corresponds to the N=N stretching of azo; 1036 cm?1 correspond to the C?I stretching mode of the iodobenzene.

Table 2 Scope of the azo compounds synthesis via the electron catalyzed approach a.

Entry	Reactant	Target product	Content^b (μg mL⁻¹)
1			24.95
2			0.44
3			14.78
4			55.83

Table 3 Scope of electron catalyzed aryl radical substitutions a.

Entry	Reactant	Target product	Content^b (μg mL⁻¹)
1			11.81
2			40.93
3			5.70
4			1.27
5			1.77

References

[1]	B. Chang, H. Zhang, S. Sun, G. Zhang, Carbon Energy, 2024, 6, e491.
[2]	T. He, Z. Zhao, R. Liu, X. Liu, B. Ni, Y. Wei, Y. Wu, W. Yuan, H. Peng, Z. Jiang, Y. Zhao, J. Am. Chem. Soc., 2023, 145, 6057-6066.
[3]	H. Cheng, L.-X. Ding, G.-F. Chen, L. Zhang, J. Xue, H. Wang, Adv. Mater., 2018, 30, 1803694.
[4]	H. He, Q.-Q. Zhu, Y. Yan, H.-W. Zhang, Z.-Y. Han, H. Sun, J. Chen, C.-P. Li, Z. Zhang, M. Du, Appl. Catal. B, 2022, 302, 120840.
[5]	D. Bao, Q. Zhang, F.-L. Meng, H.-X. Zhong, M.-M. Shi, Y. Zhang, J.-M. Yan, Q. Jiang, X.-B. Zhang, Adv. Mater., 2017, 29, 1604799.
[6]	J. W. Erisman, M. A. Sutton, J. Galloway, Z. Klimont, W. Winiwarter, Nat. Geosci., 2008, 1, 636-639.
[7]	V. Smil, Nature, 1999, 400, 415-415.
[8]	H. K. Lee, C. S. L. Koh, Y. H. Lee, C. Liu, I. Y. Phang, X. Han, C.-K. Tsung, X. Y. Ling, Sci. Adv., 2018, 4, eaar3208.
[9]	C. Du, C. Qiu, Z. Fang, P. Li, Y. Gao, J. Wang, W. Chen, Nano Energy, 2022, 92, 106784.
[10]	Y. Zhang, J. Li, J. Cai, L. Yang, T. Zhang, J. Lin, X. Wang, C. Chen, L. Zheng, C.-T. Au, B. Yang, L. Jiang, ACS Catal., 2021, 11, 4430-4440.
[11]	L. Wen, K. Sun, X. Liu, W. Yang, L. Li, H.-L. Jiang, Adv. Mater., 2023, 35, 2210669.
[12]	K. Li, S. Z. Andersen, M. J. Statt, M. Saccoccio, V. J. Bukas, K. Krempl, R. Sažinas, J. B. Pedersen, V. Shadravan, Y. Zhou, D. Chakraborty, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov, I. Chorkendorff, Science, 2021, 374, 1593-1597.
[13]	B. H. R. Suryanto, K. Matuszek, J. Choi, R. Y. Hodgetts, H.-L. Du, J. M. Bakker, C. S. M. Kang, P. V. Cherepanov, A. N. Simonov, D. R. MacFarlane, Science, 2021, 372, 1187-1191.
[14]	J. G. Chen, R. M. Crooks, L. C. Seefeldt, K. L. Bren, R. M. Bullock, M. Y. Darensbourg, P. L. Holland, B. Hoffman, M. J. Janik, A. K. Jones, M. G. Kanatzidis, P. King, K. M. Lancaster, S. V. Lymar, P. Pfromm, W. F. Schneider, R. R. Schrock, Science, 2018, 360, eaar6611.
[15]	B. Chang, Z. Cao, Y. Ren, C. Chen, L. Cavallo, F. Raziq, S. Zuo, W. Zhou, Y. Han, H. Zhang, ACS Nano, 2024, 18, 288-298.
[16]	Z. Pei, H. Zhang, D. Luan, X. W. Lou, Matter, 2023, 6, 4128-4144.
[17]	E. Merino, Chem. Soc. Rev., 2011, 40, 3835-3853.
[18]	A. S. Parveen, P. Thirukumaran, M. Sarojadevi, RSC Adv., 2015, 5, 43601-43610.
[19]	Z. Li, D. Zhang, J. Weng, B. Chen, H. Liu, Carbohydr. Polym., 2014, 99, 748-754.
[20]	B. Mondal, P. S. Mukherjee, J. Am. Chem. Soc., 2018, 140, 12592-12601.
[21]	Y. Wang, Y. Yu, R. Jia, C. Zhang, B. Zhang, Natl. Sci. Rev., 2019, 6, 730-738.
[22]	S. Chen, S. Liang, R. Huang, M. Zhang, Y. Song, Y. Zhang, S. Tao, L. Yu, D. Deng, Nat. Synth., 2024, 3, 76-84.
[23]	K. Ueno, S. Akiyoshi, J. Am. Chem. Soc., 1954, 76, 3670-3672.
[24]	C. O. Henke, O. W. Brown, J. Phys. Chem., 1922, 26, 324-348.
[25]	X. Chong, C. Liu, Y. Huang, C. Huang, B. Zhang, Natl. Sci. Rev., 2020, 7, 285-295.
[26]	J. Yount, D. G. Piercey, Chem. Rev., 2022, 122, 8809-8840.
[27]	A. Sadatnabi, N. Mohamadighader, D. Nematollahi, Org. Lett., 2021, 23, 6488-6493.
[28]	J. D. Sitter, A. K. Vannucci, J. Am. Chem. Soc., 2021, 143, 2938-2943.
[29]	K.-S. Du, J.-M. Huang, Green Chem., 2019, 21, 1680-1685.
[30]	Y.-F. Zhang, M. Mellah, ACS Catal., 2017, 7, 8480-8486.
[31]	L. A. Rettberg, J. Wilcoxen, A. J. Jasniewski, C. C. Lee, K. Tanifuji, Y. Hu, R. D. Britt, M. W. Ribbe, Nat. Commun., 2020, 11, 1757.
[32]	G. Schwarz, R. R. Mendel, M. W. Ribbe, Nature, 2009, 460, 839-847.
[33]	J. B. Broderick, B. R. Duffus, K. S. Duschene, E. M. Shepard, Chem. Rev., 2014, 114, 4229-4317.
[34]	A. S. Fajardo, P. Legrand, L. A. Payá-Tormo, L. Martin, M. T. Pellicer Martı́nez, C. Echavarri-Erasun, X. Vernède, L. M. Rubio, Y. Nicolet, J. Am. Chem. Soc., 2020, 142, 11006-11012.
[35]	A. K. Boal, A. C. Rosenzweig, Science, 2012, 337, 1617-1618.
[36]	J. A. Wiig, Y. Hu, C. C. Lee, M. W. Ribbe, Science, 2012, 337, 1672-1675.
[37]	J. Wilcoxen, S. Arragain, A. A. Scandurra, E. Jimenez-Vicente, C. Echavarri-Erasun, S. Pollmann, R. D. Britt, L. M. Rubio, J. Am. Chem. Soc., 2016, 138, 7468-7471.
[38]	M. Lübbesmeyer, D. Leifert, H. Schäfer, A. Studer, Chem. Commun., 2018, 54, 2240-2243.
[39]	J. Pinson, J. M. Saveant, J. Am. Chem. Soc., 1978, 100, 1506-1510.
[40]	J. M. Saveant, Acc. Chem. Res., 1980, 13, 323-329.
[41]	E. G. Mackay, A. Studer, Chem. Eur. J., 2016, 22, 13455-13458.
[42]	E. Shirakawa, Y. Ota, K. Yonekura, K. Okura, S. Mizusawa, S. K. Sarkar, M. Abe, Sci. Adv., 2023, 9, eadh3544.
[43]	D. Tanaka, S. Sawai, S. Hattori, Y. Nozaki, D. H. Yoon, H. Fujita, T. Sekiguchi, T. Akitsu, S. Shoji, RSC Adv., 2020, 10, 38900-38905.
[44]	R. Rowshanpour, T. Dudding, RSC Adv., 2021, 11, 7251-7256.
[45]	B. D. Akana-Schneider, D. J. Weix, J. Am. Chem. Soc., 2023, 145, 16150-16159.
[46]	A. Grirrane, A. Corma, H. García, Science, 2008, 322, 1661-1664.
[47]	R. Narayanan, M. A. El-Sayed, J. Phys. Chem. B, 2005, 109, 4357-4360.
[48]	S. Jagiella, F. Zabel, Phys. Chem. Chem. Phys., 2007, 9, 5036-5051.
[49]	W. G. Hatton, N. P. Hacker, P. H. Kasai, J. Chem. Soc., Chem. Commun., 1990, 19, 227-229.
[50]	M. Winkler, W. Sander, J. Org. Chem., 2006, 71, 6357-6367.
[51]	R. M. Parker, J. C. Gates, H. L. Rogers, P. G. R. Smith, M. C. Grossel, J. Mater. Chem., 2010, 20, 9118-9125.

A round-trip journey of electrons: Electron catalyzed direct fixation of N₂ to azos

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Ke-Xin Li, Fu-Xue Wang, Zi-Chen Zhang, Zheng-Xing Liu, Yu-Hui Ma, Chong-Chen Wang, Peng Wang. Peroxymonosulfate activation over amorphous ZIF-62(Co) glass for micropollutant degradation [J]. Chinese Journal of Catalysis, 2024, 59(4): 118-125.
[2]	Huan Xue, Jia-Run Huang, Zhi-Shuo Wang, Zhen-Hua Zhao, Wen Shi, Pei-Qin Liao, Xiao-Ming Chen. Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density [J]. Chinese Journal of Catalysis, 2023, 53(10): 102-108.
[3]	Qing-Wen Gui, Fan Teng, Peng Yu, Yi-Fan Wu, Zhi-Bin Nong, Long-Xi Yang, Xiang Chen, Tian-Bao Yang, Wei-Min He. Visible light-induced Z-scheme V₂O₅/g-C₃N₄ heterojunction catalyzed cascade reaction of unactivated alkenes [J]. Chinese Journal of Catalysis, 2023, 44(1): 111-116.
[4]	Fulin Zhang, Xia Li, Xiaoyun Dong, Huimin Hao, Xianjun Lang. Thiazolo[5,4-d]thiazole-based covalent organic framework microspheres for blue light photocatalytic selective oxidation of amines with O₂ [J]. Chinese Journal of Catalysis, 2022, 43(9): 2395-2404.
[5]	Hui Mao, Haoran Yang, Jinchi Liu, Shuai Zhang, Daliang Liu, Qiong Wu, Wenping Sun, Xi-Ming Song, Tianyi Ma. Improved nitrogen reduction electroactivity by unique MoS₂-SnS₂ heterogeneous nanoplates supported on poly(zwitterionic liquids) functionalized polypyrrole/graphene oxide [J]. Chinese Journal of Catalysis, 2022, 43(5): 1341-1350.
[6]	Yiqi Ren, Lin Tao, Chunzhi Li, Sanjeevi Jayakumar, He Li, Qihua Yang. Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives [J]. Chinese Journal of Catalysis, 2021, 42(9): 1576-1585.
[7]	Minghao Li, Fengtian Wu, Yanlong Gu. Brönsted acidic ionic liquid catalyzed synthesis of benzo[a]carbazole from renewable acetol and 2-phenylindoles in a biphasic system [J]. Chinese Journal of Catalysis, 2019, 40(8): 1135-1140.
[8]	Ruxia Yi, Leilei Qian, Boshun Wan. Synthesis of spiropyrrolidine oxindoles through Rh(II)-catalyzed olefination/cyclization of diazooxindoles and vinyl azides [J]. Chinese Journal of Catalysis, 2019, 40(2): 177-183.
[9]	Chengcheng Yan, Long Lin, Guoxiong Wang, Xinhe Bao. Transition metal-nitrogen sites for electrochemical carbon dioxide reduction reaction [J]. Chinese Journal of Catalysis, 2019, 40(1): 23-37.
[10]	Liandi Wang, Tingting Liu. Ruthenium(Ⅱ) complex catalysts bearing a 2,6-bis(tetrazolyl)pyridine ligand for the transfer hydrogenation of ketones [J]. Chinese Journal of Catalysis, 2018, 39(2): 327-333.
[11]	Jorge L. S. Milani, Igor S. Oliveira, Pamella A. Dos Santos, Ana K. S. M. Valdo, Felipe T. Martins, Danielle Cangussu, Rafael P. Das Chagas. Chemical fixation of carbon dioxide to cyclic carbonates catalyzed by zinc(Ⅱ) complex bearing 1,2-disubstituted benzimidazole ligand [J]. Chinese Journal of Catalysis, 2018, 39(2): 245-249.
[12]	Arash Ghorbani-Choghamarani, Zahra Taherinia. Synthesis of biaryls using palladium nanoparticles immobilized on peptide nanofibers as catalyst and hydroxybenzotriazole as novel phenylating reagent [J]. Chinese Journal of Catalysis, 2017, 38(3): 469-474.
[13]	R. D. Padmaja, Sourav Rej, Kaushik Chanda. Environmentally friendly, microwave-assisted synthesis of 5-substituted 1H-tetrazoles by recyclable CuO nanoparticles via (3+2) cycloaddition of nitriles and NaN₃ [J]. Chinese Journal of Catalysis, 2017, 38(11): 1918-1924.
[14]	Xingtian Huang, Zhipeng Li, Dongyang Wang, Yiqun Li. Bovine serum albumin: An efficient and green biocatalyst for the one-pot four-component synthesis of pyrano[2,3-c]pyrazoles [J]. Chinese Journal of Catalysis, 2016, 37(9): 1461-1468.
[15]	Jinwei Shi, Lili Zhu, Jian Wen, Zili Chen. Brönsted acid catalyzed addition of N¹-p-methyl toluenesulfonyl triazole to olefins for the preparation of N²-alkyl 1,2,3-triazoles with high N²-selectivity [J]. Chinese Journal of Catalysis, 2016, 37(8): 1222-1226.