电子催化剂直接固定N2生成偶氮化合物

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

催化学报 ›› 2025, Vol. 68: 386-393.DOI: 10.1016/S1872-2067(24)60179-8

电子催化剂直接固定N₂生成偶氮化合物

吴白婧^a, 李金芮^a, 罗小雪^a, 倪靖天^a, 卢伊婷^a, 邵敏华^b, 李存璞^a^,^*(), 魏子栋^a^,^*()

^a重庆大学化学化工学院, 特种化学电源全国重点实验室, 重庆 400044
^b香港科技大学化学与生物工程学系, 香港九龙

收稿日期:2024-09-06 接受日期:2024-11-12 出版日期:2025-01-18 发布日期:2025-01-02
通讯作者: * 电子邮箱: lcp@cqu.edu.cn (李存璞), zdwei@cqu.edu.cn (魏子栋).
基金资助:
国家重点研发计划(2022YFC2105904);国家自然科学基金(22478043);国家自然科学基金(22090030);国家自然科学基金(52021004);国家自然科学基金(U21A20312);国家自然科学基金(22075033)

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

Baijing Wu^a, Jinrui Li^a, Xiaoxue Luo^a, Jingtian Ni^a, Yiting Lu^a, Minhua Shao^b, Cunpu Li^a^,^*(), Zidong Wei^a^,^*()

^aState Key Laboratory of Advanced Chemical Power Sources, School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
^bDepartment of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Hong Kong, China

Received:2024-09-06 Accepted:2024-11-12 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: lcp@cqu.edu.cn (C. Li), zdwei@cqu.edu.cn (Z. Wei).
Supported by:
National Key Research and Development Program of China(2022YFC2105904);National Natural Science Foundation of China(22478043);National Natural Science Foundation of China(22090030);National Natural Science Foundation of China(52021004);National Natural Science Foundation of China(U21A20312);National Natural Science Foundation of China(22075033)

摘要/Abstract

摘要：

氮气(N₂)作为地球大气中最丰富的气体之一, 其N≡N三键具有极高的键能(约940.95 kJ mol^‒1), 使得转化为其他化合物的过程极具挑战性. 传统的哈伯-博施(Haber-Bosch)工艺将N₂转化为氨(NH₃), 该过程需要高温(350−550 °C)和高压(150−350 atm), 是当前最耗能的工业过程之一. 同时, 氨的合成是后续含氮化合物(如肥料、药物、染料等)生产的基础, 这些过程通常需要复杂的有机或无机合成步骤. 因此, 开发直接将N₂转化为具有工业和商业价值的化学产品的方法显得尤为重要.
本文提出了一种新颖的电子催化方法, 在常温、常压下, 利用循环伏安法(CV)的电子注入/拉出反应直接将N₂转化为重氮盐, 进而直接固定N₂成偶氮化合物. 不同于传统的电子催化方法通常仅将电子注入反应体系, 本文通过精确施加电压循环, 有效地调节电子的注入和拉出, 实现了直接将N₂固定为高附加值偶氮化合物. 在反应过程中, 电子首先被注入芳香卤化物, 生成芳基自由基(Ar^●), 随后该自由基经过“铲子状”过渡态与N₂分子结合, 选择性活化N₂的N≡N键中的一个π键. 通过反应体系优化, 以苯酚作为模型产物, 确定了最佳的电压范围(−3.5−3.5 V vs. Ag/Ag⁺)、扫描速率(0.2 V s⁻¹)、溶剂(乙腈)和支持电解质(Bu₄NPF₆). 在这些条件下, 以疏水碳纸作为阴极, 石墨作为阳极, Ag/Ag⁺电极作为参比电极, 在N₂氛围(1 atm)下反应能够有效地将N₂转化为偶氮化合物. 利用密度泛函理论计算研究了“铲子状”过渡态的形成过程, 分析了芳基自由基与N₂分子之间的相互作用, 证明了N₂分子的成功活化. 自由能计算表明, 本文的电子催化策略可以调节反应途径, 使活化能从3.44 eV降低到0.14 eV. ¹⁵N₂同位素实验和原位衰减全反射红外光谱实验结果表明, N₂是合成偶氮化合物的氮源, 并验证了本文提出的电子催化机理. 进一步拓展研究结果表明, 该电子催化策略不仅适用于各种偶氮化合物的合成, 还可以扩展到其它芳香卤化物和多种亲核芳香化合物的反应, 能够有效地用于合成多种具有高附加值的化学品.
综上所述, 本文设计并发展了一种电子催化策略, 控制CV的电位, 注入/拉出电子至芳香卤代化合物, 从而选择性活化N₂的一个π键, 直接固定N₂为偶氮化合物. 这种电子催化策略为N₂的固定提供了一种高效、绿色的全新解决方案, 具有重要的工业应用潜力. 该方法不仅简化了传统的偶氮合成过程, 避免了苛刻反应条件的使用, 提升了原子利用率和能量利用率, 还为开发新型含氮化合物的合成方法提供了新的思路.

关键词: 固定N₂, 偶氮化合物, 电子催化策略, “铲子状”过渡态, 芳基自由基

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

吴白婧, 李金芮, 罗小雪, 倪靖天, 卢伊婷, 邵敏华, 李存璞, 魏子栋. 电子催化剂直接固定N₂生成偶氮化合物[J]. 催化学报, 2025, 68: 386-393.

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.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60179-8

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

图/表 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

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电子催化剂直接固定N₂生成偶氮化合物

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

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