Co@NaKETS-10双功能催化剂高选择性催化伯胺脱氢制备腈

doi:10.6023/cjoc202409030

摘要/Abstract

使用碱性NaKETS-10沸石担载金属Co作为双功能催化剂, 在温和条件下催化多种伯胺发生脱氢反应, 实现了高选择性地制备腈. NaKETS-10晶体中的-Ti-O-Ti-链具有电子传输性能, 导致其中的氧原子具有高的电子密度, 因而具有优异的给电子能力. 研究发现, NaKETS-10中富电子氧是伯胺转化过程中的吸附位点, 氨基上的两个H原子同时被临近的富电子氧吸附; Co金属位点与活化后的胺分子配位, 和富电子氧协同催化吸附态胺分子的脱氢反应. 此外, 作为非均相催化剂, Co@NaKETS-10展示出了优异的稳定性, 在循环使用5次后没有明显的活性损失. 最后, 结合平行实验和对照实验结果, 初步研究了伯胺在Co@NaKETS-10催化剂上脱氢历程的基元反应步骤, 并提出了可能的反应机理.

关键词: Co@NaKETS-10, 伯胺, 脱氢反应, 富电子氧

Basic zeolite NaKETS-10 was used as a support for Co metal catalyst in the double dehydrogenation reactions of various benzylamines under mild conditions, leading to the high selective formation of nitriles. The -Ti-O-Ti- chain within NaKETS-10 crystal possesses an electron transport function, resulting in the oxygen atom possessing a high electron density and thus acting as an effective electron donor. Research indicates that the electron-rich oxygen in the NaKETS-10 framework is the adsorption and activation site for benzylamine. This study also reveals that the Co metal site coordinates with the activated benzylamine molecule, working in conjunction with the electron-rich oxygen to facilitate the dehydrogenation process of benzylamine. Furthermore, as a heterogeneous catalyst, the Co@NaKETS-10 demonstrates a remarkable stability and maintains its activity even after being recycled at least five times. Combining the results of parallel experiments and controlled experiments, the elementary reaction steps of benzylamine double dehydrogenation on the Co@NaKETS-10 catalyst were investigated, and a possible mechanism was proposed.

Key words: Co@NaKETS-10, primary amine, dehydrogenation reaction, electron-rich oxygen

引用此文

朱超杰, 王乐乐, 孟荣, 王永吉, 王成, 王小东. Co@NaKETS-10双功能催化剂高选择性催化伯胺脱氢制备腈[J]. 有机化学, 2025, 45(4): 1268-1275.

Chaojie Zhu, Lele Wang, Rong Meng, Yongji Wang, Cheng Wang, Xiaodong Wang. Highly Selective Dehydrogenation of Primary Amine to Nitrile over Bifunctional Co@NaKETS-10 Catalyst[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1268-1275.

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图/表 7

图式1. 伯胺转化为腈的方法

Scheme 1. Reaction protocols of primary amine dehydrogenation to nitrile

Sample	S_BET^a/(m²•g^－1)	V_mic^b/(m³•g^－1)	S_ext^c/(m²•g^－1)	V_mes^d/(m³•g^－1)	Co loading^e/%	Co valence state^f
NaKETS-10	335	0.12	89	0.12	—	—
Co@NaKETS-10	324	0.12	83	0.12	2.76	＋2

表1. 载体和催化剂的织构参数、金属负载量及金属价态

Table 1. Texture parameters, metal loading and metal valence of support and catalyst

图1. NaKETS-10和Co@NaKETS-10的(a) XRD谱图和(b) N2吸-脱附曲线; Co@NaKETS-10催化剂的(c) HAADF-STEM图和(d)~(h) EDS图

Figure 1. (a) XRD spectrums and (b) N2 adsorption-desorption curves of NaKETS-10 and Co@NaKETS-10; (c) HAADF-STEM and (d)~(h) EDS images of Co@NaKETS-10 catalyst

Entry	Catalyst	Temperature/℃	Time/h	GC Yield/%
1	No	90	2	n.d.^b
2	NaKETS-10	90	2	n.d.
3	Co(NO₃)₂∙6H₂O	90	2	n.d.
4	KNO₃	90	2	n.d.
5	NaNO₃	90	2	n.d.
6	Co@NaKETS-10^c	90	2	n.d.
7	Co@NaKETS-10	90	2	94
8	Co@NaKETS-10	90	3	100
9	Co@NaKETS-10	80	3	59
10	Co@NaKETS-10	100	2	95
11	Co@NaKETS-10	100	3	100

表2. 反应条件优化a

Table 2. Condition optimization

表3. 伯胺脱氢反应底物范围探索a

Table 3. Substrate scope of primary amine dehydrogenation reaction

图2. (a) 1a和1a'的脱氢动力学(产物收率是色谱收率)、(b)不同底物的脱氢实验

Figure 2. (a) Dehydrogenation kinetics of 1a and 1a' (the yield was obtained by GC instrument), and (b) dehydrogenation experiment of the substituted substrates

图式2. Co@NaKETS-10催化伯胺脱氢制腈反应机理

Scheme 2. Mechanism of primary amine dehydrogenation to nitrile over Co@NaKETS-10 catalyst

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