Highly Selective Dehydrogenation of Primary Amine to Nitrile over Bifunctional Co@NaKETS-10 Catalyst

doi:10.6023/cjoc202409030

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (4): 1268-1275.DOI: 10.6023/cjoc202409030 Previous Articles Next Articles

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Co@NaKETS-10双功能催化剂高选择性催化伯胺脱氢制备腈

朱超杰^*(), 王乐乐, 孟荣, 王永吉, 王成, 王小东

巢湖学院化学与材料工程学院合肥 238024

收稿日期:2024-09-22 修回日期:2024-10-28 发布日期:2024-11-27
基金资助:
安徽省教育厅重点研发基金(2024AH051331); 巢湖学院科研启动基金(KYQD-2023053)

Highly Selective Dehydrogenation of Primary Amine to Nitrile over Bifunctional Co@NaKETS-10 Catalyst

Chaojie Zhu(), Lele Wang, Rong Meng, Yongji Wang, Cheng Wang, Xiaodong Wang

School of Chemical and Materials Engineering, Chaohu University, Hefei 238024

Received:2024-09-22 Revised:2024-10-28 Published:2024-11-27
Contact: * E-mail: chaojiezhu@chu.edu.cn
Supported by:
Key Research and Development Plan of Anhui Province(2024AH051331); Research Start-Up Funds of Chaohu University(KYQD-2023053)

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Abstract

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

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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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Fig. & Tab. 7

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

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

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

Table 2. Condition optimization

Table 3. Substrate scope of primary amine dehydrogenation reaction

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

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

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Co@NaKETS-10双功能催化剂高选择性催化伯胺脱氢制备腈

Highly Selective Dehydrogenation of Primary Amine to Nitrile over Bifunctional Co@NaKETS-10 Catalyst

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Fig. & Tab. 7

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