氧化锰晶体作为催化材料调控氨氧化反应产物选择性

doi:10.1016/S1872-2067(21)63803-2

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2164-2172.DOI: 10.1016/S1872-2067(21)63803-2

氧化锰晶体作为催化材料调控氨氧化反应产物选择性

王海^a^,†, 罗青松^a^,†, 王亮^a^,^d^,^*(), 惠宇^b, 秦玉才^b, 宋丽娟^b, 肖丰收^a^,^c^,^#()

^a浙江大学化学工程与生物工程学院, 生物质化工教育部重点实验室, 浙江杭州310028
^b辽宁石油化工大学, 辽宁省石油化工催化科学与技术重点实验室, 辽宁抚顺113001
^c浙江大学化学系, 浙江省应用化学重点实验室, 浙江杭州310028
^d浙江大学化学工程与生物工程学院, 浙江省化工高效制造技术重点实验室, 浙江杭州310027

收稿日期:2021-02-18 接受日期:2021-02-18 出版日期:2021-12-18 发布日期:2021-05-19
通讯作者: 王亮,肖丰收
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家重点研发计划(2018YFB0604801);国家自然科学基金(21822203);国家自然科学基金(21932006);浙江省自然科学基金(LR18B030002)

Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation

Hai Wang^a^,†, Qingsong Luo^a^,†, Liang Wang^a^,^d^,^*(), Yu Hui^b, Yucai Qin^b, Lijuan Song^b, Feng-Shou Xiao^a^,^c^,^#()

^aKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, Zhejiang, China
^bLiaoning Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Shihua University, Fushun 113001, Liaoning, China
^cKey Laboratory of Applied Chemistry of Zhejiang Province and Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^dZhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2021-02-18 Accepted:2021-02-18 Online:2021-12-18 Published:2021-05-19
Contact: Liang Wang,Feng-Shou Xiao
About author:# Tel/Fax: +86-571-88273698; E-mail: fsxiao@zju.edu.cn
* Tel/Fax: +86-571-88273698; E-mail: liangwang@zju.edu.cn;
First author contact:
^†These authors contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2018YFB0604801);National Natural Science Foundation of China(21822203);National Natural Science Foundation of China(21932006);Natural Science Foundation of Zhejiang Province(LR18B030002)

摘要/Abstract

摘要：

有机腈类化合物作为一类重要的化工原料, 被广泛应用于医药/农药制造、精细化学品合成和高性能纤维/橡胶生产中. 传统合成有机腈类化合物一般使用剧毒的氰化物作为腈化试剂, 这类氰化物在危害人体健康的同时, 也会严重污染生态环境. 针对无氰化物的腈化过程, 发展了很多新的反应路线, 其中, 采用氨气作为氮源的直接氨氧化引起了广泛关注. 在该反应中, 高温气固相氨氧化反应容易发生过氧化等副反应. 与之相比, 液相体系中的氨氧化过程反应条件则相对温和, 可以有效抑制过氧化. 但是, 在液相反应中, 腈类产物很容易被水合成酰胺类化合物, 从而导致该反应的产物选择性大幅降低.

本文研究发现, 通过改变氧化锰晶体结构可以有效地调控醇类分子氨氧化反应中腈和酰胺产物的选择性. MnO₂ (包括α, β, γ和δ相)催化的氨氧化过程中, 主要得到了酰胺(选择性>99.0%), 而在相同反应条件下, α-Mn₂O₃却可以高选择性地催化醇氨氧化到腈类产物(选择性>99.0%), 在该体系中, 即使额外增加反应体系中水和催化剂的用量, 腈类产物依然不会转化为酰胺产物. 动力学研究结果表明, α-Mn₂O₃催化腈水合到酰胺的反应速率几乎为零, 这说明该类催化剂可以有效抑制腈水合反应. 原位红外光谱结果表明, α-Mn₂O₃表面无法有效活化水分子, 并且对腈类分子的吸附较弱, 这些因素都导致了腈水合反应难以进行, 从而可以高选择性地形成腈类化合物. 与之相反, MnO₂催化材料则可以高效地活化水分子, 并且对腈类分子吸附较强, 从而有效促进了水合反应并获得了酰胺产物.

综上, 通过调控氧化锰的晶体类型就可以简单、有效地改变氨氧化反应中的产物选择性. 即使在苛刻的反应条件下, 例如较大量的水存在下, α-Mn₂O₃催化的反应体系中依然可以高选择性地获得腈类化合物. 本文为高效调控氨氧化反应的产物选择性提供了一个可靠方案.

关键词: 氧化锰, 氨氧化, 腈类化合物, 酰胺类化合物, 晶体结构

Abstract:

The performances of heterogeneous catalysts can be effectively tuned by changing the catalyst structures. Here we report a controllable nitrile synthesis from alcohol ammoxidation, where the nitrile hydration side reaction could be efficiently prevented by changing the manganese oxide catalysts. α-Mn₂O₃ based catalysts are highly selective for nitrile synthesis, but MnO₂-based catalysts including α, β, γ, and δ phases favour the amide production from tandem ammoxidation and hydration steps. Multiple structural, kinetic, and spectroscopic investigations reveal that water decomposition is hindered on α-Mn₂O₃, thus to switch off the nitrile hydration. In addition, the selectivity-control feature of manganese oxide catalysts is mainly related to their crystalline nature rather than oxide morphology, although the morphological issue is usually regarded as a crucial factor in many reactions.

Key words: Manganese oxide, Ammoxidation, Nitrile, Amide, Crystal structure

王海, 罗青松, 王亮, 惠宇, 秦玉才, 宋丽娟, 肖丰收. 氧化锰晶体作为催化材料调控氨氧化反应产物选择性[J]. 催化学报, 2021, 42(12): 2164-2172.

Hai Wang, Qingsong Luo, Liang Wang, Yu Hui, Yucai Qin, Lijuan Song, Feng-Shou Xiao. Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation[J]. Chinese Journal of Catalysis, 2021, 42(12): 2164-2172.

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https://www.cjcatal.com/CN/Y2021/V42/I12/2164

图/表 10

Scheme 1. Different routes for nitrile synthesis.

Fig. 1. Data characterizing the performance of various catalysts in ammoxidation of benzyl alcohol with various catalysts. Reaction conditions: 0.4 mmol of benzyl alcohol, 100 mg of catalyst, 100 μL of aqueous NH3 (28 wt%-30 wt%), 1.5 MPa of O2, 4 mL of t-amyl alcohol, 130 °C, 18 h. Conversions and yields were determined by GC analysis. More detail about the catalytic data are shown in Table S1.

Fig. 2. Conversion of benzyl alcohol and selectivity for benzonitrile and benzamide as a function of reaction temperature (a), ammonia amount (b), water amount (c), and catalyst amount (d) over α-Mn2O3-ca catalyst. Reaction conditions: 0.4 mmol of benzyl alcohol, 100 mg of catalyst, 1.5 MPa of O2, 4 mL of t-amyl alcohol, 18 h. More detailed data were shown in Tables S2-S4.

Table 1 Catalytic ammoxidation of various alcohols over α-Mn2O3-ca and β-MnO2 catalysts.

Entry	Substrate	Catalyst	Yield (%)
Entry	Substrate	Catalyst	P₁	P₂
1		α-Mn₂O₃-ca	81.3	n.d.
1		β-MnO₂	n.d.	83.0
2		α-Mn₂O₃-ca	81.3	n.d.
2		β-MnO₂	n.d.	>99.0
3 ^a		α-Mn₂O₃-ca	74.7	n.d.
3 ^a		β-MnO₂	19.3	80.7
4		α-Mn₂O₃-ca	84.2	n.d.
4		β-MnO₂	n.d.	>99.0
5		α-Mn₂O₃-ca	77.5	n.d.
5		β-MnO₂	n.d.	>99.0
6		α-Mn₂O₃-ca	77.4	n.d.
6		β-MnO₂	n.d.	79.5
7		α-Mn₂O₃-ca	78.7	n.d.
7		β-MnO₂	n.d.	>99.0
8 ^b		α-Mn₂O₃-ca	82.0	n.d.
8 ^b		β-MnO₂	n.d.	98.0
9 ^b		α-Mn₂O₃-ca	54.1	n.d.
9 ^b		β-MnO₂	7.7	50.8
10 ^b		α-Mn₂O₃-ca	85.8	n.d.
10 ^b		β-MnO₂	n.d.	75.4
11 ^b		α-Mn₂O₃-ca	95.4	n.d.
11 ^b		β-MnO₂	n.d.	75.3
12		α-Mn₂O₃-ca	>99.0	n.d.
12		β-MnO₂	41.4	52.4
13 ^c		α-Mn₂O₃-ca	15.7	n.d.
13 ^c		β-MnO₂	28.2	3.5
14 ^c		α-Mn₂O₃-ca	6.2	n.d.
14 ^c		β-MnO₂	5.4	1.1

Fig. 3. Data characterizing the performance of various catalysts in benzonitrile hydration. Reaction conditions: 0.4 mmol of benzonitrile, 100 mg of catalyst, 75 μL of H2O, 1.5 MPa of N2, 4 mL of t-amyl alcohol, 130 °C, 18 h. Conversions and yields were determined by GC. More details were shown in Table S5. [a] 75 μL of D2O. [b] The data from Ref. [17], reaction conditions: 1 mmol of benzonitrile, Ru(OH)x/Al2O3 (4 mol% Ru), 3 mL of water, 140 °C.

Fig. 4. (a,b) Data characterizing the performance of various catalysts in benzonitrile hydration; (c) Conversion of benzonitrile as a function of α-Mn2O3 phase amount in the catalysts with different thermal treatments of β-MnO2. Reaction conditions: 0.4 mmol of benzonitrile, 100 mg of catalyst, 75 μL of H2O, 1.5 MPa of N2, 4 mL of t-amyl alcohol, 130 °C, 18 h. Conversions and yields were determined by GC. More details were shown in Tables S7 and S8. (d) Data characterizing the performance of various catalysts in ammoxidation of benzyl alcohol. Dependence of benzonitrile and benzamide yields on time over β-MnO2 (e) and α-Mn2O3(6h) (f) catalysts. Reaction conditions: 0.4 mmol of benzyl alcohol, 100 mg of catalyst, 100 μL of aqueous NH3 (28 wt%-30 wt%), 1.5 MPa of O2, 4 mL of t-amyl alcohol, 130 °C. Conversions and yields were determined by GC. More details were shown in Tables S9-S11.

Scheme 2. Catalytic selectivities of different catalysts in alcohol ammoxidation.

Fig. 5. (a-c) Conversion of different substrate as a function of time over the β-MnO2 and α-Mn2O3(6h) catalysts. Reaction conditions: (a,b) 20 mg of catalyst, 0.4 mmol of benzyl alcohol and benzaldehyde, 100 μL of aqueous NH3 (28 wt%-30 wt%), 4 mL of t-amyl alcohol, 1.5 MPa of O2 for (a), 1.5 MPa of N2 for (b), 130 °C. (c) 50 mg of catalyst, 0.4 mmol of benzonitrile, 100 μL of H2O, 4 mL of t-amyl alcohol, 1.5 MPa of N2, 130 °C. (d) Hammett plot for competitive hydration of benzonitrile and p-substituted benzonitrile derivatives over β-MnO2.

Table 2 Reaction rates (r) of different substrates over β-MnO2 and α-Mn2O3(6h) catalysts.

Catalyst	r (mmol g_cat^‒1 h^‒1)
Catalyst	Benzyl alcohol	Benzaldehyde	Benzonitrile
β-MnO₂	5.41	3.39	1.45
α-Mn₂O₃(6h)	3.59	1.97	—

Fig. 6. In-situ FTIR spectra characterizing the H2O adsorption and H/D exchange over α-Mn2O3(6h) (a) and β-MnO2 (b). Line a in (a,b): catalyst was pretreated in flowing air at 200 °C for 2 h and purged in pure He at 200 °C for 1 h, the spectra were recorded at 150 °C. Line b in (a,b): Successively, at 150 °C, the catalyst was treated in 3 vol% H2O/He for 0.5 h, purged in pure He for 0.5 h, evacuated for 0.5 h, and treated in D2O for 10 min and the spectra were recorded. In-situ FTIR spectra characterizing the benzonitrile adsorption over α-Mn2O3(6h) (c) and β-MnO2 (d).

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氧化锰晶体作为催化材料调控氨氧化反应产物选择性

Product selectivity controlled by manganese oxide crystals in catalytic ammoxidation

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