聚离子液体载MoO2/Ag催化分子氧氧化苯乙烯的研究

doi:10.11949/0438-1157.20200810

摘要/Abstract

摘要：

以氨基功能化的聚离子液体为载体，通过离子交换和水热还原，制备出负载型催化剂PVAD/MoO₂/Ag，考察了其催化苯乙烯氧化的性能。采用FT-IR、TG、XRD、SEM和BET对其所制备的催化剂进行表征。苯乙烯氧化性能研究结果表明，PVAD/MoO₂/Ag_4%表现出最佳的催化活性，在乙腈为溶剂，温度为90℃，氧气压力为0.8 MPa的条件下，反应8 h，苯乙烯的转化率为49.9%，苯甲醛的选择性达到74.4%。并且催化剂重复使用5次，活性没有明显下降，表现出良好的重复利用性。

关键词: 聚离子液体, 分子氧, 氧化, 苯乙烯, 苯甲醛

Abstract:

The supported catalyst PVAD/MoO₂/Ag was prepared by ion exchange and hydrothermal reduction using amino-functionalized polyionic liquid as the carrier, and its performance in catalyzing the oxidation of styrene was investigated. The prepared catalysts were characterized by FT-IR, TG, XRD, SEM and BET. The results showed that PVAD/MoO₂/Ag_4% showed the best catalytic activity. Under the conditions of acetonitrile as solvent, temperature of 90℃ and oxygen pressure of 0.8 MPa for 8 h, the conversion rate of styrene was 49.9%, and the selectivity of benzaldehyde reached 74.4%. Moreover, the activity did not decrease significantly after reused 5 times, showing good reusability.

Key words: polyionic liquid, molecular oxygen, oxidation, styrene, benzaldehyde

中图分类号:

TQ 028.8

吴岳峰,曲永芳,李大欢,苏苗军,刘勇. 聚离子液体载MoO₂/Ag催化分子氧氧化苯乙烯的研究[J]. 化工学报, 2020, 71(11): 4990-4998.

Yuefeng WU,Yongfang QU,Dahuan LI,Miaojun SU,Yong LIU. Study on oxidation of styrene with molecular oxygen catalyzed by MoO₂/Ag on polyionic liquid[J]. CIESC Journal, 2020, 71(11): 4990-4998.

图/表 15

图1 PVAD/MoO2/Ag的合成过程

Fig.1 The synthesis process of PVAD/MoO2/Ag

图2 聚离子液体PVAD (a)和PVAD/MoO2/Ag4% (b)的红外光谱

Fig.2 Infrared spectra of PVAD (a) and PVAD/MoO2/Ag4%(b)

图3 PVAD和PVAD/MoO2/Ag4%热重图

Fig.3 TG images of PVAD and PVAD/MoO2/Ag4%

图4 PVAD(a)和 PVAD/MoO2/Ag4%(b)的扫描电镜图片及元素分布图(c)

Fig.4 SEM images of PVAD (a) and PVAD/MoO2/Ag4% (b) and elemental (C, N, O, Mo and Ag) mapping images of PVAD/MoO2/Ag4%(c)

图5 PVAD和PVAD/MoO2/Ag4%的XRD谱图

Fig.5 XRD patterns of PVAD and PVAD/MoO2/Ag4%

图6 PVAD和PVAD/MoO2/Ag4%的N2吸/脱附曲线(a)及孔径分布图(b)

Fig.6 Isothermal N2 adsorption/desorption curve (a) and pore size distribution diagram (b) of PVAD and PVAD/MoO2/Ag4%

表1 催化剂的结构特性

Table 1 Structural properties of catalysts

催化剂	S_BET /(m²/g)	v_p/(cm³/g)	d_p/nm
PVAD	86.6	0.13	9.43
PVAD/MoO₂/Ag_4%	141.8	0.21	8.79

表2 溶剂对苯乙烯的氧化结果的影响

Table 2 Effects of solvents on the results of catalytic oxidation of styrene

溶剂	转化率/%	选择性/%
溶剂	转化率/%	苯甲醛	苯乙烯氧化物
MeCN	34.0	84.4	3.2
DMF	23.1	12.2	10.8
DCM	4.19	100	0
PhMe	1.4	100	0
EtOH	12.5	78.8	5.4

表3 Ag负载量对催化剂活性的影响

Table 3 Effect of Ag loading on catalyst activity

催化剂	转化率/%	选择性/%
催化剂	转化率/%	苯甲醛	苯乙烯氧化物
PVAD/MoO₂ PVAD/MoO₂/Ag_2%	16.7 27.3	83.9 84.9	2.3 2.8
PVAD/MoO₂/Ag_4%	34.0	84.4	3.2
PVAD/MoO₂/Ag_7%	24.0	84.7	3.0
PVAD/MoO₂/Ag_10%	19.0	83.1	2.7

图7 反应温度的影响（催化剂为PVAD/MoO2/Ag4%，反应条件为苯乙烯10 mmol，催化剂30 mg，乙腈溶剂8 ml，时间8 h， O2 0.8 MPa）

Fig.7 Effect of reaction temperature

图8 反应压力的影响(催化剂为PVAD/MoO2/Ag4%，反应条件为苯乙烯10 mmol，催化剂30 mg，乙腈溶剂8 ml，温度90℃，时间8 h)

Fig.8 Effect of reaction pressure

图9 催化剂用量的影响(催化剂为PVAD/MoO2/Ag4%，反应条件为苯乙烯10 mmol，乙腈溶剂8 ml，温度90℃，时间8 h， O2 0.8 MPa)

Fig.9 Effect of catalyst dosage

图10 反应时间的影响(催化剂为PVAD/MoO2/Ag4%，反应条件为苯乙烯10 mmol，催化剂30 mg，乙腈溶剂8 ml，温度90℃， O2 0.8 MPa)

Fig.10 Effect of reaction time

表4 不同催化剂催化氧化苯乙烯的结果

Table 4 Results of the catalytic oxidation of styrene with different catalysts

催化剂	氧化剂	温度/℃	时间/h	转化率/%	选择性/%	文献
PVAD/MoO₂/Ag	O₂	90	8	49.9	74.4	this work
PVAD/MoO₂/Ag	O₂	80	8	34.0	84.4	this work
MOF-74(Cu-30/Co-70)	O₂	80	20	30.4	43	[41]
Au NPs@XAD-4-G3.0 PAMAM	O₂	80	24	80	48	[42]
SO4^2--Fe-V/ZrO₂	H₂O₂	80	4	62.3	74.0	[43]
H₃PW₁₂O₄₀/SBA-15	H₂O₂	70	24	22.6	100.0	[44]
Mg_0.5Cu_0.5Fe₂O₄	H₂O₂	80	6	21.2	75.2	[45]
Ce_0.95Zr_0.05O₂	TBHP	80	12	70.2	31.3	[46]
ZSM-5(60)	TBHP	65	6	45.3	87.2	[47]

图11 催化剂的重复使用性(催化剂为PVAD/MoO2/Ag4%，反应条件为苯乙烯10 mmol，催化剂30 mg，乙腈溶剂8 ml，温度90℃，时间8 h， O2 0.8 MPa)

Fig.11 Reusability of catalysts

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聚离子液体载MoO₂/Ag催化分子氧氧化苯乙烯的研究

Study on oxidation of styrene with molecular oxygen catalyzed by MoO₂/Ag on polyionic liquid

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