表面氧化态可调的α-MnO2纳米线选择性催化氧化5-羟甲基糠醛

doi:10.11949/0438-1157.20211300

摘要/Abstract

摘要：

利用水热法制备了一系列α-MnO₂催化剂用于选择性催化氧化5-羟甲基糠醛（HMF）制备2，5-呋喃二甲醛（DFF）。研究结果表明，催化剂的表面平均氧化态（AOS）与活性呈正比关系，且可以通过氧化/还原气氛焙烧进行调控。其中使用最高AOS的MnO₂-NW2纳米线作催化剂，反应1 h获得了HMF转化率79%和DFF选择性99%，经过空气焙烧再生可进行6次以上的循环使用，且无失活现象。

关键词: 二氧化锰纳米线, 平均氧化态, 5-羟甲基糠醛, 选择性氧化, 2, 5-呋喃二甲醛

Abstract:

A series of α-MnO₂nanocatalysts were synthesized by hydrothermal method for the selective catalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF). The results showed that the surface average oxidation state (AOS) of the catalysts was positively correlated with the activity of the catalysts, and could be regulated by oxidation/reduction calcination. After optimization, 79% HMF conversion and almost 99% DFF selectivity were achieved in 1 h over a MnO₂-NW2 catalyst with the highest AOS of Mn. And the MnO₂-NW2 catalyst can be recycle used for more than six times under a simple redox regeneration treatment.

Key words: MnO₂ nanowire, average oxidation state, 5-hydroxymethylfurfural, selective oxidation, 2,5-diformylfuran

中图分类号:

O 643.36

赵婉娜, 周春梅, 靳玉广, 杨艳辉. 表面氧化态可调的α-MnO₂纳米线选择性催化氧化5-羟甲基糠醛[J]. 化工学报, 2021, 72(12): 6274-6281.

Wanna ZHAO, Chunmei ZHOU, Yuguang JIN, Yanhui YANG. Selective oxidation of 5-hydroxymethylfurfural over α-MnO₂ nanowires with tunable surface oxidation state[J]. CIESC Journal, 2021, 72(12): 6274-6281.

图/表 10

图1 K-OMS-2选择性氧化HMF的机理[23]

Fig.1 Catalytic mechanism of aerobic oxidation of HMF over K-OMS-2[23]

图2 不同二氧化锰催化剂的XRD谱图

Fig.2 XRD patterns of different manganese dioxides

表1 各种α-MnO2催化剂的表面性质和催化活性

Table 1 The surface properties and catalytic activity of the α-MnO2 catalysts

Catalyst	Mn⁴⁺/Mn³⁺	O_latt/O_ads	BET/(m²/g)	Conversion^①/%	Activity^②/(mmol/(m²·h))	AOS
Catalyst	Mn⁴⁺/Mn³⁺	O_latt/O_ads	BET/(m²/g)	Conversion^①/%	Activity^②/(mmol/(m²·h))	by TPR	by XPS
MnO₂-NF	0.41	1.99	122.1	25.3	0.22	3.55	3.56
MnO₂-NW1	0.48	2.26	66.4	24.2	0.47	3.76	3.72
MnO₂-NW2	0.58	2.69	30.2	29.6	0.89	3.87	3.80
MnO₂-NW3	0.49	2.66	28.1	26.4	0.60	3.78	3.75

图3 二氧化锰催化剂的SEM、TEM和HRTEM图

Fig.3 SEM, TEM and HRTEM images for MnO2-NF, MnO2-NW1, MnO2-NW2, MnO2-NW3 and MnO2-NR respectively

图4 不同二氧化锰催化剂在DMF为溶剂下的转化率和选择性[反应条件: 1 mmol HMF, 110°C, 0.5 h, 0.5 MPa, 催化剂(50 mg), n(MnO2/HMF) =0.55]

Fig.4 Product conversion and selectivity in aerobic oxidation of HMF over different MnO2 with DMF[reaction condition: 1 mmol HMF, 110°C, 0.5 h, 0.5 MPa, catalyst (50 mg), n(MnO2/HMF) =0.55]

图5 二氧化锰催化剂的表面电子结构表征

Fig.5 Characterization of surface electronic structure of manganese dioxide catalyst

图6 表面还原氧化处理对催化活性的影响[反应条件：1 mmol HMF, 110℃, 0.5 MPa O2,10 ml DMF, 1 h, n(MnO2/HMF) =0.55]

Fig.6 Effect of surface reduction oxidation treatment on catalytic activity [reaction conditions: 1 mmol HMF, 110℃, 0.5 MPa O2,10 ml DMF, 1 h, n(MnO2/HMF) =0.55]

图7 MnO2-NW2催化剂的循环使用性能

Fig.7 Recycle performances of MnO2-NW2 for the aerobic oxidation of HMF

图8 各状态MnO2-NW2催化剂的结构表征

Fig.8 Structural characterization of MnO2-NW2 catalysts in various states

图9 AOS和催化剂活性之间的关系

Fig.9 Dependence of AOS and catalytic activity for MnO2 catalysts

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表面氧化态可调的α-MnO₂纳米线选择性催化氧化5-羟甲基糠醛

Selective oxidation of 5-hydroxymethylfurfural over α-MnO₂ nanowires with tunable surface oxidation state

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