Au-Pd/MnO2催化剂的制备及其苯甲醇氧化性能

doi:10.16085/j.issn.1000-6613.2022-2123

摘要/Abstract

摘要：

以硫酸锰、过硫酸铵和硫酸铵为原料，通过水热法制备了三种不同形态的MnO₂（α型、β型和γ型），并利用溶胶-固载法负载了活性组分AuPd，然后将所制备的Au-Pd/MnO₂用于无溶剂条件下的苯甲醇催化氧化。实验结果表明：载体MnO₂的形态对催化剂的反应活性具有显著影响，苯甲醇在Au-Pd/γ-MnO₂催化剂上反应的转化频率（TOF）值可以达到68283h^-1，明显优于Au-Pd/β-MnO₂（62299h^-1）和Au-Pd/α-MnO₂（35280h^-1）。此外，循环稳定性实验表明Au-Pd/MnO₂催化剂具有良好的反应稳定性。同时，利用X射线衍射、N₂吸脱附曲线、透射电子显微镜、X射线光电子能谱等分析手段对所制备的催化剂进行结构表征，发现较小的AuPd纳米颗粒尺寸、载体上丰富的氧空位浓度和催化剂上Pd⁰活性物种的较高含量是Au-Pd/γ-MnO₂催化剂取得高活性的关键。

关键词: 苯甲醇, 催化氧化, 二氧化锰, 无溶剂

Abstract:

α-MnO₂, β-MnO₂ and γ-MnO₂ were prapered respectively with manganese sulfate, ammonium persulfate and ammonium sulfate as reactant by using hydrothermal method. Subsquently, Au-Pd nanoparticles were loaded on the MnO₂ by sol-immobiliazation method. Then the prepared Au-Pd/MnO₂ catalysts were used for the catalytic oxidation of benzyl alcohol under solvent-free condition. The experimental results indicated that the morphology of the MnO₂ significantly affected on the catalytic performance. The TOF value on Au-Pd/γ-MnO₂ reached 68283h^-1, which was much higher than those of Au-Pd/β-MnO₂ (62299h^-1) and Au-Pd/α-MnO₂ (35280h^-1). Furthermore, the cycle stability experiment demonstrated that Au-Pd/MnO₂ catalysts manifested a high durability. Meanwhile, XRD, N₂-BET, TEM and XPS were conducted to characterize the prepared catalysts, the corresponding results revealed that the excellent performance of Au-Pd/γ-MnO₂was attributed to the smaller Au-Pd nanoparticle size, the higher number of oxygen vacancies in γ-MnO₂ and the higher content of Pd⁰ active species.

Key words: benzyl alcohol, catalytic oxidation, manganese dioxide, solvent-free

中图分类号:

O643.3

郭晓宇, 李冬晨, 赵炜, 杜朕屹, 李晓良. Au-Pd/MnO₂催化剂的制备及其苯甲醇氧化性能[J]. 化工进展, 2023, 42(10): 5223-5231.

GUO Xiaoyu, LI Dongchen, ZHAO Wei, DU Zhenyi, LI Xiaoliang. Preparation of Au-Pd/MnO₂ catalyst and its catalytic performance for benzyl alcohol oxidation[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5223-5231.

图/表 14

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催化剂	Au/%		Pd/%		Au/Pd摩尔比
催化剂	理论值	实际值	理论值	实际值	Au/Pd摩尔比
Au-Pd/α-MnO₂	1.0	0.98	1.0	0.97	0.54
Au-Pd/β-MnO₂	1.0	0.97	1.0	0.95	0.55
Au-Pd/γ-MnO₂	1.0	0.99	1.0	0.96	0.55

催化剂	Au/%		Pd/%		Au/Pd摩尔比
催化剂	理论值	实际值	理论值	实际值	Au/Pd摩尔比
Au-Pd/α-MnO₂	1.0	0.98	1.0	0.97	0.54
Au-Pd/β-MnO₂	1.0	0.97	1.0	0.95	0.55
Au-Pd/γ-MnO₂	1.0	0.99	1.0	0.96	0.55

催化剂	比表面积 /m²·g^-1	孔容 /cm³·g^-1	孔径/nm	载体平均颗粒尺寸^①/nm
Au-Pd/α-MnO₂	63.5	0.38	3.1	18.3
Au-Pd/β-MnO₂	27.6	0.13	3.4	25.5
Au-Pd/γ-MnO₂	56.9	0.25	3.1	14.7

催化剂	比表面积 /m²·g^-1	孔容 /cm³·g^-1	孔径/nm	载体平均颗粒尺寸^①/nm
Au-Pd/α-MnO₂	63.5	0.38	3.1	18.3
Au-Pd/β-MnO₂	27.6	0.13	3.4	25.5
Au-Pd/γ-MnO₂	56.9	0.25	3.1	14.7

催化剂	结合能/eV				Pd⁰摩尔分数/%	Au⁰摩尔分数/%
催化剂	3d_3/2 Pd⁰	3d_3/2 Pd²⁺	3d_5/2 Pd⁰	3d_5/2 Pd²⁺	Pd⁰摩尔分数/%	Au⁰摩尔分数/%
Au-Pd/α-MnO₂	340.9	342.8	335.3	337.3	27.2	35.69
Au-Pd/β-MnO₂	340.8	342.6	335.2	337.1	25.6	38.41
Au-Pd/γ-MnO₂	341.1	342.8	335.4	337.4	42.8	40.53

Au-Pd/MnO₂催化剂的制备及其苯甲醇氧化性能

Preparation of Au-Pd/MnO₂ catalyst and its catalytic performance for benzyl alcohol oxidation

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催化剂	结合能/eV			O_ads/O_latt摩尔比	Mn³⁺/(Mn³⁺+Mn⁴⁺)摩尔比
催化剂	Mn³⁺	Mn⁴⁺	O1s (O_latt, O_ads, O_adsOH)	O_ads/O_latt摩尔比	Mn³⁺/(Mn³⁺+Mn⁴⁺)摩尔比
Au-Pd/α-MnO₂	642.1	643.5	529.5, 531.0, 533.3	0.55	0.55
Au-Pd/β-MnO₂	641.6	643.9	529.1, 530.9, 533.0	0.74	0.48
Au-Pd/γ-MnO₂	641.9	643.7	529.5, 531.0, 533.0	0.76	0.61

产物	Au-Pd/α-MnO₂选择性/%	Au-Pd/β-MnO₂选择性/%	Au-Pd/γ-MnO₂选择性/%
苯	0.84	0.99	1.18
甲苯	18.08	10.81	8.76
苯甲醛	77.42	85.46	85.60
苯甲酸	0.48	0.79	2.26
苯甲酸苄酯	3.18	1.95	2.20
碳平衡	97.85	99.16	99.04

催化剂	1次循环/%	2次循环/%	3次循环/%
Au-Pd/α-MnO₂	66.91	66.01	65.48
Au-Pd/β-MnO₂	74.93	72.55	70.90
Au-Pd/γ-MnO₂	77.31	76.23	72.11

催化剂	TOF/h^-1	0.5h转化率 /%	1次循环 /%	2次循环 /%	3次循环 /%
Au-Pd/α-MnO₂	35280	7.9	47.2	45.1	44.9
Au-Pd/β-MnO₂	62299	13.9	66.1	64.5	52.1
Au-Pd/γ-MnO₂	68283	15.2	61.5	62.1	55.2

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