Cu2-MnOx高效催化1, 2, 3, 4-四氢喹啉氧化脱氢芳构化

doi:10.3866/PKU.WHXB201811046

Abstract

Abstract:

A novel template-free oxalate route was applied to synthesize a series of MnO_x catalysts with different Cu content (MnO_x, Cu1-MnO_x, Cu2-MnO_x, Cu3-MnO_x, Cu4-MnO_x, Cu2-450, and Cu2-550), which were then used in 1, 2, 3, 4-tetrahydroquinoline (THQL) oxidative dehydrogenation aromatization. To obtain insight into the structure-activity relationships of the catalysts, the samples were characterized by thermogravimetry and heat flow analysis, X-ray diffraction (XRD), N₂ physical adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), H₂ temperature programmed reduction (H₂-TPR), and atomic absorption spectroscopy (AAS). The results showed that Cu2-MnO_x possesses the following characteristics: amorphous nature, high specific surface area, increased mesoporous average pore diameter, lower reduction temperature, highest Mn³⁺ and adsorbed oxygen content, and highest Mn³⁺/Mn⁴⁺ ratio among the seven manganese oxide catalysts. Cu2-MnO_x for the oxidative dehydrogenation aromatization of THQL showed conversion (99.1%) and selectivity (97.2%) for quinoline under mild reaction conditions, with cheap air as oxidant and no alkali additive. Cu2-MnO_x was reusable and achieved 95.8% conversion even after five reuse tests. Selectivity decreased slightly with the increase in reuse time, which could be attributed to the leaching of the Cu element. Comparison of structure-activity relationships showed increased catalytic activity when Mn³⁺ and adsorbed oxygen content were highest among these amorphous manganese oxides. Mn⁴⁺ content was related to the formation of quinoline N-oxide by over oxidation. Despite their high Mn³⁺ content and Mn³⁺/Mn⁴⁺ ratio, Cu2-450 and Cu2-550 had reduced surface area, adsorbed oxygen content, and lattice oxygen mobility, which resulted in poor catalytic performance. Although Cu3-MnO_x had the largest BET surface area, highest lattice oxygen mobility, and similar Mn³⁺ and adsorbed oxygen content as Cu2-MnO_x, the smaller average pore diameter of Cu3-MnO_x perhaps caused its conversion and selectivity to be similar to Cu2-MnO_x. The amorphous nature, Mn³⁺ and adsorbed oxygen content, Mn³⁺/Mn⁴⁺ ratio, lattice oxygen mobility, and synergistic effect between CuO and MnO_x were found to play key roles in catalytic performance. The absence of precious metals, the simple catalyst preparation process, the cheap air as the sole oxidant, no ligand and alkali, the mild reaction conditions, along with catalyst reusability and easy isolation of the aromatized products made our catalytic protocol both green and environmentally benign.

Key words: Oxalate route, Manganese oxide, CuO doping, 1, 2, 3, 4-Tetrahydroquinoline, Oxidative dehydrogenation

Fushan CHEN,Songlin ZHAO,Tao YANG,Taotao JIANG,Jun NI,Qunfeng ZHANG,Xiaonian LI. Highly Efficient Oxidative Dehydrogenation Aromatization of 1, 2, 3, 4-Tetrahydroquinoline by Cu2-MnO_x Catalyst[J]. Acta Physico-Chimica Sinica 2019, 35(7), 775-786. doi: 10.3866/PKU.WHXB201811046

Figures/Tables 16

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References 38

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Sample	BET surface area	BJH pore size/nm	BJH pore volume
Sample	(m²·g^?1)	BJH pore size/nm	(cm³·g^?1)
MnO_x	289.1	3.2	0.17
Cu1-MnO_x	253.2	4.2	0.16
Cu2-MnO_x	239.3	4.9	0.16
Cu3-MnO_x	302.9	3.4	0.22
Cu4-MnO_x	246.2	4.0	0.13
Cu2-450	47.8	14.7	0.16
Cu2-550	27.1	22.7	0.17

Sample	Surface element molar fraction
	Mn				O
	Mn²⁺	Mn³⁺	Mn⁴⁺	Mn³⁺/Mn⁴⁺	O_ads	O_latt
MnO_x	0.202	0.412	0.386	1.07	0.257	0.685
Cu1-MnO_x	0.224	0.451	0.324	1.39	0.288	0.653
Cu2-MnO_x	0.242	0.476	0.282	1.69	0.307	0.592
Cu3-MnO_x	0.244	0.470	0.288	1.63	0.293	0.675
Cu4-MnO_x	0.205	0.454	0.340	1.34	0.285	0.684
Cu2-450	0.245	0.477	0.278	1.72	0.205	0.757
Cu2-550	0.247	0.508	0.243	2.21	0.215	0.742


Entry	Catalyst	Conversion of THQL/%	Selectivity of QL/%
1	No catalyst	0.9	100
2	MnO_x	90.8	85.2
3	Fe1-MnO_x	87.1	88.2
4	Al1-MnO_x	94.1	88.6
5	Ni1-MnO_x	85.1	82.4
6	Co1-MnO_x	88.1	86.2
7	Cu1-MnO_x	97.1	92.7

Entry	Catalyst	Cu content/%^a	Conversion of THQL/%	Selectivity of QL/%^b	TOF/(mmol·mg^?1·h^?1)^c
1	Cu1-MnO_x	0.23	97.1	92.7	0.00194
2	Cu2-MnO_x	0.81	99.1	97.2	0.00198
3	Cu3-MnO_x	2.83	98.1	96.9	0.00196
4	Cu4-MnO_x	8.92	97.3	93.0	0.00195
5	CuO	—	10.6	88.3	0.00021
6	Cu2-450	—	37.5	71.7	0.00075
7	Cu2-550	—	30.4	75.1	0.00061
8 ^d	Cu2-MnO_x	0.81	92.9	86.4	0.00929
9 ^e	Cu2-MnO_x	0.81	18.0	94.6	0.00036
10 ^f	Cu2-MnO_x	0.81	39.8	98.9	0.00080
11 ^g	Cu2-MnO_x	0.81	99.9	77.1	0.00199
12 ^h	Cu2-MnO_x	0.81	80.2	86.4	0.00160
13 ⁱ	Cu2-MnO_x	0.81	82.5	56.8	0.00165

Enry	Catalyst	W_catal. /mg	t/h	Con./Sel. (%)	TOF/(mmol·mg^-1·h^?1)	Ref.
1	AMO	25	5	60/90	0.00120	16
2	K-OMS-2	25	5	65/70	0.00130	16
3	Meso-Cs/MnO_x	25	5	50/99	0.00100	16
4	Meso-MnO_x	25	5	50/99	0.00100	16
5	Ni2Mn-LDH	80	2.5	99/93	0.00247	15
6	Cu2-MnO_x	25	5	99.1/97.2	0.00198	this work

Highly Efficient Oxidative Dehydrogenation Aromatization of 1, 2, 3, 4-Tetrahydroquinoline by Cu2-MnO_x Catalyst

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Highly Efficient Oxidative Dehydrogenation Aromatization of 1, 2, 3, 4-Tetrahydroquinoline by Cu2-MnOx Catalyst

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Highly Efficient Oxidative Dehydrogenation Aromatization of 1, 2, 3, 4-Tetrahydroquinoline by Cu2-MnO_x Catalyst