锚定基团对HKUST-1/TEMPO共催化体系催化性能的影响

doi:10.7503/cjcu20190683

摘要/Abstract

摘要：

用异烟酸(Iso-NTA)为桥接分子, 将有机小分子自由基4-氨基-2,2,6,6-四甲基哌啶-1-氧自由基(4-NH₂-TEMPO)与异烟酸缩合, 合成出含吡啶官能团的TEMPO自由基(Iso-NTA-TEMPO). 与TEMPO相比, Iso-NTA-TEMPO具有较高的氧化电位, 在无Cu(Ⅱ)辅助时, Iso-NTA-TEMPO对苯甲醇的氧化效率高于TEMPO. 在与HKUST-1组成的复合催化体系中, Iso-NTA-TEMPO可通过吡啶基团与HKUST-1孔道中的Cu(Ⅱ)相互作用, 从而在催化过程中(部分)锚定在HKUST-1孔道内部. 与TEMPO/HKUST-1体系相比, Iso-NTA-TEMPO/HKUST-1体系表现出对芳香醇更加高效的催化活性. 采用模板辅助溶剂诱导结晶法合成的HKUST-1晶体表面具有较多缺陷, 更有利于Iso-NTA-TEMPO自由基分子扩散进入HKUST-1孔道内部, 也有助于提高Iso-NTA-TEMPO/HKUST-1体系的催化效率. Iso-NTA-TEMPO/HKUST-1体系可将各种取代基(苄醇、杂环醇以及二级脂肪醇)高效、高选择性地氧化成相应的醛或酮.

关键词: HKUST-1, 2,2,6,6-四甲基哌啶氧自由基, 锚定基团, 共催化剂, 模板剂

Abstract:

By using isonicotinic acid(Iso-NTA) as a bridging molecule, a pyridyl functionalized 2,2,6,6-tetramethylpiperidinyl-1-oxy(TEMPO) radical(Iso-NTA-TEMPO) was synthesized by the condensation of 4-amino-2,2,6,6-tetramethylpiperidino-1-oxy(4-NH₂-TEMPO) and isonicotinic acid. Compared with TEMPO, Iso-NTA-TEMPO exhibited higher oxidation potential, which facilitates the oxidation reaction of benzyl alcohol, without the use of Cu(Ⅱ). In the case of Iso-NTA-TEMPO/HKUST-1 hybrid catalytic system, the Iso-NTA-TEMPO can be(partially) coordinated to Cu(Ⅱ) sites of HKUST-1 by pyridyl group during catalysis. As consequence, the Iso-NTA-TEMPO/HKUST-1 catalytic system shows much higher catalytic activity than that of TEMPO/HKUST-1 system, toward the oxidation of aromatic alcohols. Moreover, HKUST-1 synthesized by template assisted solvent-induced crystallization consists a significant amount of defects, which facilitates the diffusion of Iso-NTA-TEMPO into the pores of HKUST-1, thus, improving the catalytic activity of Iso-NTA-TEMPO/HKUST-1. The Iso-NTA-TEMPO/HKUST-1 system enables the oxidation of a broad range of primary aromatic alcohols with various substituted groups and heteroatoms, as well as secondary aliphatic alcohols with high efficiency and selectivity.

Key words: HKUST-1, 2,2,6,6-Tetramethylpiperidinyl-1-oxy(TEMPO) radicals, Anchoring group, Co-catalyst, Template

中图分类号:

O643

TrendMD:

薛云,晏秘,申妍铭,毛会玲,王晨,程琥,庄金亮. 锚定基团对HKUST-1/TEMPO共催化体系催化性能的影响. 高等学校化学学报, 2020, 41(5): 1068.

XUE Yun,YAN Mi,SHEN Yanming,MAO Huiling,WANG Chen,CHENG Hu,ZHUANG Jinliang. Effects of Anchoring Group on the Catalytic Activity of HKUST-1/TEMPO Co-catalysts ^†. Chem. J. Chinese Universities, 2020, 41(5): 1068.

图/表 11

Scheme 1 Synthetic route of iso-NTA-TEMPO

Fig.1 Simulated XRD pattern(a) from HKUST-1 single-crystal data and powder XRD pattern(b) of room temperature synthesized HKUST-1 microcrystals

Fig.2 FTIR spectrum of room temperature synthesized HKUST-1

Fig.3 SEM images of room temperature synthesized HKUST-1

Fig.4 N2 adsorption/desorption isotherm and pore size distribution(inset) of HKUST-1

Table 1 Aerobic oxidation of benzyl alcohola

Entry	Catalyst	Co-catalyst	Activator	Time/h	Conversion^b(%)	Selectivity^b(%)
1	—	Iso-NTA-TEMPO	TBN	1.5	64	>99
2	—	TEMPO	TBN	1.5	18	>99
3	HKUST-1	Iso-NTA-TEMPO	TBN	1.5	>99	>99
4	HKUST-1	TEMPO	TBN	1.5	30	>99
5	HKUST-1	Iso-NTA-TEMPO	—	24	36	>99
6	HKUST-1	TEMPO	—	24	23	>99
7	HKUST-1	—	—	24	<1	—
8	Cu(NO₃)₂·3H₂O	Iso-NTA-TEMPO	TBN	1.5	43	>99
9	Cu(NO₃)₂·3H₂O	TEMPO	TBN	1.5	34	>99

Fig.5 Cyclic voltammograms of TEMPO(1 mmol/L) and Iso-NTA-TEMPO(1 mmol/L) Conditions: Pt plate working electrode, Pt wire counter electrode, Ag/AgCl reference electrode, MeCN, TBAF(50 mmol/L), scan rate=50 mV/s.

Table 2 Aerobic oxidation of various alcoholsa

Entry	Time/h	Conversion^b(%)	Selectivity^b(%)
1	3	91	>99
2	1.5	>99	>99
3	6	>99	>99
4	3	98	>99
5	1.5	>99	>99
6	6	>99	>99
7	12	>99	>99
8	12	>99	>99
9	12	>99	>99
10	12	>99	>99

Fig.6 Plots of conversion vs. time for benzyl alcohol oxidation catalyzed by Iso-NTA-TEMPO/HKUST-1(a) and TEMPO/HKUST-1(b)

Fig.7 Scheme of Cu(Ⅱ) coordinated Iso-NTA-TEMPO and TEMPO in HKUST-1

Fig.8 Reusability of Iso-NTA-TEMPO/HKUST-1 in the aerobic oxidation of benzyl alcohol

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