Highly Efficient Catalysts Based on Divanadium-Substituted Polyoxometalate and N-Doped Carbon Nanotubes for Selective Oxidation of Alkylphenols
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
ACS Catalysis
ISSN: 2155-5435
|
| Output data |
Year: 2018,
Volume: 8,
Pages: 1297-1307
Pages count
: 11
DOI:
10.1021/acscatal.7b03933
|
| Tags |
alkylphenols, benzoquinones, carbon nanotubes, heterogeneous catalysis, hydrogen peroxide, nitrogen-doped, polyoxometalate, selective oxidation |
| Authors |
Evtushok Vasiliy Yu.
1,2
,
Suboch Arina N.
1,2
,
Podyacheva Olga Yu.
1,2
,
Stonkus Olga A.
1,2
,
Zaikovskii Vladimir I.
1,2
,
Chesalov Yurii A.
1,2
,
Kibis Lidiya S.
1,2
,
Kholdeeva Oxana A.
1,2
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Lavrentieva ave. 5, Novosibirsk 630090, Russia
|
| 2 |
Novosibirsk State University, Pirogova str. 2, Novosibirsk 630090, Russia
|
|
Funding (1)
|
1
|
Federal Agency for Scientific Organizations
|
0303-2016-0005
|
Alkyl-substituted benzoquinones serve as versatile building blocks for a variety of biologically active compounds. In this work, we present an approach for the environmentally benign synthesis of alkyl-p-benzoquinones, in particular trimethyl-p-benzoquinone (TMBQ, vitamin E precursor), which employs aqueous hydrogen peroxide as oxidant and a divanadium-substituted γ-Keggin polyoxotungstate, [γ-PW10O38V2(μ-O)(μ–OH)]4– (V2-POM), immobilized on nitrogen-doped carbon nanotubes (N-CNTs) as heterogeneous catalyst. A series of supported catalysts V2-POM/N-CNTs containing 5–25 wt % of V2-POM and 0–4.8 atom % of N has been prepared and characterized by elemental analysis, N2 adsorption, SEM, TEM, XPS, and FTIR techniques. The catalytic performance of V2-POM/N-CNTs was assessed in the selective oxidation of 2,3,6-trimethylphenol (TMP) with H2O2 under mild reaction conditions (60 °C, MeCN). The presence of nitrogen in the support ensures strong adsorption and molecular dispersion of V2-POM on the carbon surface, leading to highly active and selective heterogeneous catalysts, which do not suffer from metal leaching and can be used repeatedly without loss of the catalytic performance. By application of the optimal catalyst V2-POM/N-CNTs enclosing 15 wt % of V2-POM and 1.8 atom % of N, TMBQ could be obtained with 99% yield and 80% oxidant utilization efficiency. The catalyst demonstrated the truly heterogeneous nature of the catalysis and high turnover frequencies (500 h–1) and space–time yield (450 g L–1 h–1). FTIR and XPS techniques confirmed the stability of V2-POM and N-CNT support under the turnover conditions.