TY - JOUR

T1 - Highly Efficient Catalysts Based on Divanadium-Substituted Polyoxometalate and N-Doped Carbon Nanotubes for Selective Oxidation of Alkylphenols

AU - Evtushok, Vasiliy Yu

AU - Suboch, Arina N.

AU - Podyacheva, Olga Yu

AU - Stonkus, Olga A.

AU - Zaikovskii, Vladimir I.

AU - Chesalov, Yurii A.

AU - Kibis, Lidiya S.

AU - Kholdeeva, Oxana A.

N1 - Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/2/2

Y1 - 2018/2/2

N2 - 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.

AB - 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.

KW - alkylphenols

KW - benzoquinones

KW - carbon nanotubes

KW - heterogeneous catalysis

KW - hydrogen peroxide

KW - nitrogen-doped

KW - polyoxometalate

KW - selective oxidation

KW - MESOPOROUS MOLECULAR-SIEVES

KW - ELECTRICAL-CONDUCTIVITY

KW - ALLYLIC OXIDATION

KW - IONIC LIQUID

KW - ALPHA-PINENE

KW - NITROGEN

KW - AEROBIC OXIDATION

KW - HYDROGEN-PEROXIDE

KW - SILICA

KW - HETEROGENEOUS CATALYSTS

UR - http://www.scopus.com/inward/record.url?scp=85041417110&partnerID=8YFLogxK

U2 - 10.1021/acscatal.7b03933

DO - 10.1021/acscatal.7b03933

M3 - Article

AN - SCOPUS:85041417110

VL - 8

SP - 1297

EP - 1307

JO - Topics in Catalysis

JF - Topics in Catalysis

SN - 1022-5528

IS - 2

ER -