Breaking the C[sbnd]C bond of glucose on tungsten oxide-based catalysts in aqueous phase

Qiao，Ying1; Xia，Guang Jie1,3; Cao，Wei1; Zeng，Ke Han1; Guo，Qian Li1; Yang，Xiao Feng2; Wang，Ai Qin2; Wang，Yang Gang1

2023-11-01

10.1016/j.jcat.2023.115114

Journal of Catalysis   Impact Factor & Quartile

0021-9517

1090-2694

In chemistry, selective activation of C[sbnd]C bonds enables the direct production of valuable chemicals from widely available and inexpensive natural materials but remains a fundamental challenge due to their kinetic inertness. The selective cleavage of C[sbnd]C bond in glucose by tungsten oxide-based catalysts in aqueous phase pioneers a path for converting cellulose biomass into valuable ethylene glycol. However, debates regarding the active phase and how it selectively breaks the C into C fragments have persisted for over a decade. In this study, we present a comprehensive mechanistic investigation by modeling three potential active phases, i.e. the reduced WO surface, the dissolved tungstic acid, and tungsten bronze, in explicit solvent waters. By constrained molecular dynamics simulations, we have demonstrated that the low-coordinated W center can chelate with glucose, forming a metallacyclic complex with a 5-membered ring after the protonation of carbonyl group. The formation of 5-membered ring serves as the premise for the selectivity to C fragments via homolytic cleavage of C[sbnd]C bond. Furthermore, the reduced W center is suggested to be crucial in facilitating the cleavage process by stabilizing the dissociated C intermediates via a redox process. In conclusion, we propose that the surface decoration of reduced and low-coordinated W sites can act as active heterogeneous catalysts for the selective conversion of cellulose in aqueous phase. These recent findings have the potential to provide valuable insights and strategies for C[sbnd]C bond activation in both biomass conversion and organic synthesis.

5-membered ring Aqueous phase C–C bond cleavage Molecular dynamics Tungsten oxide-based catalysts

SCI

English

First

Booz Allen Foundation[2021A1515010213];

Chemistry ; Engineering

Chemistry, Physical ; Engineering, Chemical

WOS:001079209400001

ACADEMIC PRESS INC ELSEVIER SCIENCE

CHEMISTRY

2-s2.0-85170564207

Scopus

1.Department of Chemistry and Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.State Key Laboratory of Catalysis,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian,116023,China
3.School of Physical Sciences,Great Bay University,Dongguan,Guangdong,523000,China

Qiao，Ying,Xia，Guang Jie,Cao，Wei,et al. Breaking the C[sbnd]C bond of glucose on tungsten oxide-based catalysts in aqueous phase[J]. Journal of Catalysis,2023,427.

Qiao，Ying.,Xia，Guang Jie.,Cao，Wei.,Zeng，Ke Han.,Guo，Qian Li.,...&Wang，Yang Gang.(2023).Breaking the C[sbnd]C bond of glucose on tungsten oxide-based catalysts in aqueous phase.Journal of Catalysis,427.

Qiao，Ying,et al."Breaking the C[sbnd]C bond of glucose on tungsten oxide-based catalysts in aqueous phase".Journal of Catalysis 427(2023).