Quantitative Conversion of Methanol to Methyl Formate on Graphene-Confined Nano-Oxides
Yelei Zhang,
Guojuan Liu,
Lei Shi,
Ping Wu,
Gaofeng Zeng,
Chunlei Zhang,
Nating Yang,
Shenggang Li,
Yuhan Sun
Affiliations
Yelei Zhang
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China; School of Chemical Sciences, University of Chinese Academy of Science, Beijing 100049, China
Guojuan Liu
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
Lei Shi
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
Ping Wu
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
Gaofeng Zeng
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China; School of Chemical Sciences, University of Chinese Academy of Science, Beijing 100049, China; Corresponding author
Chunlei Zhang
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China; School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai 200444, China
Nating Yang
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
Shenggang Li
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China; School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China; Corresponding author
Yuhan Sun
CAS Key Laboratory of Low-carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China; School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
Summary: We demonstrate the nearly quantitative conversion of methanol to methyl formate (MF) with a reliable durability on the reduced-graphene-oxide-confined VTiOx nanoparticles (rGO@VTiO). The rGO@VTiO exhibits superior low-temperature reactivity than the rGO-free VTiO, and the MF yield of 98.8% is even comparable with the noble metal catalysts. Both experiments and simulations demonstrate that the ultrathin rGO shell significantly impacts the shell/core interfacial electronic structure and the surface chemistry of the resultant catalysts, leading to remarkable reactivity in methanol to MF. rGO enhances the dispersion and loading rates of active monomeric/oligomeric VOx. In particular, the electron migration between the rGO shell and oxides core reinforces the acidity of rGO@VTiO in the absence of sulfate acidic sites. Moreover, both in situ NAP-XPS and DRIFTS investigations suggest that the lattice oxygen was involved in the oxidation of methanol and the MF was formed via the hemiacetal mechanism.
