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In-situ MAS NMR Investigations on Catalytic Conversion of Biogenic Molecules in the Presence and Absence of Water


EMSL Project ID
47841

Abstract

The catalyzed conversion of biomass to hydrocarbon energy carriers requires a cascade of reactions that deconstruct and reduce the polymeric, highly oxofunctionalized biomass material. This chemistry faces steep challenges, as it has to be performed in an aqueous environment under conditions that are highly corrosive towards catalysts. The anticipated scale of the transformations demands that the complex catalysts involved be highly efficient, stable, regenerable, and economically viable heterogeneous catalysts. Currently, none of the known catalysts meets these requirements. In order to develop new catalysts satisfying these requirements, a fundamental understanding of the active centers, reaction intermediates and reaction dynamics/kinetics associated with the multi-step conversion of biomass related polar molecules, i.e., the precursor molecules to fuels, on multifunctional catalytic surfaces using a range of model catalysts is critically needed. We propose to use our unique in situ magic angle spinning (MAS) NMR capabilities that have been or are being developed by the primary author and his collaborators, combined with computational modeling of NMR parameters, to carry out fundamental studies to understand the surface chemistry of metal oxide catalysts useful for individual reactions in biomass conversion, and the effects of water on the reactivity and stability of these catalytic materials. Specifically, we will use a range of model catalysts, containing either supported or unsupported metal oxides with varying acid/base and redox chemical properties, including oxides composed of pre-formed molecular cluster ions with well?defined geometrical structures such as the polyoxometallates (POMs) with an initial emphasis on PW12 materials with the Keggin structure. Besides in situ NMR and computational modeling, we will also use EMSL's advanced imaging and other spectroscopy capabilities, such as TEM, SEM and XPS to study the surface morphology of the spent catalysts from the NMR reactor after the in situ NMR analysis.

Project Details

Project type
Large-Scale EMSL Research
Start Date
2013-10-01
End Date
2015-09-30
Status
Closed

Team

Principal Investigator

Jian-zhi Hu
Institution
Pacific Northwest National Laboratory

Co-Investigator(s)

David Dixon
Institution
University of Alabama

Team Members

Karen Abreu Resende
Institution
Universidade Federal de Uberlandia

Arielle Hackel
Institution
Pacific Northwest National Laboratory

Chuan Wan
Institution
China Agricultural University

Xiongjie Xiao
Institution
Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences

Miroslaw Derewinski
Institution
Pacific Northwest National Laboratory

Sebastian Prodinger
Institution
Pacific Northwest National Laboratory

Miru Tang
Institution
Southern Illinois University, Carbondale

Zhenchao Zhao
Institution
Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Hui Shi
Institution
Pacific Northwest National Laboratory

Xuchu Deng
Institution
Xiamen University

Jianguo Wang
Institution
Zhejiang University of Technology

Zizwe Chase
Institution
Environmental Molecular Sciences Laboratory

Aleksei Vjunov
Institution
Pacific Northwest National Laboratory

Johannes Lercher
Institution
Pacific Northwest National Laboratory

Donghai Mei
Institution
Tiangong University

Qingfeng Ge
Institution
Southern Illinois University

Charles Peden
Institution
Pacific Northwest National Laboratory

Donald Camaioni
Institution
Pacific Northwest National Laboratory

Yong Wang
Institution
Washington State University

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