期刊
ACS CATALYSIS
卷 12, 期 2, 页码 1247-1257出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c04319
关键词
heterogeneous catalysis; single-site catalyst; molybdenum; alcohol dehydration; dehydrogenation
资金
- Office of Basic Energy Sciences, Department of Energy [DE-FG02-03ER154757]
- Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource [NSF ECCS-2025633]
- State of Illinois
- International Institute for Nanotechnology (IIN)
- Northwestern University Ngyuyen group
- Northwestern's MRSEC program [NSF DMR-1720139]
- Northwestern University
- NU, E. I. DuPont de Nemours Co.
- The Dow Chemical Company
- DOE Office of Science by Argonne National Laboratory [DE-AC02-06CH11357]
- Office of the Provost
- Office for Research
- Northwestern U. Information Technology
With the increasing importance of renewable resources, chemical research is focusing on substituting petrochemicals with biomass-derived analogues. In order to achieve this, understanding the mechanisms behind catalytic systems is crucial for rational design. This study discusses the structure and reactivity of a carbon-supported molybdenum-dioxo catalyst (AC/MoO2) and its role in alcohol dehydration, providing valuable insights for future biomass processes.
With the increase in the importance of renewable resources, chemical research is shifting focus toward substituting petrochemicals with biomass-derived analogues and platform-molecule transformations such as alcohol processing. To these ends, in-depth mechanistic understanding is key to the rational design of catalytic systems with enhanced activity and selectivity. Here we discuss in detail the structure and reactivity of a single-site active carbon-supported molybdenum-dioxo catalyst (AC/MoO2) and the mechanism(s) by which it mediates alcohol dehydration. A range of tertiary, secondary, and primary alcohols as well as selected bio-based terpineols are investigated as substrates under mild reaction conditions. A combined experimental substituent effect/kinetic/kinetic isotope effect/EXAFS/DFT computational analysis indicates that (1) water assistance is a key element in the transition state; (2) the experimental kinetic isotopic effect and activation enthalpy are 2.5 and 24.4 kcal/mol, respectively, in good agreement with the DFT results; and (3) several computationally identified intermediates including Mo-oxo-hydroxy-alkoxide and cage-structured long-range water-coordinated Mo-dioxo species are supported by EXAFS. This structurally and mechanistically well-characterized single-site system not only effects efficient transformations but also provides insight into rational catalyst design for future biomass processes.
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