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Title: Liquid-Phase Modeling in Heterogeneous Catalysis

Abstract

The notion that solvents can affect the chemical reactivity has been prevalent in the homogeneous catalysis community, going back as far as 1863.(1) Remarkable changes in reaction rate have been reported in the seminal work of Menschutkin, who demonstrated a change in reaction rate constant up to a factor of 700 as a function of the solvents employed for the reaction of triethylamine with ethyl iodide at 373 K.(2) It is well-known nowadays that solvents can affect the reaction rate, reaction mechanism, and selectivity of chemical reactions occurring in condensed phase. While solvent effects usually lead to changes in reaction rates of up to 3 orders of magnitude, rate increases of 9 orders of magnitude have been reported.(3, 4) In homogeneous metal catalysis such as hydroformylation, hydrogenation, and cross-coupling reactions, solvent effects have been studied systematically and exploited for industrial applications.(5) Substantial solvent effects have also been reported in heterogeneous catalysis for several hydrogenation,(6-9) oxidation,(10-12) and electrochemical reactions (where electric field effects lead in addition to an electric double layer(13-16)). However, in heterogeneous catalysis, systematic studies of solvation effects are rare, and solvent effects are generally not well understood. In this context, we note that liquid-phase processing is highly desirablemore » for process cost reduction and high product selectivity for the heterogeneously catalyzed conversion of highly functionalized lignocellulosic biomass, because the feedstocks contain significant amounts of water, are produced in aqueous-phase environments, and reactant molecules are highly water-soluble, reactive, and thermally unstable.(17-19) Processing at relatively low temperatures in condensed phase has therefore the potential to (1) minimize undesirable thermal degradation reactions, (2) increase the targeted product selectivity, and (3) facilitate the product separation from excess water because reaction products often contain less oxygen and are therefore less hydrophilic than the feed streams.« less

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1485477
Grant/Contract Number:  
SC0007167
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solvent; heterogeneous catalysis; computation; implicit solvation; explicit solvation

Citation Formats

Saleheen, Mohammad, and Heyden, Andreas. Liquid-Phase Modeling in Heterogeneous Catalysis. United States: N. p., 2018. Web. doi:10.1021/acscatal.7b04367.
Saleheen, Mohammad, & Heyden, Andreas. Liquid-Phase Modeling in Heterogeneous Catalysis. United States. doi:10.1021/acscatal.7b04367.
Saleheen, Mohammad, and Heyden, Andreas. Tue . "Liquid-Phase Modeling in Heterogeneous Catalysis". United States. doi:10.1021/acscatal.7b04367. https://www.osti.gov/servlets/purl/1485477.
@article{osti_1485477,
title = {Liquid-Phase Modeling in Heterogeneous Catalysis},
author = {Saleheen, Mohammad and Heyden, Andreas},
abstractNote = {The notion that solvents can affect the chemical reactivity has been prevalent in the homogeneous catalysis community, going back as far as 1863.(1) Remarkable changes in reaction rate have been reported in the seminal work of Menschutkin, who demonstrated a change in reaction rate constant up to a factor of 700 as a function of the solvents employed for the reaction of triethylamine with ethyl iodide at 373 K.(2) It is well-known nowadays that solvents can affect the reaction rate, reaction mechanism, and selectivity of chemical reactions occurring in condensed phase. While solvent effects usually lead to changes in reaction rates of up to 3 orders of magnitude, rate increases of 9 orders of magnitude have been reported.(3, 4) In homogeneous metal catalysis such as hydroformylation, hydrogenation, and cross-coupling reactions, solvent effects have been studied systematically and exploited for industrial applications.(5) Substantial solvent effects have also been reported in heterogeneous catalysis for several hydrogenation,(6-9) oxidation,(10-12) and electrochemical reactions (where electric field effects lead in addition to an electric double layer(13-16)). However, in heterogeneous catalysis, systematic studies of solvation effects are rare, and solvent effects are generally not well understood. In this context, we note that liquid-phase processing is highly desirable for process cost reduction and high product selectivity for the heterogeneously catalyzed conversion of highly functionalized lignocellulosic biomass, because the feedstocks contain significant amounts of water, are produced in aqueous-phase environments, and reactant molecules are highly water-soluble, reactive, and thermally unstable.(17-19) Processing at relatively low temperatures in condensed phase has therefore the potential to (1) minimize undesirable thermal degradation reactions, (2) increase the targeted product selectivity, and (3) facilitate the product separation from excess water because reaction products often contain less oxygen and are therefore less hydrophilic than the feed streams.},
doi = {10.1021/acscatal.7b04367},
journal = {ACS Catalysis},
number = 3,
volume = 8,
place = {United States},
year = {2018},
month = {1}
}

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Works referencing / citing this record:

Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
journal, February 2019

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