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Title: Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

Abstract

A single-site molybdenum dioxo catalyst, (O c) 2Mo(=O)2@C, was prepared via direct grafting of MoO 2Cl 2(dme) (dme = 1,2-dimethoxyethane) on high-surface-area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N 2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H 2 (TPR-H 2), and temperature-programmed NH 3 desorption (TPD-NH 3). The single-site nature of the Mo species is corroborated by XPS and TPR-H2 data, and it exhibits the lowest reported MoO xT max of reduction reported to date, suggesting a highly reactive Mo VI center. (O c) 2Mo(=O) 2@C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60–90 °C) and with negligible deactivation. (O c) 2Mo(=O) 2@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol –1 and ΔS = –32(2) eu. Here, the low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thusmore » an efficient, robust, and low-cost catalyst with significant potential for transesterification processes.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [4];  [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Purdue Univ., West Lafayette, IN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1604195
Grant/Contract Number:  
AC02-06CH11357; FG02-03ER15457
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
heterogeneous catalysis; molybdenum; supported catalysts; biodiesel; transesterification

Citation Formats

Mouat, Aidan R., Lohr, Tracy L., Wegener, Evan C., Miller, Jeffrey T., Delferro, Massimiliano, Stair, Peter C., and Marks, Tobin J. Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis. United States: N. p., 2016. Web. doi:10.1021/acscatal.6b01717.
Mouat, Aidan R., Lohr, Tracy L., Wegener, Evan C., Miller, Jeffrey T., Delferro, Massimiliano, Stair, Peter C., & Marks, Tobin J. Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis. United States. doi:10.1021/acscatal.6b01717.
Mouat, Aidan R., Lohr, Tracy L., Wegener, Evan C., Miller, Jeffrey T., Delferro, Massimiliano, Stair, Peter C., and Marks, Tobin J. Tue . "Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis". United States. doi:10.1021/acscatal.6b01717. https://www.osti.gov/servlets/purl/1604195.
@article{osti_1604195,
title = {Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis},
author = {Mouat, Aidan R. and Lohr, Tracy L. and Wegener, Evan C. and Miller, Jeffrey T. and Delferro, Massimiliano and Stair, Peter C. and Marks, Tobin J.},
abstractNote = {A single-site molybdenum dioxo catalyst, (Oc)2Mo(=O)2@C, was prepared via direct grafting of MoO2Cl2(dme) (dme = 1,2-dimethoxyethane) on high-surface-area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H2 (TPR-H2), and temperature-programmed NH3 desorption (TPD-NH3). The single-site nature of the Mo species is corroborated by XPS and TPR-H2 data, and it exhibits the lowest reported MoOxTmax of reduction reported to date, suggesting a highly reactive MoVI center. (Oc)2Mo(=O)2@C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60–90 °C) and with negligible deactivation. (Oc)2Mo(=O)2@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH‡ = 10.5(8) kcal mol–1 and ΔS‡ = –32(2) eu. Here, the low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and low-cost catalyst with significant potential for transesterification processes.},
doi = {10.1021/acscatal.6b01717},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 10,
volume = 6,
place = {United States},
year = {2016},
month = {8}
}

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Cited by: 14 works
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Works referencing / citing this record:

Second-generation hexavalent molybdenum oxo-amidinate precursors for atomic layer deposition
journal, January 2017

  • Jurca, T.; Peters, A. W.; Mouat, A. R.
  • Dalton Transactions, Vol. 46, Issue 4
  • DOI: 10.1039/c6dt03952a