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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-H 2 data, and it exhibits the lowest reported MoO x Tmax of reduction reported to date, suggesting a highly reactive MoVI 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. 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 anmore » efficient, robust, and lowcost catalyst with significant potential for transesterification processes.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1326936
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 6
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; biodiesel; heterogeneous catalysis; molybdenum; supported catalysts; 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.
@article{osti_1326936,
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 MoOx Tmax 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. 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 lowcost catalyst with significant potential for transesterification processes.},
doi = {10.1021/acscatal.6b01717},
journal = {ACS Catalysis},
number = ,
volume = 6,
place = {United States},
year = {Tue Aug 23 00:00:00 EDT 2016},
month = {Tue Aug 23 00:00:00 EDT 2016}
}