The role of rhenium in the conversion of glycerol to synthesis gas over carbon supported platinum-rhenium catalysts

被引：162

作者：

Kunkes, Edward L. ^{[1
]}

Simonetti, Dante A. ^{[1
]}

Dumesic, James A. ^{[1
]}

Pyrz, William D. ^{[2
]}

Murillo, Luis E. ^{[2
]}

Chen, Jingguang G. ^{[2
]}

Buttrey, Douglas J. ^{[2
]}

机构：

[1] Univ Wisconsin, Dept Biol & Chem Engn, Madison, WI 53706 USA

[2] Univ Delaware, Ctr Catalyt Sci & Technol, Dept Chem Engn, Newark, DE 19716 USA

来源：

JOURNAL OF CATALYSIS | 2008年 / 260卷 / 01期

基金：

美国国家科学基金会;

关键词：

Glycerol; Reforming; Platinum; Rhenium; Bimetallic catalyst;

D O I：

10.1016/j.jcat.2008.09.027

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Reaction kinetics measurements were carried out to study the conversion of aqueous solutions of glycerol (30 and 80 wt%) over carbon-supported Pt and Pt-Re catalysts at temperatures from 483 to 523 K. The results of these studies show that the turnover frequencies for production of H-2, CO, CO2, and light alkanes (primarily methane) all increase upon the addition of Re to Pt/C catalysts. The molar ratio of H-2/CO increases, while the CO/CO2 ratio decreases with Re addition, indicating increased rate of water-gas shift. For glycerol conversion over a Pt-Re/C catalyst with an atomic Pt:Re ratio of 1:1, increasing pressure or decreasing temperature leads to an increase in the production of alkanes and light oxygenated hydrocarbons (ethanol, methanol, propanediols, and acetone) at the expense of CO and CO2. Temperature-programmed desorption studies and microcalorimetric measurements indicate that addition of Re to Pt modifies the interaction of CO with surface sites. X-ray absorption spectroscopy and transmission electron microscopy studies provide evidence indicating that Pt-Re/C catalysts consist primarily of bimetallic nanoparticles with sizes below 2 nm, and Re inhibits the sintering of these nanoparticles during reaction conditions for glycerol conversion. The results of these reaction kinetic studies and characterization studies indicate that the performance of Pt-Re/C catalysts for glycerol conversion is related to the formation of Pt-Re nanoparticles, for which Re promotes the overall rate of glycerol reforming by reducing the binding energy of CO to Pt, thereby leading to less extensive blocking of surface sites by reaction intermediates and/or products. In addition, the presence of Re facilitates water-gas shift and C-O bond cleavage reactions. (C) 2008 Elsevier Inc. All rights reserved.

引用

页码：164 / 177

页数：14

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