Abstract

The aqueous phase reforming of glycerol, to hydrogen, alkanes and liquid phase dehydration/dehydrogenation products, was studied over a series of 1 wt% Pt/LaMO3 (where M = Al, Cr, Mn, Fe, Co, Ni) catalysts and compared to a standard 1 wt% Pt/γ-Al2O3 catalyst. The sol–gel combustion synthesis of lanthanum-based perovskites LaMO3 produced pure phase perovskites with surface areas of 8–18 m2g−1. Glycerol conversions were higher than the Pt/γ-Al2O3 (10%) for several perovskite supported catalysts, with the highest being for Pt/LaNiO3 (19%). Perovskite-based catalysts showed reduced alkane formation and significantly increased lactic acid formation compared to the standard catalyst. However, most of the perovskite materials undergo phase separation to LaCO3OH and respective M site oxides with Pt particle migration. The exception being the LaCrO3 support which was found to remain structurally stable. Catalytic performance remained stable over several cycles, for catalysts M = Al, Cr and Ni, despite phase separation of some of these materials. Materials where M site leaching into solution was observed (M = Mn and Co), were found to be catalytically unstable, which was hypothesised to be due to significant loss in support surface area and uncontrolled migration of Pt to the remaining support surface. In the case of Pt/LaNiO3 alloying between the exsoluted Ni and Pt was observed post reaction.

Highlights

  • Hydrogen has the potential to replace conventional fossil fuels as a clean energy carrier, with applications in electric generation, storage and transportation, through utilisation of fuel cell technology and direct combustion in turbines and heating [1,2,3]

  • Given the diversity in catalytic activity and selectivity of lanthanum perovskites of various B site composition, for a range of reactions including glycerol oxidation [29, 30], we have evaluated the Aqueous phase reforming (APR) performance of Pt nanoparticles supported on ­LaMO3 catalysts

  • Perovskite phases are predominant in all synthesised ­LaMO3 materials, with clear splitting of reflections indicating the presence of the expected rhombohedral or orthorhombic phases

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Summary

Introduction

Hydrogen has the potential to replace conventional fossil fuels as a clean energy carrier, with applications in electric generation, storage and transportation, through utilisation of fuel cell technology and direct combustion in turbines. Guo et al evaluated the performance of a range of other support materials with different basicity and found the more basic materials facilitated WGS reaction and higher hydrogen selectivity [19]. Given the diversity in catalytic activity and selectivity of lanthanum perovskites of various B site composition, for a range of reactions including glycerol oxidation [29, 30], we have evaluated the APR performance of Pt nanoparticles supported on ­LaMO3 catalysts (where M = Al, Cr, Mn, Fe, Co, Ni). Analysis of the main liquid products highlighted differences between the perovskite and alumina catalysts with structure–activity relationships and catalyst stability being discussed

Catalyst Preparation
Catalyst Characterisation
Catalytic Testing
Fresh Catalyst Characterisation
Catalytic Performance in the APR of Glycerol
Carbon Product Analysis
Catalyst Re‐use
Post Reaction Catalyst Characterisation
Conclusions
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