Supplementary information files for Evaluating the Activity and Stability of Perovskite LaMO3-Based Pt Catalysts in the Aqueous Phase Reforming of Glycerol

Supplemental files for article Evaluating the Activity and Stability of Perovskite LaMO3-Based Pt Catalysts in the Aqueous Phase Reforming of Glycerol

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.

本文研究了在一系列1 wt% Pt/LaMO3（其中M分别为Al、Cr、Mn、Fe、Co、Ni）催化剂上进行的甘油水相裂解反应，并与标准1 wt% Pt/γ-Al2O3催化剂进行了比较。基于镧的钙钛矿LaMO3（M=Al、Cr、Mn、Fe、Co、Ni）通过溶胶-凝胶燃烧合成，制备出纯相钙钛矿，其比表面积为8-18 m2g−1。与Pt/γ-Al2O3（10%）相比，多种钙钛矿载体催化剂的甘油转化率更高，其中Pt/LaNiO3的转化率最高（19%）。与标准催化剂相比，钙钛矿基催化剂降低了烷烃的形成，并显著增加了乳酸的形成。然而，大多数钙钛矿材料在Pt颗粒迁移的过程中发生相分离，转变为LaCO3OH和相应的M位氧化物。唯一例外的是LaCrO3载体，其结构稳定性得以保持。对于M=Al、Cr和Ni的催化剂，尽管部分材料发生相分离，催化性能在多个循环中保持稳定。在M位溶解到溶液中的材料（M=Mn和Co）被发现催化性能不稳定，这被认为是由于载体比表面积显著减少和Pt在剩余载体表面上的无控制迁移所致。在Pt/LaNiO3合金中，观察到反应后Ni和Pt之间的合金化。