Intermetallic GaPd2 Nanoparticles on SiO2 for Low- Pressure CO2 Hydrogenation to Methanol: Catalytic Performance and In Situ Characterization

Elisabetta M. Fiordaliso, Irek Sharafutdinov, Hudson W. P. Carvalho, Jan-D. Grunwaldt, Thomas W. Hansen, Ib Chorkendorff, Jakob B. Wagner, and Christian D. Damsgaard, 2015

Image courtesy of ACS Catal.

Abstract

A nanodispersed intermetallic GaPd2/SiO2 catalyst is prepared by simple impregnation of industrially relevant high-surface-area SiO2 with Pd and Ga nitrates, followed by drying, calcination, and reduction in hydrogen. The catalyst is tested for CO2 hydrogenation to methanol at ambient pressure, revealing that the intrinsic activity of the GaPd2/SiO2 is higher than that of the conventional Cu/ZnO/Al2O3, while the production of the undesired CO is lower. A combination of complementary in situ and ex situ techniques are used to investigate the GaPd2/SiO2 catalyst. In situ X-ray diffraction and in situ extended X-ray absorption fine structure spectroscopy show that the GaPd2 intermetallic phase is formed upon activation of the catalyst via reduction and remains stable during CO2 hydrogenation. Identical location–transmission electron microscopy images acquired ex situ (i.e., micrographs of exactly the same catalyst area recorded at the different steps of activation and reaction procedure) show that nanoparticle size and dispersion are defined upon calcination with no significant changes observed after reduction and methanol synthesis. Similar conclusions can be drawn from electron diffraction patterns and images acquired using environmental TEM (ETEM), indicating that ETEM results are representative for the catalyst treated at ambient pressure. The chemical composition and the crystalline structure of the nanoparticles are identified by scanning TEM energy dispersive X-ray spectroscopy, selected area electron diffraction, and atomically resolved TEM images.

Impact Statement

CO2 hydrogenation capabilities of GaPd2/SiO2 was tested inside an ETEM. Ex situ study of the same location revealed that in situ ETEM results represent similar catalytic behavior.