Low Temperature Water-Gas Shift: Enhancing Stability through Optimizing Rb Loading on Pt/ZrO2

Date

2021-02-05

Authors

Watson, Caleb D.
Martinelli, Michela
Cronauer, Donald Charles
Kropf, A. Jeremy
Jacobs, Gary

Journal Title

Journal ISSN

Volume Title

Publisher

Abstract

Recent studies have shown that appropriate levels of alkali promotion can significantly improve the rate of low-temperature water gas shift (LT-WGS) on a range of catalysts. At sufficient loadings, the alkali metal can weaken the formate C–H bond and promote formate dehydrogenation, which is the proposed rate determining step in the formate associative mechanism. In a continuation of these studies, the effect of Rb promotion on Pt/ZrO2 is examined herein. Pt/ZrO2 catalysts were prepared with several different Rb loadings and characterized using temperature programmed reduction mass spectrometry (TPR-MS), temperature programmed desorption (TPD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), an X-ray absorption near edge spectroscopy (XANES) difference procedure, extended X-ray absorption fine structure spectroscopy (EXAFS) fitting, TPR-EXAFS/XANES, and reactor testing. At loadings of 2.79% Rb or higher, a significant shift was seen in the formate ν(CH) band. The results showed that a Rb loading of 4.65%, significantly improves the rate of formate decomposition in the presence of steam via weakening the formate C–H bond. However, excessive rubidium loading led to the increase in stability of a second intermediate, carbonate and inhibited hydrogen transfer reactions on Pt through surface blocking and accelerated agglomeration during catalyst activation. Optimal catalytic performance was achieved with loadings in the range of 0.55–0.93% Rb, where the catalyst maintained high activity and exhibited higher stability in comparison with the unpromoted catalyst.

Description

Keywords

rubidium (Rb), platinum (Pt), zirconia (ZrO2), low temperature water-gas shift (LT-WGS), alkali promotion, electronic effect, formate, associative mechanism, hydrogen

Citation

Catalysts 11 (2): 210 (2021)

Department

Biomedical Engineering and Chemical Engineering
Mechanical Engineering