Abstract
Perovskite catalysts have been extensively studied for reduction-oxidation (redox) reactions; however, their acid-base catalytic properties are still under-explored. This review collects work aiming to study the acid-base catalytic properties of perovskites. Reports regarding combined acid-base/redox catalysis over perovskites lie beyond the scope of the present review. For the characterization of acid-base properties, researchers have studied the interaction of probe molecules with perovskite surfaces by means of multiple techniques that provide information about the density, strength and type of adsorption sites. The top-surface composition of perovskites, which relates to the abundance of the acid-base sites, has been studied by means of low energy ion scattering (LEIS), and, the less surface sensitive, conventional X-ray photoelectron spectroscopy (XPS). Probe reactions, with the conversion of 2-propanol as the common choice, have also been employed for characterizing the acid-base catalytic properties of perovskites. The complex nature of perovskite surfaces, which explains the still absent fundamental relations between the structure of the catalyst and reaction rates/selectivity, encounters a great challenge due to the surface reconstruction of these materials. In this review, we devote a special section to highlight recent publications that report the impact of surface reconstruction and particle shape on acid-base catalysis over perovskites. In addition, we review promising catalytic performances of perovskite catalysts for other reactions of interest. Challenges in acid-base catalysis over perovskites focus on the development of time-resolved monolayer-sensitive characterization of surfaces under operando conditions and the discernment of combined acid-base/redox reaction mechanisms. Opportunities lay on tuning the acid-base characteristics of perovskites with computation-based catalytic descriptors to achieve desired selectivities and enhanced rates.
| Original language | English |
|---|---|
| Pages (from-to) | 2877-2894 |
| Number of pages | 18 |
| Journal | Journal of Materials Chemistry A |
| Volume | 6 |
| Issue number | 7 |
| DOIs | |
| State | Published - 2018 |
Funding
This research was sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. The authors thank Victor Fung (University of California Riverside) for providing images of the perovskite bulk structure, as well as surface terminations (Fig. 1). This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/ downloads/doe-public-access-plan).