The electronic structure, surface properties, and in situ N2O decomposition of mechanochemically synthesised LaMnO3

Blackmore, RH; Rivas, ME; Tierney, GF; Mohammed, KMH; Decarolis, D; Hayama, S; Venturini, F; Held, G; Arrigo, R; Amboage, M; Hellier, P; Lynch, E; Amri, M; Casavola, M; Eralp Erden, T; Collier, P; Wells, PP

Abstract

The use of mechanochemistry to prepare catalytic materials is of significant interest; it offers an environmentally beneficial, solvent-free, route and produces highly complex structures of mixed amorphous and crystalline phases. This study reports on the effect of milling atmosphere, either air or argon, on mechanochemically prepared LaMnO3 and the catalytic performance towards N2O decomposition (deN2O). In this work, high energy resolution fluorescence detection (HERFD), X-ray absorption near edge structure (XANES), X-ray emission, and X-ray photoelectron spectroscopy (XPS) have been used to probe the electronic structural properties of the mechanochemically prepared materials. Moreover, in situ studies using near ambient pressure (NAP)-XPS, to follow the materials during catalysis, and high pressure energy dispersive EXAFS studies, to mimic the preparation conditions, have also been performed. The studies show that there are clear differences between the air and argon milled samples, with the most pronounced changes observed using NAP-XPS. The XPS results find increased levels of active adsorbed oxygen species, linked to the presence of surface oxide vacancies, for the sample prepared in argon. Furthermore, the argon milled LaMnO3 shows improved catalytic activity towards deN2O at lower temperatures compared to the air milled and sol-gel synthesised LaMnO3. Assessing this improved catalytic behaviour during deN2O of argon milled LaMnO3 by in situ NAP-XPS suggests increased interaction of N2O at room temperature within the O 1s region. This study further demonstrates the complexity of mechanochemically prepared materials and through careful choice of characterisation methods how their properties can be understood.

• Journal Article Type: Article
• Acceptance Date: Apr 7, 2020
• Online Publication Date: Jun 30, 2020
• Publication Date: Sep 14, 2020
• Deposit Date: Jul 14, 2020
• Publicly Available Date: Jul 14, 2020
• Journal: Physical Chemistry Chemical Physics
• Print ISSN: 1463-9076
• Electronic ISSN: 1463-9084
• Publisher: Royal Society of Chemistry
• Volume: 22
• Issue: 34
• Pages: 18774-18787
• DOI: https://doi.org/10.1039/d0cp00793e
• Publisher URL: https://doi.org/10.1039/D0CP00793E
• Related Public URLs: http://pubs.rsc.org/en/Journals/JournalIssues/CP
• Additional Information: Additional Information : ** From PubMed via Jisc Publications Router **Journal IDs: eissn 1463-9084 **Article IDs: pubmed: 32602489 **History: published 30-06-2020; Funders : UK Catalysis Hub Consortium;Science and Technology Facilities Council (STFC);Engineering and Physical Sciences Research Council (EPSRC); Grant Number: EP//K014706/1, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/I019693/1; Grant Number: ST/R002754/1; Grant Number: EP/R011710/1