No abstract

Nano metal oxides are becoming widely used in industrial, commercial and personal products (semiconductors, optics, solar cells, catalysts, paints, cosmetics, sun-cream lotions, etc.). However, the relationship of surface features (exposed planes, defects and chemical functionalities) with physiochemical properties is not well studied primarily due to lack of a simple technique for their characterization. In this study, solid state (31)P MAS NMR is used to map surfaces on various ZnO samples with the assistance of trimethylphosphine (TMP) as a chemical probe. As similar to XRD giving structural information on a crystal, it is demonstrated that this new surface-fingerprint technique not only provides qualitative (chemical shift) but also quantitative (peak intensity) information on the concentration and distribution of cations and anions, oxygen vacancies and hydroxyl groups on various facets from a single deconvoluted (31)P NMR spectrum. On the basis of this technique, a new mechanism for photocatalytic •OH radical generation from direct surface-OH oxidation is revealed, which has important implications regarding the safety of using nano oxides in personal care products.

The use of surface-directing species and surface additives to alter nanoparticle morphology and physicochemical properties of particular exposed facets has recently been attracting significant attention. However, challenges in their chemical analysis, sometimes at trace levels, and understanding their roles to elucidate surface structure–activity relationships in optical (solar cells) or (photo)catalytic performance and their removal are significant issues that remain to be solved. Here, we show a detailed analysis of TiO2 facets promoted with surface species (OH, O, SO4, F) with and without post-treatments by 31P adsorbate nuclear magnetic resonance, supported by a range of other characterization tools. We demonstrate that quantitative evaluations of the electronic and structural effects imposed by these surface additives and their removal mechanisms can be obtained, which may lead to the rational control of active TiO2 (001) and (101) facets for a range of applications.

Three morphology-controlled CeO2, namely nanorods (NRs), nanocubes (NCs), and nanopolyhedra (NPs), with different mainly exposed crystal facets of (110), (100), and (111), respectively, have been used as supports to prepare Ru (3 wt.%) nanoparticle-loaded catalysts. The catalysts were characterized by H2-temperature programmed reduction (H2-TPR), CO– temperature programmed desorption (CO-TPD), N2 adsorption–desorption, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (XDS). The characterization results showed that CeO2-NRs, CeO2-NCs, and CeO2-NPs mainly expose (110), (100) and (111) facets, respectively. Moreover, CeO2-NRs and CeO2-NCs present higher oxygen vacancy concentration than CeO2-NPs. In the CO2 reforming of methane reaction, Ru/CeO2-NR and Ru/CeO2-NC catalysts showed better catalytic performance than Ru/CeO2-NPs, indicating that the catalysts with high oxygen vacancy concentration are beneficial for promoting catalytic activity.