Mesoporous tetragonal RE:YPO4 nanophosphors
(RE = Eu,
Ce, Tb, and Ce + Tb) with a lenticular morphology, narrow size distribution,
and high surface area have been prepared by an homogeneous precipitation
procedure consisting of aging, at low temperature (80–120 °C)
in a microwave oven, ethylene glycol solutions containing only yttrium
acetylacetonate and phosphoric acid. This synthesis method involves
important advantages such as its simplicity, rapidness (reaction time
= 7 min), and high reaction yields. The mechanism of nanoparticle
growth has been also addressed finding that the lenticular nanoparticles
are formed through an ordered aggregation of smaller entities, which
explains their porosity. In all cases, the doping levels were systematically
varied in order to optimize the nanophosphors luminescence. All optimum
nanophosphors presented a high luminescence quantum yield (QY). In
particular, for the Eu and Tb doped systems, the obtained QY values
(60% for Eu and 80% for Tb) were the highest so far reported for this
kind of nanomaterial. The morphological, microstructural, and luminescent
properties of these nanophosphors and their dispersibility in water
make them suitable for biomedical applications.
AuPd nanoparticles supported on NiO exhibit high activity and stability in the base free oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA).
Creating a new chemical ecosystem based on platform chemicals derived from waste biomass has significant challenges: catalysts need to be able to convert these highly functionalized molecules to specific target chemicals and they need to be economicalnot relying on large quantities of precious metalsand maintain activity over many cycles. Herein, we demonstrate how Pd/NiO is able to direct the selectivity of furfural hydrogenation and maintain performance at low Pd loading by a unique dual-site mechanism. Sol-immobilization was used to prepare 1 wt % Pd nanoparticles supported on NiO and TiO 2 , with the Pd/NiO catalyst showing enhanced activity with a significantly different selectivity profile; Pd/NiO favors tetrahydrofurfuryl alcohol (72%), whereas Pd/TiO 2 produces furfuryl alcohol as the major product (68%). Density functional theory studies evidenced significant differences on the adsorption of furfural on both NiO and Pd surfaces. On the basis of this observation we hypothesized that the role of Pd was to dissociate hydrogen, with the NiO surface adsorbing furfural. This dual-site hydrogenation mechanism was supported by comparing the performance of 0.1 wt % Pd/ NiO and 0.1 wt % Pd/TiO 2 . In this study, the 0.1 and 1 wt % Pd/NiO catalysts had comparable activities, whereas there was a 10fold reduction in performance for 0.1 wt % Pd/TiO 2 . When TiO 2 is used as the support, the Pd nanoparticles are responsible for both hydrogen dissociation and furfural adsorption and the activity is strongly correlated with the effective metal surface area. This work has significant implications for the upgrading of bioderived feedstocks, suggesting alternative ways for promoting selective transformations and reducing the reliance on precious metals.
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