Topologically immobilized catalysis centre for long-term stable carbon dioxide reforming of methane.

Methane reforming at low temperatures is of growing importance to mitigate the environmental impact of the production of synthesis gas, but it suffers from short catalyst lifetimes due to the severe deposition of carbon byproducts. Herein, we introduce a new class of topology-tailored catalyst in which tens-of-nanometer-thick fibrous networks of Ni metal and oxygen-deficient Y2O3 are entangled with each other to form a rooted structure, i.e., Ni#Y2O3. We demonstrate that the rooted Ni#Y2O3 catalyst stably promotes the carbon-dioxide reforming of methane at 723 K for over 1000 h, where the performance of traditional supported catalysts such as Ni/Y2O3 diminishes within 100 h due to the precluded mass transport by accumulated carbon byproducts. In situ TEM demonstrates that the supported Ni nanoparticles are readily detached from the support surface in the reaction atmosphere, and migrate around to result in widespread accumulation of the carbon byproducts. The long-term stable methane reforming over the rooted catalyst is ultimately attributed to the topologically immobilized Ni catalysis centre and the synergistic function of the oxygen-deficient Y2O3 matrix, which successfully inhibits the accumulation of byproducts.

Multiple Cellular Transport and Binding Processes of Unesterified Docosahexaenoic Acid in Outer Blood-Retinal Barrier Retinal Pigment Epithelial Cells.

Docosahexaenoic acid (DHA, 22 : 6) is an essential omega-3 long-chain polyunsaturated fatty acid that plays a pivotal role in vision. The purpose of this study was to clarify the cellular uptake and binding processes of free and protein-bound unesterified DHA in retinal pigment epithelial cell (RPE) line ARPE-19 as a model of the human outer blood-retinal barrier and isolated porcine RPE cell fractions. Uptake of free [14C]DHA by ARPE-19 cells was saturable with a Michaelis-Menten constant of 283 µM, and was significantly inhibited by eicosapentaenoic acid, arachidonic acid, and linoleic acid, but not by oleic acid. Further, the uptakes of [14C]DHA associated with retinol-binding protein ([14C]DHA-RBP), [14C]DHA associated with low-density lipoprotein ([14C]DHA-LDL) and [14C]DHA associated with bovine serum albumin ([14C]DHA-BSA) in ARPE-19 cells increased time-dependently at 37°C, and were significantly reduced at 4°C, suggesting the involvement of energy-dependent transport processes. [14C]DHA-LDL uptake by ARPE-19 cells was significantly inhibited by excess unlabeled LDL, but not by an inhibitor of scavenger receptor B type I. Fatty acid transport protein (FATP) 2 and 4 mRNAs were expressed in ARPE-19 cells, and [14C]DHA uptake was observed in FATP2- and FATP4-expressing Xenopus oocytes. Photo-reactive crosslinking and mass spectrometry analyses identified 65-kDa retinal pigment epithelium-specific protein (RPE65) as a DHA-binding protein in porcine RPE cell membrane fractions. Thus, RPE cells possess multiple cellular transport/binding processes for unesterified DHA, involving at least partly FATP2, FATP4, LDL, RBP, and RPE65.

Nanophase-separated Ni3Nb as an automobile exhaust catalyst.

Catalytic remediation of automobile exhaust has relied on precious metals (PMs) including platinum (Pt). Herein, we report that an intermetallic phase of Ni and niobium (Nb) (i.e., Ni3Nb) exhibits a significantly higher activity than that of Pt for the remediation of the most toxic gas in exhaust (i.e., nitrogen monoxide (NO)) in the presence of carbon monoxide (CO). When subjected to the exhaust-remediation atmosphere, Ni3Nb spontaneously evolves into a catalytically active nanophase-separated structure consisting of filamentous Ni networks (thickness < 10 nm) that are incorporated in a niobium oxide matrix (i.e., NbO x (x < 5/2)). The exposure of the filamentous Ni promotes NO dissociation, CO oxidation and N2 generation, and the NbO x matrix absorbs excessive nitrogen adatoms to retain the active Ni0 sites at the metal/oxide interface. Furthermore, the NbO x matrix immobilizes the filamentous Ni at elevated temperatures to produce long-term and stable catalytic performance over hundreds of hours.

Mesoporous metallic rhodium nanoparticles.

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ∼2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

Sintering-Resistant Nanoparticles in Wide-Mouthed Compartments for Sustained Catalytic Performance.

Particle sintering is one of the most significant impediments to functional nanoparticles in many valuable applications especially catalysis. Herein, we report that sintering-resistant nanoparticle systems can be realized through a simple materials-design which maximizes the particle-to-particle traveling distance of neighbouring nanoparticles. As a demonstration, Pt nanoparticles were placed apart from each other in wide-mouthed compartments tailored on the surface of self-assembled silica nanosheets. These Pt nanoparticles retained their particle size after calcination at elevated temperatures because the compartment wall elongates the particle-to-particle traveling distance to preclude the possibility of sintering. Moreover, these Pt nanoparticles in wide-mouthed compartments were fully accessible to the environment and exhibited much higher catalytic activity for CO oxidation than the nanoparticles confined in the nanochannels of mesoporous silica. The proposed materials-design strategy is applicable not only to industrial catalysts operating in harsh conditions, but also opens up possibilities in developing advanced nanoparticle-based materials with sustained performance.