Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis.
Ontology highlight
ABSTRACT:
SUBMITTER: Jin K
PROVIDER: S-EPMC4441116 | biostudies-literature | 2015
REPOSITORIES: biostudies-literature
Publications
Partially Oxidized Sub-10 nm MnO Nanocrystals with High Activity for Water Oxidation Catalysis.
Jin Kyoungsuk K Chu Arim A Park Jimin J Jeong Donghyuk D Jerng Sung Eun SE Sim Uk U Jeong Hui-Yun HY Lee Chan Woo CW Park Yong-Sun YS Yang Ki Dong KD Kumar Pradhan Gajendra G Kim Donghun D Sung Nark-Eon NE Hee Kim Sun S Nam Ki Tae KT
Scientific reports 20150522
The oxygen evolution reaction (OER) is considered a major bottleneck in the overall water electrolysis process. In this work, highly active manganese oxide nano-catalysts were synthesized via hot injection. Facile surface treatment generated Mn(III) species on monodisperse 10 nm MnO nanocrystals (NCs). Size dependency of MnO NCs on OER activity was also investigated. Surprisingly, the partially oxidized MnO NCs only required 530 mV @ 5 mA cm(-2) under near neutral conditions. ...[more]
Similar Datasets
Project description:Ultrathin membranes with potentially high permeability are urgently demanded in water purification. However, their facile, controllable fabrication remains a grand challenge. Herein, we demonstrate a metal-coordinated approach towards defect-free and robust membranes with sub-10 nm thickness. Phytic acid, a natural strong electron donor, is assembled with metal ion-based electron acceptors to fabricate metal-organophosphate membranes (MOPMs) in aqueous solution. Metal ions with higher binding energy or ionization potential such as Fe3+ and Zr4+ can generate defect-free structure while MOPM-Fe3+ with superhydrophilicity is preferred. The membrane thickness is minimized to 8 nm by varying the ligand concentration and the pore structure of MOPM-Fe3+ is regulated by varying the Fe3+ content. The membrane with optimized MOPM-Fe3+ composition exhibits prominent water permeance (109.8 L m-2 h-1 bar-1) with dye rejections above 95% and superior stability. This strong-coordination assembly may enlighten the development of ultrathin high-performance membranes.
| S-EPMC6744495 | biostudies-literature
Project description:Published papers highlight the roles of the catalysts in plasma catalysis systems, and it is essential to provide deep insight into the mechanism of the reaction. In this work, a coaxial dielectric barrier discharge (DBD) reactor packed with γ-MnO2 and CeO2 with similar nanorod morphologies and particle sizes was used for methanol oxidation at atmospheric pressure and room temperature. The experimental results showed that both γ-MnO2 and CeO2 exhibited good performance in methanol conversion (up to 100%), but the CO2 selectivity of CeO2 (up to 59.3%) was much higher than that of γ-MnO2 (up to 28.6%). Catalyst characterization results indicated that CeO2 contained more surface-active oxygen species, adsorbed more methanol and utilized more plasma-induced active species than γ-MnO2. In addition, in situ Raman spectroscopy and Fourier transform infrared spectroscopy (FT-IR) were applied with a novel in situ cell to reveal the major factors affecting the catalytic performance in methanol oxidation. More reactive oxygen species (O22-, O2-) from ozone decomposition were produced on CeO2 compared with γ-MnO2, and less of the intermediate product formate accumulated on the CeO2. The combined results showed that CeO2 was a more effective catalyst than γ-MnO2 for methanol oxidation in the plasma catalysis system.
| S-EPMC10057529 | biostudies-literature
Project description:The ultimate frontier in nanomaterials engineering is to realize their composition control with atomic scale precision to enable fabrication of nanoparticles with desirable size, shape and surface properties. Such control becomes even more useful when growing hybrid nanocrystals designed to integrate multiple functionalities. Here we report achieving such degree of control in a family of rare-earth-doped nanomaterials. We experimentally verify the co-existence and different roles of oleate anions (OA(-)) and molecules (OAH) in the crystal formation. We identify that the control over the ratio of OA(-) to OAH can be used to directionally inhibit, promote or etch the crystallographic facets of the nanoparticles. This control enables selective grafting of shells with complex morphologies grown over nanocrystal cores, thus allowing the fabrication of a diverse library of monodisperse sub-50?nm nanoparticles. With such programmable additive and subtractive engineering a variety of three-dimensional shapes can be implemented using a bottom-up scalable approach.
| S-EPMC4729871 | biostudies-other
Project description:Electrolysis of water is key technology, not only for clean energy production, but to ensure a continued supply of hydrogen beyond fossil resources, essential to the manufacture of many chemical goods other than fuels. Cobalt nanomaterials have been widely identified as a promising candidate for the anode (oxygen evolution) reaction in this process, but much work has focused on applied materials or electrode design. Given the importance of oxidation state changes Co(III) → Co(IV) in the accepted reaction mechanism, in this work we look at size effects in small (4-10 nm) cobalt nanoparticles, where the ease of oxidation for lower cobalt oxidation states is known to change with particle size. To discriminate between geometric and chemical effects we have compared the catalysts in this study to others in the literature by turnover frequency (widely used in other areas of catalysis), in addition to the more commonly employed performance metric of the overpotential required to produce a current density of 10 mA cm-2. Comparisons are drawn to key examples of using well defined nanomaterials (where the surface are of cobalt sites can be estimated). This has enabled an estimated intrinsic turnover rate of ~ 1 O2 molecule per surface Co atom per second at an overpotential of 500 mV in the oxygen evolution reaction under typical alkaline reaction conditions (pH 14.0) to be identified.
| S-EPMC6435211 | biostudies-literature
Project description:Gold nanostars have shown enormous potential as the main enablers of advanced applications ranging from biomedicine to sensing or catalysis. Their unique anisotropic structure featuring sharp spikes that grow from a central core offers enhanced optical capabilities and spectral tunability. Although several synthesis methods yield NSs of different morphologies and sizes up to several hundred nanometers, obtaining small NSs, while maintaining their plasmonic properties in the near-infrared, has proven challenging and elusive. Here, we show that Cu2+ addition during NS synthesis in polyvinylpyrrolidone/dimethylformamide generates more crystallographic defects and promotes the directional growth, giving rise to NSs with a larger number of much sharper spikes. They are also formed at smaller volumes, enabling the generation of ultrasmall nanostars, with a volume as small as 421 nm3 (i.e., 9.2 nm of volume-equivalent diameter), while maintaining a plasmon resonance in the near-infrared. To this end, we systematically evaluate the influence of synthesis parameters on the nanostar size and optical characteristics and demonstrate their properties for applications in catalysis, surface-enhanced Raman spectroscopy sensing, and hyperthermia. The ultrasmall nanostars show excellent attributes in all of them, leveraging their small size to enhance properties related to a higher surface-to-volume ratio or colloidal diffusivity.
| S-EPMC11348798 | biostudies-literature
Project description:Although deformation processes in submicron-sized metallic crystals are well documented, the direct observation of deformation mechanisms in crystals with dimensions below the sub-10-nm range is currently lacking. Here, through in situ high-resolution transmission electron microscopy (HRTEM) observations, we show that (1) in sharp contrast to what happens in bulk materials, in which plasticity is mediated by dislocation emission from Frank-Read sources and multiplication, partial dislocations emitted from free surfaces dominate the deformation of gold (Au) nanocrystals; (2) the crystallographic orientation (Schmid factor) is not the only factor in determining the deformation mechanism of nanometre-sized Au; and (3) the Au nanocrystal exhibits a phase transformation from a face-centered cubic to a body-centered tetragonal structure after failure. These findings provide direct experimental evidence for the vast amount of theoretical modelling on the deformation mechanisms of nanomaterials that have appeared in recent years.
| S-EPMC3105591 | biostudies-literature
Project description:Atomically precise Au25 nanoclusters have garnered significant interest in the field of heterogeneous catalysis due to their remarkable activity and selectivity. However, for the extensively studied reaction of low-temperature CO oxidation, their performance has not been competitive compared to other known gold nanocatalysts. To address this, we deposited Au25(SR)18 (R = CH2CH2Ph) nanoclusters onto a manganese oxide support (Au25/MnO2), resulting in a very stable and highly active catalyst. By optimizing the pretreatment temperature, we were able to significantly enhance the performance of the Au25/MnO2 catalyst, which outperformed most other gold catalysts. Impressively, 100% conversion of CO was achieved at temperatures as low as -50 °C, with 50% conversion being reached below -70 °C. Furthermore, the existence of ligands could also influence the negative apparent activation energy observed at intermediate temperatures. Analysis using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray diffraction (XRD) techniques indicated that the Au25 nanoclusters remained stable on the catalyst surface even after pretreatment at high temperatures. In-situ modulation excitation spectroscopy (MES) spectra also confirmed that the Au cluster was the active site for CO oxidation, highlighting the potential of atomically precise Au25 nanoclusters as primary active sites at very low temperatures.
| S-EPMC10739995 | biostudies-literature
Project description:The direct production of macromolecular scale (sub-5 nm) porous nanocrystals with high surface area has been a considerable challenge over the past two decades. Here we report an interfacial site-directed capping agent-free growth method to directly produce porous ultrasmall (sub-5 nm), fully crystalline, macromolecular scale nanocrystals. The porous sub-5 nm Prussian blue nanocrystals exhibit uniform sizes (?4 ± 1 nm), high surface area (?855 m2 g-1), fast electron transfer (rate constant of ?9.73 s-1), and outstanding sustained catalytic activity (more than 450 days). The nanocrystal-based biointerfaces enable unprecedented sub-nanomolar level recognition of hydrogen peroxide (?0.5 nM limit of detection). This method also paves the way towards the creation of ultrasmall porous nanocrystals for efficient biocatalysis.
| S-EPMC5497271 | biostudies-other
Project description:The miniaturization of bioelectronic intracellular probes with a wide dynamic frequency range can open up opportunities to study biological structures inaccessible by existing methods in a minimally invasive manner. Here, we report the design, fabrication, and demonstration of intracellular bioelectronic devices with probe sizes less than 10 nm. The devices are based on a nanowire-nanotube heterostructure in which a nanowire field-effect transistor detector is synthetically integrated with a nanotube cellular probe. Sub-10-nm nanotube probes were realized by a two-step selective etching approach that reduces the diameter of the nanotube free-end while maintaining a larger diameter at the nanowire detector necessary for mechanical strength and electrical sensitivity. Quasi-static water-gate measurements demonstrated selective device response to solution inside the nanotube, and pulsed measurements together with numerical simulations confirmed the capability to record fast electrophysiological signals. Systematic studies of the probe bandwidth in different ionic concentration solutions revealed the underlying mechanism governing the time response. In addition, the bandwidth effect of phospholipid coatings, which are important for intracellular recording, was investigated and modeled. The robustness of these sub-10-nm bioelectronics probes for intracellular interrogation was verified by optical imaging and recording the transmembrane resting potential of HL-1 cells. These ultrasmall bioelectronic probes enable direct detection of cellular electrical activity with highest spatial resolution achieved to date, and with further integration into larger chip arrays could provide a unique platform for ultra-high-resolution mapping of activity in neural networks and other systems.
| S-EPMC3910633 | biostudies-literature
Project description:Glassy carbon nanofibers (GCNFs) are considered promising candidates for the fabrication of nanosensors for biosensing applications. Importantly, in part due to their great stability, carbon electrodes with sub-10 nm nanogaps represent an attractive platform for probing the electrical characteristics of molecules. The fabrication of sub-10 nm nanogap electrodes in these GCNFs, which is achieved by electrically stimulating the fibers until they break, was previously found to require fibers shorter than 2 µm; however, this process is generally hampered by the limitations inherent to photolithographic methods. In this work, to obtain nanogaps on the order of 10 nm without the need for sub-2 µm GCNFs, we employed a fabrication strategy in which the fibers were gradually thinned down by continuously monitoring the changes in the electrical resistance of the fiber and adjusting the applied voltage accordingly. To further reduce the nanogap size, we studied the mechanism behind the thinning and eventual breakdown of the suspended GCNFs by controlling the environmental conditions and pressure during the experiment. Following this approach, which includes performing the experiments in a high-vacuum chamber after a series of carbon dioxide (CO2) purging cycles, nanogaps on the order of 10 nm were produced in suspended GCNFs 52 µm in length, much longer than the ~2 µm GCNFs needed to produce such small gaps without the procedure employed in this work. Furthermore, the electrodes showed no apparent change in their shape or nanogap width after being stored at room temperature for approximately 6 months.
| S-EPMC8433410 | biostudies-literature