Ordered carbon molecular sieves exhibiting Bragg diffraction of X-ray lines have been synthesized for the first time, using mesoporous silica molecular sieves as the template. Sucrose was converted to carbon inside the mesopores of the silica molecular sieves through a mild carbonization process using a sulfuric acid catalyst. The carbon molecular sieves were obtained after the removal of the silica framework using an aqueous solution of sodium hydroxide. The X-ray diffraction, transmission electron microscopy, and pore size analysis showed that the structure of the carbon molecular sieves consisted of a three-dimensional regular array of uniform mesopores 3 nm in diameter. The structure was not simply a negative replica of the used silica template, but the synthesis mechanism involved the unique transformation into a new ordered array that was triggered by the removal of the silica frameworks. The highly ordered mesoporous texture suggested its scientific and technological importance as a new shape-selective catalyst, adsorbent, sensor, and electrode material.
Iron-nitrogen on carbon (Fe-N/C) catalysts have emerged as promising nonprecious metal catalysts (NPMCs) for oxygen reduction reaction (ORR) in energy conversion and storage devices. It has been widely suggested that an active site structure for Fe-N/C catalysts contains Fe-N coordination. However, the preparation of high-performance Fe-N/C catalysts mostly involves a high-temperature pyrolysis step, which generates not only catalytically active Fe-N sites, but also less active large iron-based particles. Herein, we report a general "silica-protective-layer-assisted" approach that can preferentially generate the catalytically active Fe-N sites in Fe-N/C catalysts while suppressing the formation of large Fe-based particles. The catalyst preparation consisted of an adsorption of iron porphyrin precursor on carbon nanotube (CNT), silica layer overcoating, high-temperature pyrolysis, and silica layer etching, which yielded CNTs coated with thin layer of porphyrinic carbon (CNT/PC) catalysts. Temperature-controlled in situ X-ray absorption spectroscopy during the preparation of CNT/PC catalyst revealed the coordination of silica layer to stabilize the Fe-N sites. The CNT/PC catalyst contained higher density of active Fe-N sites compared to the CNT/PC prepared without silica coating. The CNT/PC showed very high ORR activity and excellent stability in alkaline media. Importantly, an alkaline anion exchange membrane fuel cell (AEMFC) with a CNT/PC-based cathode exhibited record high current and power densities among NPMC-based AEMFCs. In addition, a CNT/PC-based cathode exhibited a high volumetric current density of 320 A cm in acidic proton exchange membrane fuel cell. We further demonstrated the generality of this synthetic strategy to other carbon supports.
CMK-1 ordered mesoporous carbons were synthesized using MCM-48 silica templates with a wide range of unit-cell parameters and pore sizes. Sucrose and furfuryl alcohol were employed as carbon precursors. It was confirmed that the isolation of the CMK-1 carbon via dissolution of the MCM-48 template is accompanied by a structural transformation, which manifests itself in the change of the X-ray diffraction pattern. It is suggested that the transformation is related to the disconnected nature of the two interwoven parts of the CMK-1 framework (which are formed in two enantiomeric MCM-48 channel systems separated by the silica wall) and may involve a mutual displacement of these two parts to create some contact between them and fix their mutual position. It was shown that the application of different MCM-48 templates allowed for tailoring of the CMK-1 unit-cell size. However, the primary mesopore size of CMK-1 was found to be relatively constant. This was explained as a consequence of the formation of primary mesopores of CMK-1 in the space previously occupied by the MCM-48 pore walls, and attributed to the similarity in the pore wall thickness for the MCM-48 templates used. Our study confirmed that the uniform mesopores of CMK-1 are accompanied by micropores and that the carbon prepared using MCM-41 as a template collapses upon the template removal to yield high-surface-area disordered microporous structure. It was also shown that thermogravimetric weight loss behavior under air atmosphere provides important insights to the structural integrity and quality of the CMK-1 samples.
There are many cyclic peptides with diverse biological activities, such as antibacterial activity, immunosuppressive activity, and anti-tumor activity, and so on. Encouraged by natural cyclic peptides with biological activity, efforts have been made to develop cyclic peptides with both genetic and synthetic methods. The genetic methods include phage display, intein-based cyclic peptides, and mRNA display. The synthetic methods involve individual synthesis, parallel synthesis, as well as split-and-pool synthesis. Recent development of cyclic peptide library based on split-and-pool synthesis allows on-bead screening, in-solution screening, and microarray screening of cyclic peptides for biological activity. Cyclic peptides will be useful as receptor agonist/antagonist, RNA binding molecule, enzyme inhibitor and so on, and more cyclic peptides will emerge as therapeutic agents and biochemical tools.
Pt-based intermetallic nanostructures have demonstrated higher electrocatalytic performances compared to random alloy structures. However, the origin of their enhanced catalytic properties remains elusive. Furthermore, a robust synthetic strategy for well-defined intermetallic nanostructures represents a challenge. Here, we reveal by combining theoretical and experimental results that the activity enhancement in intermetallic structures for the oxygen reduction reaction (ORR) originates from an intensified ligand effect. We prepared well-defined model nanocatalysts via confined nanospace-directed synthesis using mesoporous silica templates, which allows precise control over the size and shape of nanostructures. Importantly, this method can transform disordered alloy nanostructures into intermetallic analogues without agglomeration, enabling decoupling of an atomic ordering effect in catalysis. The prepared ordered intermetallic Pt3Co nanowires (O-Pt3Co NWs) can benefit from an intensified ligand effect, Pt-skin layer, and agglomeration-tolerant contiguous structure, which led to their enhanced ORR activity and durability compared to disordered alloy Pt3Co nanowires (D-Pt3Co NWs) and Pt/C catalysts. The multifunctionality of O-Pt3Co NWs is demonstrated with their higher activity and durability in the alkaline hydrogen evolution reaction and acidic methanol oxidation reaction than those of D-Pt3Co NWs and Pt/C catalysts. Furthermore, a proton exchange membrane fuel cell cathode based on O-Pt3Co NWs shows much better durability than a Pt/C-based one.
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