No abstract

The low capacity and unsatisfactory rate capability of hard carbon still restricts its practical application for Li/K‐ion batteries. Herein, a low‐cost and large‐scale method is developed to fabricate phosphorus‐doped hard carbon (PHC‐700) by crosslinking phosphoric acid and epoxy resin and followed by annealing at 700 °C. H3PO4 acts not only as a crosslinker to solidify epoxy resin for promoting the degree of graphitization and lowering the specific surface area, but also as phosphorus source for forming PC and PO bonds, thus providing more active sites for Li/K storage. As a result, the PHC‐700 electrode delivers a highly reversible capacity of 1294.8 mA h g−1 at 0.1 A g−1 and a capacity of 214 mA h g−1 after 10 000 cycles at 10 A g−1. As for potassium‐ion batteries, PHC‐700 exhibits a reversible capacity of 381.9 mA h g−1 at 0.1 A g−1 and a capacity of 260 mA h g−1 after 1000 cycles at 0.2 A g−1. In situ Raman and in situ NMR measurements reveal that the P‐containing bonds can enhance the adsorption to alkali metal ions, and the PC bond can participate in electrochemical redox reaction by forming Lix PCy . Additionally, P‐doped hard carbon shows better structural/interfacial stability for improved long‐term cycling stability.

Development of novel surface-enhanced Raman scattering (SERS) substrates and how they interface target analytes plays a pivotal role in determining the spectrum profile and SERS enhancement magnitude, as well as their applications. We present here the seed-mediated growth of reduced graphene oxide-gold nanostar (rGO-NS) nanocomposites and employ them as active SERS materials for anticancer drug (doxorubicin, DOX) loading and release. By this synthetic approach, both the morphology of rGO-NS nanohybrids and the corresponding optical properties can be precisely controlled, with no need of surfactant or polymer stabilizers. The developed rGO-NS nanohybrids show tunable optical properties by simply changing growth reaction parameters, improved stability as compared to bare Au nanostars, and sensitive SERS response toward aromatic organic molecules. Furthermore, SERS applications of rGO-NS to probe DOX loading and pH-dependent release are successfully demonstrated, showing promising potential for drug delivery and chemotherapy.

Four kinds of 13C-labeled polyacrylonitrile (PAN) samples were prepared respectively by solution polymerization of acrylonitrile (AN) with selective 13C labeling of different molecular sites. The composition and structure of the residues from the thermal treatment of PAN in argon at 250 and 350 °C were quantitatively analyzed in detail by one- and two-dimensional solid-state 13C nuclear magnetic resonance (ssNMR) experiments. Compared with the NMR spectrum of each labeled carbon in AN monomer unit, nine chemical structures created during the heat treatment process have been identified accurately. On this basis, four reaction routes were proposed. It is noted that the main chemical change for PAN started from a cyclization reaction at a relatively low temperature, then experienced an aromazation reaction to form a molecular chain basically composed of isolated pyridine units, instead of the commonly reported ladder structure. This work also shows that the combination of selectively 13C-labeled technique and a high spinning speed of 20 kHz in magic-angle spinning (MAS) NMR experiment could improve the detection sensitivity to nearly 2 orders of magnitude, and provide a clear ssNMR spectra with little peak overlaps, which will be helpful to discover the complex reaction mechanism in the manufacture of carbon fibers with high performance.