Limin Qi

Nanoporous Anatase TiO2 Mesocrystals: Additive-Free Synthesis, Remarkable Crystalline-Phase Stability, and Improved Lithium Insertion Behavior

Unique spindle-shaped nanoporous anatase TiO(2) mesocrystals with a single-crystal-like structure and tunable sizes were successfully fabricated on a large scale through mesoscale assembly in the tetrabutyl titanate-acetic acid system without any additives under solvothermal conditions. A complex mesoscale assembly process involving slow release of soluble species from metastable solid precursors for the continuous formation of nascent anatase nanocrystals, oriented aggregation of tiny anatase nanocrystals, and entrapment of in situ produced butyl acetate as a porogen was put forward for the formation of the anatase mesocrystals. It was revealed that the acetic acid molecules played multiple key roles during the nonhydrolytic processing of the [001]-oriented, single-crystal-like anatase mesocrystals. The obtained nanoporous anatase mesocrystals exhibited remarkable crystalline-phase stability (i.e., the pure phase of anatase can be retained after being annealed at 900 °C) and improved performance as anode materials for lithium ion batteries, which could be largely attributed to the intrinsic single-crystal-like nature as well as high porosity of the nanoporous mesocrystals.

A Systematic Examination of the Morphogenesis of Calcium Carbonate in the Presence of a Double-Hydrophilic Block Copolymer

In this paper, a systematic study of the influence of various experimental parameters on the morphology and size of CaCO3 crystals after room-temperature crystallization from water in the presence of poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) is presented. The pH of the solution, the block copolymer concentration, and the ratio [polymer]/[CaCO3] turned out to be important parameters for the morphogenesis of CaCO3, whereas a moderate increase of the ionic strength (0.016 M) had no influence. Depending on the experimental conditions, the crystal morphologies can be tuned from calcite rhombohedra via rods, ellipsoids or dumbbells to spheres. A morphology map is presented which allows the prediction of the crystal morphology from a combination of pH, and CaCO3 and polymer concentration. Morphologies reported in literature for the same system but under different crystallization conditions agree well with the predictions from the morphology map. A closer examination of the growth of polycrystalline macroscopic CaCO3 spheres by TEM and time-resolved dynamic light scattering showed that CaCO3 macrocrystals are formed from strings of aggregated amorphous nanoparticles and then recrystallize as dumbbell-shaped or spherical calcite macrocrystal.

Morphology‐Controlled Synthesis of SnO2 Nanotubes by Using 1D Silica Mesostructures as Sacrificial Templates and Their Applications in Lithium‐Ion Batteries

SnO(2) nanotubes with controllable morphologies are successfully synthesized by using a variety of one-dimensional (1D) silica mesostructures as effective sacrificial templates. Firstly, 1D silica mesostructures with different morphologies, such as chiral nanorods, nonchiral nanofibers, and helical nanotubes, are readily synthesized in aqueous solution by using the triblock copolymer Pluronic F127 and the cationic surfactant cetyltrimethylammonium bromide as binary templates. Subsequently, the obtained 1D silica mesostructures are used as sacrificial templates to synthesize SnO(2) nanotubes with preserved morphologies via a simple hydrothermal route, resulting in the formation of well-defined SnO(2) nanotubes with different lengths and unique helical SnO(2) nanotubes with a wealth of conformations. It is revealed that both of the short and long SnO(2) nanotubes showed much better performance as anode materials in lithium-ion batteries than normal SnO(2) nanopowders, which might be related to the hollow structure of the nanotubes that could alleviate the volume changes and mechanical stress during charging/discharging cycling. Moreover, the capacity and cycling performance of short nanotubes, which showed a specific discharge capacity of 468 mAh g(-1) after 30 cycles, are considerably better than those of long nanotubes because of the more robust structure of the short nanotubes.

Crystal Design of Barium Sulfate using Double-Hydrophilic Block Copolymers.

Peach, peanut, fiber, and flower (see picture) crystal morphologies are achieved from the precipitation of simple minerals in the presence of specifically adsorbing polymers. These crystal design effects are illustrated using BaSO(4) and double-hydrophilic block copolymers, the latter featuring carboxylate, sulfonate, phosphonate, and aspartic acid groups.

Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life

Facile fabrication of well-aligned Li4Ti5O12 (LTO) nanosheet arrays grown directly on conductive Ti foil was achieved by hydrothermal growth in LiOH solution. The reaction between Ti foil and LiOH led to the growth of vertically aligned, rectangular lithium titanate oxide hydrate (H-LTO) nanosheet arrays, which could be converted into LTO nanosheet arrays through topotactic transformation via thermal decomposition. An appropriate LiOH concentration was essential for the formation of densely aligned H-LTO nanosheet arrays on the substrate. It was proposed that the formation of the H-LTO nanosheet arrays was through kinetics-controlled growth during the hydrothermal metal corrosion process. When used as a binder-free anode for LIBs, the self-supported LTO nanosheet arrays standing on Ti foil exhibited an excellent rate capability (a reversible capacity of 163 mA h g−1 and 78 mA h g−1 at 20 C and 200 C, respectively) and an outstanding cycling performance (a capacity retention of 124 mA h g−1 after 3000 cycles at 50 C). Furthermore, a flexible lithium ion battery, which could be fully recharged within 30 s and was able to light an LED, was assembled by using the LTO nanosheet arrays as the anode.

Controlled Synthesis of Gold Nanobelts and Nanocombs in Aqueous Mixed Surfactant Solutions

Well-defined gold nanobelts as well as unique gold nanocombs made of nanobelts were readily synthesized by the reduction of HAuCl4 with ascorbic acid in aqueous mixed solutions of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the anionic surfactant sodium dodecylsulfonate (SDSn). Single-crystalline gold nanobelts grown along the <110> and <211> directions were prepared in mixed CTAB-SDSn solutions at 4 and 27 degrees C, respectively. Furthermore, single-crystalline gold nanocombs consisting of a <110>-oriented stem nanobelt and numerous <211>-oriented nanobelts grown perpendicularly on one side of the stem were fabricated by a two-step process with temperature changing from 4 to 27 degrees C. It was proposed that the mixed cationic-anionic surfactants exerted a subtle control on the growth of gold nanocrystals in solution due to the cooperative effect of mixed surfactants. This synthetic strategy may open a new route for the mild fabrication and hierarchical assembly of metal nanobelts in solution. The obtained gold nanobelts showed good electrocatalytic activity toward the oxidation of methanol in alkaline solution; in particular, the electrode modified with the nanobelts obtained at 27 degrees C exhibited an electrocatalytic activity considerably higher than normal polycrystalline gold electrode. Moreover, the gold nanobelts were used as the surface-enhanced Raman scattering (SERS) substrate for detecting the enhanced Raman spectra of p-aminothiophenol (PATP) molecules, and the gold nanobelts obtained at 4 degrees C exhibited an unusual larger enhancement of the b2 modes relative to the a1 modes for the adsorbed PATP molecules.

Controlled Synthesis of Dendritic Gold Nanostructures Assisted by Supramolecular Complexes of Surfactant with Cyclodextrin

Controlled synthesis of well-defined planar Au nanodendrites with a symmetric single-crystalline structure consisting of trunks and side branches grown along the 211 directions was realized by reducing chloroauric acid in aqueous mixed solutions of dodecyltrimethylammonium bromide (DTAB) and beta-cyclodextrin (beta-CD). It has been revealed that the formation of the supramolecular complexes of DTAB with beta-CD due to host-guest interaction is indispensable for the fabrication of these unique planar Au nanodendrites, and a proper CD-to-DTAB molar ratio is essential to their exclusive formation. A variety of Au nanostructures, such as branched particles consisting of rodlike branches and flowerlike particles consisting of platelike petals, could be readily obtained by simply changing the CD-to-DTAB molar ratio. Moreover, the obtained Au nanodendrites exhibited both a good electrocatalytic activity toward the oxidation of methanol and a good surface-enhanced Raman scattering (SERS) sensitivity for detecting p-aminothiophenol (PATP) molecules, indicating their potential applications including catalysis, biosensing, and nanodevices.

Formation of BaSO4 fibres with morphological complexity in aqueous polymer solutions.

BaSO4 fibres with morphological complexity were formed in aqueous solution with polyacrylate and partially monophosphonated poly(ethyleneoxide)-block-poly(methacrylic acid) additives by a simple precipitation reaction. For polyacrylate, formation of the fibrous deposits was strongly dependent on the level of supersaturation (S) and Ba2+:polymer molar ratio (R). At S=60 to 80, and R=3 to 14, highly anisotropic crystalline fibres consisting of bundles of BaSO4 nanofilaments were formed after several weeks, although the yield was low. The nanofilaments were also organized into cone-shaped aggregates at S=80, and at lower R values these formed higher-order structures that consisted of multiple cone-on-cone assemblies with remarkable self-similarity. Increasing the supersaturation produced ovoid or cross-shaped dendritic particles for the range of molar ratios studied. In contrast, BaSO4 crystallisation in the presence of a partially phosphonated block copolymer gave a high yield of BaSO4 fibres up to 100 μm in length, and consisting of co-aligned bundles of 30 nm-diameter defect-free single-crystal nanofilaments with a uniform growth tip. A model for the defect-free growth of BaSO4 nanofilaments in aqueous polymer solutions based on amorphous precursor particles, vectorially directing forces and van der Waals attraction is proposed.

Understanding charge transfer at PbS-decorated graphene surfaces toward a tunable photosensor.

An intrinsic mechanism of photoinduced hole transfer reactions occurring at the grapheme-PbS interface is described with the purpose of building a tunable photosensor with a responsivity of more than 10(3) A W(-1) . It is remarkable that rational utilization of this finding also realizes symmetric, opposing photoswitching effects, which are effectively mirror images, in a single pristine graphene device. These results highlight the vital importance of interface modification as a powerful tool for creating future ultrasensitive optoelectronic devices.

Recent advances in antireflective surfaces based on nanostructure arrays

Reducing the reflection and improving the transmission or absorption of light from wide angles of incidence in a broad wavelength range are crucial for enhancing the performance of the optical, optoelectronic, and electro-optical devices. Inspired by the structures of the insect compound eyes, nanostructure arrays (NSAs) have been developed as effective antireflective surfaces, which exhibit promising broadband and quasi-omnidirectional antireflective properties together with multifunctions. This review summarizes the recent advances in the fabrication and performance of antireflective surfaces based on NSAs of a wide variety of materials including silicon and non-silicon materials. The applications of the NSA-based antireflective surfaces in solar cells, light emitting diodes, detection, and imaging are highlighted. The remaining challenges along with future trends in NSA-based antireflective surfaces are also discussed.