In Situ Fe-Substituted Hexacyanoferrate for High-Performance Aqueous Potassium Ion Batteries.

The eco-friendliness, safety, and affordability of aqueous potassium batteries (AKIBs) have made them popular for large-scale energy storage devices. However, the cycling and rate performance of research materials, particularly cobalt hexacyanoferrate, have yet to meet satisfactory standards. Herein, a room-temperature drafted K1.66 Fe0.25 Co0.75 [Fe(CN)6 ]·0.83H2 O (KFCHCF) sample is reported using an in situ substitution strategy. A higher concentration of ferrocyanide ions decreases the water content and increases the potassium content, while citric acid works as a chelating agent and is responsible for Fe-substitution in the KFCHCF sample. The resultant KFCHCF sample exhibits good rate performance, and about 97% and 90.6% of discharge capacity are conserved after 400 and 1000 cycles at 100 and 200 mA g-1 , respectively. The full cell using the KFCHCF cathode and 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide (PNTCDA) anode maintains ≈74.93% and 74.35% of discharge capacity at 200 mA g-1 and 1000 mA g-1 for 1000 and >10,000 cycles, respectively. Furthermore, ex situ characterizations demonstrate the high reversibility of K-ions and structural stability during the charge-discharge process. Such high performance is attributed to the fast K-ion migration and crystal structure stabilization caused by in situ Fe-substitution in the KFCHCF sample. Other hexacyanoferrates can be synthesized using this method and used in grid-scale storage systems.

Achieving nitrogen-doped carbon/MnO2 nanocomposites for catalyzing the oxygen reduction reaction.

The design and synthesis of cheaper and more stable catalysts with comparable electrocatalytic performance to commercial Pt/C towards the oxygen reduction reaction is of importance for their application in fuel cells and metal-air batteries. Herein, we report the generation of nitrogen-doped carbon/MnO2 nanocomposites via pyrolyzing the polypyrrole/MnO2 precursor that is obtained based on the direct redox reaction between polypyrrole and KMnO4. The achieved sample presents an onset and half-wave potential of -0.048 and -0.124 V vs. Hg/HgO, respectively, and a current retention of 93% after 20 000 s chronoamperometry measurement. Meanwhile, it shows stronger methanol tolerance, endowing it with great potential for the corresponding applications. The excellent oxygen reduction reaction catalytic activity originates from the synergistic effect between nitrogen-doped carbon and MnO2, where the former one is helpful for MnO2 to achieve a higher Mn3+/Mn4+ ratio and a higher number of oxygen vacancies, and the existence of the latter one is beneficial for generating a higher ID/IG ratio in the carbon layer. These both contribute to the achievement of large numbers of active sites for the electrocatalytic process.

Enhancing the Catalytic Activity of Zeolitic Imidazolate Framework-8-Derived N-Doped Carbon with Incorporated CeO2 Nanoparticles in the Oxygen Reduction Reaction.

Incorporation of CeO2 nanoparticles into the cavity of zeolitic imidazolate framework-8 (ZIF-8) was followed by high-temperature pyrolysis to generate CeO2 @N-doped carbon materials. Introduction of the CeO2 nanoparticles greatly enhanced the catalytic activity of the ZIF-8-derived carbon materials in the oxygen reduction reaction (ORR) owing to the presence of Ce3+ and oxygen vacancies with high content of chemisorbed oxygen in CeO2 and the well-maintained skeleton of the original ZIF-8 with uniform mesoporous structure. The material treated at 900 °C (CeO2 @N-C-900) showed excellent ORR catalytic activity in both acidic and alkaline electrolyte. The ORR onset and half-wave potentials of CeO2 @N-C-900 were 1.003 and 0.908 V versus RHE, respectively, in 0.1 m KOH aqueous solution, which are comparable to those of Pt/C catalysts. Furthermore, it exhibited much better stability and methanol crossover tolerance than Pt/C, indicative of its good potential for applications in energy conversion.

Depletion sphere: Explaining the number of Ag islands on Au nanoparticles.

We report multi-site nucleation and growth of Ag islands on colloidal Au nanoparticles. By modifying a single factor, a range of products from Janus nanoparticles to satellite nanostructures are obtained. The identification of these key factors reveals the correlation between the concentration gradient and the choice of nucleation sites. In contrast to the inhibited homogeneous nucleation in the bulk solution, we argue that the non-steady-state concentration gradient plays a critical role in inhibiting nucleation within nanometer distance during the initial stage of growth-an essential but not yet recognized factor in colloidal synthesis. A depletion sphere model was developed, so that the multi-site nucleation is well integrated with the classic theory of nucleation and growth. Alternative explanations are carefully examined and ruled out. We believe that the synthetic know-how and the mechanistic insights can be broadly applied and are of importance to the advance of nanosynthesis.

Achieving MnO2 Nanosheets through Surface Redox Reaction on Nickel Nanochains for Catalysis and Energy Storage.

The redox reaction between KMnO4 and Ni was carried out on a chain-like Ni surface under hydrothermal conditions and γ-MnO2 nanosheets were produced through this facile route. The original Ni nanochains, as cores, dominated the final morphology of the composites with MnO2 nanosheets loaded on their surface. The uniform assemblies of MnO2 , with large amounts of exposed sites, allowed them to be good candidates for application in various fields. The reduction of 4-nitrophenol by NaBH4 was selected as model reaction to test the catalytic activity of the samples and the samples could also be made into electrodes for supercapacitor measurement. Both the results revealed the advantages of the γ-MnO2 assembled on the Ni chain surfaces. Furthermore, the magnetic cores facilitated the recycling of the sample and increased the stability upon charge-discharge cycles.

Facile Fabrication of Well-Dispersed Pt Nanoparticles in Mesoporous Silica with Large Open Spaces and Their Catalytic Applications.

In this paper, a facile strategy is reported for the preparation of well-dispersed Pt nanoparticles in ordered mesoporous silica (Pt@OMS) by using a hybrid mesoporous phenolic resin-silica nanocomposite as the parent material. The phenolic resin polymer is proposed herein to be the key in preventing the aggregation of Pt nanoparticles during their formation process and making contributions both to enhance the surface area and enlarge the pore size of the support. The Pt@OMS proves to be a highly active and stable catalyst for both gas-phase oxidation of CO and liquid-phase hydrogenation of 4-nitrophenol. This work might open new avenues for the preparation of noble metal nanoparticles in mesoporous silica with unique structures for catalytic applications.

A novel strategy to fabricate multifunctional Fe3O4@C@TiO2 yolk-shell structures as magnetically recyclable photocatalysts.

Using poly(acrylic acid) (PAA) as a template, a novel Fe3O4@C@TiO2 yolk-shell structure derived from heat treatment on Fe2O3@PAA@TiO2 core-shell structures is constructed, where the interior void volume and shell thickness are readily tuned. In this method, the PAA shell between the original spherical α-Fe2O3 nanoparticle (NP) core and the outer TiO2 shell replaces the common SiO2 template leaving out the tedious treatment procedure of the template. After calcination, the α-Fe2O3 core was reduced to the Fe3O4 core providing the NPs with magnetic properties and the middle carbon coating around the magnetic core could avoid the occurrence of photodissolution. Moreover, the obtained Fe3O4@C@TiO2 yolk-shell nanocomposites (NCs) exhibit fine photocatalytic activity for the photodegradation of organic contaminants in waste water.

Designed fabrication of unique eccentric mesoporous silica nanocluster-based core-shell nanostructures for pH-responsive drug delivery.

A novel and facile strategy using poly(acrylic acid) (PAA) as a nanoreactor and template has been proposed and applied for the first time to fabricate a novel and unique class of multifunctional eccentric Fe3O4@PAA/SiO2 core-shell nanoclusters (NCs) consisting of a single Fe3O4 nanoparticle (NP), PAA, and eccentric SiO2 NCs that are composed of a large number of small fluorescent SiO2 NPs. Interestingly, the resulting eccentric PAA shell around Fe3O4 NPs as a high water-absorbent polymer is like a "reservoir" to absorb and retain water molecules inside its net structure to confine the growth of small SiO2 NPs inside the PAA networks, resulting in the formation of an eccentric SiO2 NC with aggregated pores. The thicknesses of uniform and well-dispersed SiO2 NCs can also be precisely controlled by varying the amount of tetraethyl orthosilicate (TEOS). Importantly, the synthetic method has been confirmed to be universal and extended to other functional NPs with different compositions and shapes as eccentric cores. Furthermore, the as-prepared multifunctional eccentric Fe3O4@PAA/SiO2 core-shell NCs combined fluorescence imaging, ultrahigh drug loading capacity (1.13 mg doxorubicin/mg eccentric NCs), and pH-responsive drug release into one were taken as an example to study the applications in simultaneous fluorescence imaging and pH responsive drug delivery into prostate cancer PC3M cells.

Generalized approach to the synthesis of reversible concentric and eccentric polymer-coated nanostructures.

A very facile, general, and reproducible method is developed for the controlled synthesis of discrete and monodisperse concentric and eccentric poly(acrylic acid) (PAA)-coated nanostructures in a large-scale, independent of their size, geometry, or composition. Interestingly, the reversible structural transformation between concentricity and eccentricity can be easily achieved, which is determined by the change in interfacial energy of the synthetic system.

Measuring the unusually slow ionic diffusion in polyaniline via study of yolk-shell nanostructures.

We demonstrate a unique capability in partially oxidizing the oligoaniline shell on gold nanoparticles to polyaniline. Because of the solubility difference, the unreacted inner shell section can be selectively dissolved by 2-propanol, giving yolk-shell nanostructures and, thus, making it possible for assessing the oxidized section. The ionic diffusion through the polymer shell is found to be the rate-determining step in the overall process. Conservative estimates show that the diffusion coefficient of AuCl(4)(-) is at least 700 times slower than that of the typical rate values in traditional studies. It is most likely caused by the lack of micropores in the polymer structures. Such mircopores are hard to avoid in preparing polymer membranes by casting or drying of polymers dissolved in organic solvents. We can rule out the presence of irregular pores on the basis of the uniformly oxidized shell section. With the nanoscale shells, the system is sensitive enough to detect minute changes in the shell or small differences among the individual nanoparticles. Even with a small increase in porosity, for example, when the polyaniline shell is swollen using small amounts of DMF (3%, 5%, or 10% in aqueous solutions), the diffusion coefficient of AuCl(4)(-) increases to 4, 11, and 17 times, respectively. Thus, our study demonstrates a new methodology for studying the diffusion of ions in hydrophobic polymers.

Seeded growth of two-dimensional dendritic gold nanostructures.

We show that seeded growth can be applied to creating two-dimensional (2D) dendritic Au nanostructures on sample grids, which can be directly characterized by transmission electron microscopy (TEM). The 2D synthesis of highly consistent structures offers a novel mechanistic perspective on the aggregation of colloidal Au nanocrystals on a surface.

A symmetry-adapted shell transformation of core-shell nanoparticles for binary nanoassembly.

Binary nanoassembly was realized by mixing gold@polyaniline nanoparticles with diblock copolymers in the DMF/H(2)O system and the products present a controlled transformation from symmetrical shells into spatially distributed petal-like polymer shells on gold cores.

Triple-layer (au@perylene)@polyaniline nanocomposite: unconventional growth of faceted organic nanocrystals on polycrystalline Au.

Unconventional crystal growth: core/shell nanocrystals were obtained by growth of a dominant single-crystalline phase of perylene over polycrystalline Au nanoparticle seeds and isolated by coating with polyaniline (PANI) shells. Perylene is released in the presence of sodium dodecyl sulfate (SDS) micelles. The TEM images show (Au@perylene)@PANI nanocomposites before and after complete release of perylene leaving Au@PANI (inset).

A systems approach towards the stoichiometry-controlled hetero-assembly of nanoparticles.

A central theme in nanotechnology is to advance the fundamental understanding of nanoscale component assembly, thereby allowing rational structural design that may lead to materials with novel properties and functions. Nanoparticles (NPs) are often regarded as 'artificial atoms', but their 'reactions' are not readily controllable. Here, we demonstrate a complete nanoreaction system whereby colloidal NPs are rationally assembled and purified. Two types of functionalized gold NPs (A and B) are bonded to give specific products AB, AB(2), AB(3) and AB(4). The stoichiometry control is realized by fine-tuning the charge repulsion among the B-NPs. The products are protected by a polymer, which allows their isolation in high purity. The integration of hetero-assembly, stoichiometry control, protection scheme and separation method may provide a scalable way to fabricate sophisticated nanostructures.

Mechanistic investigation into the spontaneous linear assembly of gold nanospheres.

Understanding the mechanism of nanoparticle self-assembly is of critical significance for developing synthetic strategies for complex nanostructures. By encapsulating aggregates of Au nanospheres in shells of polystyrene-block-poly(acrylic acid), we prevent the dissociation and aggregation typically associated with the drying of solution samples on TEM/SEM substrates. In our study of the salt-induced aggregation of 2-naphthalenethiol-functionalized Au nanospheres in DMF, the trapping of the solution species under various experimental conditions permits new insights in the mechanism thereof. We provide evidence that the spontaneous linear aggregation in this system is a kinetically controlled process and hence the long-range charge repulsion at the "transition state" before the actual contact of the Au nanospheres is the key factor. Thus, the charge repulsion potential (i.e. the activation energy) a nanosphere must overcome before attaching to either end of a nanochain is smaller than attaching on its sides, which has been previously established. This factor alone could give rise to the selective end-on attachment and lead to the linear assembly of originally isotropic Au nanospheres.

3D dendritic gold nanostructures: seeded growth of a multi-generation fractal architecture.

In this report, we focus on the synthetic challenges for nanoscale 3D fractal architectures, namely the multi-generation growth with control in both size uniformity and colloidal stability; by directing the simultaneous growth of Au and polyaniline on Au seeds, fractal nanoparticles can be achieved with a topology distinctively different from those of spheres, cubes or rods.

Reducing the symmetry of bimetallic Au@Ag nanoparticles by exploiting eccentric polymer shells.

We demonstrate a facile colloidal method for synthesizing Janus nanoparticles, whose eccentric polymer shells are exploited to fabricate eccentric bimetallic cores.

Probing the kinetics of ligand exchange on colloidal gold nanoparticles by surface-enhanced Raman scattering.

We report a new approach to study the kinetics of ligand exchange on colloidal gold nanoparticles, where the coordination and dissociation of surface ligands could be monitored in situ by surface-enhanced Raman scattering.

Fabrication of polymer nanocavities with tailored openings.

A templated fabrication of open nanocavities is reported, where rational control of partial polymer attachment on sacrificial metal cores introduces openings in the polymer shells. This approach provides a facile means to modify the structural features of polymer nanocavities by manipulating the surface chemistry of colloidal nanoparticles. In particular, the anisotropic geometry of gold nanorods is exploited to promote the anisotropic polymer attachment, such that two diametric openings occurred in the polymer shell. After etching the gold nanorods, this approach yields open nanochannels that are tunable in both diameter and length. The synthetic scope of the anisotropic core/shell nanoparticles is expanded, supporting the previously proposed mechanism. We demonstrate that reducing the symmetry of nano-objects could open up new ways to create structural features using simple assembly and etching techniques. The thermostability of the open polymer nanostructures is also investigated.

Influence of external voltage on the reprotonated polyaniline films by Fourier Transform Infrared spectroscopy.

In this paper, we reported the electrical fourier transform infrared (FT-IR) spectra measurements on the reprotonated polyaniline (PANI) thin films. Application of external voltage reduced the intensity in FT-IR spectra and resulted in the shift of band situation. The FT-IR spectra as a function of temperature were also conducted in order to investigate the effect of Joule heating. We found that the influence of CC of phenyl units and the CC of quinoid were quite different as a function of external voltage and temperature. The current-voltage (I-V) curves of the PANI film measured in the range of 0-175 V showed that the resistance kept constant at 0-75 V while it increased from 75 to 175 V. The I-V curves confirmed the presence of Joule heating effect during 75-175 V. According to the experiment results, we concluded that external voltage could produce large average hopping energy, which allowed the charge transfer by hopping between the conducting domains during 0-75 V. The deprotonation of PANI was caused by Joule heating effect, resulting in the decreasing conductivity from 75 to 175 V.