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Nickel-rich layered transition metal oxides, LiNi (MnCo) O (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi Mn Co O (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

ganic CsPbX 3 QDs possess narrow full width at half maximum (FWHM) of emission (as small as 12 nm) and excellent quantum yield (QY: 50-90%). [1,8] They have a Bohr diameter up to 12 nm, [1] exhibiting a size-tunable bandgap in the visible region. It is also notable that the exchange of halide ions (Cl − , Br − , and I − ) in as-synthesized perovskite QDs is highly effective, rendering easy and rapid access to a wide range of perovskite QDs with tunable absorption and photoluminescence (PL) spectra. [1] In spite of significant advances in perovskite research noted above, a key to the success of perovskite-based materials and devices is the stability of perovskites as they are susceptible to decomposition due to their ionic crystal nature. [7,9] Recently, several methods including coating with alumina by atomic layer deposition, [10] partial coating with SiO 2 via sol-gel process, [11] physical mixing with hydrophobic polymers, [12] and encapsulation within mesoporous silica [7] or polymer beads [13] have proven to be effective in improving stability in polar and ambient environments. However, nearly all approaches described above for stability enhancement result in nanocomposites with multiple perovskite QDs encapsulated in microscopic protective matrices. These microscale nanocomposites may be disadvantageous for biomedical applications where cellular uptake is more feasible for smaller nanoscopic particles, [14] or LEDs where the processing of nanoscopic luminescent particles often leads to low scattering loss, higher loading and packing density, and thus film uniformity. [11] Clearly, the ability to deliberately and reliably improve the stability of perovskite QDs (e.g., against humidity and polar solvents) while retaining their individual nanometer size represents a critical step that underpins future advances in optoelectronic and biological applications.Herein, we report a general and robust strategy by capitalizing on judiciously designed amphiphilic star-like diblock copolymers with well-controlled molecular weight and low polydispersity of each block as molecularly engineered nanoreactors to craft uniform perovskite QDs. Remarkably, these QDs simultaneously possess precisely tunable dimensions Instability of perovskite quantum dots (QDs) toward humidity remains one of the major obstacles for their long-term use in optoelectronic devices. Herein, a general amphiphilic star-like block copolymer nanoreactor strategy for in situ crafting a set of hairy perovskite QDs with precisely tunable size and exceptionally high water and colloidal stabilities is presented. The selective partition of precursors within the compartment occupied by inner hydrophilic blocks of star-like diblock copolymers imparts in situ formation of robust hairy perovskite QDs permanently ligated by outer hydrophobic blocks via coprecipitation in nonpolar solvent. These size-and compositiontunable perovskite QDs reveal impressive water and colloidal stabilities as the surface of QDs is intimately and permanently ligated by a layer of outer ...

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Three-dimensional (3D) interconnected metal alloy nanostructures possess superior catalytic performance owing to their advantageous characteristics, including improved catalytic activity, corrosion resistance, and stability. Hierarchically structured Ni-Cu alloys composed of 3D network-like microscopic branches with nanoscopic dendritic feelers on each branch were crafted by a facile and efficient hydrogen evolution-assisted electrodeposition approach. They were subsequently exploited for methanol electrooxidation in alkaline media. Among three hierarchically structured Ni-Cu alloys with different Ni/Cu ratios (Ni Cu , Ni Cu , and Ni Cu ), the Ni Cu electrode exhibited the fastest electrochemical response and highest electrocatalytic activity toward methanol oxidation. The markedly enhanced performance of Ni Cu eletrocatalyst can be attributed to its alloyed structure with the proper Ni/Cu ratio and a large number of active sites on the surface of hierarchical structures.

A novel sulfonated diamine, 3,3′‐disulfonic acid‐bis[4‐(3‐aminophenoxy)phenyl]sulfone (SA‐DADPS), was prepared from m‐aminophenol and disodium‐3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone. The conditions necessary to synthesize and purify SA‐DADPS in high yields were investigated in some detail. This disulfonated aromatic diamine, containing ether and sulfone linkages, was used to prepare N‐methyl‐2‐pyrrolidinone‐soluble, six‐membered ring polyimide copolymers containing pendent sulfonic acid groups by a catalyzed one‐step high‐temperature polycondensation in m‐cresol. These materials showed much improved hydrolytic stability with respect to phthalimides. High‐molecular‐weight film‐forming statistical copolymers with controlled degrees of disulfonation were prepared through variations in the stoichiometric ratio of disulfonated diamine (SA‐DADPS) in its soluble triethylamine salt form to several unsulfonated diamines. Three unsulfonated diamines, bis[4‐(3‐aminophenoxy)phenyl] sulfone, 4,4′‐oxydianiline, and 1,3‐phenylenediamine, were used to prepare the copolymers. The characterization of the copolymers by 1H NMR, Fourier transform infrared, ion‐exchange capacity, and thermogravimetric analysis demonstrated that SA‐DADPS was quantitatively incorporated into the copolymers. Solution‐cast films of the sulfonated copolymers were prepared and afforded tough, ductile membranes with high glass‐transition temperatures. Methods were developed to acidify the triethylammonium salt membranes into their disulfonic acid form, this being necessary for proton conduction in a fuel cell. The synthesis and characterization of these materials are described in this article. Future articles will describe the performance of these copolymers as proton‐exchange membranes in hydrogen/air and direct methanol fuel cells. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 862–874, 2004

The ability to dynamically organize functional nanoparticles (NPs) via the use of environmental triggers (temperature, pH, light, or solvent polarity) opens up important perspectives for rapid and convenient construction of a rich variety of complex assemblies and materials with new structures and functionalities. Here, we report an unconventional strategy for crafting stable hairy NPs with light-enabled reversible and reliable self-assembly and tunable optical properties. Central to our strategy is to judiciously design amphiphilic star-like diblock copolymers comprising inner hydrophilic blocks and outer hydrophobic photoresponsive blocks as nanoreactors to direct the synthesis of monodisperse plasmonic NPs intimately and permanently capped with photoresponsive polymers. The size and shape of hairy NPs can be precisely tailored by modulating the length of inner hydrophilic block of star-like diblock copolymers. The perpetual anchoring of photoresponsive polymers on the NP surface renders the attractive feature of self-assembly and disassembly of NPs on demand using light of different wavelengths, as revealed by tunable surface plasmon resonance absorption of NPs and the reversible transformation of NPs between their dispersed and aggregated states. The dye encapsulation/release studies manifested that such photoresponsive NPs may be exploited as smart guest molecule nanocarriers. By extension, the star-like block copolymer strategy enables the crafting of a family of stable stimuli-responsive NPs (e.g., temperature- or pH-sensitive polymer-capped magnetic, ferroelectric, upconversion, or semiconducting NPs) and their assemblies for fundamental research in self-assembly and crystallization kinetics of NPs as well as potential applications in optics, optoelectronics, magnetic technologies, sensory materials and devices, catalysis, nanotechnology, and biotechnology.