Direct Immersion Annealing of Thin Block Copolymer Films

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene–poly­(methyl methacrylate) (PS–PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the “optimal long-range order” processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering

Uniform Ordered Two-Dimensional Mesoporous TiO₂ Nanosheets from Hydrothermal-Induced Solvent-Confined Monomicelle Assembly

Two-dimensional (2D) nanomaterials have been the focus of substantial research interest recently owing to their fascinating and excellent properties. However, 2D porous materials have remained quite rare due to the difficulty of creating pores in 2D nanostructures. Here, we have synthesized a novel type of single-layered 2D mesoporous TiO₂ nanosheets with very uniform size and thickness as well as ordered mesostructure from an unprecedented hydrothermal-induced solvent-confined assembly approach. The F127/TiO₂ spherical monomicelles are first formed and redispersed in ethanol and glycerol, followed by a hydrothermal treatment to assemble these subunits into single-layered 2D mesostructure owing to the confinement effect of highly adhered glycerol solvent. The obtained 2D mesoporous TiO₂ nanosheets have a relative mean size at around 500 × 500 nm and can be randomly stacked into a bulk. The TiO₂ nanosheets possess only one layer of ordered mesopores with a pore size of 4.0 nm, a very high surface area of 210 m² g^–1 and a uniform thickness of 5.5 nm. The thickness can be further manipulated from 5.5 to 27.6 nm via simply tuning precursor concentration or solvent ratio. Due to the well-defined 2D morphology and large mesoporosity as well as crystalline anatase mesopore walls, these uniform TiO₂ nanosheets are capable of providing large accessible voids for sodium ion adsorption and intercalation as well as preventing volume expansion. As expected, these mesoporous TiO₂ nanosheets have exhibited an excellent reversible capacity of 220 mAh g^–1 at 100 mA g^–1 as sodium-ion battery anodes, and they can retain at 199 mAh g^–1 after numerous cycles at different current densities. The capacity is retained at 44 mAh g^–1 even at a large current density of 10 A g^–1 after 10 000 cycles, demonstrating a remarkable performance for energy storage

Spatial Isolation of Carbon and Silica in a Single Janus Mesoporous Nanoparticle with Tunable Amphiphilicity

Like surfactants with tunable hydrocarbon chain length, Janus nanoparticles also possess the ability to stabilize emulsions. The volume ratio between the hydrophilic and hydrophobic domains in a single Janus nanoparticle is very important for the stabilization of emulsions, which is still a great challenge. Herein, dual-mesoporous Fe₃O₄@mC&mSiO₂ Janus nanoparticles with spatial isolation of hydrophobic carbon and hydrophilic silica at the single-particle level have successfully been synthesized for the first time by using a novel surface-charge-mediated selective encapsulation approach. The obtained dual-mesoporous Fe₃O₄@mC&mSiO₂ Janus nanoparticles are made up of a pure one-dimensional mesoporous SiO₂ nanorod with tunable length (50–400 nm), ∼100 nm wide and ∼2.7 nm mesopores and a closely connected mesoporous Fe₃O₄@mC magnetic nanosphere (∼150 nm diameter, ∼10 nm mesopores). As a magnetic “solid amphiphilic surfactant”, the hydrophilic/hydrophobic ratio can be precisely adjusted by varying the volume ratio between silica and carbon domains, endowing the Janus nanoparticles surfactant-like emulsion stabilization ability and recyclability under a magnetic field. Owing to the total spatial separation of carbon and silica, the Janus nanoparticles with an optimized hydrophilic/hydrophobic ratio show spectacular emulsion stabilizing ability, which is crucial for improving the biphasic catalysis efficiency. By selectively anchoring catalytic active sites into different domains, the fabricated Janus nanoparticles show outstanding performances in biphasic reduction of 4-nitroanisole with 100% conversion efficiency and 700 h^–1 high turnover frequency for biphasic cascade synthesis of cinnamic acid

Tandem Chemistry with Janus Mesopores Accelerator for Efficient Aqueous Batteries

A reliable solid electrolyte interphase (SEI) on the metallic Zn anode is imperative for stable Zn-based aqueous batteries. However, the incompatible Zn-ion reduction processes, scilicet simultaneous adsorption (capture) and desolvation (repulsion) of Zn2+(H2O)6, raise kinetics and stability challenges for the design of SEI. Here, we demonstrate a tandem chemistry strategy to decouple and accelerate the concurrent adsorption and desolvation processes of the Zn2+ cluster at the inner Helmholtz layer. An electrochemically assembled perforative mesopore SiO2 interphase with tandem hydrophilic −OH and hydrophobic −F groups serves as a Janus mesopores accelerator to boost a fast and stable Zn2+ reduction reaction. Combining in situ electrochemical digital holography, molecular dynamics simulations, and spectroscopic characterizations reveals that −OH groups capture Zn2+ clusters from the bulk electrolyte and then −F groups repulse coordinated H2O molecules in the solvation shell to achieve the tandem ion reduction process. The resultant symmetric batteries exhibit reversible cycles over 8000 and 2000 h under high current densities of 4 and 10 mA cm–2, respectively. The feasibility of the tandem chemistry is further evidenced in both Zn//VO2 and Zn//I2 batteries, and it might be universal to other aqueous metal-ion batteries