New inorganic–organic proton conducting membranes based on Nafion and [(ZrO2)·(SiO2)0.67] nanoparticles: Synthesis vibrational studies and conductivity

In this report is described the preparation of six nanocomposite membranes of formula {Nafion/_[(ZrO_2)⋅(SiO_2)0.67]ΨZrO₂}$\{\text{Nafion}/{[(\text{Zr}{\text{O}}_2)\cdot {(\text{Si}{\text{O}}_2)}_{0.67}]}_{{\Psi }_{\text{Zr}{\text{O}}_2}}\}$ with ΨZrO₂${\Psi }_{\text{Zr}{\text{O}}_2}$ ranging from 0 to 1.79 based on Nafion^® and [(ZrO₂)·(SiO₂)_0.67] nanofiller. Morphology investigations carried out by SEM measurements indicate that the composition of membranes is asymmetric. Indeed, with respect to the direction of the films after casting procedure, the top side (A-side) and bottom side (B-side) present a different nanofiller concentration. The concentration of nanofiller increases gradually from A to B side. The membranes present thicknesses ranging from 170 to 350 nm and are studied by FT-IR ATR and micro-Raman measurements.     

The influence of the CO inhibition effect on the estimation of the H2 purification unit surface

The CO inhibition effect on H₂ permeance through commercial Pd-based membranes was analysed by means of permeation measurements at different CO compositions (0–30% molar) and temperatures (593–723 K) with the aim to determine the increase of the membrane area in order to compensate the H₂ flux reduction owing to the CO inhibition effect. The permeance of H₂ fed with carbon monoxide was observed to decrease with respect to the case of pure hydrogen. At 647 K the H₂ permeance of a pure feed of 316 μmol m⁻² s⁻¹ Pa^−0.5 reduces progressively until 275 μmol m⁻² s⁻¹ Pa^−0.5 when 15% or more of CO is present in the system, until it reaches a plateau at 20%. The inhibition effect occurring when CO is present in the feed stream reduces with the progressive temperature increase; the reduction of the permeance decreases exponentially by 23% at 593 K and by 3% at 723 K with 10% of CO. The inhibition effect is seen to be reversible. An H₂ flux profile in a Sieverts' plot shows the effect produced by the increase of the CO composition along the Pd-based membrane length. The H₂ flux profile allows the area of a Pd-based membrane to be evaluated in order to have the same permeate flow rate of H₂ when it is fed with CO or as a pure stream. Moreover, a qualitative comparison between the H₂ flux profiles and a previously proposed model has been carried out.     

Optical Nanoscale Pool‐on‐Surface Design for Control Sensing Recognition of Multiple Cations

General design of optical chemical nanosensors is needed to develop efficient sensing systems with high flexibility, and low capital cost for control recognition of toxic analytes. Here, we designed optical chemical nanosensors for simple, high‐speed detection of multiple toxic metal ions. The systematic design of the nanosensors was based on densely patterned chromophores with intrinsic mobility, namely, “building‐blocks” onto three‐dimensional (3D) nanoscale structures. The ability to precisely modify the nanoscale pore surfaces by using a broad range of chromophores that have different molecular sizes and characteristics enables detection of multiple toxic ions. A key feature of this building‐blocks design strategy is that the surface functionality and good adsorption characteristics of the fabricated nanosensor arrays enabled the development of “pool‐on‐surface” sensing systems in which high flux of the metal analytes across the probe molecules was achieved without significant kinetic hindrance. Such a sensing design enabled sensitive recognition of metal ions up to sub‐picomolar detection limits (～10^?11 mol dm^?3), for first time, with rapid response time within few seconds. Moreover, because these sensing pools exhibited long‐term stability, reversibility and selectivity in detecting most pollutant cations, for example, Cr(VI), Pb(II), Co(II), and Pd(II) ions, they are practical and inexpensive. The key result in our study is that the pool‐on‐surface design for optical nanosensors exhibited significant ion‐selective ability of these target ions from environmental samples and waste disposals.     

Streptavidin‐Functionalized Three‐Dimensional Ordered Nanoporous Silica Film for Highly Efficient Chemiluminescent Immunosensing

A novel biofunctionalized three‐dimensional ordered nanoporous SiO₂ film is designed for construction of chemiluminescent analytical devices. The nanoporous SiO₂ film is prepared with self‐assembly of polystyrene spheres as a template and 5‐nm SiO₂ nanoparticles on a glass slide followed by a calcination process. Its functionalization with streptavidin is achieved by using 3‐glycidoxypropyltrimethoxysilane as a linker. Based on the high‐selectivity recognition of streptavidin to biotin‐labeled antibody a novel immunosensor is further constructed for highly efficient chemiluminescent immunoassay. The surface morphologies and fabrication processes of both the biofunctionalized film and the immunosensor are characterized using scanning electron microscopy, atomic‐force microscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The three‐dimensional ordered nanopores have high capacity for loading of streptavidin and antibody and promote the mass transport of immunoreagents for immunoreaction, thus the resulting chemiluminescent immunosensor shows wide dynamic range for fast immunoassay, and good reproducibility and stability. Using carbohydrate antigen 125 (CA 125) as a model, the highly efficient chemiluminescent immunosensing shows a linear range of three orders of magnitude, from 0.5 to 400 U mL^?1. This work provides a biofunctionalized porous nanostructure for promising biosensing applications.     

Amino‐Functionalized Silica Membranes for Enhanced Carbon Dioxide Permeation

Functionalization of silica membranes is important for enhancing surface interactions with specific chemicals in order to enhance separations. It is important to develop synthesis strategies that allow control over the density and the surface chemistry of the functional group in order to tailor the membrane separation properties. In this paper we investigate the ability of amino functionalization to enhance CO₂ transport in silica membranes. Specifically, we examine three synthesis techniques for functionalizing silica membranes with amino groups that result in different surface chemistries of the silica membranes. Silica membranes are amino‐functionalized by atomic layer deposition (ALD) with aminopropyldimethylethoxysilane (APDMES), ethylenediamine (EDA)‐assisted APDMES ALD, and direct attachment of aminopropyltriethoxysilane (APTES) from the liquid phase. Three different reaction schemes are presented and verified by using Fourier‐transform infrared (FTIR) spectroscopy. The FTIR measurements were performed on silica powders that were processed using the same reaction conditions as the membranes used in this study. The differences in reaction schemes are correlated with changes in the CO₂ facilitation characteristics. It is found that high loadings of amino groups, in which interaction with the silica surface is minimized, promote the highest CO₂ transport.     

Electrically Tunable Nanoporous Carbon Hybrid Actuators

A novel nanoporous carbon/electrolyte hybrid material is reported for use in actuation. The nanoporous carbon matrix provides a 3D network that combines mechanical strength, light weight, and low cost with an extremely high surface area. In contrast to lower dimensional nanomaterials, the nanoporous carbon matrix can be prepared in the form of macroscopic monolithic samples that can be loaded in compression. The hybrid material is formed by infiltrating the free internal pore volume of the carbon with an electrolyte. Actuation is prompted by polarizing the internal interfaces via an applied electric bias. It is found that the strain amplitude is proportional to the Brunauer‐Emmett‐Teller (BET) mass specific surface area, with reversible volume strain amplitudes up to the exceptionally high value of 6.6%. The mass‐specific strain energy density compares favorably to reported values for piezoceramics and for nanoporous metal actuators.     

Nanoporous Surface High-Entropy Alloys as Highly Efficient Multisite Electrocatalysts for Nonacidic Hydrogen Evolution Reaction

Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum-free electrocatalysts for large-scale electrochemical production of pure hydrogen fuel, but most state-of-the-art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high-entropy CuNiMoFe surface is reported to hold great promise as cost-effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high-entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm⁻² in 1 m  KOH and pH 7 buffer electrolytes, respectively; ≈46- and ≈14-fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high-performance nonacidic HER electrocatalytic electrodes in water electrolysis.     

Robust Metallic Actuators Based on Nanoporous Gold Rapidly Dealloyed from Gold–Nickel Precursors

Dealloyed nanoporous gold (np-Au) has applications as oxygen reduction catalysis in Li-air batteries and fuel cells, or as actuators to convert electricity into mechanical energy. However, it faces the challenges of coarsening-induced structure instability, mechanical weakness due to low relative densities, and slow dealloying rates. Here, monolithic np-Au is dealloyed from a single-phase Au₂₅Ni₇₅ solid-solution at a one-order faster dealloying rate, ultra-low residual Ni content, and importantly, one-third more relative density than np-Au dealloyed from conventional Au₂₅Ag₇₅. The small atomic radius and low dealloying potential of the sacrificing element Ni are intrinsically beneficial to fast produce high relative density np-Au, as predicted by a general model for dealloying of binary alloys and validated by experiments. Stable, durable, and reversible actuation of np-Au takes place under cyclic potential triggering in alkaline and acidic electrolytes with negligible coarsening-induced strain-shift. The thermal and mechanical robustness of bulk np-Au is confirmed by two-order slower ligament coarsening rates during annealing at 300 °C and 45 MPa macroscopic yielding strength distinctive from the typical early onset of plastic yielding. This article opens a rich direction to achieve high relative density np-Au which is essential for porous network connectivity, mechanical strength, and nanostructure robustness for electrochemical functionality.     

Dopamine: Just the Right Medicine for Membranes

Mussel‐inspired chemistry has attracted widespread interest in membrane science and technology. Demonstrating the rapid growth of this field over the past several years, substantial progress has been achieved in both mussel‐inspired chemistry and membrane surface engineering based on mussel‐inspired coatings. At this stage, it is valuable to summarize the most recent and distinctive developments, as well as to frame the challenges and opportunities remaining in this field. In this review, recent advances in rapid and controllable deposition of mussel‐inspired coatings, dopamine‐assisted codeposition technology, and photoinitiated grafting directly on mussel‐inspired coatings are presented. Some of these technologies have not yet been employed directly in membrane science. Beyond discussing advances in conventional membrane processes, emerging applications of mussel‐inspired coatings in membranes are discussed, including as a skin layer in nanofiltration, interlayer in metal‐organic framework based membranes, hydrophilic layer in Janus membranes, and protective layer in catalytic membranes. Finally, some critical unsolved challenges are raised in this field and some potential pathways are proposed to address them.     

Tough and Self‐Recoverable Thin Hydrogel Membranes for Biological Applications

Tough and self‐recoverable hydrogel membranes with micrometer‐scale thickness are promising for biomedical applications, which, however, rarely be realized due to the intrinsic brittleness of hydrogels. In this work, for the first time, by combing noncovalent DN strategy and spin‐coating method, we successfully fabricated thin (thickness: 5–100 µm), yet tough (work of extension at fracture: 10⁵–10⁷ J m^?3) and 100% self‐recoverable hydrogel membranes with high water content (62–97 wt%) in large size (≈100 cm²). Amphiphilic triblock copolymers, which form physical gels by self‐assembly, were used for the first network. Linear polymers that physically associate with the hydrophilic midblocks of the first network, were chosen for the second network. The inter‐network associations serve as reversible sacrificial bonds that impart toughness and self‐recovery properties on the hydrogel membranes. The excellent mechanical properties of these obtained tough and thin gel membranes are comparable, or even superior to many biological membranes. The in vitro and in vivo tests show that these hydrogel membranes are biocompatible, and postoperative nonadhesive to neighboring organs. The excellent mechanical and biocompatible properties make these thin hydrogel membranes potentially suitable for use as biological or postoperative antiadhesive membranes.