Oxygen Reduction Reaction Performance of [MTBD][beti]‐Encapsulated Nanoporous NiPt Alloy Nanoparticles

Recent advances in oxygen reduction reaction catalysis for proton exchange membrane fuel cells (PEMFCs) include i) the use of electrochemical dealloying to produce high surface area and sometimes nanoporous catalysts with a Pt‐enriched outer surface, and ii) the observation that oxygen reduction in nanoporous materials can be potentially enhanced by confinement effects, particularly if the chemical environment within the pores can bias the reaction toward completion. Here, these advances are combined by incorporating a hydrophobic, protic ionic liquid, [MTBD][beti], into the pores of high surface‐area NiPt alloy nanoporous nanoparticles (np‐NiPt/C + [MTBD][beti]). The high O₂ solubility of the [MTBD][beti], in conjunction with the confined environment within the pores, biases reactant O₂ toward the catalytic surface, consistent with an increased residence time and enhanced attempt frequencies, resulting in improved reaction kinetics. Half‐cell measurements show the np‐NiPt/C+[MTBD][beti] encapsulated catalyst to be nearly an order of magnitude more active than commercial Pt/C, a result that is directly translated into operational PEMFCs.     

Block Copolymer Permeable Membrane with Visualized High‐Density Straight Channels of Poly(ethylene oxide)

A simple fabrication, scalable to centimeter scale, of a permeable membrane made of block copolymer containing molecular transport channels is demonstrated by coating photo‐crosslinkable liquid‐crystalline block copolymer, consisting of poly(ethylene oxide) (PEO) and poly(methacrylate) (PMA) bearing stilbene (Stb) mesogens in the side chains (PEO₁₁₄‐b‐PMA(Stb)₅₂), onto a sacrificial cellulose acetate film substrate. After thermal annealing, perpendicularly aligned and hexagonally arranged PEO cylindrical domains with a surface density of 10¹¹ cm^?2 were formed and then fixed efficiently by photo‐crosslinking the stilbene moieties in the PMA(Stb) domains by [2 + 2] dimerization. The fully penetrating straight PEO cylindrical domains across the 480‐nm‐thick membrane were well‐defined and visualized as molecule‐transport channels. After exfoliated by removal of the cellulose acetate layer, the membrane could be transferred onto another substrate by either scooping or a horizontal lifting method. Throughout the processes, the fully penetrating PEO channels across the membrane are preserved to open at both ends. A simple permeation experiment demonstrates that rhodamine dyes permeate efficiently through the PEO cylindrical channels of the annealed membrane but not across a non‐annealed one.     

Solution‐Processed Nanoporous Organic Semiconductor Thin Films: Toward Health and Environmental Monitoring of Volatile Markers

Porous materials are ubiquitous in nature and have found a wide range of applications because of their unique absorption, optical, mechanical, and catalytic properties. Large surface‐area‐to‐volume ratio is deemed a key factor contributing to their catalytic properties. Here, it is shown that introducing tunable nanopores (50–700 nm) to organic semiconductor thin films enhances their reactivity with volatile organic compounds by up to an order of magnitude, while the surface‐area‐to‐volume ratio is almost unchanged. Mechanistic investigations show that nanopores grant direct access to the highly reactive sites otherwise buried in the conductive channel of the transistor. The high reactivity of nanoporous organic field‐effect transistors leads to unprecedented ultrasensitive, ultrafast, selective chemical sensing below the 1 ppb level on a hundred millisecond time scale, enabling a wide range of health and environmental applications. Flexible sensor chip for monitoring breath ammonia is further demonstrated; this is a potential biomarker for chronic kidney disease.     

Gold Nanoparticles and g‐C3N4‐Intercalated Graphene Oxide Membrane for Recyclable Surface Enhanced Raman Scattering

Toxic organic pollutants in the aquatic environment cause severe threats to both humans and the global environment. Thus, the development of robust strategies for detection and removal of these organic pollutants is essential. For this purpose, a multifunctional and recyclable membrane by intercalating gold nanoparticles and graphitic carbon nitride into graphene oxide (GNPs/g‐C₃N₄/GO) is fabricated. The membranes exhibit not only superior surface enhanced Raman scattering (SERS) activity attributed to high preconcentration ability to analytes through π–π and electrostatic interactions, but also excellent catalytic activity due to the enhanced electron–hole separation efficiency. These outstanding properties allow the membrane to be used for highly sensitive detection of rhodamine 6G with a limit of detection of 5.0 × 10^?14m and self‐cleaning by photocatalytic degradation of the adsorbed analytes into inorganic small molecules, thus achieving recyclable SERS application. Furthermore, the excellent SERS activity of the membrane is demonstrated by detection of 4‐chlorophenol at less than nanomolar level and no significant SERS or catalytic activity loss was observed when reusability is tested. These results suggest that the GNPs/g‐C₃N₄/GO membrane provides a new strategy for eliminating traditional, single‐use SERS substrates, and expands practical SERS application to simultaneous detection and removal of environmental pollutants.     

Top‐Down Fabrication of High Quality III–V Nanostructures by Monolayer Controlled Sculpting and Simultaneous Passivation

In the fabrication of III–V semiconductor nanostructures for electronic and optoelectronic devices, techniques that are capable of removing material with monolayer precision are as important as material growth to achieve best device performances. A robust chemical treatment is demonstrated using sulfur (S)‐oleylamine (OA) solution, which etches layer by layer in an inverse epitaxial fashion and simultaneously passivates the surface. The application of this process to push the limits of top‐down nanofabrication is demonstrated by the realization of InP‐based high optical quality nanowire arrays, with aspect ratios more than 50, and nanostructures with new topologies. The findings are relevant for other III–V semiconductors and have potential applications in III–V device technologies.     

Nanowrinkled and Nanoporous Polyethylene Membranes Via Entanglement Arrangement Control

Crystalline homopolymers, including polyethylene (PE), which has the simplest architecture, form a nanometer‐sized combination of crystalline and amorphous components, but their arrangement control, similar to self‐assembled phase‐separation of block‐copolymers, is usually difficult. However, molecular entanglements trapped between crystalline and amorphous components of homopolymers coincide with the segmental linking points on the interfaces of the microphase separation for block copolymers. Nanowrinkled PE membranes are prepared with a network of 30 nm‐thick homogeneous lamellae using a novel entanglement control technique composed of biaxial melt‐drawing and melt‐shrinking procedures, which are limited for highly entangled ultrahigh molecular weight materials. Such a network arrangement of nanowrinkling lamellae spreading on membrane surface and also across the membrane thickness improves the mechanical properties of both tensile strength and tearing strength. Subsequent cold‐drawing causes delamination of the lamellar interfaces, leading to the resultant nanoporous morphology composed of passing‐through channels that are several tens of nanometers in diameter, without any solvent processing.     

Earth‐Abundant and Durable Nanoporous Catalyst for Exhaust‐Gas Conversion

Precious metals (Pt and Pd) and rare earth elements (Ce in the form of CeO₂) are typical materials for heterogeneous exhaust‐gas catalysts in automotive systems. However, their limited resources and high market‐driven prices are principal issues in realizing the path toward a more sustainable society. In this regard, herein, a nanoporous NiCuMnO catalyst, which is both abundant and durable, is synthesized by one‐step free dealloying. The catalyst thus developed exhibits catalytic activity and durability for NO reduction and CO oxidation. Microstructure characterization indicates a distinct structural feature: catalytically active Cu/CuO regions are tangled with a stable nanoporous NiMnO network after activation. The results obtained by in situ transmission electron microscopy during NO reduction clearly capture the unique reaction‐induced self‐transformation of the nanostructure. This finding can possibly pave the way for the design of new catalysts for the conversion of exhaust gas based on the element strategy.     

Remarkable Improvements in Volumetric Energy and Power of 3D MnO2 Microsupercapacitors by Tuning Crystallographic Structures

Transition‐metal oxides as faradaic charge‐storage intermediates sandwiched between conductor and electrolyte are key components to store/deliver high‐density energy in microsupercapacitors for many applications in miniaturized portable electronics and microelectromechanical systems. While the conductor facilitating their electron transports, they generally suffer from a switch of rate‐determining step to their sluggish redox reactions in pseudocapacitive energy storage, during which poor cation accessibility and diffusion leads to high internal resistances and lowers volumetric capacitance and rate performance. Here it is shown that the faradaic processes in a model system of MnO₂ can be radically boosted by tuning crystallographic structures from cryptomelane (α‐MnO₂) to birnessite (δ‐MnO₂). As a result of greatly enhanced Na⁺ accessibility and diffusion, 3D layered crystalline δ‐MnO₂ microelectrodes exhibit volumetric capacitance as high as ≈922 F cm^?3 (≈1.5‐fold higher than α‐MnO₂, ≈617 F cm^?3) and excellent rate performance. This enlists δ‐MnO₂ microsupercapacitor to deliver ultrahigh stack electrical powers (up to ≈295 W cm^?3) while maintaining volumetric energy density much higher than that of thin‐film lithium battery.     

Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

An O2 Self‐Sufficient Biomimetic Nanoplatform for Highly Specific and Efficient Photodynamic Therapy

Conventional oxygen‐dependent photodynamic therapy (PDT) has faced severe challenges because of the non‐specificity of most available photosensitizers (PSs) and the hypoxic nature of tumor tissues. Here, an O₂ self‐sufficient cell‐like biomimetic nanoplatform (CAT‐PS‐ZIF@Mem) consisting of the cancer cell membrane (Mem) and a cytoskeleton‐like porous zeolitic imidazolate framework (ZIF‐8) with the embedded catalase (CAT) protein molecules and Al(III) phthalocyanine chloride tetrasulfonic acid (AlPcS₄, defined as PS) is developed. Because of the immunological response and homologous targeting abilities of the cancer cell membrane, CAT‐PS‐ZIF@Mem is selectively accumulated at the tumor site and taken up effectively by tumor cells after intravenous injection. After the intracellular H₂O₂ penetration into the framework, it is catalyzed by CAT to produce O₂ at the hypoxic tumor site, facilitating the generation of toxic ¹O₂ for highly effective PDT in vivo under near‐infrared irradiation. By integrating the immune escape, cell homologous recognition, and O₂ self‐sufficiency, this cell‐like biomimetic nanoplatform demonstrates highly specific and efficient PDT against hypoxic tumor cells with much reduced side‐effect on normal tissues.