Proton Transport in Electrospun Hybrid Organic–Inorganic Membranes: An Illuminating Paradox

Chemistry and processing have to be judiciously combined to structure the membranes at various length scales to achieve efficient properties for polymer electrolyte membrane fuel cell to make it competitive for transport. Characterizing the proton transport at various length and space scales and understanding the interplays between the nanostructuration, the confinement effect, the interactions, and connectivity are consequently needed. The goal here is to study the proton transport in multiscale, electrospun hybrid membranes (EHMs) at length scales ranging from molecular to macroscopic by using complementary techniques, i.e., electrochemical impedance spectroscopy, pulsed field gradient‐NMR spectroscopy, and quasielastic neutron scattering. Highly conductive hybrid membranes (EHMs) are produced and their performances are rationalized taken into account the balances existing between local interaction driven mobility and large‐scale connectivity effects. It is found that the water diffusion coefficient can be locally decreased (2 × 10^?6 cm² s^?1) due to weak interactions with the silica network, but the macroscopic diffusion coefficient is still high (9.6 × 10^?6 cm² s^?1). These results highlight that EHMs have slow dynamics at the local scale without being detrimental for long‐range proton transport. This is possible through the nanostructuration of the membranes, controlled via processing and chemistry.     

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.     

Integration of biohydrogen fermentation and gas separation processes to recover and enrich hydrogen

An integrated system for biohydrogen production and separation was designed, constructed and operated where biohydrogen was fermented by Thermococcus litoralis, a heterotrophic archaebacterium, and a two-step gas separation process was coupled to recover and concentrate hydrogen. A special liquid seal system was built to deliver, compress and collect the laboratory scale, low volume gas mixtures consisting of hydrogen, nitrogen and carbon dioxide. As a result, gas mixture with 73% high hydrogen content was produced by a combination of a porous and a non-porous gas separation membrane.     

Aspects of skin permeability

The self-diffusion of salicylic acid has been monitored radiochemically through pigskins (whole and dermal) and human skins (whole, dermal and epidermal).
The effects of pH, temperature and changing dimethyl formamide (DMF) concentration on the penetration of salicylic acid through the various skin membranes have been evaluated.
Conclusions have been drawn as to the mechanisms operating and some comparisons to zeolite/polystyrene membranes have been made.
Quelques aspects de la perméabilite cutanée     

纳米多孔金电化学传感器构建及其对饮品中抗坏血酸的检测

基于纳米多孔金（nanoporous gold,NPG）对抗坏血酸的强电催化氧化作用,通过酸腐蚀制备NPG,构建纳米多孔电极（NPG/GCE）检测饮料中的抗坏血酸。通过循环伏安法和差分脉冲伏安（differential pulse voltammetry,DPV）法对抗坏血酸检测条件进行优化,确定最佳检测条件为pH 4.0的柠檬酸缓冲液。在优化条件下,利用DPV法对抗坏血酸进行检测,结果表明：在6.652 8～160 μg/mL的范围内,峰电流密度与抗坏血酸质量浓度呈良好的线性关系;该电极制备简单、灵敏度高、稳定性和抗干扰能力强,对饮料中抗坏血酸的快速检测有良好的应用潜力。