Liquid organic hydrogen carrier (LOHC) technology makes it possible to safely and easily store and transport hydrogen in large quantities for extended periods of time. To improve the efficiency of hydrogen supply via LOHC, there is a growing need for new LOHCs that exhibit high hydrogen storage capacity per unit volume and weight, efficient hydrogen release, low melting points for easy transport, and high boiling points for simplifying hydrogen purification, as well as cost-effective and large-scale production. Herein, we propose a promising LOHC candidate, 1-(n-phenylethyl)naphthalene (PEN), which has a high hydrogen storage capacity (60.8 kgH2·m–3), superior physical properties (wide liquid range, from −21 to 350 °C), and mass-produced compounds at low cost. PEN exhibited reversible hydrogen storage and release performance in consecutive cycles. Furthermore, we suggest an effective way to increase dehydrogenation performance by controlling the composition of stereoisomers generated during hydrogenation.

In article number 2105199, Yeon Sik Jung and co-workers achieve highly selective, quantitative, and multiplex detection of mixed trace level aromatic compound gases through synergistically integrated multimodal sensing. The design of the 3D cross-point multifunctional nanoarchitecture (3D-CMA) significantly enhances both chemoresistive sensing and surface-enhanced Raman spectroscopy simultaneously. 3D-CMA multimodal sensors accurately identify the composition and concentrations of mixed gases with very similar molecular structures.

It is evident that the exhaustive use of fossil fuels for decades has significantly contributed to global warming and environmental pollution. To mitigate the harm on the environment, lithium–oxygen batteries (LOBs) with a high theoretical energy density (3458 Wh kg–1Li2O2) compared to that of Li-ion batteries (LIBs) have been considered as an attractive alternative to fossil fuels. For this purpose, porous carbon materials have been utilized as promising air cathodes owing to their low cost, lightness, easy fabrication process, and high performance. However, the challenge thus far lies in the uncontrollable formation of Li2CO3 at the interface between carbon and Li2O2, which is detrimental to the stable electrochemical performance of carbon-based cathodes in LOBs. In this work, we successfully protected the surface of the free-standing carbon nanofibers (CNFs) by coating it with a layer of iridium metal through direct sputtering (CNFs@Ir), which significantly improved the lifespan of LOBs. Moreover, the Ir would play a secondary role as an electrochemical catalyst. This all-in-one cathode was evaluated for the formation and decomposition of Li2O2 during (dis)charging processes. Compared with bare CNFs, the CNFs@Ir cathode showed two times longer lifespan with 0.2 VLi lower overpotentials for the oxygen evolution reaction. We quantitatively calculated the contents of CO32– in Li2CO3 formed on the different surfaces of the bare CNFs (63% reduced) and the protected CNFs@Ir (78% reduced) cathodes after charging. The protective effects and the reaction mechanism were elucidated by ex situ analyses, including scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy.

Conductive porous materials having a high surface reactivity offer great promise for a broad range of applications. However, a general and scalable synthesis of such materials remains challenging. In this work, the facile synthesis of catalytic metal nanoparticles (NPs) embedded in 2D metal–organic frameworks (MOFs) is reported as highly active and conductive porous materials. After the assembly of 2D conductive MOFs (C-MOFs), i.e., Cu3(hexahydroxytriphenylene)2 [Cu3(HHTP)2], Pd or Pt NPs are functionalized within the cavities of C-MOFs by infiltration of metal ions and subsequent reduction. The unique structure of Cu3(HHTP)2 with a cavity size of 2 nm confines the bulk growth of metal NPs, resulting in ultra-small (≈2 nm) and well-dispersed metal NPs loaded in 2D C-MOFs. The Pd or Pt NPs-loaded Cu3(HHTP)2 exhibits remarkably improved NO2 sensing performance at room temperature due to the high reactivity of catalytic metal NPs and the high porosity of C-MOFs. The catalytic effect of Pd and Pt NPs on NO2 sensing of Cu3(HHTP)2, in terms of reaction rate kinetics and activation energy, is demonstrated.

Humidity sensors are essential components in wearable electronics for monitoring of environmental condition and physical state. In this work, a unique humidity sensing layer composed of nitrogen-doped reduced graphene oxide (nRGO) fiber on colorless polyimide film is proposed. Ultralong graphene oxide (GO) fibers are synthesized by solution assembly of large GO sheets assisted by lyotropic liquid crystal behavior. Chemical modification by nitrogen-doping is carried out under thermal annealing in H2(4%)/N2(96%) ambient to obtain highly conductive nRGO fiber. Very small (≈2 nm) Pt nanoparticles are tightly anchored on the surface of the nRGO fiber as water dissociation catalysts by an optical sintering process. As a result, nRGO fiber can effectively detect wide humidity levels in the range of 6.1–66.4% relative humidity (RH). Furthermore, a 1.36-fold higher sensitivity (4.51%) at 66.4% RH is achieved using a Pt functionalized nRGO fiber (i.e., Pt-nRGO fiber) compared with the sensitivity (3.53% at 66.4% RH) of pure nRGO fiber. Real-time and portable humidity sensing characteristics are successfully demonstrated toward exhaled breath using Pt-nRGO fiber integrated on a portable sensing module. The Pt-nRGO fiber with high sensitivity and wide range of humidity detection levels offers a new sensing platform for wearable humidity sensors.

Achieving an improved understanding of catalyst properties, with ability to predict new catalytic materials, is key to overcoming the inherent limitations of metal oxide based gas sensors associated with rather low sensitivity and selectivity, particularly under highly humid conditions. This study introduces newly designed bimetallic nanoparticles (NPs) employing bimetallic Pt-based NPs (PtM, where M = Pd, Rh, and Ni) via a protein encapsulating route supported on mesoporous WO3 nanofibers. These structures demonstrate unprecedented sensing performance for detecting target biomarkers (even at p.p.b. levels) in highly humid exhaled breath. Sensor arrays are further employed to enable pattern recognition capable of discriminating between simulated biomarkers and controlled breath. The results provide a new class of multicomponent catalytic materials, demonstrating potential for achieving reliable breath analysis sensing.

The feature describes two different types of chemical sensors, i.e., chemiresistive type sensors and optical sensors. For the chemiresistive type sensors, electrical signals are modulated during the reaction with chemical gas species. On the other hand, distinctive color changes are occurred in the case of optical sensors after the reaction with chemical analytes. The feature is designed for the review paper about one-dimensional nanofibrous sensing structures for chemiresistive type sensors and optical sensors. This is reported by Seon-Jin Choi, Luana Persano, Andrea Camposeo, Ji-Soo Jang, Won-Tae Koo, Sang-Joon Kim, Hee-Jin Cho, Il-Doo Kim and Dario Pisignano, in article number 1600569.

As a futuristic diagnosis platform, breath analysis is gaining much attention because it is a noninvasive, simple, and low cost diagnostic method. Very promising clinical applications have been demonstrated for diagnostic purposes by correlation analysis between exhaled breath components and specific diseases. In addition, diverse breath molecules, which serve as biomarkers for specific diseases, are precisely identified by statistical pattern recognition studies. To further improve the accuracy of breath analysis as a diagnostic tool, breath sampling, biomarker sensing, and data analysis should be optimized. In particular, development of high performance breath sensors, which can detect biomarkers at the ppb-level in exhaled breath, is one of the most critical challenges. Due to the presence of numerous interfering gas species in exhaled breath, selective detection of specific biomarkers is also important.

This Account focuses on chemiresistive type breath sensors with exceptionally high sensitivity and selectivity that were developed by combining hollow protein templated nanocatalysts with electrospun metal oxide nanostructures. Nanostructures with high surface areas are advantageous in achieving high sensitivity because the sensing signal is dominated by the surface reaction between the sensing layers and the target biomarkers. Furthermore, macroscale pores between one-dimensional (1D) nanostructures can facilitate fast gas diffusion into the sensing layers. To further enhance the selectivity, catalytic functionalization of the 1D metal oxide nanostructure is essential. However, the majority of conventional techniques for catalytic functionalization have failed to achieve a high degree of dispersion of nanoscale catalysts due to aggregation on the surface of the metal oxide, which severely deteriorates the sensing properties by lowering catalytic activity. This issue has led to extensive studies on monolithically dispersed nanoscale particles on metal oxides to maximize the catalytic performances.

Optically reduced graphene oxide (ORGO) sheets are successfully integrated on silver nanowire (Ag NW)-embedded transparent and flexible substrate. As a heating element, Ag NWs are embedded in a colorless polyimide (CPI) film by covering Ag NW networks using polyamic acid and subsequent imidization. Graphene oxide dispersed aqueous solution is drop-coated on the Ag NW-embedded CPI (Ag NW-CPI) film and directly irradiated by intense pulsed light to obtain ORGO sheets. The heat generation property of Ag NW-CPI film is investigated by applying DC voltage, which demonstrates unprecedentedly reliable and stable characteristics even in dynamic bending condition. To demonstrate the potential application in wearable chemical sensors, NO2 sensing characteristic of ORGO is investigated with respect to the different heating temperature (22.7–71.7 °C) of Ag NW-CPI film. The result reveals that the ORGO sheets exhibit high sensitivity of 2.69% with reversible response/recovery sensing properties and minimal deviation of baseline resistance of around 1% toward NO2 molecules when the temperature of Ag NW-CPI film is 71.7 °C. This work first demonstrates the improved reversible NO2 sensing properties of ORGO sheets on flexible and transparent Ag NW-CPI film assisted by Ag NW heating networks.

Macroporous WO3 nanotubes (NTs) functionalized with nanoscale catalysts were fabricated using coaxial electrospinning combined with sacrificial templating and protein-encapsulated catalysts. The macroporous thin-walled nanotubular structures were obtained by introducing colloidal polystyrene (PS) particles to a shell solution of W precursor and poly(vinylpyrrolidone). After coaxial electrospinning with a core liquid of mineral oil and subsequent calcination, open pores with an average diameter of 173 nm were formed on the surface of WO3 NTs due to decomposition of the PS colloids. In addition, catalytic Pd nanoparticles (NPs) were synthesized using bio-inspired protein cages, i.e., apoferritin, and uniformly dispersed within the shell solution and subsequently on the WO3 NTs. The resulting Pd functionalized macroporous WO3 NTs were demonstrated to be high performance hydrogen (H2) sensors. In particular, Pd-functionalized macroporous WO3 NTs exhibited a very high H2 response (Rair/Rgas) of 17.6 at 500 ppm with a short response time. Furthermore, the NTs were shown to be highly selective for H2 compared to other gases such as carbon monoxide (CO), ammonia (NH3), and methane (CH4). The results demonstrate a new synthetic method to prepare highly porous nanotubular structures with well-dispersed nanoscale catalysts, which can provide improved microstructures for chemical sensing.

A novel catalyst functionalization method, based on protein-encapsulated metallic nanoparticles (NPs) and their self-assembly on polystyrene (PS) colloid templates, is used to form catalyst-loaded porous WO3 nanofibers (NFs). The metallic NPs, composed of Au, Pd, or Pt, are encapsulated within a protein cage, i.e., apoferritin, to form unagglomerated monodispersed particles with diameters of less than 5 nm. The catalytic NPs maintain their nanoscale size, even following high-temperature heat-treatment during synthesis, which is attributed to the discrete self-assembly of NPs on PS colloid templates. In addition, the PS templates generate open pores on the electrospun WO3 NFs, facilitating gas molecule transport into the sensing layers and promoting active surface reactions. As a result, the Au and Pd NP-loaded porous WO3 NFs show superior sensitivity toward hydrogen sulfide, as evidenced by responses (Rair/Rgas) of 11.1 and 43.5 at 350 °C, respectively. These responses represent 1.8- and 7.1-fold improvements compared to that of dense WO3 NFs (Rair/Rgas = 6.1). Moreover, Pt NP-loaded porous WO3 NFs exhibit high acetone sensitivity with response of 28.9. These results demonstrate a novel catalyst loading method, in which small NPs are well-dispersed within the pores of WO3 NFs, that is applicable to high sensitivity breath sensors.

On page 3750, S. Hong, K. No, and co-workers describe highly ordered and well-aligned PbTiO3/TiN core-shell nanotubes that are fabricated via an AAO templating route followed by TiN and TiO2 ALD deposition and a subsequent PbO vapor reaction. Because of the TiN cores, which act as mechanical pillars and a core electrode, PbTiO3/TiN nanotubes keep their original shape after the vapor phase reaction, and they display well-defined piezoresponse hysteresis curves with a remnant piezoresponse.