Cobalt-Doped Ceria Sensitizer Effects on Metal Oxide Nanofibers: Heightened Surface Reactivity for High-Performing Chemiresistive Sensors.

Chemiresistive gas sensors based on semiconducting metal oxides typically rely on noble metal catalysts to enhance their sensitivity and selectivity. However, noble metal catalysts have several drawbacks for practical utilization, including their high cost, their propensity for spontaneous agglomeration, and poisoning effects with certain types of gases. As such, in the interest of commercializing the chemiresistive gas sensor technology, we propose an alternative design for a noble-metal-free sensing material through the case study of Co-doped ceria (Co-CeO2) catalysts embedded in a SnO2 matrix. In this investigation, we utilized electrospinning and subsequent calcination to prepare Co-CeO2 catalyst nanoparticles integrated with SnO2 nanofibers (NFs) with uniform particle distribution and particle size regulation down to the sub-2 nm regime. The resulting Co-CeO2@SnO2 NFs exhibited superior gas sensing characteristics toward isoprene (C5H8) gas, a significant biomarker for monitoring the onset of various diseases through breath diagnostics. In particular, we identified that the Co-CeO2 catalysts, owing to the transition metal doping, facilitated the spillover of chemisorbed oxygen species to the SnO2 sensing body. This resulting in the sensor having a 27.4-fold higher response toward 5 ppm of C5H8 (compared to pristine SnO2), exceptionally high selectivity, and a low detection limit of 100 ppb. The sensor also exhibited high stability for prolonged response-recovery cycles, attesting to the strong anchoring of Co-CeO2 catalysts in the SnO2 matrix. Based on our findings, the transition metal-doped metal oxide catalysts, such as Co-CeO2, demonstrate strong potential to completely replace noble metal catalysts, thereby advancing the development of the commercially viable chemiresistive gas sensors free from noble metals, capable of detecting target gases at sub-ppm levels.

Hydrovoltaic Electricity Generator with Hygroscopic Materials: A Review and New Perspective.

The global energy crisis caused by the overconsumption of nonrenewable fuels has prompted researchers to develop alternative strategies for producing electrical energy. In this review, a fascinating strategy that simply utilizes water, an abundant natural substance throughout the globe and even in air as moisture, as a power source is introduced. The concept of the hydrovoltaic electricity generator (HEG) proposed herein involves generating an electrical potential gradient by exposing the two ends of the HEG device to dissimilar physicochemical environments, which leads to the production of an electrical current through the active material. HEGs, with a large variety of viable active materials, have much potential for expansion toward diverse applications including permanent and/or emergency power sources. In this review, representative HEGs that generate electricity by the mechanisms of diffusion, streaming, and capacitance as case studies for building a fundamental understanding of the electricity generation process are discussed. In particular, by comparing the use and absence of hygroscopic materials, HEG mechanism studies to establish active material design principles are meticulously elucidated. The review with future perspectives on electrode design using conducting nanomaterials, considerations for high performance device construction, and potential impacts of the HEG technology in improving the livelihoods are reviewed.

Advancing Breathability of Respiratory Nanofilter by Optimizing Pore Structure and Alignment in Nanofiber Networks.

Respiratory masks are the primary and most effective means of protecting individuals from airborne hazards such as droplets and particulate matter during public engagements. However, conventional electrostatically charged melt-blown microfiber masks typically require thick and dense membranes to achieve high filtration efficiency, which in turn cause a significant pressure drop and reduce breathability. In this study, we have developed a multielectrospinning system to address this issue by manipulating the pore structure of nanofiber networks, including the use of uniaxially aligned nanofibers created via an electric-field-guided electrospinning apparatus. In contrast to the common randomly collected microfiber membranes, partially aligned dual-nanofiber membranes, which are fabricated via electrospinning of a random 150 nm nanofiber base layer and a uniaxially aligned 450 nm nanofiber spacer layer on a roll-to-roll collector, offer an efficient way to modulate nanofiber membrane pore structures. Notably, the dual-nanofiber configuration with submicron pore structure exhibits increased fiber density and decreased volume density, resulting in an enhanced filtration efficiency of over 97% and a 50% reduction in pressure drop. This leads to the highest quality factor of 0.0781. Moreover, the submicron pore structure within the nanofiber networks introduces an additional sieving filtration mechanism, ensuring superior filtration efficiency under highly humid conditions and even after washing with a 70% ethanol solution. The nanofiber mask provides a sustainable solution for safeguarding the human respiratory system, as it effectively filters and inactivates human coronaviruses while utilizing 130 times fewer polymeric materials than melt-blown filters. This reusability of our filters and their minimum usage of polymeric materials would significantly reduce plastic waste for a sustainable global society.

Rapid Joule Heating Synthesis of Oxide-Socketed High-Entropy Alloy Nanoparticles as CO2 Conversion Catalysts.

The unorthodox surface chemistry of high-entropy alloy nanoparticles (HEA-NPs), with numerous interelemental synergies, helps catalyze a variety of essential chemical processes, such as the conversion of CO2 to CO, as a sustainable path to environmental remediation. However, the risk of agglomeration and phase separation in HEA-NPs during high-temperature operations are lasting issues that impede their practical viability. Herein, we present HEA-NP catalysts that are tightly sunk in an oxide overlayer for promoting the catalytic conversion of CO2 with exceptional stability and performance. We demonstrated the controlled formation of conformal oxide overlayers on carbon nanofiber surfaces via a simple sol-gel method, which facilitated a large uptake of metal precursor ions and helped to decrease the reaction temperature required for nanoparticle formation. During the rapid thermal shock synthesis process, the oxide overlayer would also impede nanoparticle growth, resulting in uniformly distributed small HEA-NPs (2.37 ± 0.78 nm). Moreover, these HEA-NPs were firmly socketed in the reducible oxide overlayer, enabling an ultrastable catalytic performance involving >50% CO2 conversion with >97% selectivity to CO for >300 h without extensive agglomeration. Altogether, we establish the rational design principles for the thermal shock synthesis of high-entropy alloy nanoparticles and offer a helpful mechanistic perspective on how the oxide overlayer impacts the nanoparticle synthesis behavior, providing a general platform for the designed synthesis of ultrastable and high-performance catalysts that could be utilized for various industrially and environmentally relevant chemical processes.

Free-Standing Carbon Nanofibers Protected by a Thin Metallic Iridium Layer for Extended Life-Cycle Li-Oxygen Batteries.

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.

Lithium-Air Batteries: Air-Breathing Challenges and Perspective.

Lithium-oxygen (Li-O2) batteries have been intensively investigated in recent decades for their utilization in electric vehicles. The intrinsic challenges arising from O2 (electro)chemistry have been mitigated by developing various types of catalysts, porous electrode materials, and stable electrolyte solutions. At the next stage, we face the need to reform batteries by substituting pure O2 gas with air from Earth's atmosphere. Thus, the key emerging challenges of Li-air batteries, which are related to the selective filtration of O2 gas from air and the suppression of undesired reactions with other constituents in air, such as N2, water vapor (H2O), and carbon dioxide (CO2), should be properly addressed. In this review, we discuss all key aspects for developing Li-air batteries that are optimized for operating in ambient air and highlight the crucial considerations and perspectives for future air-breathing batteries.

High-density Fibrous Polyimide Sponges with Superior Mechanical and Thermal Properties.

A relatively low compressive strength significantly limits the practical application of sponges made from electrospun fibers because of an ultralow density <10 mg/cm3. To solve this problem, fibrous polyimide sponges with high density (HDPISG) were prepared using a "self-gluing" concept. The HDPISG have a density of up to 280 mg/cm3 and porosity >80%, and showed good breathability. The compressive strength increased significantly as the sponge densities increased. The HDPISG with a density of 280 mg/cm3 has the highest compressive strength of 5190 and 35,900 kPa under 50 and 80% compression, respectively. The small HDPISG can even hold weights more than ten thousand times of the weight of the sponge. The HDPISG also possess excellent mechanical properties after thermal treatments and no loss of compressive strength can be seen after heating at 300 °C for 30 h. Further study indicates that the HDPISG can maintain their main shape after carbonization.