Flash-Thermal Shock Synthesis of Single Atoms in Ambient Air.

Single-atom catalysts feature interesting catalytic activity toward applications that rely on surface reactions such as electrochemical energy storage, catalysis, and gas sensors. However, conventional synthetic approaches for such catalysts require extended periods of high-temperature annealing in vacuum systems, limiting their throughput and increasing their production cost. Herein, we report an ultrafast flash-thermal shock (FTS)-induced annealing technique (temperature > 2850 °C, <10 ms duration, and ramping/cooling rates of ∼105 K/s) that operates in an ambient-air environment to prepare single-atom-stabilized N-doped graphene. Melamine is utilized as an N-doping source to provide thermodynamically favorable metal-nitrogen bonding sites, resulting in a uniform and high-density atomic distribution of single metal atoms. To demonstrate the practical utility of the single-atom-stabilized N-doped graphene produced by the FTS method, we showcased their chemiresistive gas sensing capabilities and electrocatalytic activities. Overall, the air-ambient, ultrafast, and versatile (e.g., Co, Ni, Pt, and Co-Ni dual metal) FTS method provides a general route for high-throughput, large area, and vacuum-free manufacturing of single-atom catalysts.

Three-Dimensional MoS2/MXene Heterostructure Aerogel for Chemical Gas Sensors with Superior Sensitivity and Stability.

The concept of integrating diverse functional 2D materials into a heterostructure provides platforms for exploring physics that cannot be accessed in a single 2D material. Here, physically mixing two 2D materials, MXene and MoS2, followed by freeze-drying is utilized to successfully fabricate a 3D MoS2/MXene van der Waals heterostructure aerogel. The low-temperature synthetic approach effectively suppresses significant oxidation of the Ti3C2Tx MXene and results in a hierarchical and freestanding 3D heterostructure composed of high-quality MoS2 and MXene nanosheets. Functionalization of MXene with a MoS2 catalytic layer substantially improves sensitivity and long-term stability toward detection of NO2 gas, and computational studies are coupled with experimental results to elucidate that the mechanism behind enhancements in the gas-sensing properties is effective inhibition of HNO2 formation on the MXene surface, due to the presence of MoS2. Overall, this study has a great potential for expansion of applicability to other classes of two-dimensional materials as a general synthesis method, to be applied in future fields of catalysis and electronics.

Bidirectional Water-Stream Behavior on a Multifunctional Membrane for Simultaneous Energy Generation and Water Purification.

Hydroelectric nanogenerators have been previously proposed to recycle various water resources and polluted water. However, as conventional hydroelectric nanogenerators only utilize water resources, they cannot provide a fundamental solution for water recycling. In this study, a water purification membrane is proposed that can simultaneously generate electricity during the purification process (electricity generation and purification membrane (EPM)) for water recycling. As polluted water passes through the EPM, the water is purified in the perpendicular direction, while electricity is simultaneously produced in the horizontal direction by the movement of ions. Notably, the EPM exhibits high energy generation performance (maximum power 16.44 µW and energy 15.16 mJ) by the streaming effect of water-streaming carbon nanotubes (CNTs). Moreover, by using a poly(acrylic acid)/carboxymethyl cellulose (PAA/CMC) binder to EPM, the energy-generation performance and long-term stability are substantially improved and outstanding mechanical stability is provided, regardless of the acidity of the water source (pH 1-10). More importantly, the EPM exhibits the water purification characteristics of >90% rejection of sub-10 nm pollutants and potentiality of ångstrom level cation rejection, with simultaneous and continuous energy generation. Overall, this study proposes an efficient EPM model, which can be potentially used as a next-generation renewable energy generation approach, thus laying the foundation for effective utilization of polluted water resources.

Ultrafast Ambient-Air Exsolution on Metal Oxide via Momentary Photothermal Effect.

The process of exsolution for the synthesis of strongly anchored metal nanoparticles (NPs) on host oxide lattices has been proposed as a promising strategy for designing robust catalyst-support composite systems. However, because conventional exsolution processes occur in harsh reducing environments at high temperatures for long periods of time, the choice of support materials and dopant metals are limited to those with inherently high thermal and chemical stability. Herein, we report the exsolution of a series of noble metal catalysts (Pt, Rh, and Ir) from metal oxide nanofibers (WO3 NFs) supports in an entirely ambient environment induced by intense pulsed light (IPL)-derived momentary photothermal treatment (>1000 °C). Since the exsolution process spans an extremely short period of time (<20 ms), unwanted structural artifacts such as decreased surface area and phase transition of the support materials are effectively suppressed. At the same time, exsolved NPs (<5 nm) with uniform size distributions could successfully be formed. To prove the practical utility of exsolved catalytic NPs functionalized on WO3 NFs, the chemiresistive gas sensing characteristics of exsolved Pt-decorated WO3 NFs were analyzed, exhibiting high durability (>200 cyclic exposures), enhanced response (Rair/Rgas > 800 @ 1 ppm/350 °C), and selectivity toward H2S target gas. Altogether, we successfully demonstrated that ultrafast exsolution within a few milliseconds could be induced in ambient conditions using the IPL-derived momentary photothermal treatment and contributed to expanding the practical viability of the exsolution-based synthetic approaches for the production of highly stable catalyst systems.

Porous Pd-Sn Alloy Nanotube-Based Chemiresistor for Highly Stable and Sensitive H2 Detection.

While H2 is indispensable as a green fuel source, it is highly flammable and explosive. Because it is difficult to detect due to its lack of odor and color, a solution for proper monitoring of H2 leakage is essential to ensure safe handling. To this end, we have successfully fabricated hollow Pd-Sn alloy nanotubes (NTs) with a Brunauer-Emmett-Teller surface area of 223.0 m2/g through electrospinning and a subsequent etching method, which is the first demonstration of synthesizing Pd-based hollow alloy nanofibers with ultrafine grain sizes. We found that the alloying of Pd with Sn could effectively prevent degradation of the sensing performance upon the α-ß phase transition during hydrogen detection. Besides, the highly porous structure with smaller nanograins offered more exposed active sites and higher gas accessibility to bulk materials. The resultant Pd-Sn NTs exhibited excellent sensitivity toward H2 (0.00005-3%). Notably, the limit of detection of 0.0001% is an outstanding achievement on H2 sensing among state-of-the-art H2 sensors. Moreover, when exposed to a high concentration of H2 (3%), Pd-Sn NTs showed excellent cycling stability with a standard deviation of 0.07% and a sensitivity of 9.27%. These obtained sensing results indicate that Pd-Sn NTs can be used as a highly sensitive and stable H2 gas sensor at room temperature (25 °C).

Confinement of Ultrasmall Bimetallic Nanoparticles in Conductive Metal-Organic Frameworks via Site-Specific Nucleation.

Conductive metal-organic frameworks (cMOFs) are emerging materials for various applications due to their high surface area, high porosity, and electrical conductivity. However, it is still challenging to develop cMOFs having high surface reactivity and durability. Here, highly active and stable cMOF are presented via the confinement of bimetallic nanoparticles (BNPs) in the pores of a 2D cMOF, where the confinement is guided by dipolar-interaction-induced site-specific nucleation. Heterogeneous metal precursors are bound to the pores of 2D cMOFs by dipolar interactions, and the subsequent reduction produces ultrasmall (≈1.54 nm) and well-dispersed PtRu NPs confined in the pores of the cMOF. PtRu-NP-decorated cMOFs exhibit significantly enhanced chemiresistive NO2 sensing performances, owing to the bimetallic synergies of PtRu NPs and the high surface area and porosity of cMOF. The approach paves the way for the synthesis of highly active and conductive porous materials via bimetallic and/or multimetallic NP loading.

Surface Activity-Tuned Metal Oxide Chemiresistor: Toward Direct and Quantitative Halitosis Diagnosis.

Continuous monitoring of hydrogen sulfide (H2S) in human breath for early stage diagnosis of halitosis is of great significance for prevention of dental diseases. However, fabrication of a highly selective and sensitive H2S gas sensor material still remains a challenge, and direct analysis of real breath samples has not been properly attempted, to the best of our knowledge. To address the issue, herein, we introduce facile cofunctionalization of WO3 nanofibers with alkaline metal (Na) and noble metal (Pt) catalysts via the simple addition of sodium chloride (NaCl) and Pt nanoparticles (NPs), followed by electrospinning process. The Na-doping and Pt NPs decoration in WO3 grains induces the partial evolution of the Na2W4O13 phase, causing the buildup of Pt/Na2W4O13/WO3 multi-interface heterojunctions that selectively interacts with sulfur-containing species. As a result, we achieved the highest-ranked sensing performances, that is, response (Rair/Rgas) = 780 @ 1 ppm and selectivity (RH2S/REtOH) = 277 against 1 ppm ethanol, among the chemiresistor-based H2S sensors, owing to the synergistic chemical and electronic sensitization effects of the Pt NP/Na compound cocatalysts. The as-prepared sensing layer was proven to be practically effective for direct, and quantitative halitosis analysis based on the correlation (accuracy = 86.3%) between the H2S concentration measured using the direct breath signals obtained by our test device (80 cases) and gas chromatography. This study offers possibilities for direct, highly reliable and rapid detection of H2S in real human breath without the need of any collection or filtering equipment.

Chemiresistive Hydrogen Sensors: Fundamentals, Recent Advances, and Challenges.

Hydrogen (H2) is one of the next-generation energy sources because it is abundant in nature and has a high combustion efficiency that produces environmentally benign products (H2O). However, H2/air mixtures are explosive at H2 concentrations above 4%, thus any leakage of H2 must be rapidly and reliably detected at much lower concentrations to ensure safety. Among the various types of H2 sensors, chemiresistive sensors are one of the most promising sensing systems due to their simplicity and low cost. This review highlights the advances in H2 chemiresistors, including metal-, semiconducting metal oxide-, carbon-based materials, and other materials. The underlying sensing mechanisms for different types of materials are discussed, and the correlation of sensing performances with nanostructures, surface chemistry, and electronic properties is presented. In addition, the discussion of each material emphasizes key advances and strategies to develop superior H2 sensors. Furthermore, recent key advances in other types of H2 sensors are briefly discussed. Finally, the review concludes with a brief outlook, perspective, and future directions.

Single-Atom Pt Stabilized on One-Dimensional Nanostructure Support via Carbon Nitride/SnO2 Heterojunction Trapping.

Catalysis with single-atom catalysts (SACs) exhibits outstanding reactivity and selectivity. However, fabrication of supports for the single atoms with structural versatility remains a challenge to be overcome, for further steps toward catalytic activity augmentation. Here, we demonstrate an effective synthetic approach for a Pt SAC stabilized on a controllable one-dimensional (1D) metal oxide nano-heterostructure support, by trapping the single atoms at heterojunctions of a carbon nitride/SnO2 heterostructure. With the ultrahigh specific surface area (54.29 m2 g-1) of the nanostructure, we obtained maximized catalytic active sites, as well as further catalytic enhancement achieved with the heterojunction between carbon nitride and SnO2. X-ray absorption fine structure analysis and HAADF-STEM analysis reveal a homogeneous atomic dispersion of Pt species between carbon nitride and SnO2 nanograins. This Pt SAC system with the 1D nano-heterostructure support exhibits high sensitivity and selectivity toward detection of formaldehyde gas among state-of-the-art gas sensors. Further ex situ TEM analysis confirms excellent thermal stability and sinter resistance of the heterojunction-immobilized Pt single atoms.

Pore-Size-Tuned Graphene Oxide Membrane as a Selective Molecular Sieving Layer: Toward Ultraselective Chemiresistors.

Conventional graphene oxide (GO)-based gas membranes, having a narrow pore-size range of less than 0.3 nm, exhibit limited gas molecular permeability because of the kinetic diameters of most volatile organic and sulfur compound (VOCs/VSCs) molecules being larger than 0.3 nm. Here, we employ GO nanosheets (NSs) with a tunable pore-size distribution as a molecular sieving layer on two-dimensional (2D) metal oxide NSs-based gas sensors, i.e., PdO-sensitized WO3 NSs to boost selectivity toward specific gas species. The pore size, surface area, and pore density of GO NSs were simply manipulated by controlling H2O2 concentration. In addition, the pore size-tuned GO NSs were coated on cellulose filtering paper as a free-standing nanoporous membrane. Holey GO membrane showed a highly selective H2S permeability characteristic, exhibiting superior cross-selectivity to CH3COCH3 (0.46 nm), C2H5OH (0.45 nm), and C7H8 (0.59 nm) with larger kinetic diameters compared with H2S (0.36 nm). Such pore-size-tuned GO nanoporous layer is scalable and robust, highlighting a great promise for designing low cost and highly efficient gas-permeable membrane for outstanding selective gas sensing platform.

High-Resolution, Fast, and Shape-Conformable Hydrogen Sensor Platform: Polymer Nanofiber Yarn Coupled with Nanograined Pd@Pt.

We report a flexible hydrogen sensing platform based on a single-strand yarn consisting of high-density electrospun nanofibers, on which nanograined Pd or Pd@Pt is coated via yarn spinning followed by sputter deposition. In general, Pd undergoes a phase transition to PdH x (α-PdH x at [H2] < 1% and ß-PdH x at [H2] > 2%), in which H atoms act as electron scattering centers, thus increasing the resistance. In our system, the sensors exhibit switchable H2 sensing behaviors, that is, (i) Δ R/ R0 > 0 at [H2] > 1% by the active electron scattering and (ii) Δ R/ R0 < 0 at [H2] < 1% derived from nanograined Pd effects. Due to high mechanical stability stemming from nanogranular morphologies of Pd, which is essential for enduring a huge volume expansion upon exposure to high-concentration H2, we could obtain a wide concentration range (4-0.0001%) H2 detection resolution. Moreover, an ultrathin Pt overlayer coated on Pd offers an accelerated H2 detection capability based on effective gas dissociation and activation properties. Furthermore, by virtue of the core (thread)-shell (nanofiber yarn) scaffold, long cycling reliability and flexibility were achieved. This facile and low-cost yarn fabrication method offers the development of single-strand thread-type wearable chemiresistors that possess a high surface area and open porosity, facilitating gas diffusion and reaction.