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Light-activated chemiresistors offer a powerful approach to achieving lower-temperature gas sensing with unprecedented sensitivities. However, an incomplete understanding of how photoexcited charge carriers enhance sensitivity obstructs the rational design of high-performance sensors, impeding the practical utilization under commonly accessible light sources instead of ultraviolet or higher-energy sources. Here, a rational approach is presented to modulate the electronic properties of the parent metal oxide phase, exemplified by this model system of Bi-doped In2O3 nanofibers decorated with Au nanoparticles (NPs) that exhibit superior NO2 sensing performance. Bi doping introduces mid-gap energy levels into In2O3, promoting photoactivation even under visible blue light. Additionally, green-absorbing plasmonic Au NPs facilitate electron transfer across the heterojunction, extending the photoactive region toward the green light. It is revealed that the direct involvement of photogenerated charge carriers in gas adsorption and desorption processes is pivotal for enhancing gas sensing performance. Owing to the synergistic interplay between the Bi dopants and the Au NPs, the Au-BixIn2-xO3 (x = 0.04) sensing layers attain impressive response values (Rg/Ra = 104 at 0.6 ppm NO2) under green light illumination and demonstrate practical viability through evaluation under simulated mixed-light conditions, all of which significantly outperforms previously reported visible light-activated NO2 sensors.
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Metal-organic frameworks (MOFs) have emerged as attractive chemical sensing materials due to their exceptionally high porosity and chemical diversity. Nevertheless, the utilization of MOFs in chemiresistive type sensors has been hindered by their inherent limitation in electrical conductivity. The recent emergence of two-dimensional conductive MOFs (2D c-MOFs) has addressed this limitation by offering enhanced electrical conductivity, while still retaining the advantageous properties of MOFs. In particular, c-MOFs have shown promising advantages for the fabrication of sensors capable of operating at room temperature. Thus, active research on gas sensors utilizing c-MOFs is currently underway, focusing on enhancing sensitivity and selectivity. To comprehend the potential of MOFs as chemiresistive sensors for future applications, it is crucial to understand not only the fundamental properties of conductive MOFs but also the state-of-the-art works that contribute to improving their performance. This comprehensive review delves into the distinctive characteristics of 2D c-MOFs as a new class of chemiresistors, providing in-depth insights into their unique sensing properties. Furthermore, we discuss the proposed sensing mechanisms associated with 2D c-MOFs and provide a concise summary of the strategies employed to enhance the sensing performance of 2D c-MOFs. These strategies encompass a range of approaches, including the design of metal nodes and linkers, morphology control, and the synergistic use of composite materials. In addition, the review thoroughly explores the prospects of 2D c-MOFs as chemiresistors and elucidates their remarkable potential for further advancements. The insights presented in this review shed light on future directions and offer valuable opportunities in the chemical sensing research field.
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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.
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The recent emerging significance of the Internet of Things (IoT) demands sensor devices to be integrated with many different functional structures and devices while conserving their original functionalities. To this end, optical transparency and mechanical flexibility of sensor devices are critical requirements for optimal integration as well as high sensitivity. In this work, a transparent, flexible, and sensitive gas sensor building platform is introduced by using multilevel self-assembly of block copolymers (BCPs) and polystyrene (PS) colloids. For the demonstration of an H2 gas sensor, a hierarchically porous Pd metal mesh structure is obtained by overlaying the two different patterned template structures with synergistic, distinctive characteristic length scales. The hierarchical Pd mesh shows not only high transparency over 90% but also superior sensing performance in terms of response and recovery time owing to enhanced Pd-to-hydride ratio and short H2 diffusion lengths from the enlarged active surface areas. The hierarchical morphology also endows high mechanical flexibility while securing reliable sensing performance even under severe mechanical deformation cycles. Our scalable self-assembly based multiscale nanopatterning offers an intriguing generalized platform for many different multifunctional devices requiring hidden in situ monitoring of environmental signals.
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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.
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Ex-solution catalysts, in which a host oxide is decorated with confined metallic nanoparticles, have exhibited breakthrough activity in various catalytic reactions. However, catalysts prepared by conventional ex-solution processes are limited by the low surface area of host oxides, the limited solubility of dopants, and the incomplete conversion of doped cations into metal catalysts. Here, the design of the host oxide structure is reconceptualized using a metal-organic framework (MOF) as an oxide precursor that can absorb a large quantity of ions while also promoting ex-solution at low temperatures (400-500 °C). The MOF-derived metal oxide host can readily incorporate metal cations, from which catalytic nanoparticles can be uniformly ex-solved owing to the short diffusion length in the nano-sized oxides. The distinct ex-solution behaviors of Pt, Pd, and Rh, and their bimetallic combinations are investigated. The MOF-driven mesoporous ZnO particles functionalized with PdPt catalysts ex-solved at 500 °C show benchmark-level of acetone oxidation activity as well as acetone-sensing characteristics by accelerating both oxygen chemisorption and acetone dissociation. Their findings provide a new route for the preparation of highly active catalysts by engineering the architecture and composition of the host oxide to facilitate the ex-solution process rationally.
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Iminosemiquinone-linker-based conductive metal-organic frameworks (c-MOFs) have attracted much attention as next-generation electronic materials due to their high electrical conductivity combined with high porosity. However, the utility of such c-MOFs in high-performance devices has been limited to date by the lack of high-quality MOF thin-film processing. Herein, a technique known as the microfluidic-assisted solution shearing combined with post-synthetic rapid crystallization (MASS-PRC) process is introduced to generate a high-quality, flexible, and transparent thin-film of Ni3 (hexaiminotriphenylene)2 (Ni3 (HITP)2 ) uniformly over a large-area in a high-throughput manner with thickness controllability down to tens of nanometers. The MASS-PRC process utilizes: 1) a micromixer-embedded blade to simultaneously mix and continuously supply the metal-ligand solution toward the drying front during solution shearing to generate an amorphous thin-film, followed by: 2) immersion in amine solution for rapid directional crystal growth. The as-synthesized c-MOF film has transparency of up to 88.8% and conductivity as high as 37.1 S cm-1 . The high uniformity in conductivity is confirmed over a 3500 mm2 area with an arithmetic mean roughness (Ra ) of 4.78 nm. The flexible thin-film demonstrates the highest level of transparency for Ni3 (HITP)2 and the highest hydrogen sulfide (H2 S) sensing performance (2,085% at 5 ppm) among c-MOFs-based H2 S sensors, enabling wearable gas-sensing applications.
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Though highly promising as powerful gas sensors, oxide semiconductor chemiresistors have low surface reactivity, which limits their selectivity, sensitivity, and reaction kinetics, particularly at room temperature (RT) operation. It is proposed that a hybrid design involving the nanostructuring of oxides and passivation with selective gas filtration layers can potentially overcome the issues with surface activity. Herein, unique bi-stacked heterogeneous layers are introduced; that is, nanostructured oxides covered by conformal nanoporous gas filters, on ultrahigh-density nanofiber (NF) yarns via sputter deposition with indium tin oxide (ITO) and subsequent self-assembly of zeolitic imidazolate framework (ZIF-8) nanocrystals. The NF yarn composed of ZIF-8-coated ITO films can offer heightened surface activity at RT because of high porosity, large surface area, and effective screening of interfering gases. As a case study, the hybrid sensor demonstrated remarkable sensing performances characterized by high NO selectivity, fast response/recovery kinetics (>60-fold improvement), and large responses (12.8-fold improvement @ 1 ppm) in comparison with pristine yarn@ITO, especially under highly humid conditions. Molecular modeling reveals an increased penetration ratio of NO over O2 to the ITO surface, indicating that NO oxidation is reliably prevented and that the secondary adsorption sites provided by the ZIF-8 facilitate the adsorption/desorption of NO, both to and from ITO.
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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.
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Conductive metal-organic framework (C-MOF) thin-films have a wide variety of potential applications in the field of electronics, sensors, and energy devices. The immobilization of various functional species within the pores of C-MOFs can further improve the performance and extend the potential applications of C-MOFs thin films. However, developing facile and scalable synthesis of high quality ultra-thin C-MOFs while simultaneously immobilizing functional species within the MOF pores remains challenging. Here, we develop microfluidic channel-embedded solution-shearing (MiCS) for ultra-fast (≤5 mm/s) and large-area synthesis of high quality nanocatalyst-embedded C-MOF thin films with thickness controllability down to tens of nanometers. The MiCS method synthesizes nanoscopic catalyst-embedded C-MOF particles within the microfluidic channels, and simultaneously grows catalyst-embedded C-MOF thin-film uniformly over a large area using solution shearing. The thin film displays high nitrogen dioxide (NO2) sensing properties at room temperature in air amongst two-dimensional materials, owing to the high surface area and porosity of the ultra-thin C-MOFs, and the catalytic activity of the nanoscopic catalysts embedded in the C-MOFs. Therefore, our method, i.e. MiCS, can provide an efficient way to fabricate highly active and conductive porous materials for various applications.
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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.
