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Transition metal dichalcogenides (TMDs) have attracted significant interest as gas‐sensing materials due to their unique crystal structure and surface. However, there are still issues when it comes to expanding the types of sensing gases for the TMD gas sensors. To extend gas‐sensing selectivity for the TMD gas sensors in this study, a monolayer (ML) 2D metal–organic framework (MOF) is introduced on top of the PtSe2 gas sensor, thereby tuning the major sensing analyte of PtSe2 from NO2 to H2S. Density functional theory calculations elucidate that the metal species of ML MOFs are attributed to the tuned selectivity of the analytes, based on the difference in binding energies. It is also demonstrated that ML MOF maintained the high responsivity of the pristine PtSe2 even at a low concentration of gas (200 ppb). This is further confirmed through the molecular dynamics simulations, which reveal that the ML feature of the ML MOF is highly essential to preserve the intrinsic ultra‐low limit detection properties of pristine PtSe2. [ABSTRACT FROM AUTHOR]

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. The immobilization of catalysts within the pores of conductive metal-organic frameworks (C-MOFs) via facile and scalable methodologies remains challenging. Here the authors report a microfluidic channel-embedded solution shearing process that enables the high throughput, large-area, single-step preparation of Pt nanocatalyst-embedded C-MOF thin films. [ABSTRACT FROM AUTHOR]

Abstract: Edges of 2D transition metal dichalcogenides (TMDs) are well known as highly reactive sites, thus researchers have attempted to maximize the edge site density of 2D TMDs. In this work, metal‐organic framework (MOF) templates are introduced to synthesize few‐layered WS2 nanoplates (a lateral dimension of ≈10 nm) confined in Co, N‐doped hollow carbon nanocages (WS2_Co‐N‐HCNCs), for highly sensitive NO2 gas sensors. WS2 precursors are assembled in the surface cavity of Co‐based zeolite imidazole framework (ZIF‐67) and subsequent pyrolysis produced WS2_Co‐N‐HCNCs. During the pyrolysis, the carbonized ZIF‐67 are doped by Co and N elements, and the growth of WS2 is effectively suppressed, creating few‐layered WS2 nanoplates functionalized Co‐N‐HCNCs. The WS2_Co‐N‐HCNCs exhibit outstanding NO2 sensing characteristics at room temperature, in terms of response (48.2% to 5 ppm), selectivity, response and recovery speed, and detection limit (100 ppb). These results are attributed to the enhanced adsorption and desorption kinetics of NO2 on abundant WS2 edges, confined in the gas permeable HCNCs. This work opens up an efficient way for the facile synthesis of edge abundant few‐layered TMDs combined with porous carbon matrix via MOF templating route, for applications relying on highly active sites. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] • 2D-MOF is connected to 3D-MOF with coordination bond to form Ni-HHTP@UiO-66NH 2. • 2D-MOF@3D-MOF affords porosity, conductivity, and active interface for sensing. • Ni-HHTP@UiO-66NH 2 shows superior sensitivity and low detection limit toward H 2 S. • A plausible mechanism is proposed from the joint experimental/computational data. Research to develop ideal sensing devices for toxic gases is on the rise, and amongst various materials, metal–organic frameworks (MOFs) have opened up promising vistas as chemiresistive sensors due to their high structural and functional tunability. Here, we report the composites of dimensionally (2D and 3D) and functionally (conductive and porous) different two MOFs in the form of a well-integrated core–shell structure. The hierarchically assembled 2D-MOF@3D-MOF exhibits new interfacial properties that are responsible for synergetically enhanced sensing performances toward toxic H 2 S gas with the lowest recorded limit of detection (1.4 ppb), superior sensitivity (ΔR/R 0 = 3.37), and outstanding selectivity at room temperature in air. The sensing mechanisms are proposed by combinational studies of experiments and calculation, which indicates that multiple changes (e.g., local structural change of the shell MOF, secondary binding sites generation from the core MOF, and free radicals formation) play a critical role in achieving synergetic chemiresistive sensing. [ABSTRACT FROM AUTHOR]

The low response and sluggish reaction kinetics of graphene-based gas sensors remain as obstacles for practical applications as wearable chemical sensors. To overcome these limitations, we demonstrate a heterogeneous sensitization of nanocatalysts using Pt and ZnO nanoparticles (NPs) on porous reduced graphene oxides (Pt_ZnO/PRGO) driven by a metal-organic framework (MOF)-templated synthesis and subsequent pyrolysis. The pyrolysis of zeolitic imidazolate framework-8 layers grown on graphene oxide leads to the creation of porous carbon frameworks decorated with catalytic Pt and ZnO NPs, which possess increased reaction sites for the target gas. In addition, we investigated the effect of pyrolysis conditions to control the size of ZnO NPs with a 10 nm scale for enhanced catalytic sensitization. As a result, Pt_ZnO/PRGO exhibited improved NO 2 sensing properties with regard to response (43.28 % to 5 ppm), selectivity, and detection limit (0.1 ppm), as well as having reversible reaction kinetics. Potential applications of MOF-derived Pt_ZnO/PRGO in wearable chemical sensors was demonstrated, in which the material exhibited excellent mechanical stability and reliable response after 450 bending cycles. [ABSTRACT FROM AUTHOR]