Hold on Tight: MOF-Based Irreversible Gas Sensors

Small, Leo J; Schindelholz, Mara; Nenoff, Tina M.

doi:10.1021/acs.iecr.1c01266

Cited by 37 publications

(22 citation statements)

References 95 publications

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“…to the metal–organic framework structure will build photoactive sensors for probing chemicals at the nanolevel. Photoactive metallic MOF clusters will act as a better platform for the target-oriented sensing analysis of antibiotics, 12 gases, 13 inorganic metals, 14 pesticides, 15 and chemical explosives. 16 MOFs have inherent luminescence centers, and their luminescence mechanisms 17 include the photoinduced electron transfer (PET) process, 18 ligand-to-metal charge transfer (LMCT), and metal-to-ligand charge transfer (MLCT).…”

Section: Introductionmentioning

confidence: 99%

ZnO@MOF-5 as a Fluorescence “Turn-Off” Sensor for Ultrasensitive Detection as well as Probing of Copper(II) Ions

et al. 2022

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Recently, the synthesis, characterization, and structural evaluation of metal–organic framework (MOF) nanocomposites gain more attention due to the versatility in their applications. In the present work, the fluorescent active ZnO@MOF-5 composite was synthesized by encapsulating ZnO nanoparticles into the zinc terephthalate metal–organic framework (MOF-5). ZnO nanoparticles were prepared by a green method using the leaf extract of Annona muricata . Incorporation of ZnO nanoparticles onto the framework structure (ZnO@MOF-5) was done by a solvothermal method. The new composite material was characterized by Fourier transform infrared spectroscopy, Powder X-ray diffraction, Ultraviolet–visible spectroscopy, Transmission Electron Microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller analysis, Dynamic light scattering, Thermogravimetry-Differential Thermal analysis, and Photoluminescence spectroscopy. The material displayed blue fluorescence with a peak at 402 nm upon excitation at 282.46 nm. ZnO@MOF-5 showed a good fluorescence sensing efficiency toward the detection as well as probing of Cu(II) ions in aqueous solution. Sensing experiments performed revealed that as the concentration of copper ions in the solution increases, the quenching efficiency of the composite also increases. A quenching efficiency of 96.20% was achieved on reaching a concentration of 5 μM. The limit of detection for the sensing of Cu 2+ ions was calculated to be 0.185 μM.

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Section: Introductionmentioning

confidence: 99%

ZnO@MOF-5 as a Fluorescence “Turn-Off” Sensor for Ultrasensitive Detection as well as Probing of Copper(II) Ions

et al. 2022

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“…In the presented studies, we offer the realization of noninvasive oxidation state modulation through the integration of photoresponsive moieties inside novel copper-containing metal–organic frameworks (MOFs). − This approach provides an opportunity to control metal oxidation states as a function of an excitation wavelength (Scheme ). In particular, we demonstrate the first example of metal oxidation state reversibility in novel two- and three-dimensional copper-based photochromic MOFs through light-induced transformations of two distinct classes of photoresponsive molecules.…”

Section: Introductionmentioning

confidence: 99%

Stimuli-Modulated Metal Oxidation States in Photochromic MOFs

et al. 2022

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Tuning metal oxidation states in metal–organic framework (MOF) nodes by switching between two discrete linker photoisomers via an external stimulus was probed for the first time. On the examples of three novel photochromic copper-based frameworks, we demonstrated the capability of switching between +2 and +1 oxidation states, on demand. In addition to crystallographic methods used for material characterization, the role of the photochromic moieties for tuning the oxidation state was probed via conductivity measurements, cyclic voltammetry, and electron paramagnetic resonance, X-ray photoelectron, and diffuse reflectance spectroscopies. We confirmed the reversible photoswitching activity including photoisomerization rate determination of spiropyran- and diarylethene-containing linkers in extended frameworks, resulting in changes in metal oxidation states as a function of alternating excitation wavelengths. To elucidate the switching process between two states, the photoisomerization quantum yield of photochromic MOFs was determined for the first time. Overall, the introduced noninvasive concept of metal oxidation state modulation on the examples of stimuli-responsive MOFs foreshadows a new pathway for alternation of material properties toward targeted applications.

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“…Metal–organic frameworks (MOFs) are crystalline, porous three-dimensional (3D) materials composed of metal nodes and organic linkers connected by coordination bonds. − The availability of a diversity of organic linkers and metal nodes, together with the inherent porosity of MOFs, makes these materials versatile test compounds for potential applications in gas storage and/or separation, , chemical catalysis, − light harvesting, − and sensing, − to name a few. Use of MOFs as active components in light-to-electrical conversion devices, − field effect transistors, or electrochromic devices , brings an additional requirement: interfacing the materials with suitable electronically conductive solid supports. − …”

Section: Introductionmentioning

confidence: 99%

Toward Ideal Metal–Organic Framework Thin-Film Growth via Automated Layer-by-Layer Deposition: Examples Based on Perylene Diimide Linkers

et al. 2022

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Photoactive metal–organic framework (MOF) thin films offer an opportunity for translating the advantages of periodic, crystalline, and tailorable light-harvesting materials directly into devices such as those for photoelectrochemical solar energy conversion. In this study, we report the fabrication of light-absorbing perylene-diimide-containing pillared-paddlewheel MOF thin films using an automated layer-by-layer (LbL) deposition technique. Our focus here is on optimizing the growth of representative chromophoric MOFs as oriented films of uniform and predefined thickness. Growth was examined as a function of metal identity, pillaring ligand composition, and supporting-surface chemical functionality. Application of atomic force microscopy (AFM) and complementary techniques revealed that the surface-supported MOFs initially display island-type film growth (Volmer–Weber growth), resulting in comparatively rough films. Further growth is accompanied by the merging of islands, resulting in films that, depending on experimental details, can be remarkably smooth (i.e., roughness on the order of ±1 nm (one structural repeat unit in the pillaring direction)). These details include the use of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a MOF pillar and ALD-grown zinc oxide as a film support (ALD = atomic layer deposition). Also helpful for mitigating island-type growth, at least in part, is the replacement of Zn2+ by Cu2+ as the metal component of the MOF. Notably, each of these adjustments entails replacing weaker chemical bonds with stronger ones.

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Hold on Tight: MOF-Based Irreversible Gas Sensors

Cited by 37 publications

References 95 publications

ZnO@MOF-5 as a Fluorescence “Turn-Off” Sensor for Ultrasensitive Detection as well as Probing of Copper(II) Ions

ZnO@MOF-5 as a Fluorescence “Turn-Off” Sensor for Ultrasensitive Detection as well as Probing of Copper(II) Ions

Stimuli-Modulated Metal Oxidation States in Photochromic MOFs

Toward Ideal Metal–Organic Framework Thin-Film Growth via Automated Layer-by-Layer Deposition: Examples Based on Perylene Diimide Linkers

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