EP3801831A2 - Metal-organic frameworks for sorption and sensing applications - Google Patents
Metal-organic frameworks for sorption and sensing applicationsInfo
- Publication number
- EP3801831A2 EP3801831A2 EP19752248.5A EP19752248A EP3801831A2 EP 3801831 A2 EP3801831 A2 EP 3801831A2 EP 19752248 A EP19752248 A EP 19752248A EP 3801831 A2 EP3801831 A2 EP 3801831A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- organic framework
- ppm
- sensor
- detecting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
- G01N27/227—Sensors changing capacitance upon adsorption or absorption of fluid components, e.g. electrolyte-insulator-semiconductor sensors, MOS capacitors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/02—Analysing fluids
- G01N29/022—Fluid sensors based on microsensors, e.g. quartz crystal-microbalance [QCM], surface acoustic wave [SAW] devices, tuning forks, cantilevers, flexural plate wave [FPW] devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- embodiments of the present disclosure relate to metal-organic frameworks for capturing and/or sensing one or more of SO2, CO2, and H2O, methods of capturing and/or sensing one or more of SO2, CO2, and H2O using the metal-organic frameworks, and the like.
- the metal-organic frameworks are selective for one of SO2, CO2, and H2O.
- the metal-organic frameworks concurrently (e.g., simultaneously) or sequentially capture and/or sense two or more of SO2, CO2, and H2O.
- embodiments of the present disclosure describe methods of capturing chemical species comprising contacting a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O, wherein the metal-organic framework comprises a square grid pillared by an inorganic building block, wherein the square grid is Ni(pyrazine)2 and the inorganic building block is selected from [NbOFs] 2 or [AlFsCthO)] 2 ; and sorbing one or more of SO2, CO2, and H2O from the fluid composition on the metal-organic framework.
- the fluid composition includes SO2 at a concentration in the range of about 25 ppm to about 500 ppm. In some embodiments, the fluid composition includes SO2 and CO2, and SO2 is preferentially sorbed over CO2 on the metal-organic framework. In some embodiments, the fluid composition includes SO2 and CO2, and SO2 and CO2 are both sorbed on the metal-organic framework. In some embodiments, SO2 and CO2 are sorbed about simultaneously on the metal-organic framework. In some embodiments, the fluid composition includes CO2 at a concentration in the range of about 400 ppm to about 5000 ppm.
- the fluid composition includes CO2 and H2O, and CO2 is preferentially sorbed over H2O on the metal-organic framework. In some embodiments, the fluid composition includes CO2 and H2O, and CO2 and H2O are both sorbed on the metal-organic framework. In some embodiments, the CO2 and H2O are sorbed about simultaneously on the metal-organic framework. In some embodiments, the sorbing proceeds at about room temperature.
- Embodiments of the present disclosure describe methods of capturing chemical species using NbOFFIVE-l-Ni comprising contacting a metal-organic framework with a fluid composition including at least SO2 and CO2, wherein the metal-organic framework is characterized by the chemical formula NiNbOF 5 (pyrazine)2 x(solv); sorbing one or more of SO2 and CO2 on the metal-organic framework; and optionally regenerating the metal-organic framework.
- Embodiments of the present disclosure describe methods of capturing chemical species using AlFFIVE-l-Ni comprising contacting a metal-organic framework with a fluid composition including at least SO2 and CO2, wherein the metal-organic framework is characterized by the chemical formula NiAlF 5 (H20)(pyrazine)2-x(solv); sorbing one or more of SO2 and CO2 on the metal-organic framework; and optionally regenerating the metal-organic framework.
- Embodiments of the present disclosure describe methods of detecting one or more analytes comprising exposing a sensor to an environment containing one or more of SO2, CO2, and H2O, wherein the sensor includes a layer of a metal-organic framework as a sensing layer, wherein the metal-organic framework comprises a square grid pillared by an inorganic building block, wherein the square grid is Ni(pyrazine)2 and the inorganic building block is selected from [NbOFs] 2 or [AlF 5 (H20)] 2 ; and detecting a presence of the SO2, CO2, H2O, or a combination thereof in the environment using the sensor.
- the detecting proceeds at about room temperature.
- the detecting includes detecting SO2 optionally in the presence of H2O.
- the detecting includes detecting between 25 ppm SO2 to about 500 ppm SO2.
- the detecting includes detecting CO2 optionally in the presence of H2O.
- the detecting includes detecting between about 400 ppm of CO2 and 5000 ppm of CO2.
- the detecting includes detecting H2O optionally in the presence of CO2.
- the detecting includes detecting relative humidity levels in the environment below about 40% RH and/or greater than about 60% RH.
- the senor is a capacitive sensor comprising an interdigitated electrode, wherein the sensing layer is deposited on the interdigitated electrode of the capacitive sensor, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in capacitance in the sensing layer.
- the sensor is a QCM sensor comprising an electrode, wherein the sensing layer is deposited on the electrode of the QCM, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in resonance frequency in the sensing layer.
- Embodiments of the present disclosure describe methods of sensing using NbOFFIVE- 1 -Ni comprising exposing a sensor to an environment containing at least SO2, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal- organic framework is characterized by NiNbOF 5 (pyrazine)2 x(solv); detecting a presence of SO2 in the environment using the sensor; and optionally regenerating the sensor.
- Embodiments of the present disclosure describe methods of sensing using A1FFIVE- l-Ni comprising exposing a sensor to an environment containing at least SO2, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal-organic framework is characterized by NiAlF 5 (H20)(pyrazine)2-x(solv); detecting a presence of SO2 in the environment using the sensor; and optionally regenerating the sensor.
- FIG. 1 is a flowchart of a method of capturing chemical species, according to one or more embodiments of the present disclosure.
- FIG. 2 is a flowchart of a method of capturing chemical species using NbOFFIVE- l-Ni, according to one or more embodiments of the present disclosure.
- FIG. 3 is a flowchart of a method of capturing chemical species using A1FFIVE-1- Ni, according to one or more embodiments of the present disclosure.
- FIG. 4 is a flowchart of a method of sensing, according to one or more embodiments of the present disclosure.
- FIG. 5 is a flowchart of a method of sensing using NbOFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- FIG. 6 is a flowchart of a method of AlFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- FIG. 7 is a schematic diagram showing the column breakthrough set-up, according to one or more embodiments of the present disclosure.
- FIG. 8 is a schematic diagram showing gas flow control and dilution system and sensor measurement set-up, according to one or more embodiments of the present disclosure.
- FIGS. 9A-9C is a schematic diagram showing crystal structure details for NbOFFIVE-l-Ni and AlFFIVE-l-Ni: (a) Square grid resulting from the connection of Ni 2+ cations and pyrazine that are further pillared by either (b) (AlFs (H2O)) 2 pillar or (c) (NbOFs) 2 pillar, according to one or more embodiments of the present disclosure.
- FIG. 10 is a graphical view of SO2 isotherm for NbOFFIVE-l-Ni at 25 °C after 105 °C activation, according to one or more embodiments of the present disclosure.
- FIGS. 11A-11D are schematic diagrams showing local views for the DFT-geometry optimized guest loaded-crystal structures: (a) SO2 and (b) CO2- loaded in NbOFFIVE-l-Ni, (c) SO2 and (d) CO2- loaded in AlFFIVE-l-Ni (Color code: Aluminum (pink), niobium (green), nickel (steel blue), fluorine (light green), nitrogen (blue), carbon (gray), hydrogen (white), oxygen (red), and sulfur (yellow)), according to one or more embodiments of the present disclosure.
- FIGS. 12A-12D are graphical views showing NbOFFIVE-l-Ni adsorption column breakthrough experiments for (a) SO2/N2: 7/93 mixture (10 cc/min, flow rate), (b) SO2/N2: 0.05/99.95 mixture (40 cc/min, flow rate), and (c) SO2/CO2/N2: 0.05/10/89.95 mixture (25 cc/min, flow rate); (d) Temperature -programed desorption after initial adsorption in the column using a mixture akin to flue gas (SO2/CO2/N2: 0.05/10/89.95), suggesting an adsorbed phase composition dominated by CO2, according to one or more embodiments of the present disclosure.
- FIG. 13 is a graphical view showing NbOFFIVE- 1 -Ni breakthrough experiments for 4% CO2, 4% SO2 (balance N2), according to one or more embodiments of the present disclosure.
- FIG. 14 is a graphical view of SO2 isotherm for AlFFIVE-l-Ni at 25 °C after 105 °C activation, according to one or more embodiments of the present disclosure.
- FIGS. 15A-15D are graphical views showing AlFFIVE-l-Ni breakthrough experiments for (a) S02/N2:7/93 (10 cc/min, flow rate), (b) SO2/N2:0.05/99.95 mixture (40 cc/min, flow rate), and (c) SO2/CO2/N2:0.05/l0/89.95 (40 cc/min, flow rate); (d) TPD experiment suggests a considerable amount of SO2 along with CO2 as adsorbed phase after a breakthrough experiment with 500ppm SO2 in the presence of 10% CO2 and balance N2, according to one or more embodiments of the present disclosure.
- FIG. 16 is a graphical view showing AlFFIVE-l-Ni breakthrough experiments for 7% SO2 (balance N2) and optimization of regeneration temperature, according to one or more embodiments of the present disclosure.
- FIG. 17 is a graphical view showing TPD analysis of adsorbed phase for AlFFIVE- l-Ni after breakthrough experiments with 500 ppm SO2 (balance N2), according to one or more embodiments of the present disclosure.
- FIGS. 18A-18B are SEM micrographs at a high and low magnification of (a) NbOFFIVE- 1 -Ni and (b) AlFFIVE-l-Ni thin films coated on the gold electrode of QCM, according to one or more embodiments of the present disclosure.
- FIGS. 19A-19B are graphical views of final Fe Bail profile refinement with observed
- FIG. 20 is a graphical view showing frequency shift comparison as a function of the SO2 concentration for the uncoated and NbOFFIVE- l-Ni or AlFFIVE-l-Ni coated QCM sensors, according to one or more embodiments of the present disclosure.
- FIGS. 21A-21B are graphical views showing variation of the peak resonance frequency (a) NbOFFIVE-l-Ni (b) AlFFIVE-l-Ni, in response to the introduction of various concentrations of dry SO2, according to one or more embodiments of the present disclosure.
- FIG. 22 is a graphical view showing plots of sensors’ responses as a function of SO2 concentration in synthetic air, according to one or more embodiments of the present disclosure.
- FIGS. 23A-23B are graphical views showing variation of the peak resonance frequency (a) NbOFFIVE-l-Ni (b) AlFFIVE-l-Ni, in response to the introduction of various concentrations of humid SO2, according to one or more embodiments of the present disclosure.
- FIG. 24 is a graphical view of temperature-programed desorption (TPD) of SO2; during typical experiment materials were saturated with water at 60% RH by flowing humid He, according to one or more embodiments of the present disclosure.
- TPD temperature-programed desorption
- FIGS. 25A-25B are graphical views of long-term stability property of the (a) NbOFFIVE-l-Ni and (b) AlFFIVE-l-Ni sensors exposed to 50, 100, and 157 ppm SO2 gas, according to one or more embodiments of the present disclosure.
- FIG. 26 is a schematic diagram illustrating the selective removal and sensing of SO2 from air using fluorinated MOF Platform NbOFFIVE-l-Ni and AlFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- FIGS. 27A-27B are SEM images of (a) NBOFFIVE-l-Ni and (B) AlFFIVE-l-Ni thin films, according to one or more embodiments of the present disclosure.
- FIG. 29 is a graphical view of a voltage to temperature calibration curve, according to one or more embodiments of the present disclosure.
- FIGS. 30A-30D are graphical views showing the capacitive sensor response for (a) NbOFFIVE- 1 -Ni and (b) AlFFIVE-l-Ni and the comparison of frequency shifts as a function of the CO2 concentration for (c) NbOFFIVE- 1-Ni and (d) AlFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- FIGS. 31A-31D are graphical views showing the stability detection of CO2 upon exposure to 60%RH of the NbOFFIVE- l-Ni and AlFFIVE-l-Ni films based on (a-b) QCM and (c-d) IDE sensors, according to one or more embodiments of the present disclosure.
- FIGS. 32A-32D are graphical views showing the variation in capacitance with relative humidity (RH) change in (a) NbOFFIVE- l-Ni and (b) AlFFIVE-l-Ni and frequency shift as a function of RH for QCM coated with (c) NbOFFIVE- l-Ni and (d) AlFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- RH capacitance with relative humidity
- FIGS. 33A-33D are graphical views showing the stability detection of H2O upon exposure to 500 ppm CO2 of the NbOFFIVE- l-Ni and AlFFIVE-l-Ni films based on (a-b) QCM and (c-d) IDE sensors, according to one or more embodiments of the present disclosure.
- FIGS. 34A-34B are graphical views showing long-term stability properties of (a) H2O upon prior exposure to 500 ppm CO2 of the AlFFIVE-l-Ni/IDE sensor and (b) CO2 upon prior exposure to 60% RH of the NbOFFIVE- l-Ni/QCM sensor, according to one or more embodiments of the present disclosure.
- Metal-organic frameworks for capturing one or more of SO2, CO2, and H2O are disclosed herein.
- Non-limiting examples of metal-organic frameworks include NbOFFIVE- 1 -Ni and AlFFIVE-l-Ni, among others.
- the metal-organic frameworks can be used in applications for removing and/or sensing one or more of SO2, CO2, and H2O from a fluid composition or an environment, either of which can proceed under dry or humid conditions and/or at room temperature.
- the metal-organic frameworks can be used as sorbents for removing SO2 from flue gas, or the metal-organic frameworks can be incorporated into QCM- or IDE-based sensors as the sensing layer for detecting and/or measuring the presence of one or more of SO2, CO2, and H2O.
- Such sensors can detect concentrations as low as 25 ppm to 500 ppm SO2, 400 ppm to 5000 ppm CO2, and relative humidity levels in an environment below 25% RH and/or above 65% RH, all of which is unprecedented.
- the sorption can be reversible such that the metal-organic frameworks may be regenerated and reused.
- contacting refers to the act of touching, making contact, or of bringing to close or immediate proximity, including at the cellular or molecular level, for example, to bring about a physiological reaction, a chemical reaction, or a physical change (e.g., in solution, in a reaction mixture, in vitro, or in vivo). Contacting may refer to bringing two or more components in proximity, such as physically, chemically, electrically, or some combination thereof. Mixing is an example of contacting.
- “contacting” may, in addition or in the alternative, refer to, among other things, feeding, flowing, passing, injecting, introducing, and/or providing the fluid composition (e.g., a feed gas).
- the fluid composition e.g., a feed gas
- “detecting” refers to determining a presence and/or concentration of one or more chemical species.
- exposing refers to subjecting to conditions of an environment.
- conditions of an environment may include, among other things, one or more of temperature, pressure, and chemical species present in the environment.
- exposing refers to subjecting to objects present in an environment.
- sorbing refers to one or more of absorbing and adsorbing. Sorbing may include selective sorption, such as sorption of a single species, subsequent sorption, such as sorption of a first species and then a second species (e.g., which may or may not replace the first species), or simultaneous sorption, such as sorption of two or more species at about the same time. Capturing is an example of sorbing.
- “capturing” refers to the act of removing one or more chemical species from a bulk fluid composition (e.g., gas/vapor, liquid, and/or solid).
- a bulk fluid composition e.g., gas/vapor, liquid, and/or solid.
- “capturing” may include, but is not limited to, interacting, bonding, diffusing, adsorbing, absorbing, reacting, and sieving, whether chemically, electronically, electrostatically, physically, or kinetically driven.
- FIG. 1 is a flowchart of a method of capturing chemical species, according to one or more embodiments of the present disclosure.
- the method 100 may comprise contacting 101 a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O; sorbing 102 one or more of SO2, CO2, and H2O from the fluid composition on the metal-organic framework; and optionally regenerating 103 the metal-organic framework.
- the step 101 includes contacting a metal-organic framework with a fluid composition including at least one or more of SO2, CO2, and H2O.
- the contacting may include bringing the metal-organic framework and fluid composition into physical contact, or immediate or close proximity. Examples of the contacting may include, but are not limited to, one or more of feeding, flowing, passing, pumping, and introducing.
- the contacting may proceed under any suitable conditions (e.g., temperature, pressure, etc.). For example, the contacting may proceed to or at a temperature ranging from about 0 °C to about 600 °C. In many embodiments, the contacting may proceed at or to a temperature less than about 200 °C. In preferred embodiments, the contacting may proceed at or to a temperature of about 25 °C (e.g., about room temperature).
- the metal-organic framework may include fluorinated metal-organic frameworks characterized by square grids and pillars.
- the metal-organic framework may include a pillar characterized by the formula MbFsCO/tbO), where Mb is Al 3+ or Nb 5+ .
- the pillar may include an inorganic pillar or inorganic building block.
- the pillar may be characterized by the chemical formula: (AlFsCtbO)) 2 .
- the pillar may be characterized by the chemical formula: (NbOFs) 2 .
- the metal-organic framework may include a square grid characterized by the formula (Mb(ligand)x), where M a is Ni and the ligand is pyrazine.
- the square grid may be characterized by the formula (Ni(pyrazine)2).
- the pillar and square grid may assemble and/or associate to form a metal-organic framework characterized by one or more of the following chemical formulas: NiNbOF 5 (pyrazine)2 x(solv) (NbOFFIVE-l-Ni) and NiAlF 5 (H20)(pyrazine)2-x(solv) (AlFFIVE-l-Ni).
- the metal- organic framework may be characterized by the chemical formula: NiNbOF 5 (pyrazine)2 x(solv).
- the metal-organic framework may be characterized by the chemical formula: NiAlF 5 (H20)(pyrazine)2-x(solv).
- the metal-organic frameworks may include a periodic array of open metal coordination sites and fluorine moieties within a contracted square-shaped one dimensional channel.
- the metal-organic frameworks may include AlFFIVE-l- Ni, wherein the AlFFIVE-l-Ni includes three pendant fluoride groups with a fluoride-fluoride distance of about 3.613 A and one potential open metal site.
- the metal-organic framework may include NbOFFIVE- 1 -Ni, wherein the NbOFFIVE-l-Ni includes four pendant fluoride groups with a fluoride-fluoride distance of about 3.210 and no open metal site.
- the fluid composition may be present in any phase.
- the fluid composition may be present in one or more of a gas/vapor phase, liquid phase, and solid phase.
- the fluid composition may be present in a gas/vapor phase.
- the fluid composition may include one or more of SO2, CO2, and water (e.g., as water vapor and/or moisture, humidity) and optionally one or more other chemical species.
- the fluid composition includes at least SO2, optionally CO2 and optionally water, and optionally one or more other chemical species.
- the fluid composition includes at least SO2.
- the fluid composition includes at least SO2 and CO2, and optionally water.
- the fluid composition includes at least SO2, CO2, and water.
- the fluid composition includes at least SO2, CO2, and water, and one or more other chemical species.
- the one or more other chemical species may include one or more of NO2 and nitrogen.
- the fluid composition may be synthetic flue gas, which may include one or more of SO2, CO2, water vapor, NO2, and nitrogen.
- the fluid composition includes CO2 and optionally H2O.
- the fluid composition includes at least CO2.
- the fluid composition includes H2O and optionally CO2.
- the fluid composition includes at least H2O.
- the fluid composition includes CO2 and H2O.
- the fluid composition may be air (e.g., for detecting a presence of SO2 at certain levels, CO2 at certain levels, and/or water at certain levels).
- the concentration of SO2 in the fluid composition may range from greater than about
- the concentration of SO2 in the fluid composition is less than about 7 wt %. In preferred embodiments, the concentration of SO2 in the fluid composition is less than about 500 ppm. In other preferred embodiments, the concentration of SO2 in the fluid composition is about 25 ppm or greater. In other preferred embodiments, the concentration of SO2 in the fluid composition may range from about 25 ppm to about 500 ppm. In some embodiments, the concentration of CO2 in the fluid composition is in the range of about 400 ppm to about 5000 ppm.
- the step 102 includes sorbing one or more of SO2, CO2, and H2O from the fluid composition on the metal-organic framework.
- the sorbing may include one or more of adsorbing, absorbing, and desorbing.
- the sorbing may include absorbing and/or adsorbing one or more of SO2, CO2, and H2O.
- the sorbing may include absorbing one or more of SO2, CO2, and H2O.
- the sorbing may include adsorbing one or more of SO2, CO2, and H2O.
- the sorbing may include absorbing one or more of SO2, CO2, and H2O. In an embodiment, the sorbing may include desorbing one or more of SO2, CO2, and H2O.
- the sorbing may include one or more of selective sorption (e.g., sorption of one or more select compounds), sequential sorption (e.g., sorption in a sequence of species and/or sorption in which a sorbed species is replaced by another species), and simultaneous sorption (e.g., sorption of two or more compounds, such as two or more select compounds).
- the sorbing may proceed under conditions that are the same as or similar to the conditions of the contacting.
- the sorbing includes sorbing SO2. In some embodiments, the sorbing includes sorbing SO2 over CO2. In some embodiments, the sorbing includes sorbing SO2 and CO2 about simultaneously or sequentially. In some embodiments, the sorbing includes sorbing SO2 in the presence of H2O. In some embodiments, the sorbing includes sorbing SO2 over CO2 in the presence of H2O. In some embodiments, the sorbing includes sorbing SO2 and CO2 about simultaneously or sequentially in the presence of H2O. In some embodiments, the sorbing includes sorbing CO2. In some embodiments, the sorbing includes sorbing H2O.
- the sorbing includes sorbing CO2 over H2O. In some embodiments, the sorbing includes sorbing CO2 in the presence of H2O. In some embodiments, the sorbing includes sorbing H2O in the presence of CO2. In some embodiments, the sorbing includes sorbing CO2 and H2O about simultaneously or sequentially.
- the fluid composition includes SO2 at a concentration in the range of about 25 ppm to about 500 ppm. In some embodiments, the fluid composition includes SO2 and CO2, and SO2 is preferentially sorbed over CO2 on the metal-organic framework. In some embodiments, the fluid composition includes SO2 and CO2, and SO2 and CO2 are both sorbed on the metal-organic framework. In some embodiments, SO2 and CO2 are sorbed about simultaneously on the metal-organic framework. In some embodiments, the fluid composition includes CO2 at a concentration in the range of about 400 ppm to about 5000 ppm.
- the fluid composition includes CO2 and H2O, and CO2 is preferentially sorbed over H2O on the metal-organic framework. In some embodiments, the fluid composition includes CO2 and H2O, and CO2 and H2O are both sorbed on the metal-organic framework. In some embodiments, the CO2 and H2O are sorbed about simultaneously on the metal-organic framework. In some embodiments, the sorbing proceeds at about room temperature.
- the metal-organic frameworks may exhibit one or more of a high removal efficiency and/or high uptake, even at low concentrations of SO2.
- the metal-organic frameworks may exhibit a removal efficiency of greater than about 70%, greater than about 80%, and/or greater than about 90%.
- the metal-organic frameworks exhibit a removal efficiency of greater than about 90%.
- the metal- organic frameworks may exhibit a removal efficiency of greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, greater than about 95%, greater than about 96%, greater than about 97%, greater than about 98%, and/or greater than about 99%.
- the metal- organic frameworks may exhibit a high uptake of SO2 even at low concentrations, such as concentrations of SO2 ranging from 25 ppm to 500 ppm.
- the metal-organic frameworks may exhibit an about equal selectivity toward SO2 and CO2 and/or a selectivity toward SO2 over CO2.
- the metal-organic framework includes NbOFFIVE-l-Ni.
- the NbOFFIVE-l-Ni may exhibit equal (e.g., about equal) selectivity toward SO2 and CO2.
- the NbOFFIVE-l-Ni may exhibit simultaneous (e.g., about simultaneous and/or substantially simultaneous) sorption of SO2 and CO2, even at low concentrations of SO2 and/or in a presence of water (e.g., water vapor, humidity).
- the NbOFFIVE-l-Ni may simultaneously sorb SCh and CO2, where a concentration of SO2 is less than about 500 ppm.
- NbOFFIVE-l-Ni may exhibit a selectivity toward SO2 over CO2.
- the metal-organic framework includes AlFFIVE-l-Ni.
- the AlFFIVE-l-Ni may exhibit a reduced affinity for CO2 (e.g., relative to NbOFFIVE-l-Ni) such that the AlFFIVE-l-Ni selectively sorbs SO2 over CO2, even at low concentrations of SO2 (e.g., less than about 500 ppm) and/or in a presence of water (e.g., water vapor, humidity).
- a selectivity of SO2/CO2 may be about 66.
- the AlFFIVE-l-Ni may exhibit a selectivity towards SO2 over CO2.
- the AlFFIVE-l-Ni may sorb SO2 to the substantial exclusion of CO2.
- the AlFFIVE-l-Ni may, at first, simultaneously sorb SO2 and CO2 and, over time, SO2 may replace the sorbed CO2, demonstrating an overall affinity for SO2.
- the AlFFIVE-l-Ni may exhibit an about equal selectivity for SO2 and CO2.
- the step 103 is optional and includes regenerating the metal-organic framework.
- the regenerating may include thermal treatment in a vacuum and/or inert gas environment (e.g., under nitrogen).
- the regenerating may include heating to or at a temperature of about 105 °C in a vacuum.
- the regenerating may include heating to or at a temperature of about 105 °C in an inert gas environment.
- the temperature of regenerating may be less than and/or greater than about 105 °C.
- FIG. 2 is a flowchart of a method of a method of capturing chemical species using NiNbOF 5 (pyrazine)2 x(solv), according to one or more embodiments of the present disclosure.
- the method 200 may comprise contacting 201 a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O, wherein the metal-organic framework is characterized by the chemical formula NiNbOF 5 (pyrazine)2 x(solv); sorbing 202 one or more of SO2, CO2, and H2O on the metal-organic framework; and optionally regenerating 203 the metal-organic framework.
- one or more of SO2, CO2, and H2O are sorbed simultaneously (e.g., about simultaneously, substantially simultaneously, simultaneously, etc.) on the metal-organic framework.
- FIG. 3 is a flowchart of a method of capturing chemical species using NiAlF 5 (H20)(pyrazine)2-x(solv), according to one or more embodiments of the present disclosure.
- the method 300 may comprise contacting 301 a metal-organic framework with a fluid composition including one or more of SO2, CO2, and H2O, wherein the metal-organic framework is characterized by the chemical formula NiAlF 5 (H20)(pyrazine)2-x(solv); sorbing 302 one or more of SO2, CO2, and H2O on the metal-organic framework; and optionally regenerating 303 the metal-organic framework.
- the metal-organic framework exhibits a selectivity towards SO2 over CO2.
- FIG. 4 is a flowchart of a method of sensing, according to one or more embodiments of the present disclosure.
- the method 400 may comprise exposing 401 a sensor to an environment containing one or more of SO2, CO2, and H2O; detecting 402 a presence of one or more of SO2, CO2, H2O in the environment using the sensor; and optionally regenerating 403 the sensor.
- the step 401 includes exposing a sensor to an environment containing one or more of SO2, CO2, and H2O.
- the exposing may include subjecting to conditions of an environment.
- the exposing may include subjecting the sensor to conditions and/or objects of an environment, which may include, but are not limited to, one or more of temperature and chemical species present in the environment.
- the environment may be an environment contaminated or potentially contaminated with SO2 and/or with harmful or unsafe levels of CO2 and/or with harmful or unsafe levels of humidity.
- the environment may be a dry and/or humid environment.
- the environment may not include any water vapor or negligible amounts of water vapor.
- the environment may include non-negligible amounts of water vapor.
- the environment may be characterized by a relative humidity (RH) ranging from about 0% RH to about 100% RH.
- the environment may be characterized by a RH greater than about 60% and/or less than about 40%.
- the environment may be characterized by any temperature ranging from about 0 °C to about 600 °C.
- the temperature of the environment may be less than about 200 °C.
- the temperature of the environment may be about 25 °C (e.g., about room temperature).
- the metal-organic framework may be deposited as a sensing layer on a substrate to form a sensor.
- the sensor includes a layer of a metal-organic framework as the sensing layer. Any of the metal-organic frameworks of the present disclosure may be used as the sensing layer of the sensor.
- the sensor includes a layer of a metal-organic framework as the sensing layer, wherein the metal-organic framework is NbOFFIVE- 1 -Ni or a metal-organic framework characterized by the formula NiNbOF 5 (pyrazine)2 x(solv).
- the senor includes a layer of a metal-organic framework as the sensing layer, wherein the metal-organic framework is AlFFIVE-l-Ni or a metal- organic framework characterized by the formula NiAlF 5 (H20)(pyrazine)2-x(solv).
- the metal- organic frameworks may be uniformly deposited (e.g., about uniformly deposited) on a substrate with low intergranular voids and/or random orientation.
- the layer may include crystallites ranging in size from about 150 nm to about 30 pm.
- the substrate may include any suitable support and/or substrate known in the art and/or commonly used in sensors.
- the substrate includes a quartz crystal microbalance (QCM) substrate.
- the substrate includes a capacitive interdigitated electrode (IDE) substrates.
- the sensors may further comprise any additional components known in the art and/or commonly included in sensors.
- the step 402 includes detecting a presence of one or more of SO2, CO2, and H2O in the environment using the sensor.
- the detecting may include measuring and/or monitoring a change in an electronic or physical property of the sensor in response to an interaction between the sensor and one or more chemical species, such as one or more of SO2, CO2, and H2O.
- the detecting may be used to determine a presence and/or concentration of one or more chemical species.
- the interaction may be characterized as a change in an electronic or physical property of the sensor upon sorbing and/or desorbing one or more chemical species.
- the sorbing and/or desorbing may proceed as described herein.
- a change in capacitance may be measured in response to the sorption and/or desorption of one or more chemical species.
- a change in resonance frequency may be measured in response to the sorption and/or desorption of one or more chemical species.
- a change in electrical resistance may be measured in response to the sorption and/or desorption of one or more chemical species.
- the electronic properties that may be monitored and/or measured include, but are not limited to, one or more of resonance frequency, capacitance, resistance, conductance, and impedance, among others.
- the detecting proceeds at about room temperature.
- the detecting includes detecting SO2 optionally in the presence of H2O.
- the detecting includes detecting between 25 ppm SO2 to about 500 ppm SO2 in the environment.
- the detecting includes detecting CO2 optionally in the presence of H2O.
- the detecting includes detecting between about 400 ppm of CO2 and 5000 ppm of CO2 in the environment.
- the detecting includes detecting H2O optionally in the presence of CO2.
- the detecting includes detecting relative humidity levels in the environment below about 40% RH and/or greater than about 60% RH.
- the senor is a capacitive sensor comprising an interdigitated electrode, wherein the sensing layer is deposited on the interdigitated electrode of the capacitive sensor, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in capacitance in the sensing layer.
- the sensor is a QCM sensor comprising an electrode, wherein the sensing layer is deposited on the electrode of the QCM, wherein the presence of one or more of SO2, CO2, and H2O is detected by measuring a change in resonance frequency in the sensing layer.
- the step 403 is optional and includes regenerating the sensor.
- the regenerating may include thermal treatment in a vacuum and/or inert gas environment (e.g., under nitrogen).
- the regenerating may include heating to or at a temperature of about 105 °C in a vacuum.
- the regenerating may include heating to or at a temperature of about 105 °C in an inert gas environment.
- the temperature of regenerating may be less than and/or greater than about 105 °C.
- FIG. 5 is a flowchart of a method of sensing using a sensor based on NbOFFIVE-l- Ni, according to one or more embodiments of the present disclosure.
- the method may comprise exposing 501 a sensor to an environment containing one or more of SO2, CO2, and H2O, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal-organic framework is characterized by NiNbOF 5 (pyrazine)2 x(solv); detecting 502 a presence of one or more of SO2, CO2, and H2O in the environment using the sensor; and optionally regenerating 503 the sensor.
- FIG. 6 is a flowchart of a method of sensing using a sensor based on AlFFIVE-l-Ni, according to one or more embodiments of the present disclosure.
- the method 600 may comprise exposing 601 a sensor to an environment containing one or more of SO2, CO2, and H2O, wherein the sensor includes a layer of a metal-organic framework as a sensing layer; wherein the metal-organic framework is characterized by NiAlF 5 (H20)(pyrazine)2-x(solv); detecting 602 a presence of one or more of SO2, CO2, and H2O in the environment using the sensor; and optionally regenerating 603 the sensor.
- Fluorinated MOF platform to address the highly challenging selective removal and sensing of S02 from flue gas and air
- the present Example relates to the use of isostructural fluorinated MOFs for (i) selective removal of SO2 from synthetic flue gas and (ii) sensing of SO2 using QCM as a transducer since the coating of MOFs on the QCM electrodes can detect the change in mass of sub nanograms upon adsorption or desorption of molecules by the MOF layer.
- the present Example describes an unprecedented concurrent removal of SO2/CO2 from synthetic flue gas and remarkable detection capability in ppm level of SO2 concentration in both dry and humid conditions.
- the experimental set-up used for dynamic breakthrough measurements is shown in FIG. 7.
- the gas manifold consisted of three lines fitted with mass flow controllers. Fine“A” was used to feed an inert gas, most commonly helium, to activate the sample before each experiment.
- the other two lines,“B” and“C” fed pure or pre-mixed gases. Whenever required, gases flowing through lines“B” and“C” were mixed before entering a column packed with the sample using a four-way valve.
- about 300-500 mg of adsorbent (in the column) was treated in situ at required temperature under He flow (about 50 cm 3 /g) for about 8 hours.
- the transducer was a 10 MHz AT-cut piezoelectric quartz crystal quartz microbalance (QCM) device with a thickness shear mode and placed between two gold electrodes for electrical connection.
- QCM piezoelectric quartz crystal quartz microbalance
- the QCM was rinsed with ethanol and dried in air.
- MOFs paste was then applied to the electrode of QCMs by spin-coating method (2 mhi thick) no prior modification of the sensors surface was required.
- the QCM sensor was then fixed in a sealed chamber. Prior to measurements the fresh coated MOFs film was activated in situ for about 4 hours to have a guest free framework. The resulting coatings were ultrathin and reproducible so that the stress upon absorption of SO2 inducing a change in the mass change of the thin film was effective.
- FIG. 8 shows the sensing set-up used in this Example for real-time measurement. All the sensor measurements were carried out at about room temperature, under a dry air total stream of about 200 seem. MFCs (Mass flow controllers) from Alicat scientific Inc. were used to control the flow rate for gases coming from certified bottles. Stainless steel delivery lines or perfluoroalkoxy alkane, PFA tubing (in regions requiring flexibility and resistivity to VOCs) were used on the setup with Vernier metering valves (from Swagelok) as a flow regulator. To detect the change in humidity level inside the chamber a commercial humidity sensor (Honeywell HIH-4000- 003) was used as a reference which has an error less than about 0.5%RH.
- MFCs Mass flow controllers
- the QCM sensor was exposed to the analyte stream until a stable response was obtained, a two-port network (Keysight E5071C ENA) circuit was used to monitor the change in resonance frequency.
- a Lab VIEW interface was used for synchronization and data acquisition by controlling the LCR meter and the multimeter. Hence, the possibility of data loss was minimized.
- NbOFFIVE-l-Ni was first investigated for SO2 sorption.
- the steep, pure SO2 adsorption isotherm collected at about 25 °C (FIG. 10) suggested a high affinity of the NbOFFIVE-l-Ni framework for SO2.
- This observation was corroborated by Density Functional Theory (DFT) calculations, which revealed high SCh/NbOFFIVE-l-Ni interaction energy of about -64.8 kJ/mol. This was due to a relatively stronger interaction between the sulfur atom of SO2 and the F-pillars with characteristic interatomic distances of about 2.9 A (FIG. 11A) along with a charge transfer between the guest and this region of the MOF.
- DFT Density Functional Theory
- FIG. 22 shows the sensor sensitivity as a function of SO2 concentration in humid conditions (60% RH) at room temperature for uncoated and coated NbOFFIVE-l-Ni, AlFFIVE-l-Ni QCMs. Uncoated QCM had a near zero response to humidity and SO2. This corroborated that the sensing response to SO2 under humid conditions was due to its affinity to NbOFFIVE-l-Ni and AlFFIVE- l-Ni films.
- the most important parameters of a sensing device are its stability and reproducibility. These parameters were investigated by cyclic exposure of the sensor to different SO2 concentrations after every forty-eight hours at about room temperature over a period of about twelve days (FIG. 25A-25B). The three results demonstrated the stability of the sensors exposed to about 50, 100, and 157 ppm SO2 gas with no significant change in the resonant frequency over time.
- the unveiled sensors were able to simultaneously detect CO2 within the 400-5000 ppm range and relative humidity levels below 40 and above 60%, using two fluorinated metal-organic frameworks - namely, NbOFFIVE-l-Ni and AlFFIVE-l-Ni - fabricated as thin films.
- Their subtle difference in a structure-adsorption relationship for H2O and CO2 was analyzed to unveil the corresponding structure-sensing property relationships using both QCM- and IDE-based sensing modes.
- Metal-organic frameworks are a unique class of porous materials that have shown great potential for gas separation/storage, catalysis, and sensing.
- a fluorinated MOF namely, AlFFIVE-l-Ni
- AlFFIVE-l-Ni fluorinated MOF
- adsorbent has offered the ability to simultaneously remove H2O and CO2 from various gas streams. This property is distinctive and remarkable as the capture of both gases usually follows a competitive adsorptive mechanism.
- the presence of two distinct actives sites those on open metal sites for the adsorption of H2O and those within cavities for the adsorption of CO2, explains this unique simultaneous adsorption process of the A1FFIVE- 1 -Ni adsorbent.
- this Example presents the development of the first sensing device with the ability to simultaneously detect and measure CO2 and H2O.
- harmful levels of CO2 between 400 and 5000 ppm
- uncomfortable levels of humidity below 40% RH and higher than 60% RH
- Gas sensitivity performances were analyzed using two different transduction techniques: one measuring changes in mass (using QCM) and the other measuring changes in dielectric properties (using an interdigitated electrode (IDE) capacitor).
- the performance of AlFFIVE-l-Ni was compared with those obtained using another fluorinated MOF, NbOFFIVE-l- Ni, which displayed a competitive adsorption process of CO2 and H2O.
- IDE-based capacitors were fabricated on a highly resistive silicon wafer using complementary metal oxide semiconductor processes.
- a 2 pm silicon dioxide layer was grown using wet thermal oxidation for electrical isolation.
- a layer of 10/300 nm Ti/Au was subsequently sputtered-deposited via physical vapor deposition in a ESC metal sputter system.
- Photolithography was used in the next step of the process, to define the IDEs (4 pm fingers with 5 pm spaces).
- the metal layer was then etched using an ion sputtering system PlasmaLab System from Oxford Instruments, with the patterned photoresist acting as the mask layer.
- AT-cut QCM (10 MHz) with 6 mm diameter electrodes from openQCM was used as substrate for the mass-based sensing technique.
- Electrodes were rinsed with acetone/ethanol and dried in air. MOF paste was then deposited on one of the electrode of QCMs/ IDEs by spin coating method (2 pm thick). No prior modification of the sensor surface was required for this method of deposition. The method was simple in yielding good quality and uniform films.
- the coated electrodes were then dried at 60 °C for 2 h under vacuum to obtain thin films of sensing materials on the electrodes.
- the sensors were then characterized in a custom-built sealed chamber. Before any measurements, the freshly coated MOF film on the sensors was activated in situ for 4 h to have a guest-free framework. The resulting coatings were ultrathin and reproducible so that the absorbed CO2 and/or water vapor induced an effective change in the mass/dielectric properties of the thin films.
- FIG. 8 shows the schematic of the setup used in this study for real-time gas sensing measurements.
- Mass flow controllers from Alicat Scientific, Inc. were used to control the flow rate of gases from certified bottles.
- Stainless steel or PFA tubing (in regions requiring flexibility) along with Vernier metering valves (from Swagelok) as a flow regulator was used as delivery line in the setup.
- a commercial humidity sensor Honeywell HIH-4000-003, error less than 0.5% RH
- the QCM-/IDE-based sensors were exposed to the analyte stream until a stable response was attained.
- a two-port impedance analyzer (Keysight E5071C ENA) circuit was used for monitoring the change in resonance frequency.
- a Lab VIEW interface was used for synchronization and data acquisition by controlling the LCR meter and the multimeter. This minimized the possibility of data loss.
- reticular chemistry allowed the fabrication of a series of fluorinated MOF materials with the ability to capture CO2 from air or to dehydrate gas streams.
- the structure of these materials can be described as having a pcu underlying topology, where a square-grid Ni(pyrazine)2 is pillared by inorganic building blocks, either [NbOFs] 2- or [AlFsCtbO)] 2- , to generate a channel-based MOF with a periodic array of fluorine moieties (FIGS. 9A-9C).
- the structural differences between these two fluorinated MOFs resulted from the presence of an open metal site in the case of AlFFIVE-l-Ni.
- QCM and IDE technologies have been proposed as new effective tools for the rapid detection of gases, volatile organic compounds, and humidity, because of their simplicity, small size, low cost, high sensitivity, shorter time of analysis, and suitability for label- free measurements.
- the resonant frequency of QCM substrates depends on the amount of adsorbed material.
- QCM can detect the change in a mass of subnanograms. The relationship between the shift in frequency and the mass loading is described by the Sauerbrey equation.
- Capacitive IDEs can be used to sense the change in sensing film permittivity upon gas adsorption and are seen as attractive candidates from a power consumption perspective.
- MOF films are generally grown on surfaces that have been functionalized with self- assembled monolayers or by seeding with small MOF crystal.
- the nanostructures of these thin films have not yet been well characterized and sometimes lead to improper growth of the desired thin film.
- Applicants have developed, for the first time, a new synthesis method to obtain a soft homogeneous MOF solution with a paste-like consistency, making it well suited for the preparation of a wide range of homogeneous thin film. Indeed, the method can easily be adapted to the deposition or spin coating of thin films from a chemical solution. A representation of this is presented in (FIGS.
- AlFFIVE-l-Ni and NbOFFIVE- 1 -Ni films contain close-packed crystal domains, exhibiting a good coalescence of microcrystals with small intergranular voids, leading to compact and uniform MOF films of excellent crystallinity.
- NbOFFIVE- 1 -Ni films comprised small cubic crystallites of approximately 150 nm, whereas larger crystallites of about 7pm were found for AlFFIVE-l-Ni. The purity and crystallinity of the deposited MOF films were confirmed by powder X-ray diffraction experiments (FIGS. 28A-28B).
- MOF thin films for sensing application required a critical activation step, permitting the attainment of a guest-free thin film before any sensing signal measurement was to be performed. For this reason, the MOF adsorbent was fully reactivated at 105 °C, before each new cycle of analyte exposure, using in situ heating provided by a HT24S metal ceramic heater from Thorlabs. The output temperature of the heater was calibrated and monitored using a FM35DZ/NOPB commercial temperature sensor from Texas Instruments (FIG. 29). This calibration was of prime importance to preserve the integrity of the MOF adsorbent and to ensure that guest-free activated NbOFFIVE-l-Ni and AlFFIVE-l-Ni were obtained before sensing experiments.
- FIGS. 30C-30D depict the concentration-dependent responses of NbOFFIVE- 1 -Ni or AlFFIVE-l-Ni coated on QCMs as sensors to different concentrations of CO2 at room temperature and under dry conditions. It was observed that when the gas entered in contact with the QCM-based sensors, CO2 molecules were adsorbed on the sensitive film and the mass increased in a proportional manner, producing a negative shift in resonance frequency. That is, the decrease in resonant frequency (FIGS. 30C-30D) as the CO2 concentration increased was seen very clearly, showing a good response of the QCM to CO2.
- the MOF-coated mass-sensitive QCM devices exhibited a lower sensitivity toward CO2 under dry conditions than the IDE capacitors. Part of the reason for this difference was that the IDE capacitors can detect larger effects of CO2 on dielectric properties of the thin films, whereas the mass-sensitive QCM devices were only able to detect small mass changes.
- NbOFFIVE- l-Ni coated on QCM as a sensor was reduced in the presence of moisture and was easily distinguishable from the response of CO2 in the air.
- the sensitivity was considerably reduced with A1FFIVE- 1 -Ni-coated QCM, and its frequency was reduced even more, especially at low CO2 concentrations.
- NbOFFIVE- 1 -Ni- and A1FFIVE-1 -Ni-coated IDE sensors were greatly affected by the presence of moisture.
- an often heard objection to capacitive sensor technology is that it is sensitive to humidity, yet the capacitive sensor is based on dielectric changes of the thin film upon water vapor uptake.
- the present Example reports, for the first time, the use of both IDE- and QCM-based sensors for the simultaneous detection of CO2 and H2O using ultramicroporous fluorinated MOFs, exhibiting unprecedented structural CO2-H2O adsorption properties.
- the sensors exhibited excellent selectivity for sensing CO2 at variable humidity levels; they also detected humidity levels at variable CO2 concentrations. It has been shown that isostructural fluorinated MOF-based capacitance sensitive sensors possessed good CO2 sensing properties under dry conditions. When working under real conditions (atmospheric conditions), the change in the dielectric constant over the change in the CO2 concentrations and at a constant humidity level of 60% RH resulted in a decrease in capacitance.
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