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1.
Mater Horiz ; 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38946305

ABSTRACT

Electrochemical deionization (ECDI) has emerged as a promising technology for water treatment, with faradaic ECDI systems garnering significant attention due to their enhanced performance potential. This study focuses on the development of a highly stable and efficient, full-polymer (polypyrrole, PPy) ECDI system based on two key strategies. Firstly, dopant engineering, involving the design of dopants with a high charge/molecular weight (MW) ratio and structural complexity, facilitating their effective integration into the polymer backbone. This ensures sustained contribution of strong negative charges, enhancing system performance, while the bulky dopant structure promotes stability during extended operation cycles. Secondly, operating the system with well-balanced charges between deionization and concentration processes significantly reduces irreversible reactions on the polymer, thereby mitigating dopant leakage. Implementing these strategies, the PPy(PSS)//PPy(ClO4) (PSS: polystyrene sulfonate) system achieves a high salt removal capacity (SRC) of 48 mg g-1, an ultra-low energy consumption (EC) of 0.167 kW h kgNaCl-1, and remarkable stability, with 96% SRC retention after 104 cycles of operation. Additionally, this study provides a detailed degradation mechanism based on pre- and post-cycling analyses, offering valuable insights for the construction of highly stable ECDI systems with superior performance in water treatment applications.

2.
Sci Rep ; 14(1): 13904, 2024 Jun 17.
Article in English | MEDLINE | ID: mdl-38886469

ABSTRACT

Prussian Blue Analogues (PBAs), which are characterized by their open structure, high stability, and non-toxic properties, have recently been the subject of research for various applications, including their use as electrode precursors for capacitive deionization, gas storage, and environmental purification. These materials can be readily tailored to enhance their affinity towards gases for integration with sensing devices. An improved understanding of PBA-gas interactions is expected to enhance material development and existing sensor deposition schemes greatly. The use of inverse gas chromatography (IGC) is a robust approach for examining the relationship between porous materials and gases. In this study, the adsorption properties of (functionalized) hydrocarbons, i.e., probe molecules, on the copper hexacyanoferrate (CuHCF) lattice were studied via IGC, demonstrating that alkylbenzenes have a higher affinity for this material than n-alkanes. This difference was rationalized by steric hindrance, π-π interactions, and vapour pressure effects. Along the same line, the five isomers of hexane showed decreasing selectivity upon increased steric hindrance. Enthalpy values for n-pentane, n-hexane and n-heptane were lower than that of toluene. The introduction of increased probe masses resulted in a surface coverage of 46% for toluene. For all n-alkane probe molecules this percentage was lower. However, the isotherms of these probes did not show saturation points and the observed linear regime proves beneficial for gas sensing. Our work demonstrates the versatility of CuHCF for gas sensing purposes and the potential of IGC to characterize the adsorption characteristics of such a porous nanomaterial.

3.
Water Res ; 255: 121469, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38493740

ABSTRACT

Soil salinization poses a significant challenge to agricultural activities. To address this, the agricultural industry seeks an irrigation water solution that reduces both ionic conductivity and sodium adsorption rate (SAR), thereby diminishing the risks of soil sodification and fostering sustainable crop production. Capacitive deionization (CDI) is an attractive electrochemical technology to advance this search. Recently, a one-dimensional transient CDI model unveiled a capacitive ion-exchange mechanism presenting the potential to adjust the treated water composition by modifying monovalent and divalent cation concentrations, thereby influencing the SAR index. This behavior would be achieved by using electrodes rich in surface functional groups able to efficiently capture divalent cations during conditioning and releasing them during charging while capturing monovalent ions. Beyond the theoretical modelling, the current experimental research demonstrates, for the first time, the effectiveness of the capacitive ion-exchange mechanism in a CDI pilot plant using real water samples spiked with solutions containing specific mono and divalent ions. Electrosorption experiments and computational modeling, specifically Density-Functional Theory (DFT), were used along with the analysis of the surface functional groups present in the electrodes to describe the capacitive ion-exchange phenomenon and validate the steps involved on it, highlighting the conditioning as a critical step. Various operational and flow modes confirm the versatility of CDI technology, achieving separation factors (RMg/Na) of 5-6 in batch, raising production from 0.5 to 0.8 L m-2 h-1 (batch) to 8.0-8.1 L m-2 h-1 when using single pass although reducing RMg/Na to 2. The reliability of the CDI technology in reducing SAR was also successfully tested with different influent compositions, including magnesium and calcium. Finally, the robustness of the capacitive ion-exchange mechanism was validated by a second CDI laboratory 9-cell stack cycled over 350 cycles. Our results confirm the reported theoretical model and expands the conclusions through the experiments in a pilot plant showing direct implications for employing CDI in agricultural applications.

4.
ACS Appl Mater Interfaces ; 15(4): 5118-5127, 2023 Feb 01.
Article in English | MEDLINE | ID: mdl-36648205

ABSTRACT

CO2 is a prominent example for an exhaust gas, and it is known for its high impact on global warming. Therefore, carbon capture from CO2 emissions of industrial processes is increasingly important to halt and prevent the disruptive consequences of global warming. Covalent organic frameworks (COFs) as porous nanomaterials have been shown to selectively adsorb CO2 in high quantities and with high CO2/N2 selectivity. Interactions with amines are recognized to selectively adsorb CO2 and help capture it from exhaust emissions. Herein, a novel COF (Me3TFB-(NH2)2BD), which was not accessible via a direct condensation reaction, was synthetized by dynamic linker exchange starting with Me3TFB-BD. Despite the linker exchange, the porosity of the COF was largely maintained, resulting in a high BET surface area of 1624 ± 89 m2/g. The CO2 and N2 adsorption isotherms at 273 and 295 K were studied to determine the performance in carbon capture at flue gas conditions. Me3TFB-(NH2)2BD adsorbs 1.12 ± 0.26 and 0.72 ± 0.07 mmol/g of CO2 at 1 bar and 273 and 295 K, respectively. The COF shows a high CO2/N2 IAST selectivity under flue gas conditions (273 K:83 ± 11, 295 K: 47 ± 11). The interaction of the aromatic amine groups with CO2 is based on physisorption, which is expected to make the regeneration of the material energy efficient.

5.
J Phys Chem C Nanomater Interfaces ; 126(50): 21338-21347, 2022 Dec 22.
Article in English | MEDLINE | ID: mdl-36582486

ABSTRACT

Covalent organic frameworks (COFs) are porous materials with high surface areas, making them interesting for a large variety of applications including energy storage, gas separation, photocatalysis, and chemical sensing. Structural variation plays an important role in tuning COF properties. Next to the type of the building block core, bonding directionality, and linking chemistry, substitution of building blocks provides another level of synthetic control. Thorough characterization and comparison of various substitution patterns is relevant for the molecular engineering of COFs via rational design. To this end, we have systematically synthesized and characterized multiple combinations of several methylated and non-methylated building blocks to obtain a series of imine-based COFs. This includes the experimental assignment of the COF structure by solid-state NMR. By comparing the properties of all COFs, the following trends were found: (1) upon methylation of the aldehyde nodes, COFs show increased Brunauer-Emmett-Teller surface areas, reduced pore collapse, blue-shifted absorbance spectra, and ∼0.2 eV increases in their optical band gaps. (2) COFs with dimethylated amine linkers show a lower porosity. (3) In tetramethylated amine linkers, the COF porosity even further decreases, the absorbance spectra are clearly red-shifted, and smaller optical band gaps are obtained. Our study shows that methyl substitution patterns on COF building blocks are a handle to control the UV absorbance of the resulting frameworks.

6.
Nanoscale ; 13(46): 19446-19452, 2021 Dec 02.
Article in English | MEDLINE | ID: mdl-34788773

ABSTRACT

Covalent Organic Frameworks (COFs) are thermally and chemically stable, nanoporous materials with high surface areas, making them interesting for a large variety of applications including energy storage, gas separation, catalysis and chemical sensing. However, pore blocking and pore collapse may limit their performance. Reducing the capillary forces by using solvents with low surface tension, like supercritical CO2, for activation, and the introduction of bulky isopropyl/methoxy groups were found to reduce pore collapse. Herein, we present an easy-to-use alternative that involves the combination of a new, methylated building block (2,4,6-trimethylbenzene-1,3,5-tricarbaldehyde, Me3TFB) with vacuum drying. Condensation of Me3TFB with 1,4-phenylenediamine (PA) or benzidine (BD) resulted in imine-linked 2D COFs (Me3TFB-PA and Me3TFB-BD) with higher degrees of crystallinity and higher BET surface areas compared to their non-methylated counterparts (TFB-PA and TFB-BD). This was rationalized by density functional theory computations. Additionally, the methylated COFs are less prone to pore collapse when subjected to vacuum drying and their BET surface area was found to remain stable for at least four weeks. Within the context of their applicability as sensors, we also studied the influence of hydrochloric acid vapour on the optical and structural properties of all COFs. Upon acid exposure their colour and absorbance spectra changed, making them indeed suitable for acid detection. Infrared spectroscopy revealed that the colour change is likely attributed to the cleavage of imine bonds, which are only partially restored after ammonia exposure. While this limits their application as reusable sensors, our work presents a facile method to increase the robustness of commonly known COFs.

7.
Langmuir ; 37(41): 12148-12162, 2021 Oct 19.
Article in English | MEDLINE | ID: mdl-34618452

ABSTRACT

In this study, a composite multilayer film onto gold was constructed from two charged building blocks, i.e., negatively charged graphene oxide (GO) and a branched polycation (polyethylenimine, PEI) via layer-by-layer (LbL) self-assembly technology, and this process was monitored in situ with quartz crystal microbalance (QCM) under different experimental conditions. This included the differences in frequency (Δf) as well as the changes in dissipation to yield information on the absorbed mass and viscoelastic properties of the formed PEI/GO multilayer films. The experimental conditions were optimized to obtain a high amount of the adsorbed mass of the self-assembled multilayer film. The surface morphology of the PEI/GO multilayer film onto gold was studied with atomic force microscopy (AFM). It was found that the positively charged PEI chains were combined with the oppositely charged GO to form an assembled film on the QCM sensor surface, in a wrapped and curled fashion. Raman and UV-vis spectra also showed that the intensities of the GO-characteristic signals are almost linearly related to the layer number. To explore the films for their use in divalent ion detection, the frequency response of the PEI/GO multilayer-modified QCM sensor to the exposure of aqueous solutions solution of Cu2+, Ca2+, Zn2+, and Sn2+ was further studied using QCM. Based on the Sauerbrey equation and the weight of different ions, the number of metal ions adsorbed per unit area on the surface of QCM sensors was calculated. For metal ion concentrations of 40 ppm, the adsorption capacities per unit area of Cu2+, Zn2+, Sn2+, and Ca2+ were found to be 1.7, 3.2, 0.7, and 4.9 nmol/cm2, respectively. Thus, in terms of the number of adsorbed ions per unit area, the QCM sensor modified by PEI/GO multilayer film shows the largest adsorption capacity of Ca2+. This can be rationalized by the relative hydration energies.

8.
ACS Appl Polym Mater ; 3(9): 4347-4374, 2021 Sep 10.
Article in English | MEDLINE | ID: mdl-34541543

ABSTRACT

The global society is in a transition, where dealing with climate change and water scarcity are important challenges. More efficient separations of chemical species are essential to reduce energy consumption and to provide more reliable access to clean water. Here, membranes with advanced functionalities that go beyond standard separation properties can play a key role. This includes relevant functionalities, such as stimuli-responsiveness, fouling control, stability, specific selectivity, sustainability, and antimicrobial activity. Polyelectrolytes and their complexes are an especially promising system to provide advanced membrane functionalities. Here, we have reviewed recent work where advanced membrane properties stem directly from the material properties provided by polyelectrolytes. This work highlights the versatility of polyelectrolyte-based membrane modifications, where polyelectrolytes are not only applied as single layers, including brushes, but also as more complex polyelectrolyte multilayers on both porous membrane supports and dense membranes. Moreover, free-standing membranes can also be produced completely from aqueous polyelectrolyte solutions allowing much more sustainable approaches to membrane fabrication. The Review demonstrates the promise that polyelectrolytes and their complexes hold for next-generation membranes with advanced properties, while it also provides a clear outlook on the future of this promising field.

9.
ACS Appl Mater Interfaces ; 12(31): 34746-34754, 2020 Aug 05.
Article in English | MEDLINE | ID: mdl-32589009

ABSTRACT

Capacitive deionization (CDI) is a desalination technique that can be applied for the separation of target ions from water streams. For instance, mono- and divalent cation selectivities were studied by other research groups in the context of water softening. Another focus is on removing Na+ from recirculated irrigation water (IW) in greenhouses, aiming to maintain nutrients. This is important as an excess of Na+ has toxic effects on plant growth by decreasing the uptake of other nutrients. In this study, we investigated the selective separation of sodium (Na+) and magnesium (Mg2+) in MCDI using a polyelectrolyte multilayer (PEM) on a standard grade cation-exchange membrane (Neosepta, CMX). Alternating layers of poly(allylamine hydrochloride) (PAH) and poly(styrene sulfonate) (PSS) were coated on a CMX membrane (CMX-PEM) using the layer-by-layer (LbL) technique. The layer formation was examined with X-ray photoelectron spectroscopy (XPS) and static water contact angle measurements (SWA) for each layer. For each membrane, i.e., the CMX-PEM membrane, CMX membrane, and for a special-grade cation-exchange membrane (Neosepta, CIMS), the Na+/Mg2+ selectivity was investigated by performing MCDI experiments, and selectivity values of 2.8 ± 0.2, 0.5 ± 0.04, and 0.4 ± 0.1 were found, respectively, over up to 40 cycles. These selectivity values indicate flexible switching from a Mg2+-selective membrane to a Na+-selective membrane by straightforward modification with a PEM. We anticipate that our modular functionalization method may facilitate the further development of ion-selective membranes and electrodes.

10.
Chem Commun (Camb) ; 56(37): 5046-5049, 2020 May 07.
Article in English | MEDLINE | ID: mdl-32242561

ABSTRACT

A novel ion separation methodology using a cation-exchange membrane modified with iron oxide nanoparticles (Fe3O4 NPs) coated with polyhexamethylene guanidine (PHMG) is proposed. The separation is performed in an electrodialysis cell, where firstly phosphate is electro-adsorbed to the PHMG@Fe3O4 NP coating, followed by a desorption step by applying an electric current.

11.
ChemSusChem ; 13(1): 136-140, 2020 Jan 09.
Article in English | MEDLINE | ID: mdl-31562787

ABSTRACT

Microporous polymer frameworks have attracted considerable attention to make novel separation layers owing to their highly porous structure, high permeability, and excellent molecular separation. This study concerns the fabrication and properties of thin melamine-based microporous polymer networks with a layer thickness of around 400 nm, supported on an α-alumina support and their potential use in organic solvent nanofiltration. The modified membranes show excellent solvent purification performances, such as n-heptane permeability as high as 9.2 L m-2 h-1 bar -1 in combination with a very high rejection of approximately 99 % for organic dyes with molecular weight of ≥457 Da. These values are higher than for the majority of the state-of-the-art membranes. The membranes further exhibit outstanding long-term operation stability. This work significantly expands the possibilities of using ceramic membranes in organic solvent nanofiltration.

12.
Chem Commun (Camb) ; 55(28): 4119-4122, 2019 Apr 02.
Article in English | MEDLINE | ID: mdl-30889233

ABSTRACT

To the best of our knowledge, for the first time MIL-53(Al) and NH2-MIL-53(Al) modified α-alumina membranes are investigated for the adsorption of organic dyes from organic solvents. These new, modified membranes show excellent adsorption of high concentrations of Rose Bengal dye in methanol and isopropanol solutions.

13.
Sensors (Basel) ; 19(4)2019 Feb 20.
Article in English | MEDLINE | ID: mdl-30791657

ABSTRACT

Capacitors made of interdigitated electrodes (IDEs) as a transducer platform for the sensing of volatile organic compounds (VOCs) have advantages due to their lower power operation and fabrication using standard micro-fabrication techniques. Integrating a micro-electromechanical system (MEMS), such as a microhotplate with IDE capacitor, further allows study of the temperature- dependent sensing response of VOCs. In this paper, the design, fabrication, and characterization of a low-power MEMS microhotplate with IDE capacitor to study the temperature-dependent sensing response to methanol using Zeolitic imidazolate framework (ZIF-8), a class of metal-organic framework (MOF), is presented. A Titanium nitride (TiN) microhotplate with aluminum IDEs suspended on a silicon nitride membrane is fabricated and characterized. The power consumption of the ZIF-8 MOF-coated device at an operating temperature of 50 ∘ C is 4.5 mW and at 200 ∘ C it is 26 mW. A calibration methodology for the effects of temperature of the isolation layer between the microhotplate electrodes and the capacitor IDEs is developed. The device coated with ZIF-8 MOF shows a response to methanol in the concentration range of 500 ppm to 7000 ppm. The detection limit of the sensor for methanol vapor at 20 ∘ C is 100 ppm. In situ study of sensing properties of ZIF-8 MOF to methanol in the temperature range from 20 ∘ C to 50 ∘ C using the integrated microhotplate and IDE capacitor is presented. The kinetics of temperature-dependent adsorption and desorption of methanol by ZIF-8 MOF are fitted with double-exponential models. With the increase in temperature from 20 ∘ C to 50 ∘ C, the response time for sensing of methanol vapor concentration of 5000 ppm decreases by 28%, whereas the recovery time decreases by 70%.

14.
Environ Sci Technol ; 53(5): 2396-2404, 2019 03 05.
Article in English | MEDLINE | ID: mdl-30574781

ABSTRACT

In this study, the preparation of a new, functional anion-exchange membrane (AEM), containing guanidinium groups as the anion-exchanging sites (Gu-100), is described as well as the membrane characterization by XPS, water uptake, permselectivities, and electrical resistances. The functional membrane was also employed in pH-dependent electrodialysis experiments using model dairy wastewater streams. The properties of the new membrane are compared to those of a commercially available anion-exchange membrane bearing conventional quaternary ammonium groups (Gu-0). Guanidinium was chosen for its specific binding properties toward oxyanions: e.g., phosphate. This functional moiety was covalently coupled to an acrylate monomer via a facile two-step synthesis to yield bulk-modified membranes upon polymerization. Significant differences were observed in the electrodialysis experiments for Gu-0 and Gu-100 at pH 7, showing an enhanced phosphate and citrate transport for Gu-100 in comparison to Gu-0. At pH 10 the difference is much more pronounced: for Gu-0 membranes almost no phosphate and citrate transport could be detected, while the Gu-100 membranes transported both ions significantly. We conclude that having guanidinium groups as anion-exchange sites improves the selectivity of AEMs. As the presented monomer synthesis strategy is modular, we consider the implementation of functional groups into a polymer-based membrane via the synthesis of tailor-made monomers as an important step toward selective ion transport, which is relevant for various fields, including water treatment processes and fuel cells.


Subject(s)
Phosphates , Wastewater , Anions , Citrates , Citric Acid , Membranes, Artificial
15.
Sci Rep ; 8(1): 16425, 2018 11 06.
Article in English | MEDLINE | ID: mdl-30401937

ABSTRACT

Fingermarks are trace evidence of great forensic importance, and their omnipresence makes them pivotal in crime investigation. Police and law enforcement authorities have exploited fingermarks primarily for personal identification, but crucial knowledge on when fingermarks were deposited is often lacking, thereby hindering crime reconstruction. Biomolecular constituents of fingermark residue, such as amino acids, lipids and proteins, may provide excellent means for fingermark age determination, however robust methodologies or detailed knowledge on molecular mechanisms in time are currently not available. Here, we address fingermark age assessment by: (i) drafting a first protein map of fingermark residue, (ii) differential studies of fresh and aged fingermarks and (iii), to mimic real-world scenarios, estimating the effects of donor contact with bodily fluids on the identification of potential age biomarkers. Using a high-resolution mass spectrometry-based proteomics approach, we drafted a characteristic fingermark proteome, of which five proteins were identified as promising candidates for fingermark age estimation. This study additionally demonstrates successful identification of both endogenous and contaminant proteins from donors that have been in contact with various bodily fluids. In summary, we introduce state-of-the-art proteomics as a sensitive tool to monitor fingermark aging on the protein level with sufficient selectivity to differentiate potential age markers from body fluid contaminants.


Subject(s)
Aging , Dermatoglyphics , Forensic Medicine/methods , Mass Spectrometry/methods , Proteome/analysis , Aged , Female , Humans , Male
16.
Biochim Biophys Acta Biomembr ; 1860(12): 2669-2680, 2018 12.
Article in English | MEDLINE | ID: mdl-30291924

ABSTRACT

Silicon semiconductors with a thin surface layer of silica were first modified with polyelectrolytes (polyethyleneimine, polystyrene sulfonate and poly(allylamine)) via a facile layer-by-layer deposition approach. Subsequently, lipid vesicles were added to the preformed polymeric cushion, resulting in the adsorption of intact vesicles or fusion and lipid bilayer formation. To study involved interactions we employed optical reflectometry, electrochemical impedance spectroscopy and fluorescent recovery after photobleaching. Three phospholipids with different charge of polar head groups, i.e. 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), 1,2-dioleoyl-sn-glycero-3-phospho-l-serine (DOPS) and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) were used to prepare vesicles with varying surface charge. We observed that only lipid vesicles composed from 1:1 (mole:mole) mixture of DOPC/DOPS have the ability to fuse onto an oppositely charged terminal layer of polyelectrolyte giving a lipid bilayer with a resistance of >100 kΩ. With optical reflectometry we found that the vesicle surface charge is directly related to the amount of mass adsorbed onto the surface. An interesting observation was that zwitterionic polar head groups of DOPC allow the adsorption on both positively and negatively charged surfaces. As found with fluorescent recovery after photobleaching, positively charged surface governed by the presence of poly(allylamine) as the terminal layer resulted in intact DOPC lipid vesicles adsorption whereas in the case of a negatively charged silica surface formation of lipid bilayers was observed, as expected from literature.


Subject(s)
Lipid Bilayers/chemistry , Phospholipids/chemistry , Polyelectrolytes/chemistry , Silicon/chemistry , Adsorption , Surface Properties
17.
Adv Mater ; 30(26): e1707234, 2018 Jun.
Article in English | MEDLINE | ID: mdl-29774609

ABSTRACT

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

18.
Nanoscale ; 10(15): 6884-6891, 2018 Apr 19.
Article in English | MEDLINE | ID: mdl-29520398

ABSTRACT

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

19.
Small ; 13(29)2017 08.
Article in English | MEDLINE | ID: mdl-28593743

ABSTRACT

The in situ electrochemical growth of Cu benzene-1,3,5-tricarboxylate (CuBTC) metal-organic frameworks, as an affinity layer, directly on custom-fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5-7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6-8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion-controlled kinetics (k = 2.9 mmol s-0.5 g-1CuBTC ). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity Ke = 174.8 bar-1 . A volume fraction fMeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu-IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100-8000 ppm.

20.
ACS Appl Mater Interfaces ; 9(29): 24926-24935, 2017 Jul 26.
Article in English | MEDLINE | ID: mdl-28440621

ABSTRACT

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0-100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

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