Gas Phase Sensing of Alcohols by Metal Organic Framework–Polymer Composite Materials

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.

[1]  S. Ecks.  Gas , 2017 .

[2]  Freek Kapteijn,et al.  Polymer–Metal Organic Framework Composite Films as Affinity Layer for Capacitive Sensor Devices , 2016 .

[3]  F. Kapteijn,et al.  Metal Organic Framework Crystals in Mixed‐Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance , 2016, Advanced functional materials.

[4]  Dc Kitty Nijmeijer,et al.  MOF-mixed matrix membranes: Precise dispersion of MOF particles with better compatibility via a particle fusion approach for enhanced gas separation properties , 2015 .

[5]  Khaled N. Salama,et al.  Insights on Capacitive Interdigitated Electrodes Coated with MOF Thin Films: Humidity and VOCs Sensing as a Case Study , 2015, Sensors.

[6]  Svetlana Mintova,et al.  Gas sensing using porous materials for automotive applications. , 2015, Chemical Society reviews.

[7]  Dennis Sheberla,et al.  Cu₃(hexaiminotriphenylene)₂: an electrically conductive 2D metal-organic framework for chemiresistive sensing. , 2015, Angewandte Chemie.

[8]  Derek R. Miller,et al.  Nanoscale metal oxide-based heterojunctions for gas sensing: A review , 2014 .

[9]  Jing Li,et al.  Luminescent Metal—Organic Frameworks for Chemical Sensing and Explosive Detection , 2014 .

[10]  H. Salavagione,et al.  Chemical sensors based on polymer composites with carbon nanotubes and graphene: the role of the polymer , 2014 .

[11]  C. Doherty,et al.  MOF positioning technology and device fabrication. , 2014, Chemical Society reviews.

[12]  M. Allendorf,et al.  MOF-based electronic and opto-electronic devices. , 2014, Chemical Society reviews.

[13]  Jing Li,et al.  Luminescent metal-organic frameworks for chemical sensing and explosive detection. , 2014, Chemical Society reviews.

[14]  F. Kapteijn,et al.  Mixed matrix membranes based on NH2-functionalized MIL-type MOFs: Influence of structural and operational parameters on the CO2/CH4 separation performance , 2014 .

[15]  Jing Bai,et al.  Titanium dioxide nanomaterials for sensor applications. , 2014, Chemical reviews.

[16]  C. Téllez,et al.  Mixed matrix membranes comprising MOFs and porous silicate fillers prepared via spin coating for gas separation , 2014 .

[17]  Jeffrey R. Long,et al.  Evaluating metal–organic frameworks for natural gas storage , 2014 .

[18]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[19]  R. Gutierrez-Osuna,et al.  Active temperature modulation of metal-oxide sensors for quantitative analysis of gas mixtures , 2013 .

[20]  Shurong Wang,et al.  Organic/inorganic hybrid sensors: A review , 2013 .

[21]  L. Lauhon,et al.  Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing. , 2013, Chemical Society reviews.

[22]  L. Ansaloni,et al.  Vapor and Liquid Sorption in Matrimid Polyimide: Experimental Characterization and Modeling , 2013 .

[23]  F. Kapteijn,et al.  Metal organic framework based mixed matrix membranes: An increasingly important field of research with a large application potential , 2013 .

[24]  C. Sarkar,et al.  High Dynamic Range Methanol Sensor Based on Aligned ZnO Nanorods , 2013, IEEE Sensors Journal.

[25]  F. Kapteijn,et al.  Interplay of metal node and amine functionality in NH2-MIL-53: modulating breathing behavior through intra-framework interactions. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[26]  Daqiang Zhang,et al.  A Survey on Gas Sensing Technology , 2012, Sensors.

[27]  Zhen Jin,et al.  Metal Oxide Nanostructures and Their Gas Sensing Properties: A Review , 2012, Sensors.

[28]  Ahmad Fauzi Ismail,et al.  A recent progress in thin film composite membrane: A review , 2012 .

[29]  Omar K Farha,et al.  Metal-organic framework materials as chemical sensors. , 2012, Chemical reviews.

[30]  Cheryl Surman,et al.  Materials and transducers toward selective wireless gas sensing. , 2011, Chemical reviews.

[31]  O. Shekhah,et al.  MOF thin films: existing and future applications. , 2011, Chemical Society reviews.

[32]  Geoff W. Stevens,et al.  Sorption of methane, nitrogen, carbon dioxide, and water in Matrimid 5218 , 2010 .

[33]  U. Mueller,et al.  Industrial Applications of Metal—Organic Frameworks , 2009 .

[34]  Freek Kapteijn,et al.  An amine-functionalized MIL-53 metal-organic framework with large separation power for CO2 and CH4. , 2009, Journal of the American Chemical Society.

[35]  Gunter Hagen,et al.  Metal-Organic Frameworks for Sensing Applications in the Gas Phase , 2009, Sensors.

[36]  Hongmin Chen,et al.  Ultrathin polymeric interpenetration network with separation performance approaching ceramic membranes for biofuel , 2009 .

[37]  Mira Josowicz,et al.  Composites of intrinsically conducting polymers as sensing nanomaterials. , 2008, Chemical reviews.

[38]  Mira Josowicz,et al.  Composites of intrinsically conducting polymers as sensing nanomaterials. , 2008, Chemical reviews.

[39]  Carl L. Yaws,et al.  The Yaws Handbook of Vapor Pressure , 2007 .

[40]  Hua Bai,et al.  Gas Sensors Based on Conducting Polymers , 2007, Sensors (Basel, Switzerland).

[41]  Rui Igreja,et al.  Dielectric response of interdigital chemocapacitors: The role of the sensitive layer thickness , 2006 .

[42]  Khalil Arshak,et al.  Development of a novel gas sensor based on oxide thick films , 2005 .

[43]  W. Koros,et al.  Non-ideal effects in organic-inorganic materials for gas separation membranes , 2005 .

[44]  Yihe Zhang,et al.  Dielectric behavior and dependence of percolation threshold on the conductivity of fillers in polymer-semiconductor composites , 2004 .

[45]  R. Igreja,et al.  Analytical evaluation of the interdigital electrodes capacitance for a multi-layered structure , 2004 .

[46]  Gábor Harsányi,et al.  Polymer films in sensor applications: A review of present uses and future possibilities , 2000 .

[47]  R. Mertens,et al.  Nanoscaled interdigitated electrode arrays for biochemical sensors , 1997, Proceedings of International Solid State Sensors and Actuators Conference (Transducers '97).

[48]  Sarfraz A. Siddiqui,et al.  Solubility Parameters , 1982 .

[49]  G. Thomson,et al.  The Antoine equation for vapor-pressure data. , 1946, Chemical reviews.