Zeolite membranes for highly selective formaldehyde sensors

Abstract A major challenge in gas sensing (e.g. breath analysis, indoor air quality monitoring, etc.) is the accurate detection of trace-level species in complex mixtures. While modern chemical gas sensors can be extremely compact, inexpensive and highly sensitive, their success is still limited by selectivity. Here, we combine sensors with highly selective zeolite membranes pre-separating gas mixtures. Zeolites – broadly applied in catalysis and gas separation – effectively separate molecules based on kinetic diameter, sorption and diffusion characteristics. Therefore, zeolite membranes are suitable filters for gas sensors removing undesired species from mixtures like exhaled breath. As proof-of-concept, a zeolite Mobile-Five (MFI)/Al2O3 membrane is placed upstream a highly sensitive but non-selective Pd-doped SnO2 sensor. Their combination exhibits exceptional selectivity (>100) for formaldehyde (down to 30 ppb) at 90% relative humidity, outperforming most state-of-the-art detectors by more than an order of magnitude. This novel concept is readily extendable to other tracers, as many combinations of widely tunable microporous membranes and gas sensors can be realized in this modular sensing device. This could enable a new class of highly sensitive and selective portable breath detectors or compact indoor air monitors.

[1]  Philippe Benech,et al.  Gas separation with a zeolite filter, application to the selectivity enhancement of chemical sensors , 2000 .

[2]  P. Mazzone,et al.  Detection of lung cancer by sensor array analyses of exhaled breath. , 2005, American journal of respiratory and critical care medicine.

[3]  S. Pratsinis,et al.  In Situ Monitoring of the Deposition of Flame-Made Chemoresistive Gas-Sensing Films. , 2017, ACS applied materials & interfaces.

[4]  K. Persaud,et al.  Analysis of discrimination mechanisms in the mammalian olfactory system using a model nose , 1982, Nature.

[5]  O. Terasaki,et al.  Stable single-unit-cell nanosheets of zeolite MFI as active and long-lived catalysts , 2009, Nature.

[6]  Yuehe Lin,et al.  Synthesis of submicron polycrystalline MFI zeolite films on porous ceramic supports , 1998 .

[7]  J. Smith,et al.  Silicalite, a new hydrophobic crystalline silica molecular sieve , 1978, Nature.

[8]  J. Santamaría,et al.  Removal of pollutants from indoor air using zeolite membranes , 2004 .

[9]  Berend Smit,et al.  Towards a molecular understanding of shape selectivity , 2008, Nature.

[10]  H. Verweij,et al.  Transport properties of alkanes through ceramic thin zeolite MFI membranes , 1996 .

[11]  Nicolae Barsan,et al.  Direct formation of highly porous gas-sensing films by in situ thermophoretic deposition of flame-made Pt/SnO2 nanoparticles , 2006 .

[12]  Sheikh A. Akbar,et al.  A selective room temperature formaldehyde gas sensor using TiO2 nanotube arrays , 2011 .

[13]  Kiran Chikkadi,et al.  E-Nose Sensing of Low-ppb Formaldehyde in Gas Mixtures at High Relative Humidity for Breath Screening of Lung Cancer? , 2016 .

[14]  David Smith,et al.  A longitudinal study of ammonia, acetone and propanol in the exhaled breath of 30 subjects using selected ion flow tube mass spectrometry, SIFT-MS , 2006, Physiological measurement.

[15]  M. V. Leeuwen Derivation of Stockmayer potential parameters for polar fluids , 1994 .

[16]  Hui Yang,et al.  Zeolitic imidazolate framework as formaldehyde gas sensor. , 2014, Inorganic chemistry.

[17]  Alessandro Ragnoni,et al.  Monitoring breath markers under controlled conditions , 2015, Journal of breath research.

[18]  J. Weitkamp,et al.  Zeolites and catalysis , 2000 .

[19]  U. Weimar,et al.  Understanding the fundamental principles of metal oxide based gas sensors; the example of CO sensing with SnO2 sensors in the presence of humidity , 2003 .

[20]  Stephan Steinhauer,et al.  Local CuO Nanowire Growth on Microhotplates: In Situ Electrical Measurements and Gas Sensing Application , 2016 .

[21]  Donghun Kim,et al.  Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets , 2017, Nature.

[22]  Qin Zhu,et al.  A highly sensitive and selective formaldehyde gas sensor using a molecular imprinting technique based on Ag–LaFeO3 , 2014 .

[23]  O. Levenspiel Chemical Reaction Engineering , 1972 .

[24]  Anton Amann,et al.  Lung cancer detection by proton transfer reaction mass-spectrometric analysis of human breath gas , 2007 .

[25]  Freek Kapteijn,et al.  Zeolite based films, membranes and membrane reactors: Progress and prospects , 2006 .

[26]  Hiroyuki Kudo,et al.  Biochemical gas sensor (bio-sniffer) for ultrahigh-sensitive gaseous formaldehyde monitoring. , 2010, Biosensors & bioelectronics.

[27]  Hang Zhou,et al.  Ultrathin hydrophobic MFI membranes , 2014 .

[28]  Sotiris E. Pratsinis,et al.  Selective sensing of NH3 by Si-doped α-MoO3 for breath analysis , 2016 .

[29]  G. Vardon,et al.  Respiratory water loss. , 1980, Respiration physiology.

[30]  W. Miekisch,et al.  Breath gas aldehydes as biomarkers of lung cancer , 2009, International journal of cancer.

[31]  Separation of alcohols and alcohols/O2 mixtures using zeolite MFI membranes , 1998 .

[32]  L. Francis,et al.  Dispersible Exfoliated Zeolite Nanosheets and Their Application as a Selective Membrane , 2011, Science.

[33]  S. Pratsinis,et al.  Dispersed nanoelectrode devices. , 2010, Nature nanotechnology.

[34]  Thanh Huu Nguyen,et al.  Oriented MFI Membranes by Gel‐Less Secondary Growth of Sub‐100 nm MFI‐Nanosheet Seed Layers , 2015, Advanced materials.

[35]  Mengmeng Li,et al.  Zeolitic Imidazolate Framework Coated ZnO Nanorods as Molecular Sieving to Improve Selectivity of Formaldehyde Gas Sensor , 2016 .

[36]  J. Falconer,et al.  Separation of binary C5 and C6 hydrocarbon mixtures through MFI zeolite membranes , 2006 .

[37]  R. Noble,et al.  Designing the Next Generation of Chemical Separation Membranes , 2011, Science.

[38]  Noriane A. Sievi,et al.  Noninvasive Body Fat Burn Monitoring from Exhaled Acetone with Si-doped WO3-sensing Nanoparticles. , 2017, Analytical chemistry.

[39]  Hossam Haick,et al.  Volatile organic compounds of lung cancer and possible biochemical pathways. , 2012, Chemical reviews.

[40]  Sotiris E. Pratsinis,et al.  Selective sensing of isoprene by Ti-doped ZnO for breath diagnostics. , 2016, Journal of materials chemistry. B.

[41]  Robert Golden,et al.  Identifying an indoor air exposure limit for formaldehyde considering both irritation and cancer hazards , 2011, Critical reviews in toxicology.

[42]  Udo Weimar,et al.  Water–oxygen interplay on tin dioxide surface: Implication on gas sensing , 2005 .

[43]  C. Hagleitner,et al.  Smart single-chip gas sensor microsystem , 2001, Nature.