Sensor devices comprising a metal-organic framework material and methods of making and using the same
Inventors
Chang, Chih-Hung • Kim, Ki-Joong • Wang, Alan X. • Zhang, Yujing • Chong, Xinyuan • Ohodnicki, Paul R.
Assignees
US Department of Energy • Oregon State University
Publication Number
US-10274421-B2
Publication Date
2019-04-30
Expiration Date
2036-02-09
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Abstract
Disclosed herein are embodiments of sensor devices comprising a sensing component able to determine the presence of, detect, and/or quantify detectable species in a variety of environments and applications. The sensing components disclosed herein can comprise MOF materials, plasmonic nanomaterials, redox-active molecules, a metal, or any combinations thereof. In some exemplary embodiments, optical properties of the plasmonic nanomaterials and/or the redox-active molecules combined with MOF materials can be monitored directly to detect analyte species through their impact on external conditions surrounding the material or as a result of charge transfer to and from the plasmonic nanomaterial and/or the redox-active molecule as a result of interactions with the MOF material.
Core Innovation
The invention disclosed herein concerns sensor devices comprising a substrate coupled to a sensing component capable of determining the presence of, detecting, and/or quantifying detectable species in various environments and applications. The sensing components may include metal-organic framework (MOF) materials, plasmonic nanomaterials, redox-active molecules, metals, or combinations thereof. Optical properties of plasmonic nanomaterials and/or redox-active molecules combined with MOF materials can be monitored directly to detect analyte species by their impact on external conditions or through charge transfer resulting from interactions with the MOF material.
The problem addressed by the invention is the lack of highly sensitive and specific signal transduction methods for sensors using MOFs, which has limited their industrial implementation. Existing infrared absorption sensors are expensive and not easily transported, and fiber-optic sensors have been limited by low molecule density, high selectivity issues in complex gas mixtures, and difficulties detecting gases due to the absence of fundamental vibration bands in the near-infrared (NIR) region. Furthermore, conductive MOFs grown on gold substrates functionalized by thiol-based self-assembled monolayers face issues such as poor thermal and chemical stability, and insulating nature leading to poor electrical contact.
The disclosed sensor devices overcome these limitations by utilizing MOF materials, alone or combined with plasmonic nanomaterials, to improve sensitivity and absorption efficiency. The devices can serve as NIR absorption sensors for gas detection that are transportable, low-cost, compact, and exhibit distributed sensing capability. The MOF materials can be combined with plasmonic nanomaterials that have surface plasmon resonance properties sensitive to environmental changes or charge transfer interactions, enabling detection of optical constant changes directly or indirectly through modifications to the plasmonic materials. The invention also includes methods for controlled formation of highly oriented MOF films on chemically modified substrate surfaces for use as electrically conductive chemical sensors incorporating redox-active molecules, resulting in improved conductivity and selective detection of gases such as CO2.
Claims Coverage
The patent includes multiple independent claims covering sensor devices comprising substrates coupled to sensing components with specific material compositions and configurations, as well as methods of using these devices to detect detectable species, particularly gases.
Sensor device with MOF material and plasmonic nanoparticles or nanocrystals
A sensor device comprising a substrate delivering light to a sensing component that includes a metal-organic framework material comprising a first metal and organic ligand, and a plasmonic nanoparticle and/or nanocrystal comprising a second metal, metal alloy, metal oxide, metal sulfide, dopant, or combinations thereof. The plasmonic nanomaterial is explicitly not spherical or ellipsoidal gold nanoparticles and does not directly contact the substrate, which does not include a grating.
Sensor device utilizing near-infrared light and fiber optic substrates
The sensor device where the substrate is a light guide selected from a multi-mode or single-mode optical fiber and the light delivered is near-infrared (NIR) light.
Selection of metal components in MOF and plasmonic materials
The first metal in the MOF can be selected from copper, silver, gold, aluminum, zinc, cobalt, nickel, magnesium, manganese, iron, cadmium, beryllium, calcium, titanium, tin, chromium, vanadium, or combinations thereof. The metal oxide plasmonic nanomaterial can be selected from indium oxide, tin oxide, titanium oxide, zirconium oxide, cesium oxide, zinc oxide, copper oxide, gallium oxide with dopants including Pt, Au, Sn, Al, Nb, or Ta.
Configurations of sensing component and substrate coupling
The sensing component can be coupled to the entire substrate or a portion (0.01% to 10% surface area), and the substrate can be coupled to multiple sensing components or multiple substrates each with an individual sensing component. The plasmonic nanomaterials can be embedded within internal pores of the MOF or encapsulated within one or more layers of MOF material. The sensing component layers can be thin (1 nm to <500 nm) or thick (500 nm to 50 μm). Coupling to the substrate can be physical and/or chemical.
Electrically conductive sensor device with redox-active molecule
A sensor device comprising a substrate coupled to a metal-organic framework material comprising an organic ligand, a redox-active molecule, and a detectable gas species. The device does not comprise a thiol-based self-assembled monolayer, and may include a metal ion species in the MOF material, a metal coupled to the substrate, or both. The redox-active molecule includes organocyanide-containing ligands, polyaniline, or combinations thereof. The substrate can be a silicon wafer with a silicon dioxide top layer, the MOF includes benzene-1,3,5-tricarboxylic acid, a detectable gas molecule, and TCNQ, and the device includes gold electrodes.
Methods of detecting presence of a detectable species
Methods comprising exposing a sample to the sensor device containing MOF and plasmonic nanomaterials, and analyzing for a near-infrared signal produced by detectable species absorbed by the sensing component. Alternatively, methods using electrically conductive sensor devices comprising MOF material and redox-active molecules include analyzing changes in optical properties, electrical conductivity, or both, indicative of the presence of detectable gas species.
The patent claims cover sensor devices employing specific compositions of MOF materials combined with plasmonic nanomaterials, arranged in particular spatial and structural configurations on substrates, as well as electrically conductive devices integrating redox-active molecules and metal electrodes. Methods for detecting gases via optical and electrical property changes are also claimed, highlighting innovations in sensitivity, specificity, and device architecture.
Stated Advantages
The sensor devices are transportable, low in cost, compact in size, and exhibit distributed sensing capability.
Using MOF materials in combination with plasmonic nanomaterials improves sensitivity and absorption efficiency in detecting gases.
Electrically conductive MOF films with redox-active molecules exhibit conductivities over seven orders of magnitude higher than unmodified MOFs, enabling selective detection of gases such as CO2.
The sensor devices exhibit rapid response times, e.g., 0.1 seconds to 100 seconds for absorption and desorption.
The disclosed sensor devices achieve detection limits suitable for various concentrations, e.g., 500 ppm CO2 detection limit demonstrated.
Documented Applications
Detecting gases such as CO2, SF6, water vapor, NO, CH4, C2H4, NH4, and benzene.
Monitoring greenhouse gas emissions and environmental protection.
Detecting gases produced in gas lines, engines, pipes, and detecting gas leaks.
Monitoring hazardous gases or other products produced during use of explosives, fertilizers, and similar materials.
Forming sensor networks for large-scale detection, monitoring, and quantification of detectable species in atmospheric and enclosed environments.
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