Significant scientific efforts have been made to mimic and potentially supersede the mammalian nose using artificial noses based on arrays of individual cross-sensitive gas sensors over the past couple decades. To this end, thousands of research articles have been published regarding the design of gas sensor arrays to function as artificial noses. Nanoengineered materials possessing high surface area for enhanced reaction kinetics and uniquely tunable optical, electronic, and optoelectronic properties have been extensively used as gas sensing materials in single gas sensors and sensor arrays. Therefore, nanoengineered materials address some of the shortcomings in sensitivity and selectivity inherent in microscale and macroscale materials for chemical sensors. In this article, the fundamental gas sensing mechanisms are briefly reviewed for each material class and sensing modality (electrical, optical, optoelectronic), followed by a survey and review of the various strategies for engineering or functionalizing these nanomaterials to improve their gas sensing selectivity, sensitivity and other measures of gas sensing performance. Specifically, one major focus of this review is on nanoscale materials and nanoengineering approaches for semiconducting metal oxides, transition metal dichalcogenides, carbonaceous nanomaterials, conducting polymers, and others as used in single gas sensors or sensor arrays for electrical sensing modality. Additionally, this review discusses the various nano-enabled techniques and materials of optical gas detection modality, including photonic crystals, surface plasmonic sensing, and nanoscale waveguides. Strategies for improving or tuning the sensitivity and selectivity of materials toward different gases are given priority due to the importance of having cross-sensitivity and selectivity toward various analytes in designing an effective artificial nose. Furthermore, optoelectrical sensing, which has to date not served as a common sensing modality, is also reviewed to highlight potential research directions. We close with some perspective on the future development of artificial noses which utilize optical and electrical sensing modalities, with additional focus on the less researched optoelectronic sensing modality.
We report a multimodal electronic nose system based on photoactive carbonaceous hybrid nanomaterials for the detection and quantification of gaseous odors. The e-nose system comprises a high-density flexible sensor array, colorimetric and electrical measurement electronics, data acquisition software, and data analysis algorithms. The e-nose system combines the unique advantages of electrical, chemical, and physical properties of single-walled carbon nanotubes (SWNTs) with optical and chemical properties of various classes of organic macrocyclic compounds, such as pyrenes, porphyrins, and phthalocyanines, for multimodal gas sensing. Photoactive macromolecules such as metalloporphyrins and metallophthalocyanines have been previously developed into colorimetric sensors to various gas analytes. Their intrinsically low electrical conductivity prevents direct application of porphyrins and phthalocyanines in chemiresistive sensors. However, when used as a secondary sensing material via functionalization onto SWNTs, which intrinsically lacks chemical selectivity, these macromolecules confer their chemical selectivity and optical properties to the intrinsically semiconducting SWNT channel. This hybrid nanostructure allows both chemiresistive sensing and colorimetric sensing modalities. Another beneficial property of this hybrid nanostructure is the optoelectronic tunability of the nanomaterial to allow for direct modulation of chemical and electrical behaviors leading to tunable gas sensing capability. Using the high-density array containing 118 individually addressable sensors, over 60 different secondary sensing materials (functionalized onto SWNTs) were investigated, which include chemical derivatives of pyrenes, porphyrins, and phthalocyanines, which have a large variety of side-groups, and metal centers. Additionally, by integrating a large variety of secondary sensing materials into each sensing element of the 118-sensor array, we take advantage of the different chemical and electrical characteristics of each macromolecules which allow for different affinities to specific VOC species to enhance overall selectivity of the e-nose system. The functionality of the multimodal e-nose system was demonstrated to distinguish and quantify various volatile organic compounds (VOCs).
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