Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air

We report the results of a zinc oxide (ZnO) low-power microsensor for sub-ppm detection of NO<sub>2</sub> and H<sub>2</sub>S in air at 200 °C. NO<sub>2</sub> emission is predominantly produced by the combustion processes of fossil fuels, while coal-fired power pla...

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Main Authors: Engin Ciftyurek, Zheshen Li, Klaus Schierbaum
Format: Article
Language:English
Published: MDPI AG 2024-11-01
Series:Sensors
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Online Access:https://www.mdpi.com/1424-8220/24/23/7694
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author Engin Ciftyurek
Zheshen Li
Klaus Schierbaum
author_facet Engin Ciftyurek
Zheshen Li
Klaus Schierbaum
author_sort Engin Ciftyurek
collection DOAJ
description We report the results of a zinc oxide (ZnO) low-power microsensor for sub-ppm detection of NO<sub>2</sub> and H<sub>2</sub>S in air at 200 °C. NO<sub>2</sub> emission is predominantly produced by the combustion processes of fossil fuels, while coal-fired power plants are the main emitter of H<sub>2</sub>S. Fossil fuels (oil, natural gas, and coal) combined contained 74% of USA energy production in 2023. It is foreseeable that the energy industry will utilize fossil-based fuels more in the ensuing decades despite the severe climate crises. Precise NO<sub>2</sub> and H<sub>2</sub>S sensors will contribute to reducing the detrimental effect of the hazardous emission gases, in addition to the optimization of the combustion processes for higher output. The fossil fuel industry and solid-oxide fuel cells (SOFCs) are exceptional examples of energy conversion–production technologies that will profit from advances in H<sub>2</sub>S and NO<sub>2</sub> sensors. Porosity and surface activity of metal oxide semiconductor (MOS)-based sensors are both vital for sensing at low temperatures. Oxygen vacancies (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold">V</mi></mrow><mrow><mi mathvariant="bold">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula>) act as surface active sites for target gases, while porosity enables target gases to come in contact with a larger MOS area for sensing. We were able to create an open porosity network throughout the ZnO microstructure and simultaneously achieve an abundance of oxygen vacancies by using a heat treatment procedure. Surface chemistry and oxygen vacancy content in ZnO were examined using XPS and AES. SEM was used to understand the morphology of the unique characteristics of distinctive grain growth during heat treatment. Electrical resistivity measurements were completed. The valance band was examined by UPS. The Engineered Porosity approach allowed the entire ZnO to act as an open surface together with the creation of abundant oxygen vacancies (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold">V</mi></mrow><mrow><mi mathvariant="bold">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula>). NO<sub>2</sub> detection is challenging since both oxygen (O<sub>2</sub>) and NO<sub>2</sub> are oxidizing gases, and they coexist in combustion environments. <i>Engineered porosity ZnO</i> microsensor detected sub-ppm NO<sub>2</sub> under O<sub>2</sub> interference, which affects mimicking realistic sensor operation conditions. <i>Engineered porosity ZnO</i> performed better than the previous literature findings for H<sub>2</sub>S and NO<sub>2</sub> detection. The exceptionally high sensor response is attributed to the <i>high number of oxygen vacancies (</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold-italic">V</mi></mrow><mrow><mi mathvariant="bold-italic">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula><i>)</i> and <i>porosity extending through the thickness of the ZnO with a high degree of tortuosity</i>. These features enhance gas adsorption and diffusion via porosity, leading to high sensor response.
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spelling doaj-art-09e7fa77133c479893288d3fb9c6c6bc2025-08-20T02:50:41ZengMDPI AGSensors1424-82202024-11-012423769410.3390/s24237694Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in AirEngin Ciftyurek0Zheshen Li1Klaus Schierbaum2Department of Materials Science, Institute for Experimental Condensed Matter Physics, Heinrich Heine University of Düsseldorf, 40225 Düsseldorf, GermanyASTRID2 Synchrotron Light Source, ISA, Centre for Storage Ring Facilities, Department of Physics and Astronomy, Aarhus University, Ny Munkegade 120, 8000C Aarhus, DenmarkDepartment of Materials Science, Institute for Experimental Condensed Matter Physics, Heinrich Heine University of Düsseldorf, 40225 Düsseldorf, GermanyWe report the results of a zinc oxide (ZnO) low-power microsensor for sub-ppm detection of NO<sub>2</sub> and H<sub>2</sub>S in air at 200 °C. NO<sub>2</sub> emission is predominantly produced by the combustion processes of fossil fuels, while coal-fired power plants are the main emitter of H<sub>2</sub>S. Fossil fuels (oil, natural gas, and coal) combined contained 74% of USA energy production in 2023. It is foreseeable that the energy industry will utilize fossil-based fuels more in the ensuing decades despite the severe climate crises. Precise NO<sub>2</sub> and H<sub>2</sub>S sensors will contribute to reducing the detrimental effect of the hazardous emission gases, in addition to the optimization of the combustion processes for higher output. The fossil fuel industry and solid-oxide fuel cells (SOFCs) are exceptional examples of energy conversion–production technologies that will profit from advances in H<sub>2</sub>S and NO<sub>2</sub> sensors. Porosity and surface activity of metal oxide semiconductor (MOS)-based sensors are both vital for sensing at low temperatures. Oxygen vacancies (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold">V</mi></mrow><mrow><mi mathvariant="bold">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula>) act as surface active sites for target gases, while porosity enables target gases to come in contact with a larger MOS area for sensing. We were able to create an open porosity network throughout the ZnO microstructure and simultaneously achieve an abundance of oxygen vacancies by using a heat treatment procedure. Surface chemistry and oxygen vacancy content in ZnO were examined using XPS and AES. SEM was used to understand the morphology of the unique characteristics of distinctive grain growth during heat treatment. Electrical resistivity measurements were completed. The valance band was examined by UPS. The Engineered Porosity approach allowed the entire ZnO to act as an open surface together with the creation of abundant oxygen vacancies (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold">V</mi></mrow><mrow><mi mathvariant="bold">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula>). NO<sub>2</sub> detection is challenging since both oxygen (O<sub>2</sub>) and NO<sub>2</sub> are oxidizing gases, and they coexist in combustion environments. <i>Engineered porosity ZnO</i> microsensor detected sub-ppm NO<sub>2</sub> under O<sub>2</sub> interference, which affects mimicking realistic sensor operation conditions. <i>Engineered porosity ZnO</i> performed better than the previous literature findings for H<sub>2</sub>S and NO<sub>2</sub> detection. The exceptionally high sensor response is attributed to the <i>high number of oxygen vacancies (</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mrow><mi mathvariant="bold-italic">V</mi></mrow><mrow><mi mathvariant="bold-italic">O</mi></mrow><mrow><mo>•</mo><mo>•</mo></mrow></msubsup></mrow></semantics></math></inline-formula><i>)</i> and <i>porosity extending through the thickness of the ZnO with a high degree of tortuosity</i>. These features enhance gas adsorption and diffusion via porosity, leading to high sensor response.https://www.mdpi.com/1424-8220/24/23/7694hydrogen sulfide (H<sub>2</sub>S)nitrogen dioxide (NO<sub>2</sub>)sensoroxygen vacancyadsorbed oxygenXPS
spellingShingle Engin Ciftyurek
Zheshen Li
Klaus Schierbaum
Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
Sensors
hydrogen sulfide (H<sub>2</sub>S)
nitrogen dioxide (NO<sub>2</sub>)
sensor
oxygen vacancy
adsorbed oxygen
XPS
title Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
title_full Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
title_fullStr Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
title_full_unstemmed Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
title_short Engineered Porosity ZnO Sensor Enriched with Oxygen Vacancies Enabled Extraordinary Sub-ppm Sensing of Hydrogen Sulfide and Nitrogen Dioxide Air Pollution Gases at Low Temperature in Air
title_sort engineered porosity zno sensor enriched with oxygen vacancies enabled extraordinary sub ppm sensing of hydrogen sulfide and nitrogen dioxide air pollution gases at low temperature in air
topic hydrogen sulfide (H<sub>2</sub>S)
nitrogen dioxide (NO<sub>2</sub>)
sensor
oxygen vacancy
adsorbed oxygen
XPS
url https://www.mdpi.com/1424-8220/24/23/7694
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AT zheshenli engineeredporosityznosensorenrichedwithoxygenvacanciesenabledextraordinarysubppmsensingofhydrogensulfideandnitrogendioxideairpollutiongasesatlowtemperatureinair
AT klausschierbaum engineeredporosityznosensorenrichedwithoxygenvacanciesenabledextraordinarysubppmsensingofhydrogensulfideandnitrogendioxideairpollutiongasesatlowtemperatureinair