Flame-made gas sensing devices of high selectivity
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spread the fragrance of knowledge…
St. Paul's 2nd Letter Corinthians 2:14-15
Flame-made gas sensing devices of high selectivity
Sotiris E. Pratsinis
Particle Technology Laboratory, Department of Mechanical &
Process Engineering, ETH Zurich, Switzerland
1
The pdf of this talk is available upon request
Flame Synthesis of Materials [1]
Fundamentals Particle
structure
and size
distribution
[2]
π k
fv =
6
∑N d
i =1
i
2.22
m ,i d p0.78
[3]
[4]
J. Catal., 213, 296-304 (2003)
to 5 kg/h @ univ. labs
1. Kelesidis, Goudeli, SEP, Carbon, 121, 527-535 (2017).
2.
3.
4.
Kelesidis, SEP, Combustion and Flame, 209, 493-499 (2019)
Kelesidis, SEP, Proc. Comb. Instit. 38, 1189-1196 (2021).
Strobel, SEP, J. Mater. Chem., 17, 4743 - 4756 (2007).
Applications 2
Flame Synthesis of Materials
Fundamentals
x=1 2 6 10 25 50 75 95 98
antibacterial nano-silver
London Stock Exchange
December 2020, 127 M £
Gas Sensing Devices
J. Catal., 213, 296-304 (2003)
Applications
G.A. Sotiriou, SEP, Environ. Sci. Technol., 44, 5649 (2010)
M.J. Height, SEP. EP1846327, 2007 Catalysis, Batteries, Biomaterials, etc 3
J. van den Broek, I.C. Weber, A.T. Güntner, SEP, Mater. Horiz. 8, 661-684 (2021).
Gas Sensors $2.3 B/y[1].
Much higher impact (like catalysis):
False fire alarms in the UK alone £1 billion in 2014 [2].
Costs associated with asthma $56 billion in 2011[3].
Carbon Black $17 B/y[4].
11 Mt/y
Soot
1. https://www.grandviewresearch.com/industry-analysis/gas-sensors-market; 2021 [14.03.2021].
8 Mt/y[5].
2. Chagger R, Smith D. The causes of false fire alarms in buildings, https://www.bregroup.com/projects-reports/causes-of-
false-fire-alarms-in-buildings-bre-trust-briefing-paper/; 2014 [06.04.2021].
3. Nunes C, Pereira AM, Morais-Almeida M. Asthma costs and social impact. Asthma Research and Practice. 2017;3:1,
4. https://www.grandviewresearch.com/industry-analysis/carbon-black-market; 2021 [14.3.2021].
5. Bond, T. C.; Doherty, S. J.; Fahey, D., et al. J Geophys Res 2013, 118, 5380 4
Gas Sensors
Air Quality:
Indoors & Oudoors
Food and
Agriculture
Health and Lifestyle
Medical diagnostics, Fitness tracking
M. Righettoni, A. Amman, SEP, “Breath analysis by nanostructured metal
oxides as chemo-resistive gas sensors”, Mater. Today, 18, 63–171 (2015).
5
A.T. Güntner, S. Abegg, K. Königstein, P.A. Gerber, A. Schmidt-Trucksäss,
SEP, Breath Sensors for Health Monitoring, ACS Sensors, 4, 268-280 (2019).
Gas Sensors
n-type
p-type
- Sensitivity - Response time
3S
- Recovery //
- Stability
- Selectivity 2R
Porous, high surface-area films
1 µm
6
N Bârsan and U Weimar 2003 J. Phys.: Condens. Matter 15 R813
Assembly of Gas Sensors
Why use flames?
1. No liquid by-products
2. Unique metastable phases by
rapid heating-cooling
3. Few and fast unit operations
4. Transport (e.g. diffusion) is
well understood to
facilitate design from
first principles.
5. Extremely porous but
robust films
R. Strobel, SEP “Flame aerosol synthesis of smart nanostructured materials”, J. Mater. Chem., 17, 4743 - 4756 (2007).
Aerosol-based Technologies in Nanoscale Manufacturing: from Functional Materials to Devices through Core Chemical 7
Engineering, AIChE J., 56, 3028-3035 (2010)
Assembly of Flame-made Gas Sensors
R. Strobel, SEP “Flame aerosol synthesis of smart nanostructured materials”, J. Mater. Chem., 17, 4743 - 4756 (2007).
C.O. Blattmann, A.T. Güntner, SEP, “In Situ Monitoring of the Deposition of Flame-Made Chemoresistive Gas-Sensing 8
Films, ACS Appl. Mater. Interf., 9, 23926-23933 (2017).
Flame-made TiO2 Sensors for CO:
direct (FAD) vs. conventional deposition (FWD)
Tolmachoff E, Memarzadeh S, Wang H. Nanoporous titania gas sensing films prepared
in a premixed stagnation flame. J Phys Chem C. 2011;115:21620-8, 9
Flame-made Gas Sensors
5μ
a Lace-like c qualiflower-like
5 µm 5 μm
5 μm S. Kühne, M. Graf, A. Tricoli, F. Mayer,
A. Tricoli, M. Graf, F. Mayer, S. Kühne, A. Hierlemann, SEP, “Micropatterning Layers by SEP, A. Hierlemann, J. Micromech. 10
Flame Aerosol Deposition - Annealing”, Adv. Mater., 20, 3005-10 (2008). Microeng. 18, 035040 (2008).Selective gas sensors made by combustion
Acetone2 Ammonia3 Isoprene4
Cr-1 & Si-doped ε-WO3 Si-doped MoO3 Ti-doped ZnO
400 °C
1. L. Wang, A. Teleki, SEP, P.I. Gouma, Chem.Materials, 2008, 20, 4794-6.
2. Righettoni, M.; Tricoli, A.; SEP. Anal. Chem., 82, 3581–3587 (2010)
3. Güntner, A. T.; Righettoni, M.; SEP,. Sens. Actuators B 2016, 223, 266-273. 1111
4. Güntner, A. T.; Pineau, N. J.; Chie, D.; Krumeich, F.;SEP. J. Mater. Chem. B 2016, 4, 5358-5366Interference by ethanol breath analysis & indoor air quality
Methane3
Concentration, ppm
100
Ethanol, disinfectant4
Acetone2 Orders of magnitude
H23
Ethanol, 0.38 ‰
10 higher ethanol
concentration!
Benzene1
in blood5
1
high selectivity
0.1
required
1. M. Barker, M. Hengst, J. Schmid, H.J. Buers, B. Mittermaier, D. Klemp, R. Koppmann, Eur. Respir. J.
2006, 27, 929–936.
2. Turner, C. Španel, P. Smith, Physiol. Meas. 2006, 27, 321–337.
3. Calloway DJ, Murphy EL, Bauer D, Am. J. Dig. Dis. 1969, 14, 811.
4. Bessonneau, V. Thomas, O. Int. J. Environ. Res. Public Health 2012, 9, 868–879.
5. Vukovic J, Modun D, Markovic D, Sutlovic D, J Subst Abuse Alcohol, 2015, 3 1029.Filter-enhanced sensor selectivity
van den Broek J, Weber IC, Güntner AT, SEP. Mater Horiz. 2021;8:661-84,
13•
•
•
Commercial powder (1 g)
Mesoporous
High specific surface area (155 m2/g)
Adsorption
• Hydrophilic surface
Activated Alumina Filter
Flame-
made
Pt:SnO2
van den Broek J, Güntner AT, SEP.
ACS Sens. 2018;3:677-683.
Isoprene response
unchanged
Hydrophilic compounds
held back
Isoprene selectivity >100Methanol Poisoning from Laced Liquor
14’000 victims and 3’900 fatalities since 2017 worldwide:
Mexico (189 deaths, May 2020) and Turkey (50 deaths, Oct. 2020)
Oct. 2018
Dec. 2019
Feb. 2019 Toxic coconut wine kills at least
11 people during Christmas
celebrations in the Philippines
Added to save cost
Incorrect distillation
Frequent poisoning outbreaks
in developing countries with
thousands of victims.1
1. Médecins sans Frontiéres, Oslo University Hospital. Suspected methanol poisoning incidents. 2018. (Accessed 15th January 2019).Design of Gas Sensing Device van den Broek, J., Abegg, S., SEP, Güntner, A. T. Nature Commun.10, 4220 (2019)
Concept of Gas Sensing Device
Detection Concept
50% RH
1. Scientific Instrument Services (SIS). Tenax® TA Breakthrough Volume Data. https://www.sisweb.com/index/referenc/tenaxta.htm. Accessed 14th January
2014.Sensing Device for Methanol Detection
Inlet
Capillaries
Microcontroller
Separation
column
Sample
PCB
Pump
Outlet
Sensor
chamber
S. Abegg, L. Magro, J. van den Broek, SEP, A.T. Güntner, Nature Food, 1, 351–354 (2020)Detection of Methanol in the presence of Ethanol S. Abegg, L. Magro, J. van den Broek, SEP, A.T. Güntner,, Nature Food, 1, 351–354 (2020)
[2]
[1]
1. Fleischer, M., Kornely, S., Weh, T., Frank, J. & Meixner, H.. Sensors and Actuators B-Chem. 69, 205–210 (2000) 20
2. Sahm T, Rong W, Bârsan N, Mädler L, Friedlander SK, Weimar U. J Mater Res. 2007;22:850-7Our filter concept:
Filter and sensor are decoupled for flexible (modular)
operation!
21Flame-made1 Flame-made
1. R. Strobel, W.J. Stark, L.
Maedler, SEP, A. Baiker J.
Catal., 213, 296-304, (2003).
b d
Ethanol
Ammonia
Isoprene
CO
H2
CO
I.C. Weber, H.P. Braun, F. Krumeich, A.T. Güntner, SEP, Adv. Sci., 7, 2001503 (2020).Catalytic Filter Acetone Sensing @
Exceptional Selectivity (600 – 2000)
99.6 ± 0.5% 99.8 ± 0.3%
90% RH
a PTR-ToF-MS c
Pt/Al2O3 at 135 °C 23.2 ± 3.1%
1 ppm analyteMonitoring Lipolysis from Breath Acetone Ongoing: Randomized Clinical trial, 72 volunteers I.C. Weber, N. Derron, K. Königstein, P.A. Gerber, A.T. Güntner, SEP, Monitoring Lipolysis by Sensing Breath Acetone down to ppb, Small Sci. 2100004 (2021)
Noble metal content in SnO2 gas sensors
Korotcenkov G, Brinzari V, Boris Y, Ivanov M, Schwank J, Morante J. Thin Solid Films. 2003;436(1):119-126
Fundamentals
[2]
spill-over” effect (i.e.
chemical sensitization)
300 oC, 0% RH, 200 ppm
[1]
Wet made (precipitation) Pd
on SnO2
• optimum at 0.15 mol% Pd
Low noble metal concentrations
most effective in gas sensing
Applications
[1] Mädler L, Sahm T, Gurlo A, Grunwaldt JD, Barsan N, Weimar U, SEP. J Nanopart Res. 2006;8:783-96,
[2] Suematsu, K.; Shin, Y.; Hua, Z.Q.; Yoshida, K.; Yuasa, M.; Kida, T.; Shimanoe, K., ACS Appl Mater Inter, 2014, 6:5319-5326
25Embedded Pd fraction in flame-made Pd/MOx
Flame spray
pyrolysis
[1] Fujiwara, K.; SEP., Appl Catal B-Environ (2018)
26
[2] van Vegten, N.; Maciejewski, M.; Krumeich, F.; Baiker, A., Appl Catal B-Environ (2009)Experimental
27Embedded Pd fraction in SnO2 N.J. Pineau, S.D. Keller, A.T. Güntner, SEP, Palladium embedded in SnO2 enhances the sensitivity of flame-made chemoresistive gas sensors, Microchim. Acta, 187, 96 (2020).
Embedded Pd fraction in flame-made Pd/SnO2 in
comparison to Pd/MOx
[1] Fujiwara, K.; SEP., Appl Catal B-Environ (2018).
[2] van Vegten, N.; Maciejewski, M.; Krumeich, F.; Baiker, A., Appl Catal B-Environ 93 (2009) 38–49 .
[3] N.J. Pineau, S.D. Keller, A.T. Güntner, SEP, Microchim. Acta, 187, 96 (2020).
29Sensing of CO by SnO2 with
embedded Pd
[2]
2x
7x
90x 350 oC
50% RH
Consistent
with [1]
[1] Suematsu, K.; Shin, Y.; Hua, Z.Q.; Yoshida, K.; Yuasa, M.; Kida, T.; Shimanoe, K., ACS Appl Mater Inter, 2014, 6:5319-5326
[2] N.J. Pineau, S.D. Keller, A.T. Güntner, SEP, Microchim. Acta, 187, 96 (2020).Conclusions
Combustion enables
synthesis of new gas
sensors
Highly-selective devices are
made by flame technology.
Methanol is quantified in liquor, sanitizers & even
human breath in the presence of much more ethanol.
Embedded Pd (40 – 65 wt%) in flame-made
2x
7x SnO2 much increases the sensor response
90x
(esp. @ 1 – 3 wt% Pd) to CO, acetone and
ethanol, most likely by transducing effects.Thank you for listening!
Aletsch Glacier, Fieschalp Riederalp suspension bridge Belalp Switzerland
Psalm (102) 103:2 Eὐλόγει, ἡ ψυχή μου, τὸν Κύριον καὶ μὴ ἐπιλανθάνου πάσας
τὰς ἀνταποδόσεις αὐτοῦ
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