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Ines C. Weber1, Hugo P. Braun1, Frank Krumeich1, Andreas T. Güntner2, Sotiris E. Pratsinis1
1 Particle Technology Laboratory, ETH Zürich, Switzerland2 Department of Endocrinology, Diabetology, and Clinical Nutrition, University Hospital Zürich, Switzerland
15.06.2021Ines Weber 1
Superior Selectivity of Acetone in Gas Mixtures By Pt/Al2O3 Catalyst-Filtered Si/WO3 Sensors
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Acet
one2
Breath acetone detection
15.06.2021Ines Weber 2
Acetone: marker for fat-burn (among others) Metabolic health monitoring Non-invasive Personalized on-line monitoring
> 1’000 interferants1
Detector requirements Sensitivity (down to ppb) Fast, compact & inexpensive Humidity Robustness Selectivity Complex gas mixtures (e.g, breath)
1. Drabinska N, Flynn C, Ratcliffe N, Belluomo I, Myridakis A, Gould O, Fois M, Smart A, Devine T, de Lacy Costello, P J. Breath Res. 2021, 14, 034001.
2. Turner, C.; Španel, P.; Smith, Physiol. Meas. 2006, 27, 321–337.
3. Güntner AT, Kompalla JF, Landis H, Theodore SJ, Geidl B, Sievi NA, Kohler M, Pratsinis SE, Gerber PA, Sensors 2018, 18, 3655.
4. Königstein K, Abegg S, Schorn AN, Weber IC, Derron N, Krebs A, Gerber PA, Schmidt-Trucksäss A, Güntner AT, J. Breath Res. 2020, 15, 016006
5. King, J.; Kupferthaler, A.; Unterkofler, K.; Koc, H.; Teschl, S.; Teschl, G.; Miekisch, W.; Schubert, J.; Hinterhuber, H.; Amann, A. J. Breath Res. 2009, 3, 027006.
6. Deveci, SE, Deveci, F, Acik, Y, Ozan AT, Respiratory Medicine, 2004, 98, 551-556.
7. D. J. Calloway, E. L. Murphy, D. Bauer, Am. J. Dig. Dis. 1969, 14, 811. [24]
8. Bessonneau, V.; Thomas, O. Int. J. Environ. Res. Public Health 2012, 9, 868–879.102
103
104
105
Con
cent
ratio
n, p
pb
102
103
104
105
Con
cent
ratio
n, p
pb
102
103
104
105
Con
cent
ratio
n, p
pb
102
103
104
105
Con
cent
ratio
n, p
pb
Hyd
roge
n7CO
6NH
32
Isop
rene
5
Etha
nol8
Die
t4Ex
erci
se3
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MaterialSelectivity (SAcetone/SAnalyte), [-]
Ethanol Isoprene H2 CO NH3
Com
posi
tes SnO2 / reduced graphene oxide1 4.3 - - 9.5 9.5
SnO2 / multi-walled carbon nanotubes2 1.8 - - 2.9 -
Ni-SnO2 / graphene3 1.9 - 18 - -
Met
al O
xide
s Al/ZnO4 - 3.6 - 7.4 6.9Au-vertical hematite nanotubes5 2.4 - 87 86 36
Si/WO36 11.4 0.5 139 289 140
Nb/WO37 23 - 120 >50 100
1. Choi SJ, Jang BH, Lee SJ, Min BK, Rothschild A, Kim ID, ACS Appl. Mater. Interfaces 2014, 6, 2588.2. Narjinary M, Rana P, Sen A, Pal M, Mater. Des. 2017, 115, 1583. Singkammo S, Wisitsoraat A, Sriprachuabwong C, Tuantranont A, Phanichphant S, Liewhiran C, ACS Appl. Mater. Interfaces 2015, 7, 3077.4. Yoo R, Güntner AT, Park Y, Rim HJ, Lee HS, Lee W, Sensors Actuators, B 2019, 283, 107.5. Kim DH, Kim TH, Sohn W, Suh JM, Shim YS, Kwon KC, Hong K, Choi S, Byun HG, Lee JH, Jang HW, Sensors Actuators, B Chem. 2018, 274, 587.6. Weber IC, Braun HP, Krumeich F, Güntner AT, Pratsinis SE, Adv. Sci. 2020, 7, 20015037. Choi HJ, Chung JH, Yoon, JW, Lee JH, Sensors Actuators, B 2021, 338, 129823. 3
State-of-the-art
15.06.2021Ines Weber
MaterialSelectivity (SAcetone/SAnalyte), [-]
Ethanol Isoprene H2 CO NH3
Com
posi
tes SnO2 / reduced graphene oxide1 4.3 - - 9.5 9.5
SnO2 / multi-walled carbon nanotubes2 1.8 - - 2.9 -
Ni-SnO2 / graphene3 1.9 - 18 - -
MaterialSelectivity (SAcetone/SAnalyte), [-]
Ethanol Isoprene H2 CO NH3
Com
posi
tes SnO2 / reduced graphene oxide1 4.3 - - 9.5 9.5
SnO2 / multi-walled carbon nanotubes2 1.8 - - 2.9 -
Ni-SnO2 / graphene3 1.9 - 18 - -
Met
al O
xide
s Al/ZnO4 - 3.6 - 7.4 6.9Au-vertical hematite nanotubes5 2.4 - 87 86 36
Si/WO36 11.4 0.5 139 289 140
Nb/WO37 23 - 120 >50 100
Pt/Al2O3 + Si/WO36 >500 >1000 >250 >1000 >1000
|| 415.06.2021Ines Weber
Si/WO3 at 400 °CPt/Al2O3 at 135 °C
Selective sensors enabled by catalytic filters
Continuous interferant removal by chemical reaction2
Rapid measurements Differentiate between VOCs3
Configuration: packed bed or overlayer4
1. Güntner AT, Weber IC, Pratsinis SE, ACS Sensors, 2020, 5, 1058 – 1067.2. Portnoff MA, Grace R, Guzman AM, Runco PD, Yannopoulos LN, Sens. Actuators, B, 1991, 5, 231–2353. Van den Broek J, Weber IC Güntner AT, Pratsinis SE, Materials Horizons, 2021, 8, 661 - 684.4. Moon, YK, Jeong SY, Jo YM, Jo YK, Kang YC, Lee JH, Advanced Science, 2021, 8, 2004078
1
Pt/Al2O3Quartz wool
|| 15.06.2021Ines Weber 5
Selective acetone detector
s s s
0.1
1
10
Resp
onse
(-)
S >
1000
> 10
00
> 50
0
> 25
0
> 10
00Acet
one
Isop
rene
NH
3
Etha
nol
Hyd
roge
n
CO
Catalytic filter enables superior acetone selectivity!
90% RH
Res
pons
e, -
0.1
1
10Si/WO3 Pt/Al2O3 + Si/WO3
Weber IC, Braun HP, Krumeich F, Güntner AT, Pratsinis SE, Advanced Science, 2020, 7, 2001503.
Pt/Al2O3 at 135 °C
20% loss
1 ppm
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Selective acetone sensing in gas mixtures
6
0 50 100 150 2000
1
2
3
4
5R
esis
tanc
e, M
Ω
Time, min0 50 100 150 200
0
1
2
3
4
5R
esis
tanc
e, M
Ω
Time, min
Ines Weber 15.06.2021
Acetone only// with 5000 ppb interferants
50 ppb 100
250
500 7501000
Acetone sensing despite orders of magnitude higher interferants
Interferants:Each 1000 ppb Ethanol Isoprene H2 CO NH3
Response time:55 s
SNR:> 100
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Catalyst conversion mechanism
7Ines Weber 15.06.2021
50 100 150 200 250
0
25
50
75
100
Con
vers
ion,
%
Temperature, °C
90 % RH
50 100 150 200 250
0
25
50
75
100
Con
vers
ion,
%
Temperature, °C
90 % RH
50 100 150 200 250
0
25
50
75
100
Con
vers
ion,
%
Temperature, °C
90 % RH
Interferant conversion on surface-adsorbed hydroxyl species1
Acetone conversion is blocked by water that dissociates on Lewis acid sites2
1. Mallat T, Baiker A, Chem. Rev. 2004, 104, 30372. Panov AG, Fripiat JJ, J. Catal. 1998, 178, 1883. Weber IC, Wang, CT, Güntner AT, Materials, 2021, 14, 1839
135
°C
Mass Spectrometry
Pt/Al2O3 at 135 °C
3 mol% Pt
0 25 50 75Relative Humidity, %
Ethanol Isoprene Ammonia Hydrogen (50 ppm) Acetone
0.2 mol% Pt
50 100 150 200 250Temperature, °C
Room temperaturecatalyst3
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Reality check: Breath
0 60 120 180 2401
2
3
4
Time, min
Acet
one,
ppm
0 60 120 180 2401
2
3
4
Time, min
Acet
one,
ppm
8Ines Weber 15.06.2021
Pt/Al2O3 + Si/WO3
IMCS 02-1342: Multiple volunteers, 146 samples
Weber IC, Derron N, Königstein K, Gerber PA, Güntner AT, Pratsinis SE. Small Science, 2021, 2100004
Requirements Sensitivity (down to ppb) Fast, compact & inexpensive Humidity robustness Selectivity Complex gas mixtures (e.g, breath)
Mass spectrometry
Exercise Rest
|| 15.06.2021Ines Weber 9
Conclusions
0.1
1
10
Resp
onse
(-)
s s s
S >
1000
> 10
00>
500
> 25
0 >
1000Ac
eton
e Isop
ren
e NH
3
Etha
nol
Hyd
roge
n
CO
Without filter With filter
90% RH
Res
pons
e, -
0.1
1
10
Unprecedented acetone selectivity bycatalytic Pt/Al2O3 filter
Acetone detection in gas mixtures withorders of magnitude higher interferants
Miniaturization potential: catalyst at roomtemperature
Accurate acetone quantification in breath
0 50 100 150 2000
1
2
3
4
5
Res
ista
nce,
MΩ
Time, min0 50 100 150 200
0
1
2
3
4
5
Res
ista
nce,
MΩ
Time, min
Acetone only// with 5000 ppb interferants
50
ppb
100
250500 750 1000
Pt/Al2O3 + Si/WO3
Mass spectrometry
0 60 120 180 2401
2
3
4
Time, min
Acet
one,
ppm
Ongoing: Randomized Clinical trial72 volunteers