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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

||

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

|| 15.06.2021Ines Weber 10Weber IC, Braun HP, Krumeich F, Güntner AT, Pratsinis SE, Advanced Science, 2020, 7, 2001503.