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Hybrid Materials for Low Cost Volatile
Organic Compound Sensor System
Wei-Fang Su*, Geza Toth, Ákos Kukovecz and
Alejandro Alija
2015/09/15
National Taiwan University, Taiwan
Nanordic Oy, Finland
University of Szeged, Hungary
Ingenieros Asesores, Spain
M-ERA.NET PROJECT
Why do we need VOCs sensor?
2
http://china-heatpipe.net/
http://home.focus.cn/
http://www.fengtay.org.tw
Volatile organic compounds (VOC)
Metabolic and pathophysiologic
processes for diagnosing diseases
VOCs used in our daily life
Chemical explosions in Taiwan
3
Toluene leakage in chemical plant
and explosion incident in 2012.
Propene leakage in underground
pipes and explosion incident in 2014.
2015 Chemical Explosion in Tianjin, China
4
Toxic chemical vapors and harmful dusts after the accident: toluene, chloroform, DNBP, ethylene oxide (epoxyethane), trichloroethylene…
Common VOCs
5
Pentane
Hexane
Octane
Decane
Dodecane
Chloroform
Dichloromethane
1,2-Dichloroethane
Tetrachloroethylene
Chlorobenzene
Dichlorobenzene
Trichlorobenzene
Alkanes
Aromatics
Chlorides
Chloro-
aromatics
Benzene
Toluene
Xylenes
Others
Acetaldehyde
Acetone
Diethyl Ether
Tetrahydrofuran
Objectives of this project
6
Low cost, high sensitivity, mobile VOC sensor system to
prevent disastrous, keep clean and healthy environment
Measurement range: 0-20,000ppm
Sensitivity/Detection limits: ppm, below OSHA PELS (8
hour time weight average)
Response time: less than 1 min
New hybrid materials and adding automated data
acquisition system.
The system enables warning through visible and/or
audible alarm, smart cell phone or computer message.
Team communication and teamwork
7
Kick-Off Meeting in Taipei, 2013
First Year Review Meeting
in Szeged, 2014
http://www.vocsensor.com/
Teamwork
8
Advantage of our sensors (NTU)
9
Commercial VOCs sensors usually detects hydrogen sulfide,
carbon oxides, ammonia, alcohols… etc.
Aromatic or chloride based compounds are hard to detect even
with large tolerance.
Our sensors based on optical property difference are suitable
for detection of these hazards.
450 500 550 600 6500.00
0.02
0.04
0.06
0.08
0.10
0.12
Ab
so
rba
nc
e (
N.A
.)
Wavelength (nm)
initial 15 min
1 min 30 min
3 min 60 min
5% toluene
Incident light
Glass Hybrid film
(UV-Vis spectrum)
Before VOCs exposure
Expose to VOC
After VOCs exposure
Sensor chips evolution
10
Before Project
YEAR 1 YEAR 2 YEAR 3
Gen 4
HT71-5F1
HT71-5F3
HT71-5F5
HT71-5F10
HT71-3F1
HT71-3F3
HT71-3F5
HT71-3F10
HT71-1F1
HT71-1F3
HT71-1F5
HT71-1F10
Gen 1 HT61B
HT61F
Gen 2
HT71
OT71
Gen 3
H1O1
H1O3
H3O1
Sen
siti
vit
y
Structure effect on sensors (1)
11
Chemical P3BT:PC71BM P3HT:PC71BM P3OT:PC71BM
Water (ref.) 0.00 0.00 0.01
Methanol 0.01 0.03 0.00
Ethanol 0.03 0.03 0.00
1-Butanol -0.01 0.03±0.01 0.00 1-Propanol 0.01 0.03 0.01
i-Pentane 0.07 0.81±0.02 0.31 n-Hexane 0.15±0.01 0.85±0.05 0.44
n-Octane 0.03 0.78±0.06 0.26 n-Decane 0.01 0.47±0.06 0.28
n-Dodecane 0.03 0.49±0.03 0.27
Summary of P3AT:PC71BM films sensing at saturated vapor pressure of various VOCs for
10 min.*
*The average value of R600/480 from 5 samples.
Structure effect on sensors (2)
12
Chemical P3BT:PC71BM P3HT:PC71BM P3OT:PC71BM
Toluene 0.49 1.25±0.01 0.38 m-Xylene 0.38 1.07 0.46
o-Xylene 0.32 1.07±0.05 0.49
p-Xylene 0.36 1.14±0.02 0.41
Pyridine 0.35 1.08±0.03 0.68
Chlorobenzene 0.46±0.01 1.01±0.04 0.52
Dichlorobenzene 0.22 0.97±0.06 0.40
Trichlorobenzene 0.34 0.98±0.10 0.47
Dichloromethane 0.57±0.01 1.34±0.20 0.36
Chloroform 0.47 1.19±0.03 0.76
1,2-Dichloroethane 0.47 1.06±0.05 0.45
Tetrachloroethylene 0.52 1.12±0.03 0.50
Acetaldehyde 0.23 0.73±0.03 0.27
Acetone 0.11 0.70±0.05 0.24
Diethyl ether 0.39 1.22±0.08 0.52
Tetrahydrofuran 0.39 1.18±0.08 0.65
P3OT has showed faster and sharper response than P3HT mainly due to longer alkyl side chain.
It’s crucial for polymers to have high chain mobility and tendency to crystalline since lower concentration of VOCs provides lower driving force.
Detection Baseline
13
A600/480 of P3AT:PCBM films have
variation in air due to instability of UV-
vis spectrometer, air flow, minor
temperature fluctuation and moving
tendency of polymer chain.
The detection of VOC needs to
overcome the natural signal fluctuation.
0 10 20 30 40 50 60-0.01
0.00
0.01
0.02 P3OT H1O3 H1O1
H3O1 P3HT
A600/4
80 (
a.u
.)
Eclipse time (min)
A600/480 of different sensors in air at 20°C.
Normalized absorbance as sensing response for P3AT:
𝐑𝟔𝟎𝟎/𝟒𝟖𝟎 =𝐀𝟔𝟎𝟎/𝟒𝟖𝟎 𝐚𝐟𝐭𝐞𝐫 𝐞𝐱𝐩𝐨𝐬𝐮𝐫𝐞 − 𝐀𝟔𝟎𝟎/𝟒𝟖𝟎(𝐛𝐞𝐟𝐨𝐫𝐞 𝐞𝐱𝐩𝐨𝐬𝐮𝐫𝐞)
𝐀𝟔𝟎𝟎/𝟒𝟖𝟎(𝐛𝐞𝐟𝐨𝐫𝐞 𝐞𝐱𝐩𝐨𝐬𝐮𝐫𝐞)
Threshold response: R600/480 = 0.02
𝐀𝟔𝟎𝟎/𝟒𝟖𝟎 = 𝐀𝟔𝟎𝟎/𝐀𝟒𝟖𝟎
Gasoline Test
14
Large and fast response to
all 4 kinds of commercial
gasoline
Promising applications in oil
leakage in pipes/ tanks/
factories for warning.
0 20 40 600.0
0.2
0.4
0.6 98 92 95 Diesel
R6
00/4
80 (
a.u
.)
Eclipse Time (min)
Gasoline
type 92 95 98 diesel
Detection
Time (min) 4 6 2 18
BTX Test
15 Total VOC concentration: 10000ppm
A
B
C
D
Benzene
Toluene Xylene
A
B C D
0 10 20 30 40 50 600.0
0.2
0.4
0.6
0.8 A B
C D
R600/4
80 (
a. u
.)
Eclipse Time (min)
VOC adsorption on sensor candidates
(SZTE, Hungary)
16
Thiomethoxam adsorption on CNTs
Chemosphere 141 (2015) 87-93.
Chlorinated phenol adsorption on MWCNTs
RSC Advances 5 (2015) 24920-24929.
Basic research on interface phenomena
17
MWCNT/organic solvent interface
“evaporation profile”
Microporous and Mesoporous Materials 209 (2015) 105-112.
Water adsorption and proton transport
mechanism study on CePO4 nanowires
ACS Applied Materials and Interfaces 7 (2015) 9947-9956.
Electrochemical detection of Pb2+ and Cd2+ using a BiOCl modified
MWCNT system
Talanta 134 (2015) 640-649.
Models of Fluctuation Enhanced Sensing are
developed for several inorganic materials
18
Low temperature conversion of titanate nanotubes into nitrogen-doped
TiO2 nano particles
CrystEngComm 16 (2014) 7486-7492.
Other papers
Carbon Paste Electrodes Bulk-Modified with Carbon Nanotubes and Chemically Oxidized Carbon Nanotubes for the Determination of Hydrogen Peroxide, Sensing in Electroanalysis, Vol. 8 (K. Kalcher, R. Metelka, I. Švancara, K. Vytr ̌as; Eds.), pp. 195−211. 2013/2014 University Press Centre, Pardubice, Czech Republiic, 2014
Three different clay-supported nanoscale zero-valent iron materials for industrial azo dye degradation: A comparative study, J TAIWAN INST CHEM E 2014: 1, 2014
Decoration of titanate nanowires and nanotubes by gold nanoparticles: XPS, HRTEM and XRD characterization, E-J SURF SCI NANOTECH 12: 252-258, 2014
Synthesis and characterization of polyvinyl alcohol based multiwalled carbon nanotu be nanocomposites, PHYSICA E 61: 129-134, 2014
Toxic metal immobilization in contaminated sediment using bentonite- and kaolinite-supported nano zero-valent iron, J NANOPART RES 16: (8) , 2014
Dynamic origin of the surface conduction response in
adsorption-induced electrical processes, Chemical Physics
Letters 607 (2014) 1-4.
Water-Induced Changes in the Charge-Transport Dynamics of Titanate
Nanowires, LANGMUIR 30: (8) 1977-1984, 2014
Project device evolution (Nanodic, Finland)
19
Existing proof of concept
Development of a conventional design
Development of a prined
intelligence design
(image source: vtt.fi)
(estimated month 30)
(month 18)
VOC Cell – Reflection type
20
• Advantage taken on multiple passes through
the sensing layer/other interfaces
VOC Cell – Reflection/advanced type
21
• Tray function for multiple samples
• Fan assisted VOC delivery
VOC Cell – Transmission type
22
• Tray mechanism
• Small form factor
VOC Cell – Transmission type
23
Working prototype
• OLED display
• Menu function
• One button testing
• Programmable
Future generation device development
24 Smart IoT devices, with touch interface
VOCSENSOR IoT device: Design and Prototyping
(IA, Spain)
25
3D computer design 3D printing
VOCSENSOR prototype D&D by IA.
ABS-like plastic material printed by 3D optical lithography Free solidification, also known as SLA.
More info here: https://youtu.be/sHqHWTK-Esg?t=44
VOCSENSOR IoT device: In Lab tests
26
Dilutor 1
Dilutor 2
Bubbler
Vocsensor
device
Nitrogen
bottle
PC
N2
N2
N2 N2
N2
N2Y + CH2CL2
VOCSENSOR IoT device: Results sample
27
1000
1200
1400
1600
1800
2000
1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55
Tra
nsm
ite
d i
nte
nsi
ty
(co
un
ts)
Resistance (a.u)
Dicloromethane 50% saturation N2 balance
590 nm 10 min470 nm 10 min590 nm 30 min470 nm 30 min590 nm ambient470 nm ambient590 nm 1 min
Intensity amber
Blue wavelenght
Amber
wavelenght
VOCSENSOR IoT device: Application Mockup
28
Conclusions
29
Several new sensing
materials are
developed and have
improved sensitivity
more than 10 times.
Low price sensor
prototype is realized
through device
design and 3-D
printing.
BTXs testing,
humidity tests and
on-field tests all show
positive results.
Models of Fluctuation
Enhanced Sensing
are developed.
Sensor box Warning light
Circuit
Plexiglas box
VOCs sensor publication
30
Romantic Story or Raman Scattering Rose Petals as Ecofriendly, Low-Cost Substrates for Ultrasensitive Surface-Enhanced
Raman Scattering,” 2015, Analytical Chemistry, 87, 6017-6024
“Trifluoroacetylazobenzene for optical and electrochemical detection of amines,” 2015, Journal of Materials Chemistry A, 3,
4687-4694
“Hybrid Poly(3-hexyl thiophene):TiO2 Nanorods Oxygen Sensor,” 2014, RSC Advances, 4 (44), 22926-22930.
“Photocatalytic Activity of Nitrogen doped TiO2-based Nanowires:A Photo-Assisted Kelvin Probe Force Microscopy Study,”
2014, Journal of Nanoparticle Research, 16:2143-2154.
“Surface-enhanced Raman Scattering Substrate Based on Ag Coated Monolayer Sphere Array of SiO2 for Organic Dye
Detecting,” 2013, RSC Advances 4, 10043-10050.
“Conjugated Polymer/ Nanoparticles Nanocomposites for High Efficient and Real-Time Volatile Organic Compounds
Sensors,” 2013, Analytical Chemistry 85, 9305-9311.
“Decoration of Titanate Nanowires and Nanotubes by Gold Nanoparticles: XPS, HRTEM and XRD Characterization,” 2014,
e-Journal of Surface Science and Nanotechnology, 12, 252-258.
“Dynamic origin of the surface conduction response in adsorption-induced electrical processes,” 2014, Chemical Physics
Letters, 607, 1-4.
“Water-induced changes in the charge-transport dynamics of titanate nanowires,” 2014 Langmuir 30 1977-1984.
“Carbon Paste Electrodes Bulk-Modified with Carbon Nanotubes and Chemically Oxidized Carbon Nanotubes for the
Determination of Hydrogen Peroxide,” 2013/2014 Sensing in Electroanalysis 8 195-211.
“Synthesis and characterization of polyvinyl alcohol based multiwalled carbon nanotube nano composites,” 2014 Physica E
61 129-134.
“Low temperature conversion of titanate nanotubes into nitrogen-doped TiO2 nano particles,” 2014 CrystEngComm 16
7486-7492.
“Toxic metal immobilization in contaminated sediment using bentonite- and kaolinite-supported nano zero-valent iron,” 2014
Journal of Nanoparticle Research.
“Three different clay-supported nanoscale zero-valent iron materials for industrial azo dye degradation: A comparative
study,” 2014 Journal of the Taiwan Institute of Chemical Engineers.
31
32
Field test movie
https://www.youtube.com/
watch?v=Mjo4sLiByA0&feat
ure=player_embedded
Project website
http://www.vocsensor.com/
Thank you for your attention!