Dyes and Pigments 220 (2023) 111690

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Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Double-bounded diphenyl-contained fluorene polymers for Sc-SWCNTs

composite to ammonia gas sensors: Diphenylethene
or diphenylmethanimine
Pengwei Nie , Jieyun Zhang , Hairong Du , Xieraili Maimaitiyiming *
State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, College of Chemistry, Xinjiang University, Urumqi, 830046, Xinjiang, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Semiconductor-type carbon nanotubes, renowned for their exceptional optoelectronic properties, are considered
Single-walled carbon nanotubes as the most promising candidates to replace conventional silicon-based semiconductors. However, the obtaining
Ammonia gas vapor detection high purity of semiconductor-type single-walled carbon nanotubes (sc-SWCNTs) is a challenging task. In this
Suzuki coupling reaction
study, the Suzuki coupling reaction was employed to synthesize two structurally similar alternating copolymers,
Copolymers
Selectivity
which effectively separated the sc-SWCNTs from commercially plasma single-walled carbon nanotubes. As result,
Surface the copolymers exhibited outstanding selectivity for sc-SWCNTs with 99.9% of purity. Generation of a complex
film at the surface. Employing these polymer/sc-SWCNTs composite materials, the ammonia gas sensing devices
were fabricated. The results showed that both devices demonstrated rapid and exceptional response towards
ammonia gas vapor. Test results revealed that when the ammonia gas vapor concentration of 20 ppm, the two
polymer/sc-SWCNTs-based sensors exhibited response values of 5.0% and 3.3%, respectively, and the calculated
limits of detection (LOD) of the sensors were 64.5 ppb and 53.5 ppb. These sensors demonstrated significant
advantages in response and selectivity towards ammonia gas vapor compared to previous studies.

1. Introduction
Since the 21st century, global technology has been rapidly devel­
oped, leading to a significant increase in the iteration frequency of
various technological products, such as smartphones, tablets, and
computers. However, this rapid technological development inevitably
exacerbates the emission of industrial pollutants [1]. These industrial
emissions include numerous toxic gases, such as NH3, NOx, COx, H2S,
and SO2. These toxic gases are considered secondary pollutants that are
harmful to both human health and the environment and can even cause
acute respiratory diseases [2]. Among them, ammonia gas is a colorless
toxic gas that can further react to form other substances, such as
ammonium sulfate and ammonium nitrate, thereby contributing to the
formation of particulate matter (PM2.5) and environmental pollution
[3]. Ammonia has been designated a hazardous substance by the Na­
tional Fire Protection Association (NFPA) in the United States. High
levels of NH3 in the air severely impact human health. Its strong
corrosiveness and toxicity cause intense irritation to the skin, eyes, and
nose. Inhalation of high levels of ammonia gas can irritate the respira­
tory tract, causing headaches, nausea, and breathing difficulties. In
severe cases, it can lead to pulmonary edema, brain damage, and even
death [4]. According to regulations set by authoritative organizations
such as the Occupational Safety and Health Administration (OSHA) in
the United States and the Health and Safety Executive (HSE) in the
United Kingdom, the maximum exposure time for individuals in an
ammonia gas environment with a concentration of 25 ppm is approxi­
mately 8 h, and it should not exceed 15 min at 35 ppm. As the con­
centration of ammonia gas increases, the exposure time for individuals
decreases rapidly [5]. However, lower concentrations of ammonia gas
are used in biomedical applications for the diagnosis of specific diseases.
In living organisms, ammonia-related substances are produced through
amino acid metabolism, and their analysis in exhaled gas is crucial for
medical diagnosis and the assessment of biological diseases, such as
cirrhosis, renal failure, or Helicobacter pylori infection [6]. Therefore,
monitoring NH3 gas is of paramount importance to ensure health and
safety and to limit environmental pollution. Consequently, the devel­
opment of efficient gas sensing technologies has become a focal point of
research worldwide due to their diverse applications. There are many
detection methods for NH3 concentration, and the selection of sensing
materials with high sensitivity, selectivity, and stability is of significant

* Corresponding author.
E-mail address: 380731363@qq.com (X. Maimaitiyiming).

https://doi.org/10.1016/j.dyepig.2023.111690
Received 20 July 2023; Received in revised form 5 September 2023; Accepted 8 September 2023
Available online 9 September 2023
0143-7208/© 2023 Elsevier Ltd. All rights reserved.
P. Nie et al.
importance in developing reliable NH3 gas sensors.
The main categories can be summarized as solid-state and optical
methods [7]. The solid-state approach encompasses various types of
sensors, including those based on metal oxides (ZnO) [8], organic
polymers (PANI) [9], and carbon nanomaterials (SWCNTs) [10]. On the
other hand, the optical method primarily refers to optical sensors uti­
lizing tunable diode laser spectroscopy, which detect ammonia through
the absorption of infrared radiation [11]. Compared to the optical
method, the solid-state approach primarily utilizes nanoscale structures
as the active components of the sensors. Due to their small size and large
surface area, nanomaterials hold great potential for providing sensors
with low detection limits, high responsiveness, and cost-effectiveness.
Thus, incorporating nanomaterials as substrates is an effective way of
achieving extremely high sensitivity and low power consumption. Metal
oxides, in particular, offer advantages such as broad gas detection, high
sensitivity, and low cost. However, their high operating temperatures
(above 200 ◦ C) limit their wide applications [12]. Conducting polymers,
owing to their large surface area and excellent conductivity, also possess
significant advantages in gas sensing. Nonetheless, without surface
modification, their selectivity towards specific gases is relatively poor
[3].
Carbon nanomaterials present a promising alternative to chemir­
esistive gas sensors due to their large specific surface area, excellent
chemical stability and high charge carrier mobility [7]. The thanks to
unique hollow structure, the single-walled carbon nanotubes (SWCNTs)
exhibit exceptional specific surface area and aspect ratios than other
carbon nanomaterials. Typically size of the SWCNTs ranging from 0.8 to
1.6 nm in diameter, which are comparable to certain target gas mole­
cules [10]. This implies that individual molecules adsorbed on the
sidewalls of nanotubes can locally influence the electronic structure,
leading to changes in the nanotubes’ resistance and enabling sensing
capabilities.
Despite the respectable position of SWCNTs in the field sensing, there
is still a challenging issue that hinders their development. Commercially
produced SWCNTs tend to intertwine into bundles due to strong van der
Waals forces between the tubes. Moreover, they exist as a complex
mixture comprising metallic-type m-SWCNTs (1/3), semiconductor-type
sc-SWCNTs (2/3) and small amount of catalystsand amorphous carbon
[13]. Catalysts and amorphous carbon directly affect device stability
[14]. Recent findings by V. Bezugly suggest that devices based on pure
sc-SWCNTs exhibit superior sensitivity to NH3 compared to unsorted
SWCNTs, B-SWCNTs (boron-doped nanotubes) and N-SWCNTs (nitro­
gen-doped nanotubes) [10]. To address these challenges, it is crucial to
separate the semiconductor-type tubes to enhance the sensing perfor­
mance of sc-SWCNT-based ammonia sensors. Among these separation’
approaches, polymer encapsulation emerges as one of the most powerful
and scalable strategies, offering advantages such as simplicity, shorter
processing time and non-destructive treatment of CNT surfaces. Notably,
conjugated polymers with larger conjugation systems, particularly
diphenyl-contained fluorene Polymers, exhibit outstanding selectivity,
enabling the isolation of sc-SWCNTs with purity levels of 99.9% [15].
Secondly, isoprene units were demonstrated to improve the sorting ef­
ficiency of SWCNTs in the study of Moses et al. [16]. And in Kanimozhi’s
study, it was revealed that the inclusion of –C– – N- in the molecular
structure favors the separation of SWCNTs [17]. Following the previous
studies, the molecular structures of the polymers are incorporated with
–C– – C- and –C– – N- units, and we discuss the effect of the difference in
electron distribution between the two polymers on the separation of
SWCNTs.
In this study, we designed and synthesized two structurally analo­
gous conjugated polymers, poly[9,9-dioctylfluorene-co-4,4′-trans-stil­
bene] (PDF-DTS) and poly[9,9-dioctylfluorene-co-N-
benzylideneaniline] (PDF-N-DTS). Using them, the high-purity of sc-
SWCNTs was obtained through ultrasonic separation. The results sug­
gested that the polymer PDF-DTS with –C– – C- has a more uniform
electron cloud distribution, which is more beneficial for the separation
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Dyes and Pigments 220 (2023) 111690
of sc-SWCNTs. The sc-SWCNTs modified with organic conjugated
polymers were utilized as composite materials for gas sensing applica­
tions. Generation of a complex film at the surface. Under the same
conditions, the responses of the two composite ammonia sensors were
systematically studied at room temperature and humidity. Furthermore,
the specific selectivity of the sensors to ammonia gas was investigated at
ambient temperature and humidity. The results demonstrated that these
two polymer/SWCNTs-based composites exhibit high sensitivity, rapid
response, and excellent selectivity towards ammonia under ambient
temperature and humidity conditions.
2. Experimental
2.1. Materials
9,9-Dioctylfluorene-2,7-diboronic acid bis(pinacol) ester, 4,4′-
Dibromo-trans-stilbene, 4-Bromoaniline, and 4-Bromobenzaldehyde
were obtained from J & K Science Co.Ltd., Beijing, China. The plasma
nanotube powder RN-220 (batch number RNB781-220-210604) was
purchased from XFNANO Materials Tech Co. Ltd. Additional informa­
tion about the reagents can be found in the supporting information, and
all chemicals used were of analytical grade.
2.2. Synthesis of monomers and polymers
By referencing the improved methods described in the literature
[18], we synthesized the monomer 4-Bromo-N-(4-bromobenzylidene)
aniline (N-DTS). Through the Suzuki coupling reaction, we success­
fully synthesized poly[9,9-dioctylfluorene-co-4,4′-dibromo-trans-­
stilbene] (PDF-DTS) and poly[9,9-dioctylfluorene-co-N-benzyli
deneaniline] (PDF-N-DTS). As illustrated in Scheme 1, it is evident
that the two polymers are not entirely identical; they exhibit structural
distinctions. PDF-DTS incorporates C– – C double bonds, whereas
PDF-N-DTS features C–– N double bonds (for a detailed synthesis, refer to
the “Supplementary Information").
2.3. Preparation of complexes
The 4 mg PDF-DTS was fully dissolved in 12 mL of toluene (TL)
solvent using ultrasonication. The solution was then filtered through a
polytetrafluoroethylene filter and evenly distributed into four sample
vials. To each vial, 1 mg of pristine single-walled carbon nanotubes
(raw-SWCNT) was added. The mixture was subjected to temperature-
controlled (20 ◦ C) ultrasonication for 2 h, resulting in an ink mixture.
After centrifugation (10 ◦ C, 15000 rpm) for 0.5 h, the supernatant was
carefully collected, followed by the addition of 10 mL of THF solvent to
wash and filter the free polymers. This washing process was repeated
three times, and the resulting filter cake was collected. Finally, the filter
cake was uniformly dispersed in THF solvent, yielding a well-prepared
dispersion of polymer/semiconductor-type single-walled carbon nano­
tube (PDF-DTS/SWCNT) composite. The preparation method for PDF-N-
DTS/SWCNT composite dispersion was identical to the aforementioned
process. Polytetrafluoroethylene (PTFE) filters with pore sizes of 0.45
and 0.22 μm, made of nylon 66, were utilized for filtration. The ultra­
sonic treatment was conducted using the KQ5400KDE slot-type ultra­
sonic machine located in Kunshan, Jiangsu, China.
2.4. Assembly of ammonia sensors
The utilized device in the experiment was an interdigital electrode,
as depicted in Fig. 1a. From Fig. 1a, the substrate of the electrode is
made of quartz, which can withstand corrosion from various solvents,
thus minimizing experimental errors caused by the substrate. The
channel width of the electrode is 5 μm, as shown in the Figure.
The assembly procedure of the sensor device is as follows: Firstly,
immerse the interdigital electrode in toluene (TL) solvent at 50 ◦ C for 1 h
P. Nie et al.
Scheme 1. Schematic representation of the synthesis of monomeric N-DTS and the two polymers, PDF-DTS and PDF-N-DTS.
Fig. 1. (a) Diagram shows the basic parameters of a quartz interdigital elec­
trode (IDE). (b) Diagram shows the assembly of the device using the drop in­
jection method. (c) Diagram depicting the device with composite material
deposited in the channel. (d) Figure provides a close-up schematic of the
localized zoomed-in deposition of the device composite.
to remove surface impurities. After removing the electrode, place it on a
50 ◦ C hotplate for 2 min to quickly eliminate any remaining solvent on
the electrode surface. Rinse the electrode surface with deionized water,
repeating the process 2–3 times, and then dry it in a 40 ◦ C vacuum
drying oven for 1 h. Next, using a microliter syringe, carefully drop the
prepared dispersion of PDF-DTS/SWCNTs onto the channel (5 μm) of the
interdigital electrode (drop-casting), as shown in Fig. 1b. Anneal the
electrode at 65 ◦ C for 30 min to facilitate stable deposition within the
Fig. 2. Schematic diagram of ammonia gas vapor sensor setup and testing method [19].
3
Dyes and Pigments 220 (2023) 111690
channel. After cooling, place the assembled electrode in a vacuum
drying oven for 2 h. Repeat the above steps until the resistance stabilizes
around 1–2 kΩ, indicating the successful assembly of Device 1 (Fig. 1c
and d). Generation of a complex film at the surface. Test the device
under ambient temperature conditions. Repeat the same method to
obtain Device 2.
2.5. Testing of ammonia sensors
Prior to measurement, the entire gas path and chamber were purged
with fresh air for approximately 30 min. Subsequently, the meticulously
prepared sensor device was placed in the testing chamber, and air
continued to flow through, allowing the device to stabilize its resistance
under ambient conditions before commencing the testing (Fig. 2). The
gas flow rate in the measurement chamber was controlled by two
different-range mass flow controllers (MFCs). The resistance changes of
the sensor were monitored in real-time using a Keithley 2400, with an
output current of 0.1 mA and a clamp voltage of 5 V. The response time
of the measurement setup was set at 50 s. During the recovery process,
the MFC-2 (Q2 M = 10–3000 sccm) connected to the injection of
ammonia gas vapor was disconnected, while another MFC-1 (Q1 M =
10–1000 sccm) was used to purge fresh air, and the expelled ammonia
gas vapor was treated with an exhaust gas absorption device. The con­
centration of ammonia gas vapor was regulated by controlling the valve
opening of MFC-1. The ammonia gas vapor concentration was moni­
tored in real-time using an ammonia gas vapor detector (SMART
P. Nie et al.
SENSOR AR8500). The experiments were conducted in a fume hood
(ammonia gas vapor being an irritant) at a temperature of 25 ◦ C ± 1 ◦ C.
3. Results and discussion
3.1. Characterisation of monomers and polymers
The structure of the monomer 4-bromo-N-(4-bromobenzyl)aniline
(N-DTS), the polymer poly[9,9-di-n-octylfluorene-co-4,4’-(9-fluo­
renylidene)diphenylene] (PDF-DTS), and the polymer poly[9,9-di-n-
octylfluorene-co-N-(methylenediphenylamine)] (PDF-N-DTS) were
characterized by nuclear magnetic resonance (NMR) and infrared (IR)
spectroscopy, confirmed their successful synthesis. NMR spectra are
detailed in S1 and S2, IR spectra are detailed in S3(c) and (d), and IR
contrast spectra are detailed in S4. The average molecular weight of the
polymers was determined using a liquid gel chromatography analyzer.
The specific spectra and analysis can be found in the supporting infor­
mation. The following instrument specifications and parameters were
used: 1H NMR and 13C NMR spectra were recorded on a BRUKER-
AVANCE NEO 600 MHz spectrometer in CDCl3, using trimethylsilane
(0.1 vol%) as an internal standard. The infrared spectroscopy was per­
formed using a BRUKER-VERTEX 70 RAMI instrument from Bruker
Spectroscopy. The liquid gel chromatography analyzer (GPC) utilized an
Agilent PL-GPC50 system equipped with three columns (HT3, HT4,
HT6), with tetrahydrofuran as the mobile phase at a flow rate of 1 mL/
min.
3.2. Density functional theory (DFT)
The geometrical structures of PDF-DTS and PDF-N-DTS were opti­
mized using Gaussian 16 software, employing density functional theory
(DFT) calculations at the B3LYP-D3BJ/def2-SVP level of theory. The
simulations were conducted to mimic the experimental environment,
with toluene chosen as the solvent. From the electron density distribu­
tion maps (ESP) in Figures S5-(a) and S5-(c), it can be shown that both
polymers exhibit excellent π-π conjugatio n and are electron-rich sys­
tems. The presence of electron-rich polymers contributes to the prefer­
ential selection to sc-SWCNTs due to π-π stacking interactions [20].
Figures S5-(b) and S5-(d) illustrate the HOMO and LUMO energy level
4
Dyes and Pigments 220 (2023) 111690
diagrams for PDF-DTS and PDF-N-DTS, respectively. The energy of the
highest occupied molecular orbital (HOMO) in PDF-DTS is − 5.40 eV,
while the energy of the lowest unoccupied molecular orbital (LUMO) is
− 1.78 eV and energy difference (ΔE) is 3.62 eV. In PDF-N-DTS, the
HOMO energy is − 5.53 eV, the LUMO energy is − 1.88 eV, and ΔE re­
mains the same at 3.64 eV. This signifies that both possess notably wide
bandgaps, rendering them well-suited for applications in semiconductor
materials.
3.3. Characterisation of composite materials
Vis-NIR absorption spectroscopy serves as a crucial method for
characterizing the types of SWCNTs. In addition to the ability of UV–Vis
absorption spectroscopy to reveal their distinctive features, Raman
scattering is also employed to investigate the vibrational behavior of C
atoms, serving as one of the most effective tools to assess the degree of
carbon nanotube defects [21]. The Vis-NIR spectrum was recorded using
the Shimadzu UV-3600 (UV-VIS-NIR) spectrophotometer, while the
Raman measurements were conducted using the HORIBA HR Evolution
(France) Raman spectrometer.
Fig. 3a displays the normalized Vis-NIR absorption spectra of the
PDF-DTS/SWCNT (red) and PDF-N-DTS/SWCNT (blue) composites in
toluene solution, allowing for convenient comparison. Within the range
of 400–2000 nm, four distinct regions can be observed [22]. Among
them, three correspond to the spectral bands (yellow) of sc-SWCNTs,
namely S11, S22, and S33, spanning the intervals of 1400–1900 nm,
800–1150 nm, and 440–600 nm, respectively. The spectral band (blue)
of a m-SWCNT, M22, is identified within the range of 600–750 nm. Both
PDF-TDS and PDF-N-DTS exhibit relatively shallow absorption features
in the metallic region of 600–750 nm, indicating the presence of mini­
mal m-SWCNT content in the two composites. Furthermore, the posi­
tions of the absorption minima for both composites are closely aligned.
We speculate two factors contribute to this observation: the similarity in
the structures of the two polymers and the comparable energy level
differences between the HOMO and LUMO obtained from DFT calcula­
tions. These results indicate a similar capability for selective sorting of
sc-SWCNTs, consistent with the DFT calculations. In Fig. 3b, the purities
(Φ) and yields of sc-SWCNTs in the two composites are presented [23].
The specific calculation method and images for purity reference can be
Fig. 3. (a) Visible-near-infrared absorption spectra of
the composite dispersions of PDF-DTS/SWCNT and
PDF-N-DTS/SWCNT. (b) Purity and absorbance of sc-
SWCNT in the composite dispersions of PDF-DTS/
SWCNT and PDF-N-DTS/SWCNT. (c) Raman spectra
of pristine SWCNTs, PDF-DTS/SWCNT, and PDF-N-
DTS/SWCNT at an excitation wavelength of 633
nm. (d) Radial breathing mode (RBM) Raman spectra
of pristine SWCNTs, PDF-DTS/SWCNT, and PDF-N-
DTS/SWCNT at an excitation wavelength of 785 nm.
P. Nie et al.
found in the supporting information. It can be observed that the purity
(Φ) of sc-SWCNTs in the PDF-DTS/SWCNTs composite reaches a
remarkable value of 0.42, while in the other composite, the Φ value is
precisely 0.40(Figure S6). When Φ ≥ 0.4, it indicates that the purity of
sc-SWCNTs in the composite is as high as 99.9%. The magnitude of
absorbance indirectly reflects the yield of sc-SWCNTs in the composite,
where higher absorbance corresponds to a higher yield. The graph re­
veals that the PDF-DTS/SWCNTs composite exhibits a slightly higher
yield of sc-SWCNTs compared to the PDF-N-DTS/SWCNTs composite,
primarily attributed to the strong π-π conjugation of PDF-TDS, which
clearly observed in the ESP diagrams from DFT calculations. This finding
suggests that an electron-rich system contributes to the selective sorting
of semiconductor-type carbon nanotubes.
To further elucidate the results obtained from the Vis-NIR analysis
and determine the purity of sc-SWCNTs in the composites, further
investigation was conducted using Raman spectroscopy. Fig. 3c and
d depict the Raman spectra obtained at excitation wavelengths of 633
nm and 785 nm, respectively, for the PDF-N-DTS (blue), and PDF-DTS
(red). By comparing with the pristine carbon nanotubes, it was
observed that at an excitation wavelength of 633 nm, the peak intensity
at 1320 nm remained almost unchanged, indicating a non-covalent
separation of the polymer from sc-SWCNTs without surface disruption
or introduction of new defects, thereby minimizing experimental vari­
ables [21]. Additionally, two distinct regions can be identified between
1480 and 1650 nm, with the pink region representing the metallic-type
carbon nanotubes (G- m) spanning 1480–1580 nm, and the blue region
representing the semiconductor-type carbon nanotubes (G+ sc) span­
ning 1590–1650 nm [24]. In comparison to the pristine carbon nano­
tubes, both PDF-N-DTS and PDF-DTS exhibited a significant reduction in
the intensity and smoothness of the G- m peak and a pronounced
enhancement and sharpness of the G+ sc peak, confirming the absence
of m-SWCNTs. The radial breathing mode (RBM) at an excitation
wavelength of 785 nm provided a more intuitive observation, with
sc-SWCNTs resonating in the range of 240–300 cm− 1, the metallic-type
peak completely disappeared, and a slight increase in the
semiconductor-type peak. These characterization analyses unequivo­
cally demonstrate the complete separation of semiconductor-type car­
bon nanotubes, the absence of m-SWCNTs.
In this paper, the mechanisms underlying the separation of sc-
SWCNTs by the two polymers are elucidated as follows: According to
current research, the selective dispersion of semiconductor single-
walled carbon nanotubes (sc-SWCNTs) arises from the polarity
disparity between semiconductor and metallic single-walled carbon
nanotubes (m-SWCNTs). In comparison to sc-SWCNTs, m-SWCNTs
exhibit a polarization rate exceeding 103 due to their high carrier con­
centration [25]. The strong polarization of m-SWCNTs has led theoret­
ical studies to suggest that m-SWCNT/polymer complexes entail a more
robust charge transfer interaction when compared to their
sc-SWCNT/polymer counterparts [26]. Consequently, highly polar
m-SWCNT/polymer complexes tend to aggregate or bundle in nonpolar
solvents, resulting in precipitation upon centrifugation, whereas
sc-SWCNT/polymer complexes remain in the supernatant. Specifically,
the PDF-DTS polymer, characterized by its even electron distribution
owing to the presence of C– – C double bonds, is more inclined to asso­
ciate with metallic carbon nanotubes, leading to their precipitation. In
this manner, successful separation of semiconductor-type carbon nano­
tubes is achieved.
3.4. Sensing response
To investigate the response and sensitivity of chemical resistive
sensors based on PDF-DTS/SWCNTs/IDE (Device 1) and PDF-N-DTS/
SWCNTs/IDE (Device 2) towards NH3, the electrical resistance mea­
surements of both sensors were conducted under identical environ­
mental conditions. The sensor response of the devices was defined as the
relative change in device resistance (ΔR), which was calculated using the
5
Dyes and Pigments 220 (2023) 111690
following formula [27]:
Sensitivity (%) = ΔR / R0 × 100% = ((Ra − R0) / R0) × 100% (1)
The resistance change (ΔR) represents the difference in device
resistance before and during exposure to ammonia gas vapor, where Ra
is the resistance during gas exposure and R0 is the initial resistance
before gas exposure. Resistor-type sensors respond to the increase in
resistance when exposed to NH3, as the electronic properties of single-
walled carbon nanotubes (SWCNTs) undergo changes. This occurs
because charge transfer takes place from the analyte gas (electron
donor) to the surface of the carbon nanotubes through π-π stacking,
altering their density state [28]. Fig. 4a and c depict the dynamic
response changes under continuous exposure to NH3 at concentrations
of 20, 30, 40, 50, and 60 ppm, respectively, under ambient temperature
and humidity conditions. The response intensity of the sensor increases
with higher ammonia vapor concentrations, consistent with the
response characteristics of p-type semiconductors. Upon exposure to air,
the resistance values recover, following the reaction mechanism previ­
ously described in the literature [28]. Fig. 4a represents the sensor based
on PDF-DTS/SWCNTs assembly, with 50 s of ammonia gas vapor in­
jection each time (controlled by MFC). After each exposure, the testing
chamber is flushed with fresh air for approximately 10 min to facilitate
the recovery process, without applying any additional measures, such as
heating or UV irradiation to expedite gas desorption and avoid intro­
ducing other variable conditions. This sensor demonstrates excellent
sensitivity and rapid response, displaying favorable responses at
different concentrations. At NH3 concentrations of 20, 30, 40, 50, and
60 ppm, the responses reached 5.0%, 5.2%, 5.6%, 6.0%, and 6.4%,
respectively. On the other hand, Fig. 4c represents the sensor assembled
using PDF-N-DTS/SWCNTs as the substrate, using similar experimental
conditions and methods. While it also exhibits the same features as
Device 1, including fast response and high sensitivity, the response at
NH3 concentrations ranging from 20 to 60 ppm is 3.3%, 4.0%, 4.5%,
4.9%, and 5.4%, respectively. Compared to Device 1, the average
response level is approximately 3/4, and it is unable to fully recover to
the initial position as Device 1 does. This indicates that
PDF-DTS/SWCNTs/IDE shows a higher response at the same ammonia
gas vapor concentration. The main reason for this might be closely
related to the imine bonds in PDF-N-DTS/SWCNTs [29], as explained in
the mechanism section.
Fig. 4b and d represent the linear fitting curves of PDF-DTS/
SWCNTs/IDE and PDF-N-DTS/SWCNTs/IDE sensors within the
ammonia gas vapor concentration range of 20–60 ppm under ambient
temperature and humidity conditions. From the figures, it can be seen
that the gas sensing performance of both Device 1 and Device 2 appears
to exhibit a linear increase with the increment of NH3 concentration.
Both sensors demonstrate excellent linearity, with correlation co­
efficients (R2) of 0.9891 and 0.9897, respectively [30]. Due to experi­
mental constraints, we could only conduct limited testing. However, the
detection curves indicate that this is far from the detection limit of
sensors based on sc-SWCNTs. Directly measuring the detection limit
(LOD) of sc-SWCNT-based sensors presents challenges. Therefore, based
on literature references [31], the combination of linear correlation co­
efficient and LOD detection limit calculation, taking into account a
signal-to-noise ratio (RMS >3), provides a reliable estimation of the
lowest detection limit. The theoretical lowest detection limit for
PDF-DTS/SWCNTs/IDE is 64.5 ppb, while for
PDF-N-DTS/SWCNTs/IDE, it is 53.5 ppb (refer to table S1and S2 in the
supporting information).
In practical applications, periodicity and reproducibility are also
crucial factors for evaluating the gas sensors. To evaluate those, further
investigations were conducted. Under ambient conditions, the success­
fully prepared Device 1 and Device 2 were subjected to five consecutive
tests in a 20 ppm NH3 environment. Fig. 5b displays the five-cycle
reproducibility graphs for both devices, with Device 1 exhibiting
P. Nie et al. Dyes and Pigments 220 (2023) 111690

Fig. 4. (a) Dynamic response curves of PDF-DTS/SWCNTs/IDE to ammonia gas vapor at various concentrations.(b) Linear fitting curve of PDF-DTS/SWCNTs/IDE.(c)
Dynamic response curves of PDF-N-DTS/SWCNTs/IDE to ammonia gas vapor at different concentrations.(d) Linear fitting curve of PDF-N-DTS/SWCNTs/IDE.

Fig. 5. (a) Amplified response comparison of the two devices at the same concentration (20 ppm). (b) Response variations of PDF-DTS/SWCNTs/IDE and PDF-DTS/
SWCNTs/IDE to ammonia gas vapor (20 ppm) under ambient temperature and humidity conditions.

response values of approximately 5.0%. It can be observed that this
device demonstrates excellent repeatability and stability, consistently
returning to its initial state after each test. In contrast, Device 2 main­
tains a high degree of consistency with the aforementioned gradient
curve, but fails to recover to its initial state. Despite its inability to return
to the initial state, Device 2 still exhibits good cyclic stability, with
response values fluctuating around 3.3%. For a more convenient and
intuitive comparison, the first set of data was magnified (Fig. 5a), clearly
indicating a slightly higher slope for PDF-DTS/SWCNTs/IDE, suggesting
a higher sensitivity for this device. Additionally, the recovery time is
shorter compared to Device 2. Overall, these findings strongly suggest
that Device 1 showed better performance than Device 2.
Above results demonstrated that the both PDF-DTS/SWCNTs/IDE
and PDF-N-DTS/SWCNTs/IDE exhibit real-time sensitivity to NH3
under ambient temperature and humidity conditions. This means these
two composite materials possess effective detection capabilities for NH3.
In order to further investigate the specific response of the two devices to
ammonia and validate their selectivity towards ammonia, interference
tests with volatile organic compounds (VOCs) were conducted under the
same ambient temperature and humidity conditions [32]. The selected
organic volatile gases are commonly used experimental solvents that
readily evaporate into the gas phase. These gases include dichloro­
methane (DCM), methanol (MeOH), ethanol (EtOH), toluene (TL),
xylene (DTL), and isopropanol (IPA). The concentrations of these
interfering gases were calculated based on the formula described in the
literature [33].
1000 × Vspl × dspl × ω × R × T
C= (2)
Vac × M × P
In this formula, Vspl represents the chemical liquid injected using a

6
P. Nie et al.
microsyringe (in μL), dspl corresponds to the density of the sample liquid
under examination (in g/mL), ω denotes the mass fraction of the sample
liquid, representing its purity parameter. R stands for the ideal gas
constant (0.0820574587 L atm mol− 1⋅K− 1), T denotes the laboratory
temperature (297 K), Vac represents the total volume of the sensing
chamber (in mL) (in this study, 350 mL), M represents the molecular
weight of the volatile substance under examination, and P represents the
atmospheric pressure in the laboratory (1.005 atm). Using the afore­
mentioned formula, the concentrations of the interfering gases under
examination were calculated. For specific preparation details, please
refer to the supporting materials. Humidity (RH) also exerts a significant
influence on the device performance and serves as a critical factor in
evaluating gas sensors. To investigate the impact of relative humidity
(RH) on the previously reported sc-SWCNTs-based sensors, tests were
conducted at different humidity levels to examine the sensor’s response
to ammonia vapor. The ammonia gas vapor concentration was fixed at
20 ppm, and tests were carried out across various humidity ranges
(20%–40%). The effects of humidity on the sensing behavior of Device 1
and Device 2 are depicted in Fig. 6c and d, respectively.
Fig. 6a and b reveals that for other organic VOCs, both devices
exhibit extremely weak responses in an environment with a concentra­
tion of 250 ppm, which is significantly lower than that of ammonia gas
vapor. The concentration of organic interfering gases is 12.5 times that
of ammonia vapor, yet the response is less than 1. In contrast, the
response to ammonia gas (20 ppm) is 5.0 and 3.3, respectively. This
indicates a minimal interference to the devices’ specificity in detecting
ammonia gas vapor, while the excellent selectivity and specific response
of both devices towards NH3, indicating their significant potential for
practical ammonia detection. Regarding humidity, the response of both
sensors increases with the rise in relative humidity, consistent with the
findings of this study. This can be attributed to the competitive
adsorption between the target gas and water vapor on the sensing layer’s
surface.
Fig. 6. (a) and (b) depict the selectivity tests of PDF-DTS/SWCNTs/IDE and PDF-N-DTS/SWCNTs/IDE towards different gases. (c) and (d) illustrate the response of
PDF-DTS/SWCNTs/IDE and PDF-N-DTS/SWCNTs/IDE at room temperature (20 ppm) under varying humidity levels.
7
Dyes and Pigments 220 (2023) 111690
4. Sensing mechanism
In the realm of biotechnology and chemical sensing, sc-SWCNTs have
demonstrated their potential as highly sensitive devices within nano­
materials. Their unique electrical properties, high surface-to-volume
ratio, and high aspect ratio contribute to their suitability for such ap­
plications [34]. Additionally, ammonia molecules tend to preferentially
adsorb onto CNTs, primarily due to lattice mismatches and
strain-induced surface energy variations at the interfaces between CNTs
and other atoms. This phenomenon results in higher energy levels at the
surface compared to the channel region, facilitating ready adsorption
[35]. These characteristics endow the sensor with remarkable sensitivity
towards specific analytes, enabling the detection of individual
molecules.
The sensing response of sc-SWCNTs relies primarily on their bandgap
rather than their chirality, as it determines the availability of screened
charge carriers at room temperature. Since the bandgap is inversely
proportional to the diameter of sc-SWCNTs, larger bandgaps are ex­
pected to yield smaller currents and higher sensitivity [36]. The signif­
icant disparity in sensitivity between sc-SWCNTs and m-SWCNTs is
attributed to the low resistivity of the metallic paths in the latter. Despite
the adsorption of a small number of gas molecules, m-SWCNTs generate
higher currents on the device, and the position shift of the Fermi level in
m-SWCNTs leads to a completely flat density of states in the conduction
band, resulting in minimal impact on conductivity [37]. Therefore,
m-SWCNTs are not chosen as the active substrate material or composite
for the sensor. Conversely, sc-SWCNTs exhibit a Fermi level shift from
the middle of the bandgap to the valence band, contributing signifi­
cantly to the conductivity through the generation of free charge carriers
[38]. Specifically, upon contact with single-walled carbon nanotubes,
charge transfer occurs when the analyte interacts with them. With the
adsorption of NH3, this leads to a decrease in carrier concentration [37].
During this process, electrons from ammonia are transferred to
sc-SWCNTs and received by the valence band of sc-SWCNTs (Fig. 7a),
reducing the number of holes and widening the gap between the valence
P. Nie et al. Dyes and Pigments 220 (2023) 111690

Fig. 8. Mechanism Diagram illustrating the influence of polymer structure on

the response of the device to ammonia gas vapor.

Table 1
Fig. 7. Simulated graph and mechanistic diagram depicting the response of
NH3 sensing characteristics based on various carbon nanomaterials.
carbon nanotubes to ammonia gas vapor.
materials Sensitivity(%) ammonia (ppm) refs

band and the Fermi level (Fig. 7a). As a result, a space charge region rGO 2.10 20 ppm [8]
forms on the surface of sc-SWCNTs, increasing resistance and enhancing ZIF8-ZnO 2.95 20 ppm [8]
ZIF8-ZnO/rGO 4.65 20 ppm [8]
the sensor’s response with increasing ammonia concentration [39].
B-SWCNT 1.06 20 ppm [10]
However, the PDF-N-DTS/SWCNTs/IDE, i.e., Device 2, exhibited N-SWCNT 1.58 20 ppm [10]
irrecoverable behavior during the experimental investigation. All con­ rGO-ZnO 1.50 20 ppm [42]
ditions, except for the structure, remained the same without any other PDF-DTS/SWCNTs 5.0 20 ppm this work
variables. Therefore, we speculate that the primary cause of this dif­ PDF-N-DTS/SWCNTs 3.3 20 ppm this work

ferential change is the imine group (Fig. 8).

The main mechanisms that could have influenced this phenomenon
are as follows: (1) according to the previously reported by researchers
[40], imine groups (C– – N) in the nanocomposite materials can serve as
primary adsorption sites by forming hydrogen bonds with water mole­
cules. (2) It is well known that NH3 readily dissolves in water, primarily
attributed to the reversible chemical reaction between NH3 and H2O
molecules. NH3 molecules at the same concentration react and absorb on
the material surface due to hydrogen bonding with water molecules
[41]. The reaction can be represented as follows:
NH3 + ⋅H2 O ⇄ NH4+ + OH − (3)
This precisely agreement with our experimental findings. Some
ammonia molecules, due to their absorption with water molecules, fail
to provide electron pairs, resulting in reduced charge transfer and
increased carrier concentration compared to PDF-DTS/SWCNTs/IDE,
leading to a deteriorated response. However, during the analysis pro­
cess involving 10 min of air purging, the adsorbed ammonia on carbon
nanotubes easily desorbs, resulting in increased carrier concentration
and decreased resistance. Simultaneously, due to the instability and
volatility of NH+ 4⋅OH− , reverse reactions occur, replenishing charge at
the analysis sites of pristine carbon nanotubes with some of the released
ammonia. Consequently, the resistance of Device 2 remains unable to
recover to its initial position.
Up to now, the application of carbon nanomaterials holds promise as
a prevailing trend for the next generation of ammonia gas vapor sensors.
A comparative analysis of the sensing characteristics of the successfully
assembled Device 1 and Device 2 with previously reported ammonia gas
vapor sensors was conducted (see Table 1). In comparison to the past,
their sensing performance largely surpasses these ammonia gas vapor
sensors. Semiconductor carbon nanotube composites also serve as
promising candidates for ammonia detection, offering valuable insights
for further extensive research in the future.
5. Conclusion
In summary, this study involved the design and synthesis of two
structurally similar alternating polymers, PDF-DTS and PDF-N-DTS.
Both of the polymers successfully facilitated the selectively sorting of
sc-SWCNTs, from which purity of the sc-SWCNTs reached to 99.9%.
Subsequently, we employed a drop-casting method to deposit the PDF-
DTS/sc-SWCNTs and PDF-N-DTS/sc-SWCNTs composite materials onto
interdigitated electrodes (IDE), and assembled two devices, namely PDF-
DTS/SWCNTs/IDE and PDF-N-DTS/SWCNTs/IDE. Investigation of their
performance for ammonia gas vapor sensing revealed that at a concen­
tration of 20 ppm, the two sensors achieved response values of 5.0% and
3.3% respectively, with corresponding calculated LOD of 64.5 ppb and
53.5 ppb. Both sensors demonstrated excellent response and selectivity
towards ammonia gas vapor, exhibiting notable improvements in
various aspects compared to previous works.
CRediT authorship contribution statement
Pengwei Nie: Conceptualization, Validation, Data curation, Writing
– original draft. Jieyun Zhang: Data curation. Hairong Du: Writing –
review & editing. Xieraili Maimaitiyiming: Supervision, Writing – re­
view & editing.
Declaration of competing interest
The authors declare that we have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (No. 51763021, 51363020, 21164012). The authors thank
Haijiao Xie from Shiyanjia Lab (www.shiyanjia.com) for their help in
the DFT and ESP calculations of molecular structures.

8
P. Nie et al.
Appendix A. Supplementary material
Synthesis of monomers and polymers, Characterization of monomers
and polymers, Density Functional Theory (DFT), Purity of sc-SWCNT,
Calculation of detection limit (LOD).
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