Carbohydrate Polymers 288 (2022) 119312

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Graphene oxide quantum dots attached on wood-derived nanocellulose to

fabricate a highly sensitive humidity sensor
Lijun Huang a, b, Yutong Yang a, b, Pu Ti a, b, Guoting Su a, b, Quanping Yuan a, b, *
a
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China
b
MOE Key Laboratory of New Processing Technology for Non-ferrous Metals and Materials & Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured
Materials, Guangxi University, Nanning 530004, China

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

Keywords: Herein, cellulose nanofibril (CNF) with various carboxyl amounts were prepared via regulating its oxidation
Wood-derived nanocellulose degree using TEMPO oxidation. The CNF dispersion was dropped onto the interdigital electrode to be capacitive
Graphene oxide quantum dots humidity sensor by the subsequent vacuum freeze-drying. Pure CNF-7 (NaClO content of 7 mmol/g) humidity
Aerogel
sensor involves in orderly porous structure, which displays better performance than other CNFs for its moderate
Flexibility
Capacitive humidity sensor
carboxyl content and dimension. As uniformly adding appropriate content of graphene oxide quantum dots
(GOQD) with larger surface area and active sites, it can be attached on the CNF to construct a three-dimensional
interconnected porous structure for their excellent aqueous dispersity as well as differences in morphology and
size. Consequently, the CNF/GOQD sensor exhibits the sensitivity as high as 51,840.91 pF/% RH, short response
time (30 s)/recovery time (11 s) and excellent reproducibility. The proposed method can provide effective
guidance for the design of humidity sensors based on nanomaterials.

1. Introduction
Cellulose ((C6H10O5)n) is a stereoregular, semicrystalline poly­
saccharide consisting of a linear chain from several hundred to several
tens of thousands of repeating units of β-D-glucopyranose (n), covalently
linked by 1–4 glycosidic bonds. Cellulose based humidity sensor displays
excellent sensitivity and fast response for its abundant hydrophilic
groups, such as hydroxyl group and carboxyl group (Kim et al., 2021; Li
et al., 2021; Wang et al., 2020). Therefore, cellulose can be considered as
a humidity sensitive material to prepare high-performance humidity
sensors for its high-value utilization. Now, humidity sensors are widely
used in many fields, such as industry and agriculture (Yeo et al., 2008),
especially in food and pharmaceutical packaging (Bridgeman et al.,
2014), hazardous goods storage, protection of electronic equipment
(Rouleau et al., 2000), paper products storage (Zhao et al., 2019), and
laboratory humidity monitoring (Farahani et al., 2014). If the changes of
humidity cannot be quickly and accurately measured on these occasions,
mildew (Zhao et al., 2020), damage (Hewson et al., 2013; Kemppainen
et al., 2013; Schito et al., 2019) and safety (Exposito et al., 2019) issues
may occur. It is necessary to develop highly sensitive humidity sensors,
in which sensing dielectric material should have excellent hydrophilic­
ity, larger surface area and abundant active sites. Such as paracetamol
(Wang et al., 2019), MgO (Pan et al., 2020), graphene (Lv, Hu, et al.,
2019), cellulose nanofiber/carbon nanotube (CNT) (Zhu et al., 2020),
polyvinylidene fluoride (PVDF)-BaTiO3 (Mallick et al., 2020), poly­
dopamine (PDA) coated cellulose nanocrystal (CNC)/graphene oxide
(GO) (PDA@CNC/GO) (Yao, Huang, Chen, et al., 2020), etc. Of which,
cellulose nanofibre as a kind of nanocellulose has outstanding hydro­
philic property for its abundant hydroxyl group, and its sensor has a
sensitivity of 2.82 MHz/% RH in the range of 55–100% RH (Eyebe et al.,
2017). cellulose nanofiber can form a porous structure with CNT that it
rapidly exchanges water molecules with environment (Zhu et al., 2020).
After PDA was deposited on CNC, it could provide more adsorption
active sites to improve its humidity sensitivity (Yao, Huang, Chen, et al.,
2020). Cellulose as substrate has been considered to be a feasible
method to effectively solve the problems of rigid structure and high cost
of traditional humidity sensor (Zhu et al., 2021).
Besides, carbon materials were frequently applied in the preparation
of the humidity sensors. Of which, GO formed porous or folded struc­
tures that it combined with iron nanoparticles (Kumar et al., 2019),
silver nanoparticles (Li et al., 2017), nanofibrillated cellulose (NFC) and
polydimethylsiloxane (Yang et al., 2021), CNT and silicon adhesives
(Chani et al., 2019), thus their sensitivity reached 14.12 pF/% RH
(70–95% RH), 25809 pF/% RH (11–97% RH), 6576.41 pF/% RH

* Corresponding author at: School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China.
E-mail address: yuanquanping@gxu.edu.cn (Q. Yuan).

https://doi.org/10.1016/j.carbpol.2022.119312
Received 27 November 2021; Received in revised form 28 February 2022; Accepted 1 March 2022
Available online 4 March 2022
0144-8617/© 2022 Elsevier Ltd. All rights reserved.
L. Huang et al. Carbohydrate Polymers 288 (2022) 119312

(11–97% RH) and 1336.7 pF/% RH (36–94% RH), respectively. As a GO Chengdu Chron Chemicals Co., Ltd. (Chengdu, China). GOQD dispersion
derivative material, graphene oxide quantum dots (GOQD) have larger with the concentration of 1 mg/mL was provided by Jiangsu XFNANO
specific surface area and more surface oxygen-containing groups (Ding Technology Co., Ltd. (Nanjing, China).
et al., 2018; Frecha et al., 2021). Meanwhile, the quantum confinement
effect caused by the nanoscale size forms a high concentration of surface
2.2. Preparation of CNF with different carboxyl content and their
adsorption sites, which leads to the enhancement of humidity sensing
humidity sensors
response (Kan et al., 2019). Therefore, GOQD is also an ideal dielectric
material to improve the performance of humidity sensors. For example,
CNF dispersion with different carboxyl content was prepared under
the response/recovery times of humidity sensor prepared by GOQD and
the room temperature via TEMPO oxidation method as follows. Firstly,
polymer (diallydimethylammonium chloride) is 32/48 ms in the range
3 g pulp, 0.048 g TEMPO and 0.48 g NaBr were stirred in 200 mL
of 49–93% RH, which is mainly attributed to the abundant hydrophilic
deionized water. At the same time, NaClO solution (relative dosage to
groups on GOQD and its nano-sized lamellar structure (Li et al., 2016).
pulp: 3 mmol/g, 7 mmol/g, 11 mmol/g, respectively) were added slowly
The GOQD film humidity sensor had a sensitivity of 81 Hz/% RH in the
at the beginning of the reaction. Then, 0.1 mol/L HCl or 0.1 mol/L NaOH
range of 11–97% RH. In the GOQD film, continuous ion conduction
were added to maintain the pH of the system at about 10.00. When the
paths are constructed after the adsorbed water molecules are ionized to
pH changed in the deviation of ±0.01 within 15 min, 10 mL anhydrous
form hydrated hydrogen ions (H3O+) as charge carriers under electric
ethanol was added and stirred for another 10 min to terminate the re­
field (Ding et al., 2018). Similarly, the response/recovery time of hu­
action, then CNF slurry was prepared. The specific time in this oxidation
midity sensor based on carbon quantum dot (CQD) film was as short as
process depends on the content of NaClO. Secondly, the slurry was
25/60 s in the range of 7–43% RH, in which it was easy to form hydrogen
centrifuged at 6000 rpm for 10 min, by which it was washed with
bonds with water molecules, thereby significantly promoted electronic
deionized water for several times until the slurry became neutral.
migration (Zhang et al., 2013). Small radial dimension and abundant
Thirdly, the slurry was ultrasonically dispersed for 30 min under the
oxygen-containing functional groups of GOQD (Ding et al., 2018) can
power of 1000 W in ice bath. CNF dispersion at different oxidation de­
improve its dispersity in substrate, which has high potential in
gree (different carboxyl content) were obtained with various NaClO
enhancing humidity sensitivity.
contents of 3 mmol/g, 7 mmol/g and 11 mmol/g, which were denoted as
In this study, a high humidity sensitive material was presented by
CNF-3, CNF-7, CNF-11, respectively. Then, concentration of the CNF
introducing the two dielectric materials of cellulose nanofibril (CNF)
was calculated after drying at 105 ◦ C for 10 h. The CNFs dispersion in a
and GOQD. Both them with large specific surface area as well as abun­
concentration of 3.5 mg/mL was prepared via the process as follow.
dant oxygen-containing groups on their surface, were evenly mixed to
Such as the preparation of the CNF-7 dispersion with the set concen­
prepare CNF/GOQD aerogel. On the other hand, it has been verified that
tration of 3.5 mg/mL and the total dry mass of 40 mg, after 2.63 g CNF-7
nanocellulose has strong binding force with GO, including strong
with the calculated concentration of 1.52 wt% was weighed in a beaker,
hydrogen bond and van der Waals force (Li et al., 2020). As a GO de­
4.5 mL deionized water and 4.5 mL anhydrous ethanol were added.
rivative material, GOQD can also be well combined to CNF. A porous
Then, the mixture was treated under ultrasonic power of 1000 W for 65
system was constructed that had abundant interconnected pores pos­
min.
sessing abundant active sites and excellent structural regularity in the
After that, the aerogel of CNF (CNF-3, CNF-7, CNF-11) and its hu­
CNF/GOQD aerogel, mainly ascribing to the morphological difference
midity sensor were prepared (Fig. 1a). First of all, 4 μL CNF dispersion
between the fibrous CNF and the nano-sized lamellar GOQD. In which,
with the concentration of 3.5 mg/mL were dropped onto the effective
GOQD can be attached on the surface of CNF along its length via their
area of the flexible interdigital electrode, while the remaining dispersion
strong intermolecular interaction, which increase the surface hydro­
was poured into a round plastic dish. Both them were frozen for 3 h and
philic groups on the hole wall and enlarge the specific surface area.
then dried for 12 h via freezing dry, then the CNF humidity sensor and
Consequently, abundant adsorption sites and migration channels for
CNF aerogel were prepared, respectively. Finally, the test wire was
water molecules can be formed, thus effectively enhance the humidity
welded on electrode pad of the CNF humidity sensor via employing
sensitivity. A hypothesis that there is synergistic effect for CNF com­
electric iron (Fig. 1). The CNF dispersion and its aerogel were used to
bined with GOOD to enhance its humidity sensitivity had been put
characterize the morphology, structure and chemical properties, while
forward. The presented structure and method of the biomass humidity
the CNF humidity sensor was used to test the humidity sensing
sensor will provide reference for the structure optimization of the
performance.
similar sensor.

2. Experimental section 2.3. Preparation of the CNF/GOQD humidity sensors

2.1. Materials
Lithium chloride, anhydrous magnesium chloride, sodium bromide,
sodium chloride, potassium chloride, potassium sulfate, sodium hy­
droxide (NaOH ≥96.0%), were purchased from Tianjin Damao Chemical
Reagent Factory (Tianjin, China) with analytically pure. Bleached kraft
pulp of coniferous wood were provided by Tianjin Woodelf Biotech­
nology Co., Ltd. (Tianjin, China), containing 78.2% cellulose, 20.1%
hemicellulose, as well as the less than 0.5% content of residual lignin.
Flexible interdigital electrode in size of 5 mm × 10 mm was obtained
from Huizhou Xingwenxiong Commerce & Trade Co., Ltd. (Huizhou,
China). 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) of
analytically pure, was purchased from Shanghai Macklin Biochemical
Co., Ltd. (Shanghai, China). Sodium hypochlorite solution (NaClO,
effective chlorine ≥10.0%) with analytically pure was supplied by
Chengdu Jinshan Chemical Test Co., Ltd. (Chengdu, China). Hydro­
chloric acid (36.0–38.0%) with analytically pure, was obtained from
CNF/GOQD dispersion with different contents of GOQD was pre­
pared as follows. Such as the sensor with 5 wt% GOQD, concentration of
the CNF/GOQD mixture dispersion was also set as 3.5 mg/mL with the
total dry mass of 40 mg. Firstly, after 2.5 g CNF-7 with concentration of
1.52 wt% was weighed in a beaker, 3.5 mL deionized water and 3.5 mL
anhydrous ethanol were added. Then, the mixture was treated under
ultrasonic power of 1000 W for 10 min. Next, 2 mL GOQD dispersion
was poured into the CNF dispersion, following by ultrasonic dispersion
for 55 min to obtain CNF/GOQD dispersion. Finally, CNF/GOQD aerogel
and its humidity sensors were assembled using the method as same as
that of the above CNF aerogel and sensors (Fig. 1b). On the basis of the
above process, CNF/GOQD aerogel and its humidity sensors with the
GOQD content of 0.2 wt%, 0.6 wt%, 1 wt%, 3 wt%, 5 wt%, 7 wt%, and 9
wt% were prepared, respectively. Similarly, the CNF/GOQD dispersion
and its aerogel were used to characterize the morphology, structure and
chemical properties, while the CNF/GOQD humidity sensor was used to
test the humidity sensing performance.

2
L. Huang et al.
Fig. 1. (a) Preparation process of CNF aerogel and humidity sensor, (b) preparation process of CNF/GOQD aerogel and humidity sensor, (c) measurement on hu­
midity sensing performance.
2.4. Characterization and performance test
S-3400N scanning electron microscope (SEM, 5 kV acceleration
voltage) was used to observe the morphology of aerogel after the sam­
ples were sprayed with gold. The morphology of CNF, GOQD and CNF/
GOQD was observed and analyzed under the Hitachi HT7700 trans­
mission electron microscope (TEM, 100 kV acceleration voltage), and
their average particle size was obtained using Nano Measurer 1.2 soft­
ware on the basis of the TEM results. The carboxyl content of CNF
dispersion was determined by employing conductivity meter with DDS-
307A model and via conducting titration and calculation on basis of the
equation 1 (Islam et al., 2021).
C × ΔV
H= (1)
m
Among them, H is the carboxyl content of the CNF dispersion (mmol/
g); c is the concentration of NaOH solution (mol/L); ΔV is the volume
change of NaOH solution under the conductivity equilibrium stage (mL);
m is the mass of pure cellulose (g).
The infrared spectrum of the sample was obtained with the Fourier
transform infrared spectrometer (FT-IR, NicoletiS 50) in the range of
4000–400 cm− 1. Oxygen-containing group of the CNF/GOQD aerogel
was also characterized by X-ray photoelectron spectroscopy (XPS,
ESCALAB 250XI+). The hydrophilicity of pure CNF and CNF/GOQD
aerogel was measured using contact angle meter of JCY series. Pure CNF
and CNF/GOQD humidity sensors were placed in sealed containers with
saturated salt of LiCl (11% RH), MgCl2 (33% RH), NaBr (58% RH), NaCl
(75% RH), KCl (85% RH), and K2SO4 (97% RH) for humidity sensitivity
test (Fig. 1c). The specific methods and steps for humidity sensing
measurement on sensitivity, response speed, humidity hysteresis and
reproducibility were referred to the references (Yang et al., 2021). Of
which, the humidity hysteresis value was generally calculated from the
equation 2 (Zhang et al., 2019).
Cd − Ca
He = (2)
S
3
Carbohydrate Polymers 288 (2022) 119312
where He represents the hysteresis value of the humidity sensor; Cd and
Ca represent the capacitance value of the humidity sensor in the process
of dehumidification and humidification respectively; S represents the
sensitivity value of the humidity sensor.
3. Results and discussion
3.1. Analysis on morphology, structure, and chemical properties
CNF aerogel has stable network structure because of its rich hydro­
philic groups including hydroxyl and carboxyl, which can physically
self-crosslink in the form of intramolecular and intermolecular hydrogen
bonds (Liu et al., 2021). The particle size of CNF will change as varying
the TEMPO oxidation degree, which directly affects its assembly per­
formance to the functional additives. As shown in Fig. 2a–f, CNF-7
aerogel has more regularly and orderly distributed porous structure on
its surface than the others. All the aerogels exhibit excellent porosity
calculated on basis of the method (Yang et al., 2021), while they have
different pore structure and its distribution. Therefore, an appropriate
amount of hydrophilic groups on CNF will be conducive to obtain a
uniform and stable network structure, which can provide a large number
of channels and adsorption sites for water molecules, thereby enhancing
humidity sensitivity of the aerogel sensor.
It can be found from Fig. 2g that GOQD is uniformly distributed black
dots. The average particle size of GOQD (Fig. 2j) is about 8.9 nm (the
dots stack with each other) via the calculation using Nano Measurer 1.2
software, which is close to the size results of GOQD reported in related
studies (Hu et al., 2018; Song et al., 2016). CNF intertwine with each
other to form a network structure (Fig. 2h). Fig. 2i shows that GOQD in
the form of black dots are uniformly dispersed in the network structure
of CNF. The observed large differences in morphology and size between
CNF and GOQD suggest that GOQD could attach on the CNF to construct
the sensing channels and adsorption sites after they were combined. In
the structure, CNF with high aspect ratio and elastic modulus can be
seen as substrate (Pottathara et al., 2019), while GOQD attached on the
substrate as a functional filler. Moreover, both them can be combined
L. Huang et al.
Fig. 2. SEM images of CNF aerogel, (a) and (b) CNF-3, (c) and (d) CNF-7, (e) and (f) CNF-11. (g) TEM image of pure GOQD, (h) TEM image of pure CNF, (i) TEM
image of CNF/GOQD, (j) particle size distribution of GOQD.
with each other through hydrogen bonding, and a network structure
with excellent permeability can be built (Lv, Zhou, et al., 2019), thereby
contributing to enhance the humidity sensing performance.
All the CNF/GOQD aerogels formed a complete structure presenting
white sponge morphology shown in Fig. 3. As adding appropriate con­
tent of GOQD, homogeneous surface can be attained on the aerogel, as
well as the perforated structure. Of which, the CNF/GOQD aerogel ex­
hibits smoother surface (Fig. 3a–e). The excellent surface quality and
pore structure also own to the addition of anhydrous ethanol (Kang
et al., 2019). In addition, Fig. 3(f, g) displays the characteristics of ultra-
low density of the obtained CNF/GOQD aerogel.
After the volume change of NaOH solution shown in Fig. 3h was
obtained, carboxyl content of CNF-3, CNF-7 and CNF-11 dispersion is
calculated as 1.4 mmol/g, 2.0 mmol/g and 2.6 mmol/g via Eq. (1) (Seen
in Fig. 3i), respectively, increasing linearly as adding amount of NaClO.
4
Carbohydrate Polymers 288 (2022) 119312
The carboxyl can interact with water molecules via hydrogen bonding,
which not only enhances the adsorption and migration of water mole­
cules (Islam et al., 2021), but also improves the dispersibility of CNF
itself in water.
In Fig. 4a, absorption peaks of the FT-IR spectra near 3435 cm− 1,
2910 cm− 1, 1745 cm− 1, 1625 cm− 1 and 1043 cm− 1 are attributed to
–OH, –CH, C– – O, H–O–H, C–O stretching vibration, respectively,
indicating excellent hydrophilicity of CNF. On the one hand, the spectra
of different CNF/GOQD aerogels showed the similar –OH, C– – O, C–O–C
and C–O characteristic absorption peaks to the pure GOQD and pure
CNF (Fig. 4b). The absorption peaks near 3435 cm− 1 of pure GOQD is
wider and higher than that of CNF, indicating that GOQD is an enhancer
to the adsorption of water molecules. On the other hand, CNF/GOQD
aerogel is mainly composed of carbon and oxygen elements, and the
carbon‑oxygen ratio is 1.25 (Fig. 4c). In addition, the C1s spectrum has
L. Huang et al.
Fig. 3. CNF/GOQD aerogel with various GOQD content (a) 1 wt% GOQD, (b) 3 wt% GOQD, (c) 5 wt% GOQD, (d) 7 wt% GOQD, (e) 9 wt% GOQD; (f) and (g) ultra-
light CNF/GOQD aerogel; (h) the volume change of NaOH solution in different CNF dispersion at the equilibrium stage of conductivity, (i) carboxyl contents of
different CNF dispersion.
three peaks at 287.2 eV, 285.8 eV and 284.3 eV (Fig. 4d), corresponding
to C–
– O, C–O and C–C (Lv, Zhou, et al., 2019). The peak of the O1s
spectrum appearing at 532.4 eV and 531.2 eV (Fig. 4e) are attributed to
C–OH/C–O and C– – O (Liu et al., 2017). Therefore, the adsorption of
water molecules on CNF/GOQD aerogel is enhanced for the abundant
oxygen-containing groups.
3.2. Analysis on humidity sensing performance of pure CNF humidity
sensor
Fig. 5a shows that the sensitivity of CNF-3, CNF-7 and CNF-11 hu­
midity sensors are 16,921.39 pF/% RH, 33,783.25 pF/% RH, 10,466.15
pF/% RH in the range of 11–97% RH, in which the sensitivity increased
firstly and then decreased even the continuously added hydrophilic
groups on CNF. CNF-7 humidity sensor that is in the medium oxidation
degree has the relative high sensitivity in this work. As increasing the
amount of NaClO, porous structure of the CNF aerogel was affected for
the excessively decreased size and oxidized degree of CNF, becoming
unconsolidated, which can be seen in Fig. 2(e, f). So the sensitivity is
weakened. Compared with the humidity sensor based on indium tin
oxide and alumina ink with the sensitivity of 0.85–7.76 pF/% RH (at
5–95% RH) (McGhee et al., 2020) and Ti3C2/TiO2 composite humidity
sensor with the sensitivity of 1614 pF/% RH (at 7–97% RH) (Li, Jiang,
5
Carbohydrate Polymers 288 (2022) 119312
et al., 2019), pure CNF humidity sensors present great potential sensing
performance.
A small hysteresis occurs in the humidity range between 33% RH and
85% RH (Fig. 5b). It can be found that the hysteresis of the presented
CNF-7 and the reported CNC humidity sensors (Yao, Huang, Zhang,
et al., 2020) are about 11.62% RH and 7.3% RH, respectively, which
indicates that both them have comparatively low hysteresis value. In the
range of 11–97% RH, sensing behavior of the CNF-7 humidity sensor
displays better reproducibility. It can be observed that the humidity
sensor shows a similar response law even it was repeated three times
(Fig. 5c). The response/recovery time of the CNF-7 humidity sensor is as
less as 35/24 s (Fig. 5d), while that of the reported pure CNC and bac­
terial cellulose (BC) humidity sensor are 60/15 s in the range of
47–97.3% RH (Yao, Huang, Zhang, et al., 2020) and 89/62 s in the range
of 60–70% RH (Hu et al., 2011), respectively. Consequently, CNF-7
humidity sensor has a fast response/recovery speed for its stable
network structure and moderate number of hydrophilic groups, in which
water molecules can be quickly adsorbed and desorbed.
Stable output signal curves (similar to rectangles) were obtained
even in the four repeated tests (Fig. 5e). Therefore, the sensors have
considerable humidity-sensitive reproducibility, similar to the sensors
prepared by carboxymethyl cellulose-stabilized AgNPs (Marzouk et al.,
2016) and cellulose acetate-polypyrrole-glycerol-10 wt% WO3 (Abdel
L. Huang et al. Carbohydrate Polymers 288 (2022) 119312

Fig. 4. (a) FT-IR spectra of CNF, (b) FT-IR spectra of pure GOQD and CNF/GOQD aerogel with various GOQD contents, (c) XPS whole spectrum of the CNF/GOQD
aerogel with 1 wt% GOQD, (d) C1s spectra, (e) O1s spectra.

Fig. 5. (a) Capacitance-relative humidity curve of CNF humidity sensor, (b) hysteresis characteristics of CNF-7 humidity sensor, (c) and (d) response/recovery time
of CNF-7 humidity sensor, (e) reproducibility of response/recovery behavior of CNF-7 humidity sensor.

Rahman et al., 2021). It can be concluded that the higher the humidity 3.3. Analysis on humidity sensing performance of different CNF/GOQD
is, and the better the reproducibility is. humidity sensors

As shown in Fig. 6a, water contact angle on the CNF/GOQD aerogel

6
 L. Huang et al.
7

Fig. 6. (a) Water contact angle on pure CNF aerogel and CNF/GOQD aerogel, (b) sensitivity of CNF/GOQD humidity sensors with various GOQD contents, (c) and (d) response/recovery time of CNF/GOQD humidity
sensor containing 1 wt% GOQD, (e) humidity hysteresis of CNF/GOQD humidity sensor containing 1 wt% GOQD, (f) capacitance-humidity fitting curve of CNF/GOQD humidity sensor containing 1 wt% GOQD, (g)

Carbohydrate Polymers 288 (2022) 119312

reproducibility of CNF/GOQD humidity sensor containing 1 wt% GOQD.
L. Huang et al. Carbohydrate Polymers 288 (2022) 119312

is smaller than that on pure CNF aerogel. Therefore, the introduction of
GOQD has elevated the hydrophilicity of the aerogel, thus enhances its
humidity sensitivity. As seen from Fig. 6b, the CNF/GOQD humidity
sensor has a higher sensitivity (51,840.91 pF/% RH) than pure CNF-7
sensor (33,783.25 pF/% RH). With the increase of GOQD content,
there is a positive linear correlation between GOQD content and sensi­
tivity in the range of 0–1 wt%. When the GOQD content increased to 1
wt%, the sensitivity climbs up to the maximum. However, there is a
linear negative correlation between the content of GOQD and the
sensitivity value in the range of 1–9 wt%. The sensitivity decreased as
continuously adding the content of GOQD more than 1 wt%. Therefore,
GOQD at an appropriate doping content will be conducive to the
improvement of sensitivity of the sensor. Similar to the previously re­
ported humidity sensors shown in Table 1, the CNF/GOQD humidity
sensor also exhibits quite high sensitivity. Radial dimension of lamellar
GOQD shown in the TEM analysis (Fig. 2) is less than that of CNF. GOQD
can attach on the surface of CNF along its length in aerogel network via
their intermolecular interaction, which increases the surface hydrophilic
groups and enlarge the specific surface area. In addition, the attached
GOQD along the CNF can be seen as the strong adsorption site to form
migration pathway for its quick adsorption and desorption of the water
molecule.
Moreover, excellent reproducibility of the CNF/GOQD humidity
sensor is shown in Fig. 6c. Its response/recovery time is about 30/11 s
(Fig. 6d), which is less than that of CNF (Fig. 5d). CNF/GOQD humidity
sensor also has faster response and recovery than that of pure CNF
sensor. Its response speed is higher than that of some sensors listed in
Table 1, and its recovery speed is little lower as compared with some of
the listed humidity sensors.
As seen in Fig. 6e, desorption response of the CNF/GOQD humidity
sensor in the dehumidifying process lags behind that in the hygroscopic
process from 85% RH to 33% RH. The hysteresis value is about 12.99%
RH, while there are 8.4% RH (Zhu et al., 2020) and 4.3% (Yao, Huang,
Chen, et al., 2020) in the published work. Furthermore, there is a rela­
tionship of exponential curve (Fig. 6f) between capacitance and hu­
midity with the relevancy R2 of 0.9999 (equation 3). Parameters a, b,
and c are 5,607,150 ± 38,348.93, 0.0778 ± 0.0012, and 193.74 ±
15.12, respectively. So, environment humidity can be estimated using
the sensor to test capacitance by this relationship, which will exactly
help its application.
( )c
y = a 1 − e− bx (3)
Stable output signal curves (similar to rectangles) were also obtained
in the CNF/GOQD humidity sensor (seen in Fig. 6g), demonstrating its
excellent humidity-sensitive reproducibility, similar to that of the sen­
sors prepared by GO (Le et al., 2019) and polyaniline/GO (Zhang et al.,
2018), as well as the above CNF sensor. It also indicates that better
reproducibility can be attained in the higher humidity.
3.4. Application and response mechanism of the CNF/GOQD humidity
sensor
Fig. 7a shows a measurement system for monitoring human respi­
ration. The humidity sensor was attached on vent of the mask and
exposed to human breath. Then, it was employed to monitor human
respiration through connecting the sensor to LCR digital bridge. The
measurement ambient temperature and humidity was 20 ◦ C and 55%
RH. The humidity sensor also has rapid response rate of about 3 s for the
change increasing from the capacitance of around 6628.77 pF to
13,870.10 pF in the controlled breathing rate of 12 breathes per minute,
as well as its capacitance changes regularly (Fig. 7b,c). Therefore, the
humidity sensor displays a potential for the application in monitoring
human respiration with enough response performance.
In the high humidity environment, water molecules are adsorbed on
the surface of CNF/GOQD aerogel and penetrated into the gap of CNF
and GOQD fragments. As seen in Fig. 7d, the water molecules are ionized
to produce hydrated hydrogen ions under the action of electric field
(Ding et al., 2018). Afterwards, a continuous ionic conduction path is
formed by charge transfer between hydrated hydrogen ions and water
molecules, which changes the dielectric properties of CNF/GOQD aer­
ogel on the interdigital electrode, thereby enhancing the capacitive
response of the humidity sensor (Yang et al., 2021).

Table 1 4. Conclusion
Sensitivity and response/recovery characteristics of the previously reported
sensors and the presented humidity sensor. CNF with various carboxyl contents were prepared via TEMPO
Sensor Test range Sensitivity Response/ References method by controlling the content of NaClO, which were made into
materials (% RH) recovery time (s) aerogel and humidity sensors by ultrasonic and vacuum freeze-drying
In2O3/GO 11–97 1061.6 pF/% 15/2.5 (test (Li, Tian, et al., strategy. The sensitivity of the sensors varies with the change of
RH range at 0–43% 2019) TEMPO oxidation degree of CNF for its alterative carboxyl group and
RH) dimension. CNF-7 humidity sensor has better performance than other
GO/PDDA 11–97 1552.3 pF/% − /− (Zhang et al., CNFs for its moderate carboxyl content and dimension.
RH 2014)
The addition of the GOQD has contributed to constructing the highly
GO 10–90 3215.25 pF/ 15.8/− (test (Lan et al.,
% RH range at 20–80% 2020) sensitive humidity sensing aerogel with perforated and interconnected
RH) porous structure. Moreover, the GOQD can attached on the surface of
GO/ 11–97 3080.24 pF/ 70/− (test range (Zhang et al., CNF along its length via their strong intermolecular interaction, which
Nafion/ % RH at 0–97% RH) 2019)
increase the surface hydrophilic groups on the hole wall and enlarge the
In2O3
GO/Ag 11–97 25,809 pF/% 8/12 (Li et al., 2017)
specific surface area, thus form more migration pathway for the water
RH molecule. The CNF/GOQD humidity sensor has the outstanding sensing
NFC/GO/ 11–97 6576.41 pF/ 57/2 (Yang et al., performance, which exhibits the sensitivity as high as 51,840.91 pF/%
PDMS % RH 2021) RH, quick response (30 s)/recovery (11 s) speed and excellent repro­
NFC/ 11–95 69.9% (ΔI/ 330/377 (Zhu et al.,
ducibility. On the one hand, GOQD in the form of black dot are uni­
MWCNTs I0) 2019)
RGO/SnO2 11–97 1604.89 pF/ 102/6 (Zhang et al., formly dispersed in the network structure of CNF. On the other hand, the
% RH 2016) humidity sensitivity of CNF/GOQD is significantly improved compared
CNF/PANI/ 30–100 – 41/46 (Anju et al., with that of pure CNF. Thus, the hypothesis that there is synergistic
PVA 2019)
effect for CNF combined with GOOD to enhance its humidity sensitivity
PANI/Cu- 30–95 12 pF/ RH 42/24 (Parangusan
ZnS et al., 2020)
has been demonstrated in this work. In summary, the CNF/GOQD hu­
GOQs/CS 11–95 39.2 Hz/% 36/3 (Qi et al., 2019) midity sensor can be applied to humidity monitoring in the special
RH occasion.
CNF/ 11–97 51,840.91 30/11 This work
GOQD pF/% RH

8
L. Huang et al.
Fig. 7. Monitoring on human respiration by using the CNF/GOQD humidity sensor (a), response of capacitance of the humidity sensor at respiration rate of 12
breaths per minute (b) and 6 breaths per minute (c), response mechanism of CNF/GOQD humidity sensor (d).
CRediT authorship contribution statement
Lijun Huang: Methodology, Validation, Formal analysis, Investiga­
tion, Writing – original draft, Writing – review & editing, Visualization.
Yutong Yang: Conceptualization, Methodology, Validation, Formal
analysis, Investigation, Writing – original draft, Visualization. Pu Ti:
Methodology, Investigation. Guoting Su: Methodology, Investigation.
Quanping Yuan: Conceptualization, Methodology, Investigation,
Writing – review & editing, Supervision, Project administration, Fund­
ing acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (NSFC) (No. 32071695).
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