Preview
Janus Mesostructures for
Simultaneous
Multivariable Gases Sensors
Jin-Long Wang1 and Shu-Hong Yu1,*
Conventional mesoporous materials-based transducers generally possess sym-
metrical geometries and are unable to easily distinguish two or more compo-
nents in mixtures and reject the interferences. In this issue, Zhao et al. develop
Janus mesostructures to realize a simultaneous multivariable gases sensor using
solvent evaporation-induced self-assembly (EISA) with subsequent surface
modifications.
To date, gas sensors are becoming one
of the most representative techniques
in monitoring of health care, chemical
synthesis, environmental safety, and in-
dustrial process.1–3 The key challenges
for gas sensors are their sensitivity and
selectivity, which are highly dependent
on the high surface-to-volume ratio of
the sensors and interaction between
sensors and gases. Mesoporous mate-
rials with high surface areas or uniform
channels have been widely applied in
realizing gas sensors with much higher
performance.4,5 However, the present
sensors based on the mesoporous
structure are mostly limited in detecting
specific single gases, which is far from
being desired for the increasing
requirement for sensing platforms. As
a result, the design of mesoporous ma-
terials-based sensors with multiple
sensitivity for various gases in one unit
is critical to overcome the limitation of
existing sensors.
Intensive efforts have been paid in
fabrication of multivariable sensors,
including nonresonant and resonant-
impedance sensors, electromechanical
resonant sensors, field-effect transistor
sensors, photonic resonant sensors,
and so on.6 It was exciting that recently
the group led by Dongyuan Zhao at
Fudan University, China, has demon-
1110 Matter 1, 1104–1118, November 6, 2019 ª 2019 Published by Elsevier Inc.
strated an outstanding sensor device
for simultaneously detection of multiple
gases based on the Janus mesoporous
carbon/silica films with asymmetric
mesostructures and disparate active
sites (–NH2 and –COOH groups).7
These Janus mesoporous sensor
devices exhibited very excellent
performances in detection of H2S and
NH3, including distinct ultrafast
response times (2 s for H2S, 10 s for
NH3), ultralow limits of detection (0.01
ppm for H2S, 0.1 ppm for NH3), superior
stability, and high selectivity. A facile
solvent evaporation-induced self-as-
sembly (EISA) method and subsequent
surface modifications (Figure 1A) were
applied to prepare the highly ordered
mesostructured and uniform films (Fig-
ure 1B). Briefly, the mesostructured sil-
ica layer was formed (step 1), and then
the mesostructured carbon layer was
further coated on the silica layer to
form asymmetric Janus structures (step
2). After a thermal treatment in an inert
atmosphere, ordered mesoporous car-
bon/silica Janus structures that modi-
fied with –COOH groups on the surface
of the mesoporous carbon layer could
be formed (step 3). PMMA was coated
on the mesoporous carbon layer to
protect the -COOH groups during
amino modification (step 4), during
which the (3-aminopropyl) triethoxysi-
lane (APTES) was used to modify the sil-
ica mesopore walls with –NH2 groups
(step 5).
According to the nitrogen adsorption
isotherms, the Brunauer-Emmett-Teller
(BET) surface area and pore volume of
the Janus thin film reach 497 m2$g 1
and 0.47 cm3$g 1, with mesopores
centered at 24.0 (top mesoporous car-
bon layer) and 6.5 nm (silica layer). This
mesopore distribution provides a large
accessible surface area and sufficient
exposed active sites for ultrafast gas
diffusion and unimpeded contact with
gas molecules. The results of Fourier
transform infrared (FT-IR) spectrum
and X-ray photoelectron spectroscopy
(XPS) and high-resolution N1s spec-
trum demonstrate that the -NH2
groups are successfully grafted on the
surface of the silica mesopore walls
with -COOH groups remaining on the
top layer of mesoporous carbon.
They used this asymmetric architecture
with independent –NH2 and –COOH
sites as platform to detect multiple
gases by the mass-sensitive sensing
mode at room temperature (Figure 1C).
The results (Figure 1D) show that
the response time and corresponding
frequency shifts of the device are 2 s
(10 s) and 171 Hz ( 49 Hz) when
exposed to pure H2S (NH3). Notably,
when exposed to mixed H2S and NH3,
the device shows a fast frequency
decrease in first 2 s and a moderate
drop in next 8 s with frequency shifts
of 183 Hz and 38 Hz, demonstrating
that no cross-responses are involved in
the Janus mesoporous sensor during
simultaneous H2S and NH3 sensing pro-
cess. When the sensor device was fabri-
cated with the symmetric film that
1Department of Chemistry, University of Science
and Technology of China, Jinzhai Road 96, Hefei
230026, Anhui, China
*Correspondence: shyu@ustc.edu.cn
https://doi.org/10.1016/j.matt.2019.10.009
Figure 1. Fabrication of Janus Mesoporous Sensor Device and Its Sensing Performance
(A) Schematic illustration of the process for preparation of Janus mesoporous carbon/silica thin film device via the successive solvent evaporation-
induced self-assembly approach and selective surface functionalization strategy.
(B) Cross-section field emission scanning electron microscope (FESEM) image of the Janus mesoporous carbon/silica thin film. Scale bar, 100 nm.
(C) Schematic illustration of the gas sensor device based on the Janus mesoporous carbon/silica thin films with independent –NH 2 and –COOH groups.
(D) Response and recovery curves of the Janus mesoporous carbon/silica thin film (orange)-, mesoporous silica thin film (green)-, and mesoporous
carbon thin film (blue)-based sensors to 20 ppm of NH 3 , 20 ppm of H2 S, and mixed gases of NH3 (20 ppm) and H 2 S (20 ppm).

the COOH groups are obscured after
NH2 functionalization, the frequency
shift of this device to H2S is about
325 Hz and no response to NH3, sug-
gesting the necessity of Janus architec-
ture for multiple sensing outputs
simultaneously.
Furthermore, theoretical calculations
based on the Langmuir adsorption
model, the following derived equation,
and the kinetic Monte Carlos revealed
that the different free energy between
NH3 and H2S to the Janus mesoporous
carbon/silica led to the different
response times. Thus, both the experi-
mental and theoretical results indicate
that this designed unique Janus
mesoporous architecture is a promising
candidate for the next generation of
multivariable sensors for multiple gas
sensing, which are highly demanded
in chemical industries, environmental
monitoring, and other related fields.
1. Mao, S., Chang, J., Pu, H., Lu, G., He, Q.,
Zhang, H., and Chen, J. (2017). Two-
dimensional nanomaterial-based field-effect
transistors for chemical and biological sensing.
Chem. Soc. Rev. 46, 6872–6904.
2. Tchalala, M.R., Bhatt, P.M., Chappanda, K.N.,
Tavares, S.R., Adil, K., Belmabkhout, Y., et al.
(2019). Fluorinated MOF platform for selective
removal and sensing of SO2 from flue gas and
air. Nat. Comm. 10, 1328.
3. Zhu, Y., Zhao, Y., Ma, J., Cheng, X., Xie, J., Xu,
P., Liu, H., Liu, H., Zhang, H., Wu, M., et al.
(2017). Mesoporous Tungsten Oxides with
Crystalline Framework for Highly Sensitive and
Selective Detection of Foodborne Pathogens.
J. Am. Chem. Soc. 139, 10365–10373.
4. Lakhi, K.S., Park, D.H., Al-Bahily, K., Cha, W.,
Viswanathan, B., Choy, J.H., and Vinu, A.
(2017). Mesoporous carbon nitrides: synthesis,
functionalization, and applications. Chem.
Soc. Rev. 46, 72–101.
5. Li, Y., Luo, W., Qin, N., Dong, J., Wei, J., Li, W.,
et al. (2014). Highly Ordered Mesoporous
Tungsten Oxides with a Large Pore Size and
Crystalline Framework for H2S Sensing.
Angew. Chem. Int. Ed. 53, 9035–9040.
6. Potyrailo, R.A. (2016). Multivariable Sensors for
Ubiquitous Monitoring of Gases in the Era of
Internet of Things and Industrial Internet.
Chem. Rev. 116, 11877–11923.
7. Wang, R., Lan, K., Chen, Z., Zhang, X., Hung,
C.-T., Zhang, W., Wang, C., Wang, S., Chen, A.,
Li, W., et al. (2019). Janus Mesoporous
Sensor Devices for Simultaneous Multivariable
Gases Detection. Matter 1, this issue, 1274–
1284.

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