Analytica Chimica Acta 1149 (2021) 338211

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Analytica Chimica Acta

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

Convenient detection of H2S based on the photothermal effect of

Au@Ag nanocubes using a handheld thermometer as readout
Yingzhou Tao a, Yisheng Lin a, Fang Luo a, b, **, Caili Fu c, Cuiying Lin a, ***, Yu He a,
Zongwei Cai d, Bin Qiu a, Zhenyu Lin a, *
a
MOE Key Laboratory for Analytical Science of Food Safety and Biology, Fujian Provincial Key Laboratory of Analysis and Detection Technology for Food
Safety, College of Chemistry, Fuzhou University, Fuzhou, 350116, China
b
College of Biological Science and Engineering, Fuzhou University, Fuzhou, Fujian, 350116, China
c
Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business University (BTBU), Beijing, 100048, China
d
State Key Laboratory of Environmental and Biological Analysis, Department of Chemistry, Hong Kong Baptist University, Hong Kong SAR, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A simple and sensitive photothermal

assay is developed for quantitative
detection of H2S.

The photothermal conversion prop-
erties of Au@Ag nanocube can be
changed by the addition of H2S.

The molecular detection can be
translated into a simple temperature
test.

This method can be applied to detect
H2S around dumps with a simple
sample pretreatment.

a r t i c l e i n f o a b s t r a c t

Article history: Hydrogen sulfide (H2S), as a hazardous gas, is often found around dump areas. Long term exposure can
Received 11 September 2020 cause harm to health, it is highly necessary to develop some simple and sensitive methods for on-site H2S
Received in revised form detection. Herein, a convenient photothermal assay has been designed for the quantitation of H2S using a
31 December 2020
handheld thermometer as readout. Au@Ag nanocubes (Au@Ag NCs), a core-shell nanocomposite with
Accepted 6 January 2021
Available online 12 January 2021
strong light absorption at ~450 nm, was chosen as a novel photothermal agent in this study. Under the
laser irradiation at 450 nm, the Au@Ag NCs show a strong photothermal effect, and a significant tem-
perature enhancement can be measured by the thermometer easily. The presence of H2S can lead to the
Keywords:
Au@Ag nanocubes
deposition of sulfur onto Au@Ag NCs, altering the localized surface plasmon resonance absorption, size,
Hydrogen sulfide surface composition, and morphology of Au@Ag NCs and hence leading to the reduction of photothermal
Photothermal effect effect. The change of the temperature has a linear relationship with the H2S concentration in the range of
Temperature 0.5e80.0 mM with a detection limit of 0.35 mM. By combining with simple sample purification proced-
Thermometer ures, the developed method has been applied to detect H2S in garbage odor gas with satisfactory results.
© 2021 Elsevier B.V. All rights reserved.

* Corresponding author.
** Corresponding author. MOE Key Laboratory for Analytical Science of Food Safety and Biology, Fujian Provincial Key Laboratory of Analysis and Detection Technology for
Food Safety, College of Chemistry, Fuzhou University, Fuzhou, 350116, China.
*** Corresponding author.
E-mail addresses: luofang@fzu.edu.cn, zylin@fzu.edu.cn (F. Luo), lcuiying007@163.com (C. Lin).

https://doi.org/10.1016/j.aca.2021.338211
0003-2670/© 2021 Elsevier B.V. All rights reserved.
Y. Tao, Y. Lin, F. Luo et al.
1. Introduction
Hydrogen sulfide (H2S) is one of the highly toxic environmental
pollutants [1e3]. Excessive H2S in the environment can cause the
paralysis of the human respiratory system, the impairment of brain
function, the loss of the sense of balance, even sudden death.
Consequently, the development of simple and sensitive technology
for H2S detection is of paramount importance. Commercial lead
acetate paper is widely used for the detection of H2S, however, it is
limited by the low sensitivity and the potential environmental
damage caused by the lead [4,5]. Fluorescence, electrochemistry,
chromatography, and electrochemiluminescence technologies have
been applied for H2S detection [6e10]. Although these methods are
sensitive and reliable, the bulk instruments and the experienced
operator are usually required, which limits the use in the resource-
poor areas.
Colorimetric method is one of the most used strategies for on-
site detection, which has been designed to detect H2S frequently
[11,12]. Au@Ag nanoparticles, with tunable optical properties that
can be affected by the size, component, and surface coating, have
been widely used in the development of colorimetric methods for
H2S detection owing to the reaction between Ag and sulfur in the
presence of oxygen [13e15]. For example, an analytical approach
was developed for H2S, which was based on H2S-induced shifting of
localized surface plasmon resonance (LSPR) absorption peak of
Au@Ag nanorods [16]. A rapid color analysis was reported for the
reliable detection of H2S using the Au@Ag nanosphere as a probe
[17]. However, these methods only can achieve the qualitative or
semi-quantitative detection of H2S. The quantitative detection of
H2S still relies on large instruments, which is high-cost and non-
portable (as shown in Table S1). Many efforts are still needed for
the development of new quantitative detection strategies for H2S
with easily available readout.
In this study, a photothermal detection system has been
developed to detect H2S using a simple thermometer as readout.
The reaction between Au@Ag NCs and H2S leads to the change in
LSPR absorption and light-to-heat transition efficiency of Au@Ag
NCs. An obvious temperature variation of the Au@Ag NCs can be
measured with the addition of H2S, providing a novel and simple
quantitative method for H2S using a thermometer as readout.
Moreover, this photothermal assay is expanded for the detection of
H2S around dumps with the assistance of simple purification
procedures.
2. Experimental section
2.1. Materials and chemicals
The chloroauric acid tetrahydrate (HAuCl4$4H2O), cetyl-
trimethylammonium bromide (CTAB), cetyltrimethylammonium
chloride (CTAC) were purchased from Sinopharm Chemical Reagent
(Shanghai, China). Sodium borohydride (NaBH4) and sodium sul-
fide nonahydrate were acquired from Aladdin (Shanghai, China).
Ascorbic acid (AA) was purchased from Sigma-Aldrich (Shanghai,
China). All other reagents were of analytical reagent grade.
2.2. Instruments
The UVevisible absorption spectrum was obtained by a micro-
plate spectrophotometer (Multiskan GO, Thermo Scientific, USA).
The transmission electron microscopy (TEM) images were acquired
on a Tecnai G2 F20 STWIN microscope. High angle annular dark
field-scanning transmission electron microscopy (HAADF-STEM)
images and elemental mapping images were obtained from the FEI
Talos F200S microscope. The temperatures were measured by a
2
Analytica Chimica Acta 1149 (2021) 338211
portable digital thermometer (CIE 305 P). The hand-held laser
(450 nm, 1 W) was purchased from OXLasers Electronics Co., Ltd.
(Shanghai, China).
2.3. Synthesis of AuNPs and Au@Ag NCs
The synthesis of Au@Ag NCs was based on early literature with a
slight modification because of the difference in the reagents and
materials [18]. The slight modification refers to that the AuNPs for
the preparation of Au@Ag NCs are synthesized in a different
method. In this study, AuNPs were prepared according to the pre-
vious work [19,20]. In brief, the HAuCl4 solution (100 mL, 0.25 mM)
was heated to 120  C for 30 min under continuous stirring. Then
sodium citrate solution (10 mL, 1%) was added and heated at 120  C
for 20 min. Before being used, the prepared AuNPs were centri-
fuged and washed three times with CTAC (20 mM). To synthesize
the Au@Ag NCs, the above prepared AuNPs (3.0 mL) was mixed
with CTAC (7.0 mL, 20 mM), then AA (3.0 mL, 100 mM) was intro-
duced. The solution was reacted at 60  C for 20 min under stirring.
Subsequently, AgNO3 (0.6 mL, 10 mM) was introduced to the
mixture and held at 60  C for another 3 h. Then the mixed solution
was naturally cooled to room temperature. After centrifugation
(5000 rpm, 10 min) and washed three times, the Au@Ag NCs were
collected for future study. Before use, the prepared Au@Ag NCs
(3.0 mL) was mixed with 1% (v/v) Tween-80 (30 mL).
2.4. Photothermal assay for H2S
A simple process was applied for the photothermal assay of H2S
using a split tube and a polytetrafluoroethylene (PTFE) membrane.
The tube was split into two parts, and the top half part was com-
bined with the PTFE membrane. Au@Ag NCs solution was dropped
on the PTFE membrane, only allowing gas to pass through and
insulate the water. H2S standard solution with different concen-
tration was freshly prepared using Na2S as the source. Na2S solution
was added to the bottom of the tube, followed by the addition of
H2SO4 (10 mL, 0.5 mM, pH 3.0) to generate H2S. Then the split tube
was integrated and sealed immediately. H2S was evaporated from
acid solution and trapped in the Au@Ag NCs solution on the PTFE
membrane [12]. Subsequently, Au@Ag NCs solution that was reac-
ted with H2S on the PTFE membrane was transferred into the
photothermal assay device. The total volume was set as 200 mL in
each assay to avoid the influence of different volumes on the
photothermal measurement. With the irradiation of the laser, the
temperature change of the system was measured by a handheld
thermometer.
2.5. Collection and purification of samples
Gas samples were collected from the garbage station at Fuzhou
University (Fuzhou, China). The collection procedures were the
same as those in the reported work [21,22]. Briefly, the gas was
extracted using an air pump (2 L min 1) for 10 min. By this means,
the H2S gas could react with NaOH to form Na2S. The solution was
transferred into the bottom of a split tube with a PTFE membrane.
Other procedures were the same as those mentioned above. Then,
the concentration of H2S measured by our method was compared
with that obtained by a commercial H2S kit. The commercial H2S kit
was obtained from Hangzhou Lohand Biological Co. Ltd (Hangzhou,
China), and the batch number is 8307230.
Y. Tao, Y. Lin, F. Luo et al.
3. Results and discussion
3.1. Principle of the photothermal assay system
Scheme 1 shows the principle of the designed photothermal
assay system for H2S and the photograph of the photothermal assay
device. Under the laser irradiation at 450 nm, the Au@Ag NCs show
a great photothermal effect, transferring the light energy to heat
energy efficiently and hence resulting in the sharp temperature
increase that can be measured by a hand-held thermometer easily.
In the presence of H2S, Ag can bind to S2, leading to the formation
of Ag2S (Ksp ¼ 6.3  1050). The reaction equation is as follows
(4Ag þ 2 S2 þ O2 þ 2H2O / 2 Ag2S þ 4OH). The generated Ag2S
changes the surface composition of Au@Ag NCs, inducing a
decrease of the LSPR absorption peak of nanoparticles at 450 nm. As
the photothermal effect of nanoparticles is governed by the light
absorption, the addition of H2S weakens the photothermal effect of
Au@Ag NCs under the laser at 450 nm, leading to a decrease in
temperature enhancement. The degree of the decrease strongly
relies on the concentration of the added H2S. Thus, the quantifi-
cation of H2S can be converted to a measurement of temperature,
and a convenient photothermal assay system can be established for
H2S using a common thermometer as readout.
As shown in Figure S1, TEM was used for the characterization of
the morphology and structure of the Au@Ag NCs before and after
the reaction with H2S. Moreover, to confirm the composition
changing of the Au@Ag NCs after the addition of H2S, HAADF-STEM
and elemental mapping were employed to analyze the distribution
of elements. Those result implied that the addition of H2S leads to
the deposition of sulfur onto Au@Ag NCs and changes the
morphology and structure of Au@Ag NCs [23e27]. In addition, the
effect of the non-specific aggregation on the photothermal effect of
Au@Ag NCs was tested. As shown in Figure S2, the addition of
Tween-80 can avoid the change of photothermal effect of Au@Ag
NCs caused by non-specific aggregation. Meanwhile, the presence
of Tween-80 did not affect the change of photothermal effect of
Au@Ag NCs caused by the addition of H2S.
Scheme 1. (A) Schematic mechanism of the nanoparticles-based photothermal detection system for H2S. (B) Photograph of the photothermal assay system.
3
Analytica Chimica Acta 1149 (2021) 338211
3.2. Feasibility study
Previous literature has demonstrated that the photothermal
effect of nanoparticles is strongly dependent on the plasmon
resonance wavelength, particle volume, shell coating, and assembly
[28]. In this study, the detection mechanism is based on the
different photothermal effect of Au@Ag NCs before and after reac-
tion with H2S. Au@Ag NCs showed strong light absorption at
450 nm, leading to a high light-to-heat conversion efficiency under
the laser irradiation at 450 nm. However, after reaction with H2S,
the LSPR absorption at 450 nm was weakened, subsequently
resulting in a decrease of photothermal effect of Au@Ag NCs. The
changes in the photothermal effect were reflected by the different
temperature changes under the laser irradiation. As the change of
temperature could be decreased by the addition of H2S to the sys-
tem, a photothermal assay for H2S was developed by correlating the
H2S concentration with temperature changes. Simple control as-
says were performed to test the feasibility of the designed
nanoparticles-based photothermal assay for H2S detection. The
UVevis spectrum was obtained to characterize the Au@Ag NCs
before and after mixing with H2S (Fig. 1A). The synthesized Au@Ag
NCs showed a strong absorption peak at 450 nm (curve a). How-
ever, after reaction with H2S, the absorption value of the mixed
solution at around 450 nm decreased (curve b). Besides, the ab-
sorption peak was slightly red shift. The decrease and red-shift of
the absorption peak at around 450 nm may probably because of the
formation of Ag2S on the surface of Au@Ag NCs, as the LSPR ab-
sorption peak of nanoparticles is governed by the size, morphology,
and composition of nanoparticles [29e31]. Then the difference of
the photothermal effect of the nanoparticles was tested. As pre-
sented in Fig. 1B, an obvious temperature enhancement was
observed in Au@Ag NCs solution under the laser irradiation (curve
a). But after reaction with H2S, the temperature enhancement
decreased greatly (curve b). The results imply that the addition of
H2S can effectively alter the photothermal effect of Au@Ag NCs,
which can be applied in the photothermal assay of H2S. Moreover,
the long-term stability of Au@Ag NCs was tested during the irra-
diation with laser and the addition of H2S. As shown in Figure S3,
under the irradiation with laser, the temperature of Au@Ag NCs
Y. Tao, Y. Lin, F. Luo et al.
Fig. 1. (A) UVevis absorption spectra of Au@Ag NCs before and after the addition of H2S. (B)Temperature comparison between Au@Ag NCs before and after addition of H2S during
the irradiation for 5 min. (C) The optimization of the dosage of the volume of Au@Ag NCs.
increased at the first 4 min and then reached a plateau. When the
irradiation was prolonged, no significant temperature decrease was
observed from 4 to 10 min, suggesting that Au@Ag NCs have suf-
ficient stability in the photothermal assay (curve a). Similarly, the
long-term stability of Au@Ag NCs upon the addition of H2S was
tested. The addition of H2S did weak the photothermal effect of
Au@Ag NCs; however, under the relatively long-term irradiation, no
temperature decrease was observed in time intervals of 4e10 min,
suggesting that Au@Ag NCs have sufficient stability in photo-
thermal assay (curve b).
3.3. Optimization of experimental conditions
To obtain the best analytical performance, experimental con-
ditions were optimized. In the above assay (Fig. 1B), the tempera-
ture of the system reached a plateau after the 4 min of laser
irradiation. Hence, the temperature value recorded at 4 min was
used for the next study. The dosage of Au@Ag NCs was optimized
because it may affect the temperature change range of the system
and the sensitivity of detection. As shown in Fig. 1C, the change of
temperature enhancement (DT, defined as the difference of the
temperature change before and after the addition of H2S) was
utilized to study the effect of the various dosages of Au@Ag NCs.
The total volume under the irradiation was fixed as 200 mL, and the
concentration of H2S was set as 40 mM. The value of DT was low
when the dosage of Au@Ag NCs was less than 5 mL, which is
probably because the low dosage of Au@Ag NCs only can absorb
small amount of light energy, resulting in insignificant temperature
changes even when H2S was not added. However, when the dosage
of Au@Ag NCs was higher than 5 mL, the DT decreased with the
increased dosage. This is probably because the excessive use of
Au@Ag NCs causes strong light-to-heat conversion, and the influ-
ence of the H2S on the light-to-heat conversion of Au@Ag NCs is
weakened. Hence the dosage of Au@Ag NCs is a key factor for the
sensitive detection of H2S. The maximum DT was obtained when
the dosage was 5 mL, hence 5 mL of Au@Ag NCs was used for the
following study.
3.4. Performance of the developed photothermal assay system
The analytical performance of this photothermal detection
system was tested under the optimized experimental conditions.
The temperature changes in our assay were obtained from the
light-to-heat energy conversion. The principle of this study lies in
that the Au@Ag NCs have different photothermal effects before and
after the reaction with H2S. The Au@Ag NCs can effectively absorb
laser at 450 nm; however, after the reaction with H2S, the Au@Ag
4
Analytica Chimica Acta 1149 (2021) 338211
NCs has week absorption at 450 nm. As shown in Fig. 2A, owing to
the strong light-to-heat energy conversion of the Au@Ag NCs under
the irradiation with a 450 nm laser, the temperature of Au@Ag NCs
changed from 25  C to 55  C when the H2S was not added (0 mM).
The temperature of the system decreased with the growing con-
centrations of H2S. There was a linear relationship between the DT
and the logarithm of H2S concentration in the range of 0.5e80 mM
(Fig. 2B). The corresponding linear regression equation was
DT ¼ 6.032 lg CH2S þ 4.52 (R2 ¼ 0.998) and the limit of detection
(LOD) was 0.35 mM (S/N ¼ 3). LOD was calculated based on the
traditional and typical approach reported in the previous reference.
[32] The detail can be found in Supporting Information. Without
the use of bulk instruments, the sensitivity of this designed method
for H2S is comparable to that in previous reported literature
[11,33e35]. The target-induced nanoparticles color change was
usually used to design the colorimetric analysis method. However,
as obtained in the inset of Fig. 2B, the color change induced by the
H2S was not obvious when the concentration of H2S was too close
(e.g. 2.0 and 5.0 mM), whereas the DT measured by the hand-held
thermometer had obvious difference, which enables the accurate
quantitation of the target. Besides, compared with the common
colorimetric method for H2S, the consumption of nanoparticles in
this work is much smaller because of the strong photothermal ef-
fect of Au@Ag NCs.
The selectivity of this photothermal system for H2S detection
was evaluated by using common ions (F, Cl, Br, HCO2 2
3 , CO3 ,
2 þ þ 2þ 2þ
SO4 , NH4 , K , Ca , Mg ) and common substances in garbage
odor gas (CH3SH, H2O2, SO2) as interferences [36]. The concentra-
tion of interferences was 0.15 mM, which is 10 times higher than
that of H2S. As shown in Fig. 3, the addition of H2S resulted in an
obvious temperature change, while the introduction of other sub-
stances led to insignificant temperature changes. In addition, the
highest tolerate concentrations of these interferences were deter-
mined, in which the relative error in measurement of H2S con-
centration was lower than 5.0%. The highest tolerate concentration
for F, Cl, Br, HCO2 2 2 þ þ 2þ 2þ
3 , CO3 , SO4 , NH4 , K , Ca , Mg , and H2O2
was 0.1 M. This is probably because a simple sample purification
procedure is initially used to avoid the interference of other com-
pounds. The samples containing interference are firstly dissolved in
NaOH solution, and H2SO4 is subsequently added to release H2S. In
this process, most interferents are dissolved in NaOH, absorbed by
H2SO4, or converted into other substances. Only H2S can be released
and reacted with photothermal agents. The highest tolerate con-
centrations for CH3SH andSO2 was 0.2 mM and 0.4 mM, respec-
tively. This phenomenon is probably because the solubility of sulfur
dioxide (11.3 g/mL) and methyl mercaptan (2.33 g/mL) is larger
than that of H2S (0.385 g/mL) at room temperature. Thus, the H2S is
Y. Tao, Y. Lin, F. Luo et al. Analytica Chimica Acta 1149 (2021) 338211

Fig. 2. (A) Temperature comparison of Au@Ag NCs with different H2S concentrations during the irradiation for 5 min (from the curve a to g, the concentration of H2S is 0, 0.5, 2, 5,
15, 40, 80 mM). (B) Calibration curve for quantification of the H2S concentration. Insets are the photographs of the samples.

was tested. The samples were collected and purified with simple
procedures mentioned in section 2.5. As shown in Table 1, the H2S
concentration value measured by the photothermal detection sys-
tem was consistent with that measured by the commercial H2S kit.
Moreover, in the recovery assay, the recovery rates were varied in
95.0e101.0% and the relative standard deviations (RSDs) were
lower than 5.0%. Besides, the proposed method was compared with
gas chromatography for the real gas sample detection as shown in
Table S2. The results indicated that these two methods are in
agreement with each other.

4. Conclusion

In summary, a convenient photothermal assay has been devel-

Fig. 3. (A) Selectivity of the proposed photothermal assay towards H2S.
easier to be released from solution and reacted with Au@Ag NCs.
Although high concentrations of sulfur dioxide and methanol may
affect the measurement of H2S, this method provides enough
selectivity in our practical application, because that H2S has been
identified as a major contributor to odors at landfills among the
sulfur compounds [37].
3.5. Application in real samples analysis
To investigate the performance of the designed photothermal
detection system in complex samples, the H2S in garbage dump gas
oped for H2S based on the photothermal effect variation of Au@Ag
NCs. The different temperature changes of Au@Ag NCs caused by
the addition of H2S can be measured by a thermometer, thus
enabling it possible to transform the target molecular recognition
into a simple temperature measurement. This method shows some
advantages including low cost, portability, high selectivity, and
sensitivity. This simple and portable photothermal assay may
provide an excellent platform for the in-situ quantitative detection
of H2S and shows great potential to ensure environmental safety,
especially in areas lacking large equipment and skilled personnel.
CRediT authorship contribution statement
Yingzhou Tao: Conceptualization, Methodology, Investigation,
Writing - original draft. Yisheng Lin: Investigation. Fang Luo:
Software, Project administration, Writing - review & editing. Caili
Fu: Validation. Cuiying Lin: Formal analysis. Yu He: Software.
Zongwei Cai: Formal analysis, Visualization. Bin Qiu: Visualization.
Zhenyu Lin: Resources, Writing - review & editing, Supervision.

Table 1
Determination of H2S in the garbage odor gas samples (n ¼ 3).

Sample Found in the concentrated solution Corresponding concentration in gas samplesa Detected by a commercial kit Added Total found Recovery RSD
(mM) (ppb) (mM) (mM) (mM) (%) [%]

1 9.1 20.4 9.3 10.0 18.7 96.0 3.9

2 9.4 21.0 9.5 10.0 18.9 95.0 4.2
3 10.2 22.8 10.4 10.0 20.3 101.0 4.5
a
The total volume of the collected gas sample was 20 L. The amount of H2S dissolved in NaOH solution was detected firstly and then converted to the gas concentration.

5
Y. Tao, Y. Lin, F. Luo et al.
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.
Acknowledgment
This project was financially supported by National Science
Foundation of China (91843301, 21904020, 21775026), the Sciences
Foundation of Fujian Province (2018J05018, 2018J01685,
2018J01682), “Thirteenth Five-Year Plan” Marine Economy Inno-
vation and Development Demonstration Project (Grant No.
FZHJ19), China Postdoctoral Science Foundation Funded Project
(2020M671933). This project was financially supported by the
Open Project Program of Beijing Key Laboratory of Flavor Chemis-
try, Beijing Technology and Business University (BTBU), Beijing
100048, China (Grant no.: SPFW2019YB04).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.aca.2021.338211.
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