Temperature Self-compensated Fiber-Optic Pb (II) Sensor with Improved

Selectivity By Resorcylaldehyde Post-Modified Organic Metal Framework

ed
Fang-Fei Shi,1 Ling-Xin Kong,1,* Wei-Zhun Dong,1 Ying Liang,2 Kun-Shan Yang,1
1Optical Fiber Based Intelligent Sensing and Micromachines Laboratory, Yantai University, Yantai 264005, China

iew
2Department of Optoelectronic Information Science and Engineering, Jiangsu University, Zhenjiang, 212013, China.
Corresponding author Email:[email protected]

Abstract: Post-modification of metal-organic framework (MOF) materials is an effective means to enhance

their efficient and selective adsorption for heavy metal ion. In this article, we presented a reflection-type

v
optical fiber surface plasmon resonance (SPR) sensor based on dual core fiber (DCF) coated with UiO-66-

re
RSA (UiO-66-NH2 post-modified with resorcinol aldehyde) film for the specific detection of Pb (II) in
aqueous media. The composite material UiO-66-RSA exhibits stronger affinity and specificity for Pb (II) than
UiO-66-NH2. The adsorption of Pb (II) can change the equivalent refractive index (RI) of UiO-66-RSA film,
er
causing a regular shift in SPR spectra. Experiments have shown that the limit of detection (LOD) of the SPR
Pb (II) sensor can reach 0.1 nM. Meanwhile, research has found that the SPR sensor is accompanied by
pe
temperature crosstalk of 0.356 nm/°C. Therefore, we constructed a Michelson temperature interferometer
using polymer micro tips on the end face of the fiber core to achieve temperature compensation. Based on the
above two sensing channels, dual parameter demodulation of Pb (II) concentration and temperature can be
ot

achieved with an error rate of less than 0.5 %. This article has potential research value in exploring the
application of post modification techniques of MOF in fiber optic lead ion detection.
tn

Keywords: Optical fiber sensor, Metal organic framework, Post modification, Lead ion, Temperature
rin
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 1. Introduction

Lead ions are highly toxic, non-degradable and can be deposited in living organisms, leading to serious

ed
environmental problems and posing a threat to human and animal health [1-2]. Although traditional lead ion
detection methods [3], including stripping voltammetry, atomic absorption spectroscopy, atomic emission
spectroscopy and so on, can achieve sensitivity and selectivity analysis of lead ions. However, their expensive

iew
instruments, long detection cycles, and the need for professional personnel limit their application in on-site
detection [4]. Therefore, developing in-situ, fast, real-time, and accurate methods for detecting heavy metal
ions is of great significance. In recent years, fiber optic sensing technology has become a hot research direction
in the field of heavy metal ion detection, which has advantages such as high sensitivity, high integration,

v
carrying electromagnetic interference, and multi-point deployment control. The optical fiber lead ion sensors

re
have been proposed and studied for over a decade [5]. Before 2015, lead ion detection was mainly achieved
by combining fluorescent materials with optical fibers in the field of fiber optic sensing [6]. Subsequently,
with the development of fiber optic devices and sensitive materials, research on fiber optic lead ion sensors is
er
also constantly advancing. The currently reported fiber optic devices for lead ion sensors include fiber gratings
[7], Mach-Zehnder interferometer [8], microfiber resonators [9], U-shaped fibers [10] and so on, while the
pe
sensitive materials include black phosphorus [11], L-glutathione [12], polydopaminemaleic acid [13], maleic
acid [14] and so on. The above research indicates that although the sensitivity of optical fibers for detecting
lead ions has greatly improved, how to improve the selectivity of sensors remains a challenge in research [15].
ot

Optical fiber heavy metal ion sensors based on MOF materials [16] have been a hot research topic in recent
years. MOFs have unique advantages in heavy metal ion adsorption and specific recognition : 1) The pore
tn

structure increases the contact area and interaction between the host structure and guest molecules, which is
conducive to the adsorption and pre enrichment of heavy metal ions; 2) The large specific surface area, diverse
metal centers, and organic ligands provide a large number of active sites for the specific recognition of heavy
rin

metal ions; 3) It is also easy to achieve specific detection requirements by introducing various functional
groups or post-modifications with other functional materials. Among them, UiO-66-NH2 has good water
stability, excellent porosity and large specific surface area, providing sufficient adsorption sites to effectively
ep

capture heavy metal ions [17]. Therefore, heavy metal ion sensors based on UiO-66-NH2 composite materials
have been widely reported in recent years [18]. In 2019, Fu et al. proposed a new modified material UiO-66-
Pr

RSA, which exhibits significantly better selectivity towards lead ions than UiO-66-NH2 [19]. We introduced
this new synthetic MOF material into fiber optic devices.
In this article, we proposed a reflective DCF-SPR sensor as a fixed carrier for UiO-66-RSA. When Pb (II)
2

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 is enriched and selectively adsorbed, the RI of the UiO-66-RSA film changes, leading to a change in the phase
of the SPR spectrum. The LOD of the SPR sensor obtained by phase demodulation of spectra can reach 0.1

ed
nM. The two fiber cores embedded in the DCF form Michelson interference and utilize laser-induced polymer
tips on the end face to enhance its temperature sensitivity. Based on the above two sensing channels, the sensor
can achieve detection of Pb (II) concentration and temperature compensation. The research content of this

iew
article aims to explore the potential application of MOF post modification technology in enhancing selectivity
in fiber optic lead ion detection, as well as methods for compensating for temperature crosstalk.

2. Structure and Preparation

v
2.1 Synthesis of UiO-66-RSA

re
Firstly, dissolve 5.5 g of ZrCl4 and 5 g of H2BDC-NH2 in a mixture of 4 ml of H2O, 50 ml of HCOOH, 0.5
ml of HCl, and 250 ml of N, N-dimethylformamide (DMF), and then react at 130 °C for 24 hours. At the end
of the reaction, the crystals were recovered by centrifugation and washed with DMF. Then, dry the crystal in
er
an 80 °C oven for 12 hours to obtain UiO-66-NH2. Add 4.0 g of UiO-66-NH2 and 4.0 g of resorcinol aldehyde
to anhydrous ethanol and react at 70 °C for 24 hours. After the reaction is completed, separate and wash the
remaining solid with anhydrous ethanol and distilled water. Finally, the solid after washing was dried at 80 °C
pe
for 12 hours to obtain UiO-66-RSA. Break the N-H bond in UiO-66-NH2 and the N bond is attached to
resorcinol aldehyde. Addition of -OH to the molecule. Fig.1 (a) shows the molecular structure of UiO-66-
RSA. The excellent adsorption capacity of UiO-66-RSA for Pb (II) depends on -OH and -N. DMF, HCOOH
and ZrCl4 were purchased from Aladdin Instruments Corporation. Resorcyl aldehyde, 2,5-
ot

Diaminoterephthalic acid and HCl were purchased from Tianjin Ruijinte Chemistry Co. Ltd.

2.2 Preparation of Fiber Sensor

tn

Fig.1 (b) shows that the sensor consists of a SMF-MMF-DCF-microtip structure. The single-mode fiber
(SMF) has a cladding and core diameter of 125 μm and 9 μm, respectively. The multimode fiber (MMF) has
a cladding and core diameter of 125 μm and 100 μm, respectively. The length of MMF is 1 mm, which is an
rin

optimized length for reference. The DCF consists of two fiber cores: a central single-mode fiber core and a
biased dual-mode fiber core, as shown in Fig.2(c). The diameter of central single-mode fiber core is 5.5 μm.
The diameter of biased dual-mode fiber core is 8.5 μm. The distance between the two fiber cores is 30 μm.
ep

These two fiber cores construct a Michelson interferometer. In order to enhance the temperature response of
Michelson interference, we assembled a micropillar with a diameter of 15 μm on the end facet of dual-mode
fiber core. A layer of silver film with a thickness of 1-2 μm is sputtered onto the end face of the optical fiber
Pr

to isolate humidity. A layer of nano-gold film was deposited on the surface of MMF, and a layer of UiO-66-
RSA was grown on the surface of the gold film, as shown in Fig.1 (c). Step-1: The gold film coated fiber is
immersed in a solution of 4-carboxyphenyl azomethane sulfonate for 15 min. The diazo salts can generate free
3

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 radicals and react with gold bonds to graft onto the surface of the gold film. Step-2: Soak the dried fibers in
UiO-66-RSA solution, remove them, wash with DMF and chloroform, and dry at room temperature, as shown
in Fig.2 (e). Step-3: Finally, the sensor is placed in a lead ion aqueous solution, and the UiO-66-RSA surface

ed
adsorbs a large amount of lead ions.

v iew
re
er
pe
ot
tn

Fig.1 (a) Schematic diagram of UiO-66-RSA structure; (b) Sensor structure diagram; (c) Fiber Optic Surface Coating
Process.

2.3 Structural Characterization

rin

Fig. 2 is a partial physical image of the fiber optic sensor. Fig. 2 (a) is the microscope image of a fiber after
it has been coated with a gold film. Fig. 2 (b) is the image of the microtip under the microscope. Fig. 2 (c) is
the microscopic image of the DCF end face. Fig. 2 (d) and Fig. 2 (e) are the electron microscope images of
ep

the UiO-66-NH2 crystals and UiO-66-RSA crystals, respectively. Fig. 2 (g) shows the FTIR spectral features
of UiO-66-NH2 before modification. The vibrational peaks appeared at 1636 cm-1, 3299 cm-1 and 3416 cm-1,
proving that UiO-66-NH2 was synthesized efficiently. Fig. 2 (h) shows that the vibrational peak of the
Pr

hydroxyl group appeared at 3321 cm-1 and the vibrational peak of the -NH2 group disappeared, which indicated
that our modification of UiO-66-RSA was successful. Fig. 2 (f) shows the electron microscopy image of UiO-
66-RSA on the surface of optical fibers. Pb (II) ion is a soft acid, while UiO-66-RSA is a soft base. According

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 to the HSAD theory, weak acids are more likely to react with soft bases. Meanwhile, UiO-66-RSA contains
N and O atoms in its functional groups after replacing NH2 with RSA, which can form stable chelates with Pb
(II). The bond lengths of O-Pb and N-Pb are 2.308 Å and 2.217 Å, respectively. Therefore, UiO-66-RSA is

ed
more selective towards Pb (II) than UiO-66-NH2.

v iew
re
er
pe
ot

Fig.2 (a) Microscopic image of gold film coated dual core optical fiber; (b) Microscopic image of microtip on the end facet
tn

of dual core optical fiber; (c) DCF end face; (d-e) Electron micrograph of UiO-66-NH2 and UiO-66- RSA; (f) Electron
micrograph of UiO-66-RSA after growth on fiber, the image in the upper right corner shows the thickness of the UiO-66-
RSA; (g-h) Infrared spectra of UiO-66-NH2 and UiO-66-RSA.
rin

3. Design of Optical Fiber SPR Lead Ion Sensor

3.1 Sensing Mechanism of Optical Fiber SPR Lead Ion Sensor

ep

The sensor consists of two channels: the Michelson temperature interferometer and the SPR lead ion sensor.
The SPR lead ion sensor can be explained by a three-layer Kretschmann model this paper. Transmission light
generates evanescent waves on the cladding surface of the DCF, which can be divided into s-light propagating
Pr

along the surface and p-light vertically penetrating. Among them, p-light can also excite surface plasmon
resonance. The incident wave vector component of p-light in the x-direction is expressed as kx. The x-direction

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 wave vector of the surface plasma wave of the metal film layer is expressed as ksp. When kx is equal to ksp, it
will cause resonance of the plasma on the metal surface [20]:

ed
  1 2
kx  1 sin    ksp (3)
c c 1   2

𝜀0, 𝜀1, and 𝜀2 are the dielectric constants of the optical fiber, the gold film, and the UiO-66-RSA,

iew
respectively. 𝜔 is the angular frequency, 𝜃 is the angle of incidence, 𝑐 is the speed at which light propagates
in a vacuum. According to Fresnel's formula, the reflection coefficient of p-light in SPR sensor can be obtained
[20]:
2

v
2 r01  r12 exp(2ik1z d gold )
r  r012  (4)
1  r01r12 exp(2ik1z d gold )

re
 0 k1z  1k0 z
r01  (5)
 0 k1z  1k0 z
1k2 z   2 k1z
r12  (6)
er 1k2 z   2 k1z
2
 
kiz     i  k02z , i  0,1, 2 (7)
pe
c

𝑟01, 𝑟12 are the reflectivity between the optical fiber and the gold film, and the reflectivity between the gold
film and the UiO-66-RSA, respectively. 𝑟012is the reflectivity between the three-layer structure of optical fiber,
gold film, and UiO-66-RSA. 𝑑𝑔𝑜𝑙𝑑 is the thicknesses of the gold film. 𝑘0𝑧, 𝑘1𝑧 and 𝑘2𝑧 are the wave vector
ot

components of optical fiber, gold film, and UiO-66-RSA, respectively. Based on the above analysis, it can be
concluded that the total reflection coefficient of p-light in SPR sensor is:
tn

M
1
R
M
r
j1
N
 I   (8)

The total number of reflections of light at the interface between the optical fiber and the gold film is set to
rin

N. M is the number of propagation modes. 𝐼(𝛼) is the energy distribution liked Gaussian. After determining
the light source and material, the main discussion is on the length L of the sensing area and the thickness dgold
ep

of the gold film of the sensor.

3.2 Experimental Analysis of Optical Fiber SPR Lead Ion Sensor

Pr

3.2.1 Experimental analysis of sensors coated with UiO-66-RSA

After optimization analysis, the thickness of the gold film was selected as 40 nm, and the length of the DCF
was selected as 10mm. Fig. 3 (a) shows the spectra of the SPR sensor before and after MOF coating, as well
6

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 as after MOF adsorption of lead ions. Fig. 3 (b) shows the entire time process of sensor gold plating, MOF
growth. Throughout the process, the SPR spectrum exhibited good MOF, and a red shift of the SPR peak was

ed
observed. After several experiments, the MOF growth time was finally determined to be 350 min, and the
thickness was 150 nm. Place the SPR sensor in different concentrations of lead ion aqueous solutions with a
concentration range of 0-100 nM, and observe the variation of resonance peak displacement over time until it

iew
reaches stability. Maintain the ambient temperature of the experimental solution at 25 °C. The response peak
shifts corresponding to different concentrations are basically stable after 60 seconds, as shown in Fig. 3 (c).
Four adsorption isotherms were used to investigate the experimental data (Freundlich, Langmuir, Temkin,

v
Dubinin-Radushkevich), and the Langmuir adsorption isotherm with the largest correlation coefficient was
finally selected, as shown in Fig. 3 (d). It indicates that the adsorption of Pb (II) by UiO-66-RSA is an

re
isothermal curve of monolayer adsorption. There are a certain number of lead ion adsorption sites on UiO-66-
RSA, and when all the adsorption sites are occupied, the adsorption rate reaches equilibrium with the
desorption rate. It can be seen that when the lead ion concentration is below 10 nM, the response line of the
sensor follows a linear pattern.
er
pe
ot
tn
rin
ep
Pr

Fig. 3 (a) Changes in spectra when coating the surface of optical fibers；(b) the entire time process of sensor gold plating,
MOF growth; (c) Wavelength shift versus time curves at different Pb (II) concentrations; (d) Langmuir adsorption isotherm
curve;
7

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 3.2.2 Comparison of sensors coated with UiO-66-RSA and sensors coated with UiO-66-NH2
As shown in Fig. 4 (a-b), we grew UiO-66-RSA and UiO-66-NH2 on the fiber surface, respectively. Two

ed
sensors were placed in the same concentration of lead ion solution for detection. The sensitivity of the sensor
with surface-grown UiO-66-NH2 to lead ions was only 0.943 nm/nM. Much lower than that of the sensor with
surface-grown UiO-66-RSA. The theoretical detection limit of the sensor with surface-grown UiO-66-RSA

iew
can reach to 0.046 nM when the spectrometer resolution is 0.2 nm. We further set the minimum concentration
of the solution to 0.1 nM. The purpose of this setting is to ensure the accuracy of the spectrometer reading.
The sensor undergoes a linear response of 4.176 nm/nM when the lead ion concentration is 0-0.5 nM. This

v
indicates that the actual LOD of the sensor is lower than 0.1 nM. Next, we conducted 10 repeated tests on the
sensor, and the results showed that the sensor's measurement results could maintain good stability, as shown

re
in Fig. 4 (c). Used 20 ml of thiourea and 0.5 ml of nitric acid as an eluent to remove lead ions adsorbed. The
sensor after adsorption of lead ions was placed in an eluent for 4 h and rinsed with deionized water. From the
figure, it can be noticed that at the seventh repetition, there is a decrease in the spectral shift. This may be due
er
to the shedding of UiO-66-RSA from the fiber during the elution process. From Fig. 4 (d), it can be seen that
the sensitivity is highest at pH =4. This is because when the pH value is low, there are a large number of
pe
hydrogen ions in the solution, and UiO-66-RSA reacts with the hydrogen ions in the solution, which affects
the adsorption of Pb (II) on the sensitive membrane. When the pH value of the solution is above 4, Pb (II) will
combine with -OH to form a precipitate. Fig. 4 (d-e) indicate that the sensor exhibits selectivity towards lead
ot

ions in both single and mixed ion solutions. It can also be seen that UiO-66-RSA is more selective for Pb (II)
than UiO-66-NH2.
tn
rin
ep
Pr

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 ed
v iew
re
er
pe
Fig .4 (a) Spectral curves of sensor coated with UiO-66-NH2 at different Pb (II) concentrations; (b) Spectral curves of
sensor coated with UiO-66-RSA at different Pb (II) concentrations; (c) Reusability of sensors; (d) Sensitivity at different pH
values; (e) Sensor selectivity test diagram; (f) Sensor selectivity in mixed solutions.

From Fig. 5 (a-b), it can be seen that temperature affects the position of the SPR resonance peak. When the
ot

temperature changes, the refractive index of the liquid undergoes a blue shift, which is due to the decrease in
refractive index of the UiO-66-RSA caused by the increase in temperature. Therefore, temperature
tn

compensation for sensors is very important. In the following content, we will describe the Michelson
temperature interferometer integrated into the SPR sensor.
rin
ep
Pr

Fig .5 (a) Temperature Effects on Sensors; (b) Linear fit of temperature to resonance peak position.

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 4. Design of Michelson Temperature Interferometer

4.1 Principles of Michelson Temperature Interferometer

ed
The sensor consists of two channels: the Michelson temperature interferometer and the SPR lead ion sensor.
When light enters the DCF from the MMF, light is divided into three paths for transmission: one path enters

iew
the middle core, one path enters the bias core, and the other path enters the cladding of DCF. In order to
enhance the temperature response of the Michelson interferometer, a polymer microtip was grown on the DCF
core by in situ growth method. Induced generation of polymer microtips at the end of optical fibers [21]. The
end of the sensor is deposited with a silver film with a thickness of approximately 1 µm as a reflector and

v
waterproof layer. The optical path of the two fiber cores forms Michelson interference, which can be expressed

re
as [22]:

I  I core 1  I core  2  2 I core 1 I core  2 cos  (9)

Where 𝐼𝑐𝑜𝑟𝑒―1 and 𝐼𝑐𝑜𝑟𝑒―2 are the total light intensity of the two core modes, respectively. 𝛷 is the phase
er
difference.
4
    n n   L  nmicrotip  H  (10)
  core 1 core  2
pe
𝜆 is the wavelength of the propagating light. L is the length of the DCF. H is the height of polymer microtip.
𝑛𝑚𝑖𝑐𝑟𝑜𝑡𝑖𝑝 is the refractive index of polymer. 𝑛𝑐𝑜𝑟𝑒―1 and 𝑛𝑐𝑜𝑟𝑒―2 are the refractive indices of the DCF fiber core
and side core, respectively. The core of a DCF grows a segment of microtip at the end of the core, which can
ot

effectively increase the optical path difference and improve the sensitivity of the sensor. The interference light
intensity reaches a minimum when the phase difference satisfies ∆Φ = (2𝑚 + 1)𝜋,(𝑚 = 0, ± 1, ± 2,⋯). At
tn

this point, the interference valley corresponds to a wavelength of [22]:

4
  ncore 1  ncore  2   L  nmicrotip  H  (11)
2m  1 
When the temperature around the sensor changes, due to the coefficient of thermal expansion of the fiber
rin

and the thermo-optic effect, the length of the fiber and the refractive index of the two cores change. At the
same time, this refractive index and height of the polymer change. The temperature sensitivity can be
ep

expressed as [22]:

 

T neff  L  nmicrotip  H
 H1  nmicrotip 2  (12)
Pr

∆𝑛𝑒𝑓𝑓 is the difference between the effective refractive indices of DCF cores. 𝛼1 =-4.5×10-4 RIU/°C and 𝛼2
=4.9×10-5 /°C are the thermo-optical coefficients and thermal expansion coefficients of the polymers,

10

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 respectively. Microtip length: H =150 μm. Δ𝑛𝑒𝑓𝑓 is too small to be ignored. The wavelength shift is calculated

to be: -0.43 nm/°C.

ed
4.2 Experimental Analysis of Michelson Temperature Interferometer
Firstly, the DCF length L and microtip height H of the sensor were optimized, as shown in Fig. 6. Firstly,
when there is no microtip (H =0), the occurrence of Michelson interference is due to the different parameters

iew
of the two fiber cores and the different modes transmitted. As the length of the DCF increases, the temperature
sensitivity of the Michelson interferometer is slightly improved, as shown in Fig. 6(b). Considering the
compactness of the structure, the length of the DCF is chosen to be around 10 mm. Then, we explored the
height H of the microtip on the DCF, as shown in Fig.6 (c-d). Experimentally obtained sensitivities do not

v
differ much from calculated results. When the external environmental temperature changes, it will cause

re
changes in the effective refractive index and volume of the polymer microtip, thereby affecting the optical
difference between the two beams entering the DCF. Its sensitivity to temperature increases with the height
of the microtip.
er
pe
ot
tn
rin
ep

Fig.6 (a) Interference spectra of the sensor for different DCF lengths; (b) Temperature sensitivity of sensors of different
lengths; (c) Interference spectra of sensors at different microtip heights; (d) Sensor sensitivity to temperature at different
Pr

microtip heights.
The optimization of the above sensors before the integration of SPR sensor. Next, we will test the integrated
dual channel sensor with the following parameters: DCF length: L =10 mm, gold film thickness of 40 nm,
11

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 microtips are made in three lengths: 126.4 μm, 151.3 μm, and 176.8 μm. Due to the Michelson interferometer
being embedded in the SPR sensor and protected by a silver film, theoretically it does not respond to changes
in lead ion concentration. From Fig. 7 (a-b), it can be seen that the sensor is not sensitive to lead ions. The

ed
temperature experimental results of this sensor are basically consistent with the previous analysis, as shown
in Fig. 7 (c-d). Considering the final length of the sensor, the microtip height was selected to be 151.3 μm.

v iew
re
er
pe
ot

Fig.7 (a) Effect of lead ion concentration on MI channels; (b) Sensitivity of different microtip heights to lead ion
tn

concentration; (c) Interference spectra of the sensor at different temperatures; (d) Temperature sensitivity of different
microtip heights.
5 Dual channel demodulation of Lead ion concentration and temperature
rin

The final parameters of the sensor are: DCF length: L =10 mm, Microtip height: H =151.3 μm, Gold film
thickness of 40 nm. The position of the resonance peak shifts in response to changes in the external
environment. When lead ion concentration and temperature are changed simultaneously, the wavelength shift
ep

of the MI and SPR inclination can be expressed in terms of a sensitivity matrix [23]:

 SPR   K SPR K SPR   T 

T C


    T   (13)
 MI   K MI K MI   C 
C
Pr

𝐾𝑇𝑆𝑃𝑅 and 𝐾𝐶𝑆𝑃𝑅 are temperature and lead ion concentration sensitivities of SPR channels. 𝐾𝑇𝑀𝐼 and 𝐾𝐶𝑀𝐼 are
the sensitivities of MI channels to temperature and lead ion concentration. As shown in Fig. 9 (a) and (b), the
SPR channel wavelength was shifted by 13.827 nm and the MI channel wavelength was shifted by -8.232 nm
12

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 when the temperature was varied from 20 °C to 40 °C and the concentration of lead ions was varied from 0
nM to 5 nM. In order to investigate the overall performance of the sensor while varying the lead ion
concentration and temperature. Morphing Eq. (13) gives Eq. (14)

ed
 T  1  K MI
C
 K SPR
C
  SPR 
 C   K T K C  K C K T  T T     (14)
  SPR MI   K MI K SPR   MI 
SPR MI 

iew
𝐾𝑇𝑆𝑃𝑅 =-0.356 nm/°C is the temperature sensitivity of the SPR channel, 𝐾𝐶𝑆𝑃𝑅 =4.176 nm/Nm is the lead ion
concentration sensitivity of the SPR channel, 𝐾𝑇𝑀𝐼 =-0.438 nm/°C is the temperature sensitivity of the MI
channel, 𝐾𝐶𝑀𝐼 =0.0423 nm/Nm is the lead ion concentration sensitivity of the MI channel. They are obtained
by bringing them into Eq. (14): ΔT =20.08; Δ𝐶 =5.023. The calculated error rate is: E (ΔT) =0.4 %; E (ΔC)

v
=0.46 %.

re
er
pe

Fig.9 (a) Changes in experimental spectra of SPR channels; (b) Changes in experimental spectra of MI channels.
ot

Due to the high sensitivity characteristics of the SPR sensor, this work performs better than other types of
fiber optic lead sensors, as shown in Table 1. The results show that the sensor not only has high sensitivity
tn

but also has unique advantages in terms of measurement accuracy.

Table 1. Compared with other optical fiber sensors.

Selective Temperature
rin

Structure Film Materials LOD Sensitivity

Comparison Compensation
U-shaped
Oxalic acid
optical fiber
functionalized 8.93nM -- NO NO
[10]
AuNPs
ep

Hybrid fiber
grating CCS-NGO/PAA 2.547
0.5 nM YES YES
(LPG+FBG) nanocomposite nm/nM
[7]
Mach-Zehnder
24.52 8.155 × 10-4 NO
Pr

interference smart hydrogel NO

nM nm/nM
[8]
Tapered
Polydopamine- 0.185
microfiber 8.1 nM YES NO
maleic acid nm/nM
interferometer
13

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 [13]

Michelson
4.176
interference UiO-66-RSA 0.1 nM YES YES
nm/nM

ed
and SPR.

5. Conclusion

iew
In this article, we have designed a dual parameter integrated fiber optic sensor, which includes an SPR lead
ion sensor and a Michelson temperature interferometer. The reflection-type optical fiber SPR sensor is coated
with UiO-66-RSA film for the specific detection of Pb (II) in aqueous media. The composite material UiO-
66-RSA exhibits stronger affinity and specificity for Pb (II) than UiO-66-NH2. Meanwhile, we constructed a

v
Michelson temperature interferometer based on the two built-in fiber cores by laser induced polymer microtip

re
on the central fiber core end face, which can effectively compensate for temperature crosstalk. Research has
shown that the fiber optic sensor proposed in this article provides a new solution for precise detection of lead
ions.
er
Acknowledgement
pe
This work was jointly supported by National Natural Science Foundation of China (NSFC) (62105278 and
62105307), Natural Science Foundation of Shandong Province under Grant No. ZR2021QF139, China Postdoctoral
Science Foundation (2023M741435), Doctoral Initiation Fund of Yantai University (Grant No. WL20B129).
ot

References
[1]. Y. Cai, J. Zhang, M. Zhang, M.H. Wang, Y. Zhao, The optical fiber sensing platform for ferric ions detection: A practical
application for carbon quantum dots, Sens. Actuators B-Chem. 364 (2022) 131857.
tn

[2]. P.Q. Zhu, J.J. Wang, F. Rao, C.Y. Yu, G.Y. Zhou, X.G. Huang, Differential Fresnel-reflection-based fiber biochemical
sensor with temperature self-compensation for high-resolution measurement of Cd2+ concentration in solution, Sens.
Actuators B-Chem. 282 (2019) 644-649.
[3]. Z. Chen, Z.Y. Zhang, J. Qi, J.M. You, J.P. Ma, L.X. Chen, Colorimetric detection of heavy metal ions with various
rin

chromogenic materials: Strategies and applications, J. Hazard. Mater. 441 (2023) 129889.
[4]. S. Bilge, L. Karadurmus, A. Sınağ, S. A. Ozkan, Green synthesis and characterization of carbon-based materials for
sensitive detection of heavy metal ions, Trends Analyt Chem.145 (2021) 116473.
[5]. N. Aksuner, Development of a new fluorescent sensor based on a triazolo-thiadiazin derivative immobilized in polyvinyl
ep

chloride membrane for sensitive detection of lead (II) ions, Sens. Actuators-B-Chem. 157 (2011) 162-168.
[6]. R.Y. Wang, X.H. Zhou, H.C. Shi, Triple functional DNA–protein conjugates: Signal probes for Pb2+ using evanescent
wave-induced emission, Biosens. Bioelectron. 74 (2015) 78-84.
[7]. S Ghosh, K Dissanayake, S. Asokan, T. Sun, B. M. Azizur Rahman, K. T. V. Grattan, Lead (Pb2+) ion sensor development
Pr

using optical fiber gratings and nanocomposite materials, Sens. Actuators-B-Chem. 364 (2022) 131818.
[8]. G.S. Li, Z. Liu, J.X. Feng, G.Y. Zhou, X.G. Huang, Pb2+ fiber optic sensor based on smart hydrogel coated Mach-Zehnder
interferometer, Opt Laser Technol. 145 (2022) 107453.
[9]. Y. Yin, S. Li, S. Wang, S. Jia, J. Ren, G. Farrell, E. Lewis, P. Wang, Ultra-high-resolution detection of Pb2+ ions using a

14

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448
 black phosphorus functionalized microfiber coil resonator, Photon. Res. 7 (2019) 622-629.
[10]. B. S. Boruah, R. Biswas, Localized surface plasmon resonance based U-shaped optical fiber probe for the detection of
Pb2+ in aqueous medium, Sens. Actuators-B-Chem. 276 (2018) 89-94.

ed
[11]. C. Liu, Z. Sun, L. Zhang, J. Lv, X.F. Yu, L. Zhang, X. Chena, Black phosphorus integrated tilted fiber grating for
ultrasensitive heavy metal sensing, Sens. Actuators-B-Chem. 257 (2018) 1093-1098.
[12]. S.H.K. Yap, Y.H. Chien, R. Tan, A.R. bin Shaik Alauddin, W.B. Ji, S.C. Tjin, K. T. Yong, An advanced hand-held
microfiber-based sensor for ultrasensitive lead ion detection, ACS Sens. 3 (12) (2018) 2506-2512.

iew
[13]. G.Q. Wang, D.D. Sun, L.L. Liang, G.J. Wang, J. Ma, Highly sensitive detection of trace lead ions concentration based
on a functional film-enhanced optical microfiber sensor, Opt Laser Technol. 161 (2023) 109171.
[14]. NV. Kumar, BS. Kavitha, S. Asokan, Selective detection of lead in water using etched fiber Bragg grating sensor, Sens.
Actuators-B-Chem. 354 (2022) 131208.
[15]. J.Y. Chu, B.B. Chu, C.Q. Lu, Q.H. Gu, W.Z. Li, R. Lin, J. Lu, X.G. Chen, Highly sensitive detection of lead ions and
cadmium ions based on UiO-66-NH2@carbon nanohorns composites enhanced by bismuth film in water environment, J.

v
Environ. Chem. Eng. 10 (2022) 108753.
[16]. Z.Q. Wang, H.Y. Ma, X.H. Yang, N. Copner Y.H. Jiang, K. Li, Ethanol sensor based on cascaded tapered optical fiber

re
with surface modification of ZIF-8, Sens. Actuators-B-Chem. 402 (2024) 135084.
[17]. Y.T. Qian, F.F. Zhang, D.J. Kang, H. Pang, A Review of Metal-Organic Framework-Based Compounds for
Environmental Applications, Energy Environ. Mater. 6 (2023) 12414.
[18]. C.W. Chang, Q. Xue, R Wang, Z.Y. Liu, Y. Liu, L. He, F. Liu, H.J. Xie, Development of a novel sensor based on Bi2O3
er
and carbonized UiO-66-NH2 nanocomposite for efficient detection of Pb (II) ion in water environment, Appl. Surf. Sci. 616
(2023) 156510.
[19]. L.K. Fu, S.X. Wang, G. Lin, L.B. Zhang, Q.M. Liu, H.H. Zhou, C.X. Kang, S.Y. Wan, H.W. Li, S. Wen, Post-
pe
modification of UiO-66-NH2 by resorcyl aldehyde for selective removal of Pb (II) in aqueous media, J. Clean. Prod. 229
(2019) 470-479.
[20]. L.X. Kong, Y. X. Zhang, W.G Zhang, Y.S. Zhang, T.Y. Yan, P.C. Geng, B. Wang, Lab-on-tip: Protruding-shaped all-
fiber plasmonic microtip probe toward insitu chem-bio detection, Sens. Actuators-B-Chem. 301 (2019) 127128.
[21]. G. Kostovski, P.R. Stoddart, A. Mitchell, The Optical Fiber Tip: An Inherently Light‐Coupled Microscopic Platform for
ot

Micro‐ and Nanotechnologies. Adv. Mater. 2014, 26(23):3798-3820.

[22]. J.T. Zhou, Y.P. Wang, C.R. Liao, B. Sun, J. He, G.L Yin, S. Liu, Z.Y. Li, G.J. Wang, X.Y. Zhong, J. Zhao, Intensity
modulated refractive index sensor based on optical fiber Michelson interferometer, Sens. Actuators-B-Chem. 208 (2015) 315-
tn

319.
[23]. Y.Q. Zhen, X.T. Tu, J.J. Zhu, Y.B. Tong, L.F. Liu, N. Yao, P. Wang, L.M. Tong, L. Zhang, Atomically Smooth Gold
Microflake-Enabled Fiber-Tip Fabry–Perot Interferometer for Temperature and Pressure Sensing, ACS Appl. Mater. Inter.
15(29) (2023)351161-35169.
rin
ep
Pr

15

This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4718448