Article

Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX pubs.acs.org/IC

NH2‑MIL-53(Al) Metal−Organic Framework as the Smart Platform for

Simultaneous High-Performance Detection and Removal of Hg2+
Liang Zhang,† Jing Wang,† Ting Du,† Wentao Zhang,† Wenxin Zhu,† Chengyuan Yang,† Tianli Yue,†
Jing Sun,‡ Tao Li,§ and Jianlong Wang*,†
†
College of Food Science and Engineering, Northwest A&F University, 22 Xinong Road, Yangling 712100, Shaanxi, China
‡
Qinghai Provincial Key Laboratory of Qinghai-Tibet Plateau Biological Resources, Northwest Institute of Plateau Biology, Chinese
Academy of Sciences, 23 Xinning Road, Xining 810008, Qinghai, China
§
Shaanxi Institute for Food and Drug Control, Xi’an 710065, China
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*
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ABSTRACT: The worsening pollution due to mercury species makes it

inevitable to explore prospective versatile materials, which not only can detect
mercury ions (Hg2+) with high sensitivity but also possesses efficient capture
and removal ability. In this study, a series of classic organic ligand-based
luminescence MOFs materials with high oxidation state central metals (Al3+,
Zr4+, Cr3+, Fe3+, and Ti4+) were synthesized and were screened to achieve
simultaneously Hg2+ detection and removal through the strong coordination
of amino groups or nitrogen centers with Hg2+ and the intrinsic fluorescence
intensity of MOFs regulated by the ligand-to-metal charge transfer (LMCT)
effect. Among these checked materials, NH2-MIL-53(Al) exhibited the
excellent ability for Hg2+ detection with wide response interval (1−17.3 μM),
low detection limit (0.15 μM), good selectivity, wide pH adaptation (4.0−10.0), and strong anti-interference ability. Meanwhile,
the resultant NH2-MIL-53(Al) possessed an efficient removal capability toward Hg2+, accompanied by a fast uptake kinetics
(within 60 min) and large loading capacity (153.85 mg g−1). Furthermore, NH2-MIL-53(Al) also displayed satisfactory stability
before and after Hg2+ treatment because of the formation of strong coordination bonds between high oxidation state aluminum
(Al3+) and organic carboxylate ligands. Notably, the prepared NH2-MIL-53(Al) had no significant loss of adsorption
performance even after being reused four times. All of these superior properties render the smart NH2-MIL-53(Al)
nanohexahedron a great potential for simultaneous Hg2+ detection and removal from water.

1. INTRODUCTION the quantitative determination of Hg2+.9−11 As another parallel

Environmental pollution derived from multiple heavy metal
ions has caused the increasing public health problem globally.1
In particular, mercury ions, as a highly toxic carcinogen, are
distributed in a wide range of water environments because of
natural sources such as volcanic emissions and various
anthropogenic activities including mining operations, coal
burning, battery production, electronics manufacturing, and
waste incineration.2−4 With its nonbiodegradable and extreme
bioaccumulation, Excessive exposure to Hg2+ can trigger a
series of deadly diseases such as minamata, renal failure,
acrodynia, nervous disorder, and immune system dysfunction
even at low concentrations.5−7 Furthermore, the trans-
membrane ability and lipid solubility of organic mercury
formed by the reaction of Hg2+ with microorganisms in water
environment make it more harmful to living systems than
inorganic species.8 Considering the above deleterious con-
sequences of Hg2+, it is imperative but extremely challenging to
explore a new methodology for simultaneously detecting and
removing this toxicant. To date, numerous efforts have been
made to establish various rapid detection approaches including
fluorescence, colorimetric, and electrochemical methods for
branch, a series of remediation techniques, such as
precipitation, ion-exchange, nanofiltration, and adsorption
have been employed in Hg2+ removal.12,13 Alternately, by
virtue of some unique advantages including eco-friendliness,
simple operation, and cost-effectiveness, fluorescence sensing
and adsorption as promising technologies have attracted wide
attention in the field of monitoring and segregation of various
pollutants.14,15 In fact, a large number of reported materials can
show only one function as either sensing or adsorption. In
contrast, it is obviously favorable to integrate these two
functions into one body, but this is often overlooked. For
instance, using such a versatile material will not only facilitate
independent adsorption/detection operations but also improve
the remediation efficiency and achieve cost-effectiveness.16,17
Therefore, exploiting an intelligent material that integrates
both detection and removal function for efficient Hg2+ control
is very significant.
Received: April 27, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.inorgchem.9b01242

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Inorganic Chemistry Article

Metal−organic frameworks (MOFs), as an emerging class of Scheme 1. Synthetic Routes of the Five Selected Water-
microporous crystalline compounds composed of organic Stable MOF Materials
ligands and central metals, could be a good candidate to
integrate detection and adsorption into one body with many
distinct advantages.18−20 First of all, the large specific surface
area significantly increases the interaction probability of targets
and materials, thereby greatly enhancing the effective capture
of the target pollutants and further facilitating the removal
efficiency.21,22 Second, the inherent porous structure and a
well-developed pathway can accelerate the mass transport
process, which gives the MOFs a short response time and high
capture efficiency.17,23 Accordingly, the pre-enrichment of
MOFs toward targets by virtue of its connected channels will
be responsible for the improvement of detection sensitivity.24
In particular, the tailorability of organic ligands or metal
centers in MOFs provides a prerequisite for the introduction of
needed functionality,25,26 which not only ensures that desired
fluorophore can be successfully grafted into the interior and
surface of MOFs for sensing27,28 but also makes it possible to
integrate specific identification and efficient removal for
analytes.27−29 All of these characteristics indicate that MOF
materials are the most promising platforms for simultaneous
Hg2+ sensing and removal.
Until now, the reported sensing and trapping mechanism of
most MOFs toward Hg2+ be summarized as follows: (i) the
coordination of amino groups or nitrogen centers with Hg2+;
(ii) the soft−soft interaction between sulfur-rich probes and
Hg 2+ .4 Although sulfur-rich probes exhibit reasonable the different degrees of LMCT effect, controlled by the
selectivity and sensitivity, the drawback is the inability to category of central metals in MOFs. In detail, various central
provide a suitable response in the presence of large amounts of metals in these MOF materials may result in different degrees
Hg2+, which is a hindrance for its practical application.30 In this of electron transfer efficiency due to their different electron-
regard, amino-modified MOFs may be attractive. In fact, a acquisition abilities and thus lead to a difference in
range of amino-decorated MOFs such as NH2−Zn-MOFs, fluorescence intensity.17,40,41 Consistently, NH2-MIL-53(Al)
NH2−Ln-MOFs, and NH2−Cd-MOFs have been designed possesses the optimal Hg2+ detection performance in aqueous
and been applied to sensing various targets with excellent media with wide linear interval, low detection limit, good
sensitivity.31−33 Meanwhile, the strong coordination between selectivity, and excellent antijamming capability. Meanwhile,
amino groups and Hg2+ may give amino-based MOFs the the qualified Hg2+ adsorption capacity was verified by various
potential as smart adsorbents to achieve simultaneously Hg2+ adsorption experiments, in which the isothermal and kinetics
detection and removal. Furthermore, the inherent fluorescence reveal its large loading capacity and high adsorption efficiency
intensities of materials not only affect the detection perform- for Hg2+, respectively. The good water stability and reusability
ance but also determine the cost-effectiveness. Actually, were verified through SEM, XRD, and BET analysis and
although most MOF materials are built based on the same consecutive adsorption−desorption experiment, indicating the
luminescent organic ligand, they show different fluorescence feasibility of practical application of prepared NH2-MIL-
intensities at the same concentration. The ligand-to-metal 53(Al). Furthermore, the possible mechanisms for Hg2+
charge transfer (LMCT) effect can explain this phenomenon, detection and adsorption were also discussed via UV spectrum,
in which the differential Lewis acidity and empty orbital fluorescence lifetime imaging, FT-IR, and XPS analysis.
numbers of various central metals can induce the differ-
ent degrees of electron withdrawal from the organic ligands, 2. RESULTS AND DISCUSSION
thus resulting in different fluorescence intensities.34−36 In this 2.1. Preparation and Characterization. The selected
view, the ideal fluorescence performance of MOFs may be five classic organic ligand-based luminescence MOFs were
tailored by choosing the right high oxidation state center metal. synthesized based on the traditional solvothermal or hydro-
Furthermore, the formation of strong coordination bonds thermal methods with some modifications. The XRD analysis
between high oxidation state metals and organic carboxylate was carried out to explore the crystal structures. As illustrated
ligands can improve the stability of MOFs, which makes it in Figure S1, the XRD patterns of obtained five materials well
possible for practical applications.37−39 matched with the simulated one, indicating that well-defined
Herein, five classic organic ligand-based luminescence MOF crystal structures were formed and the materials were
materials with high oxidation state central metals (Al3+, Zr4+, successfully prepared.42−46 Considering the fluorescence
Cr3+, Fe3+, and Ti4+) were synthesized via traditional quenching process of Hg2+ detection, the strong fluorescence
hydrothermal or solvothermal methods with partial modifica- intensities of materials are a prerequisite for their superior
tions and were screened for the Hg2+ detection and removal detection capability. Therefore, the intrinsic fluorescence
from water (Scheme 1). Among the five prepared MOFs, the intensities of above MOFs were measured at the same
obtained NH2-MIL-53(Al) shows the strongest fluorescence concentration. The results presented in Figure 1a implied
characteristic under the same concentration, which is related to that prepared NH2-MIL-53(Al) possesses the strongest
B DOI: 10.1021/acs.inorgchem.9b01242
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Inorganic Chemistry Article

Figure 1. (a) Fluorescence emission spectra of five selected MOFs at the same concentration (1 × 10−3 mg L−1). (b, c) Overall and magnified SEM
images of NH2-MIL-53(Al). (d) Corresponding elemental mappings of the Al, C, O, and N.

Figure 2. (a) Fluorescence quenching rates of five prepared MOF materials after treatment with the same concentration of Hg2+ (50 and 200 mg
L−1). (b) Comparison of adsorption properties of five obtained MOFs.

Figure 3. (a) Fluorescence emission spectra of NH2−H2BDC and NH2-MIL-53(Al) at 330 nm excitation under the same concentration. (b)
Optimization of the excitation wavelength of NH2-MIL-53(Al). (c) pH effect on the fluorescence intensity of NH2-MIL-53(Al). (d) Fluorescence
stability of the NH2-MIL-53(Al) (1 × 10−3 mg L−1).

fluorescence intensity compared to other four MOF materials, MOFs.40,44 In detail, various central metals (Al3+, Zr4+, Cr3+,
which may be determined by the different degrees of LMCT Fe3+, and Ti4+) in these MOF materials may result in different
effect, controlled by the category of central metals in degrees of ligand-to-metal electron transfer efficiency due to
C DOI: 10.1021/acs.inorgchem.9b01242
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Inorganic Chemistry Article

Figure 4. (a) Fluorescence intensities of the NH2-MIL-53(Al) suspension (1 × 10−3 mg L−1) upon adding different concentrations (0−997 μM) of
Hg2+ at 330 nm excitation. (b) Corresponding Stern−Volmer fitting curves of NH2-MIL-53(Al) toward Hg2+ (the inset represents the linear
response range). (c) Selectivity and anti-interference capability of NH2-MIL-53(Al) for Hg2+ detection (the light blue bars represent the
fluorescence intensity ratio of NH2-MIL-53(Al) solution in the presence of different metal ions (2.0 equiv); the navy blue bars mean the
fluorescence intensity ratio of the above NH2-MIL-53(Al) solution after adding Hg2+ (1.0 equiv)).

their different electron-acquisition abilities thus lead to a
difference in fluorescence intensity.34−36 Further, based on the
positive relationship between fluorescence lifetime and
electron transfer efficiency, the fluorescence lifetimes of the
five prepared materials were measured.47−49 The results
presented in Table S1 suggested that the NH2-MIL-53(Al)
has a shortest average fluorescence lifetime, indicating its
lowest ligand-to-metal charge transfer efficiency. Therefore, the
NH2-MIL-53(Al) may possess the strongest fluorescence
intensity, which are consistent with the experimental results
(Figure 1a). Inspired by the ideal fluorescence characteristics
of NH2-MIL-53(Al), further characterizations were performed
to explore the morphology. As displayed in Figure 1, parts b
and c, the prepared NH2-MIL-53(Al) shows a three-dimen-
sional hexahedral structure with good uniformity and an
average size of about 600 nm. The distribution of different
elements in this material was also mapped by EDX and the
results showed the characteristic elements (C, O, N, and Al)
are uniformly distributed throughout the material area (Figure
1d).
2.2. Screening of the Optimal MOF for Hg 2+
Detection and Removal. Considering the differences in
Hg2+ detection and removal capabilities of five prepared
MOFs, relevant comparative experiments were conducted to
select the optimal one for simultaneous Hg2+ detection and
removal. First, the fluorescence quenching rates of these MOFs
under the same concentration of Hg2+ treatment were
calculated. The results presented in Figure 2a demonstrated
that the NH2-MIL-53(Al) possesses an optimal Hg2+ detection
performance among the five prepared MOFs, which is
consistent with its strongest fluorescence intensity. Further-
more, the Hg2+ adsorption properties of five selected MOFs
were also compared by measuring the maximum adsorption
capacity in the same concentration of Hg2+. As displayed in
Figure 2b, these MOFs exhibited a superior Hg2+ adsorption
performance by virtue of the strong coordination between
amino groups and Hg2+.1,50 In detail, there are still minor
differences in adsorption performance between prepared
materials, which could be derived from their dispersibility
and specific surface area. Notably, despite the optimal Hg2+
adsorption properties of NH2−UiO-66(Zr) in checked MOF
materials, poor Hg2+ detection performance seriously hinders
its application in the field of simultaneous Hg2+ detection and
removal. In contrast, the NH2-MIL-53(Al) not only possesses
the optimal Hg2+ detection performance, but also shows
satisfactory Hg2+ adsorption capacity. All of these results
D DOI: 10.1021/acs.inorgchem.9b01242
indicated that prepared NH2-MIL-53(Al) can be an intelligent
platform for simultaneous Hg2+ detection and removal from
water.
2.3. Optical Properties of NH2 -MIL-53(Al). The
emission spectra of NH2−H2BDC linker and NH2-MIL-
53(Al) were collected to explore the luminescence properties.
As depicted in Figure 3a, the pure ligand showed a strong
emission peak at 427 nm (λem = 330 nm), which is derived
from π → π* electron transitions of the benzene ring.51
Furthermore, the NH2-MIL-53(Al) showed similar emission at
427 nm based on the same excitation, indicating that its
fluorescence characteristics may be attributed to the organic
ligand component. However, the fluorescence intensity of
NH2-MIL-53(Al) was slightly weaker than that of the ligand at
the same concentration, which is caused by LMCT effect.52
Moreover, it is not difficult to found that the optimal excitation
wavelength of this MOF was 330 nm (Figure 3b). The pH
effect on the luminescence performance of this material was
also investigated by monitoring the fluorescence intensity
change under different pH (1.0−14.0). The results presented
in Figure 3c showed an almost unchanged fluorescence
intensity in the pH range of 4.0−10.0, which suggested that
the NH2-MIL-53(Al) possesses excellent pH-independent
fluorescence characteristics in the range of pH = 4.0−10.0
and the results are consistent with amino modified MOFs
reported in previous literatures.53,54 Considering that Hg2+
ions usually exist as precipitates under alkaline conditions (pH
= 7.0−14.0) and the Hg2+ detection is implemented under a
weak acid environment (pH = 5.0−6.0) in this work, the NH2-
MIL-53(Al) can well meet the Hg2+ detection requirements
and the results are not affected by the pH environment.
Furthermore, the excellent fluorescence stability of NH2-MIL-
53(Al) was demonstrated by the fluorescence intensity without
significant change despite being placed in solution for 7 days
(Figure 3d). These remarkable properties motivate us to
explore its application in the field of fluorescence detection.
2.4. Hg2+ Detection Capability of NH2-MIL-53(Al). To
further investigate the potential Hg2+ sensing behavior of NH2-
MIL-53(Al), related fluorescence quenching experiments were
performed under different Hg2+ concentrations. As displayed in
Figure 4a, the NH2-MIL-53(Al) displayed strong fluorescence
intensity without Hg2+, whereas obvious fluorescence quench-
ing was observed after adding Hg2+ in NH2-MIL-53(Al)
solution. Furthermore, it was also demonstrated by visual color
change of the solution under UV light irradiation (the inset in
Figure 4a). In detail, the fluorescence intensity decreased
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Inorganic Chemistry
gradually along with increasing Hg2+ concentration (1−997
μM). Besides this, the quenching effect was further evaluated
by the Stern−Volmer equation: I0/I = 1 + KSV[M], in which I0
and I represent the luminescence intensity of material in the
absence and presence of analyte, respectively. [M] means the
molar concentration of target, and KSV is the Stern−Volmer
constant, which is related to the slope of I0/I versus [M] plot.
As presented in Figure 4b, the obtained Stern−Volmer plots
obeyed a good linear fitting (R2=0.993) in the low Hg2+
concentration range (1−17.3 μM). Furthermore, the limit of
detection (LOD) was calculated via the following equation:
LOD = 3SD/m, where SD means the standard deviation of
blank measurement, and m represents the slope of linear plot.
The calculated values of LOD and KSV are 0.15 μM and 5.7 ×
104 M−1 based on the above experimental results, which is
comparable to most of the reported materials.55−57 All of these
results suggest that prepared NH2-MIL-53(Al) material is an
attractive sensor for Hg2+ detection and highlight its great
application potential for the determination of Hg2+.
2.5. Selectivity and Anti-Interference Ability of NH2-
MIL-53(Al) for Hg2+ Detection. Considering the complexity
and feasibility of practical application environment, the specific
identification of analytes and excellent antijamming ability are
also necessary criteria to ensure that the material becomes an
ideal sensor. Thus, the Hg2+ detection selectivity of NH2-MIL-
53(Al) was studied by separately monitoring the effects of
different metal ions (Li+, K+, Na+, Ni2+, Co2+, Ca2+, Pb2+, Cd2+,
Zn2+, Mn2+, and Mg2+) on the fluorescence intensity. As shown
in Figure 4c, Hg2+ ions exhibited optimal fluorescence
quenching ability and resulted in a final fluorescence intensity
that is about two-fifths of the initial fluorescence intensity.
Furthermore, although Ni2+ and Pb2+ can cause a certain
fluorescence quenching at higher concentrations (2.0 equiv),
most of the interfering ions showed a negligible effect on the
fluorescence intensity of NH2-MIL-53(Al), suggesting its
qualified selectivity for Hg2+ detection. Meanwhile, the
competition experiments were performed by adding various
interference ions (2.0 equiv) to the NH2-MIL-53(Al) solution
containing Hg2+ (1.0 equiv) to explore its anti-interference
ability for Hg2+ detection. As presented in Figure 4c, it can be
found that the prepared material had no significant change in
the response to Hg2+ despite the presence of various interfering
ions, further suggesting that the prepared NH2-MIL-53(Al)
sensor possesses an excellent antijamming capability.
The possible Hg2+ detection mechanism was explored by
collecting UV−vis spectrum of Hg2+ and fluorescence
spectrum of the NH2-MIL-53(Al). As shown in Figure 5a,
Figure 5. (a) UV−vis absorption spectra of Hg2+ and fluorescence
spectra of NH2-MIL-53(Al) (I means the UV−vis absorption spectra
of Hg2+; II and III represent the excitation and emission spectra of
NH2-MIL-53(Al)). (b) Fluorescence decay curves of NH2-MIL-
53(Al) in the presence and absence of Hg2+.
E DOI: 10.1021/acs.inorgchem.9b01242
Article
the absorption band of Hg2+ has a broad overlap with the
excitation band of NH2-MIL-53(Al), which suggests that the
fluorescence quenching process could take place via the inner
filter effect (IFE) or fluorescence resonance energy transfer
(FRET).58,59 For further exploration, the lifetime decay curves
of NH2-MIL-53(Al) before and after Hg2+ treatment were
measured under the pulsed excitation of 330 nm (λem = 427
nm). As displayed in Figure 5b, there was some change in the
fluorescence lifetime with adding Hg2+. In detail, the average
fluorescence lifetime values of this material in the presences of
different concentrations of Hg2+ were calculated as 9.57, 7.89,
and 7.25 ns, respectively (Table S2). All of these results
suggested that the FRET may dominate the fluorescence
quenching process.60
2.6. Hg2+ Adsorption Properties of NH2-MIL-53(Al).
Compared to specific recognition and accurate detection,
efficient removal of contaminants to reduce the harm is the
ultimate goal of environmental governance. Therefore, relevant
adsorption experiments were implemented to investigate the
Hg2+ removal efficiency of prepared NH2-MIL-53(Al). We
consider that the pH of target solution not only affects the
functional groups of adsorbents but also determines the
existence form of target. The adsorption ability of NH2-MIL-
53(Al) toward Hg2+ within a pH range from 1.0 to 7.0 was
explored as a result of the fact that Hg2+ ions are unstable
under alkaline solution. As illustrated in Figure 6a, the
adsorption capacity of NH2-MIL-53(Al) increases significantly
with rising pH, and optimal adsorption performance was
achieved at pH = 6.0. However, the prepared adsorbent
showed a poor adsorption amount at low pH (1.0−2.0). This
phenomenon is derived from the protonation of the amino
groups thus leading to the formation of positive charges, and
the competition between the H+ and Hg2+ in low pH solution.
At higher pH values, the amino group of NH2-MIL-53(Al) is
ionized, which reduces electrostatic repulsion and enhances
competitive adsorption of Hg2+.61,62 In this view, subsequent
experiments were completed at pH = 6.0.
The kinetic adsorption experiments were carried out at
ambient temperature (25 °C) to explore the relationship
between treatment time and adsorption capacity, in which the
amount of adsorbent was 0.25 g L−1 and the initial Hg2+
concentrations were 50, 100, and 300 mg L−1, respectively. As
illustrated in Figure 6b, there is a sharp increase in the
captured amount of Hg2+ in the first 10 min and the loading
reaches 96% of the maximum loading capacity at the different
initial Hg2+ concentrations. Adsorption equilibrium was
quickly reached in 60 min, and the corresponding maximum
adsorption values of 55.33, 89.67, and 141.61 mg g−1 were
observed, separately. Thus, the equilibrium adsorption time
was set to 2 h for all adsorption experiments. For further
exploration, different kinetic models were applied to assess the
obtained experimental data. The results displayed in Figure 6c
indicated that the pseudo-second-order model can better fit
the kinetic data with high correlation coefficients (R2 = 0.991,
0.984, 0.987) under different initial Hg2+ concentrations, and
the related parameters were summarized in Table S3, which
suggested that the chemisorption dominates the Hg 2+
adsorption process.63 Moreover, the diffusion mechanism was
further studied through the intraparticle diffusion model. As
illustrated in Figure S2, the plots of qt versus t1/2 possesses two
linear segments with different slopes, in which the first stage
means the boundary layer diffusion and the second stage with a
lower slope is interpreted as the rate-limiting by internal Hg2+
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Inorganic Chemistry Article

Figure 6. (a) The pH effect on the removal capacity of NH2-MIL-53(Al) toward Hg2+. (b) Kinetic study of NH2-MIL-53(Al) toward Hg2+ under
various initial Hg2+ concentrations (50, 100, and 300 mg L−1). (c) Corresponding linear fitting curves via the pseudo-second-order kinetic model.
(d) Langmuir isotherm of prepared NH2-MIL-53(Al) toward Hg2+ under different temperature conditions (298, 308, and 318 K). (e)
Corresponding linear fitting curves of Langmuir model. (f) Four consecutive adsorption−desorption cycles of NH2-MIL-53(Al) toward Hg2+ (200
mg L−1).

diffusion. However, the plots did not pass through the origin,
implying that the intraparticle diffusion is a participator to limit
the rate of Hg2+ adsorption but not the only rate-determining
step.64,65
Isotherm adsorption experiments were performed under the
different temperatures to further explore the Hg2+ adsorption
process. As presented in Figure 6d, the Hg2+ uptake capacity is
increasing with the increase of initial Hg2+ concentration and
the Hg2+ ions can be almost completely removed (96%) by the
prepared NH2-MIL-53(Al) when the original concentration is
below 10 mg L−1. Further, the obtained isotherm data were
evaluated via the different isotherm models. The results
presented in Figure 6e and Table S4 showed that the Langmuir
model can be better match with the isotherm data with the
high correlation coefficients (R2 = 0.963, 0.943 and 0.995)
under the different temperatures, indicating that the monolayer
chemisorption dominates the adsorption process and the active
sites of obtained NH2-MIL-53(Al) are uniformly distrib-
uted.66−68 Furthermore, the calculated maximum adsorption
capacity of NH2-MIL-53(Al) toward Hg2+ is 153.85 mg g−1,
which is comparable to most existing adsorbents (Table S5).
The superior adsorption performance may benefit from large
specific surface areas, well-developed pore channels, and
abundant active sites.
2.7. Recyclability and Stability of NH2-MIL-53(Al).
Good reusability and stability are a prerequisite for the
practical application of adsorbents. Thus, the regeneration and
recycling performance of NH2-MIL-53(Al) was explored by
observing the uptake capacity change during continuous
adsorption−desorption cycles, in which 0.1 M HCl solution
containing 10% thiourea was used as the eluent. As presented
in Figure 6f, it can be observed that the capture capacity of this
adsorbent only lost less than 10% even after four cycles,
suggesting the excellent reusability of prepared NH2-MIL-
53(Al) for Hg2+ adsorption. To further explore the reasons for
the loss of some adsorption capacity, XPS analysis of Hg2+-
loaded NH 2-MIL-53(Al) before and after elution was
F DOI: 10.1021/acs.inorgchem.9b01242
implemented, and the results illustrated in Figure S3 and
Table S6 indicated that although the Hg2+-loaded NH2-MIL-
53(Al) was eluted three times with the eluent, about 8.63% of
the loaded Hg2+ was not eluted and occupied some of the
binding sites, which is a good explanation for the decreased
loading capacity of NH2-MIL-53(Al) as the number of cycles
increases. Furthermore, various characterizations were tested
to evaluate the stability of NH2-MIL-53(Al). First, the XRD
was tested under different pH conditions. As presented in
Figure S4, the similar XRD patterns of NH2-MIL-53(Al) were
observed even it was treated for 8 h under different pH
conditions (pH = 1.0−14.0), suggesting the excellent acid−
base stability, which may be derived from the strong
coordination between organic carboxylate ligands and high
oxidation state aluminum (Al3+).14 Second, the hexahedral
morphology was well maintained after Hg2+ adsorption as
demonstrated by the SEM (Figure S5). Further, the N2
adsorption−desorption isotherms of NH2-MIL-53(Al) before
and after Hg2+ treatment were also tested to explore the
stability of microstructure. The results presented in Figure S6
and Table S7 showed that the pore volume and specific surface
area of this material after Hg2+ treatment were only slightly
reduced due to the large loading of Hg2+, indicating its good
water stability. Finally, the similar XRD patterns of NH2-MIL-
53(Al) before and after Hg2+ treatment further indicated the
excellent stability of crystalline structure (Figure S7). All the
results suggested that selected NH2-MIL-53(Al) not only
possesses excellent recyclability but also exhibits superior
stability, which endows it with great potential for practical
application in water decontamination.
To explore the possible adsorption mechanism, the EDS,
FT-IR, and XPS spectra of this adsorbent before and after Hg2+
treatment were collected. The elemental mappings indicated
that Hg2+ ions were present and evenly distributed in the NH2-
MIL-53(Al) (Figure S8), initially suggesting that Hg2+ ions
were adsorbed by prepared NH2-MIL-53(Al). As displayed in
Figure 7a, the N−H peaks of NH2-MIL-53(Al) at 3498, 3383,
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Inorganic Chemistry
Figure 7. (a) FT-IR curves of NH2-MIL-53(Al) before and after Hg2+
treatment. (b) XPS spectra of NH2-MIL-53(Al) before and after Hg2+
adsorption.
and 1647 cm−1 were weakened to varying degrees after Hg2+
adsorption, which suggests the excellent Hg2+ adsorption
property could be related to the strong coordination between
amino groups and Hg2+. The results were further proved by
XPS analysis. As presented in Figure 7b, the appearance of Hg
4f peaks after adsorption indicated that Hg2+ ions were
successfully loaded on the adsorbent. In detail, the peaks of Hg
4f7 and Hg 4f5 were located at 101.7 and 105.7 eV (Figure
S9a), respectively, which had a remarkable shift compared to
the purified Hg2+ binding energies as previously reported (Hg
4f7, 99.9 eV; Hg 4f5, 103.9 eV).69 This phenomenon implied a
strong affinity between Hg2+ and NH2-MIL-53(Al), which is
consistent with FT-IR result. Furthermore, the N 1s spectrum
showed that a new peak was observed at 400.57 eV after Hg2+
adsorption (Figure S9b), which probably due to the interaction
between N and Hg2+.70 The above results suggested that the
superior Hg2+ adsorption performance of NH2-MIL-53(Al) is
derived from its amino groups.
3. CONCLUSION
In summary, five amino-based MOFs with high oxidation state
central metals based on the same luminescent organic ligand
have been successfully fabricated and were screened for
simultaneous detection and removal of toxic Hg2+. In
particular, the prepared NH2-ML-53(Al) not only can be
utilized as a smart optical probe for Hg2+ detection with fast
response time, high sensitivity, good selectivity, wide pH
adaptation, and strong anti-interference ability but also exhibits
superior adsorption performance toward Hg2+, accompanied
by a large loading capacity and high adsorption efficiency as a
result of the strong coordination between amino groups and
Hg2+. In particular, the adsorption process can accelerate the
preconcentration of Hg2+, which can increase the sensitivity of
Hg2+ detection. Furthermore, the excellent water stability and
reusability highlight its feasibility in complicated environ-
mental samples. The above collective features prove that
resulting NH2-ML-53(Al) is a promising platform for
synchronous detection and segregation of Hg2+ from water
environment, providing a new perspective on monitoring water
quality and treating wastewater.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b01242.
Experimental section (materials, equipment, synthetic
method; experimental operation for detection and
G DOI: 10.1021/acs.inorgchem.9b01242
Article
adsorption); XRD patterns; parameters of kinetic and
isotherm adsorption; XPS spectra; SEM images; SEM-
mapping images; data for N2 adsorption−desorption
isotherms; table of comparison of adsorption properties;
intraparticle diffusion curves; and table of average
fluorescence lifetime (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*(J.W.) E-mail: wanglong79@yahoo.com.
ORCID
Jianlong Wang: 0000-0002-2879-9489
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was financed by the National Natural Science
Foundation of China (No. 21675127), the Shaanxi Provincial
Science Fund for Distinguished Young Scholars (2018JC-011),
the Development Project of Qinghai Provincial Key Labo-
ratory (No. 2017-ZJ-Y10), and Capacity Building Project of
Engineering Research Center of Qinghai Province (2017-GX-
G03).
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I DOI: 10.1021/acs.inorgchem.9b01242
Inorg. Chem. XXXX, XXX, XXX−XXX