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Robust Co(II)-Based Metal−Organic Framework for the Efficient

Uptake and Selective Detection of SO2
Valeria B. López-Cervantes,# Alfredo López-Olvera,# Juan L. Obeso,# Iván Kaleb Torres,
Eva Martínez-Ahumada, Paulina Carmona-Monroy, Elí Sánchez-González, Diego Solís-Ibarra,*
Enrique Lima, Elnaz Jangodaz, Ravichandar Babarao, Ilich A. Ibarra,* and Shane G. Telfer*
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sı Supporting Information

ABSTRACT: MUF-16 is a porous metal−organic framework comprising cobalt(II) ions and 5-

aminoisophthalate ligands. Here, we measured its reversible SO2 adsorption−desorption
isotherm around room temperature and up to 1 bar and observed a high capacity for SO2 (2.2
mmol g−1 at 298 K and 1 bar). The uptake of SO2 was characterized by Fourier transform
infrared (FT-IR) spectroscopy, which indicated hydrogen bonding between the SO2 guest
molecules and amino functional groups of the framework. The location and packing of the SO2
molecules were confirmed by computational studies, namely, density functional theory (DFT)
calculations of the strongest adsorption site and grand canonical Monte Carlo (GCMC)
simulations of the adsorption isotherm. Furthermore, MUF-16 showed a remarkable selective
fluorescence response to SO2 compared to other gases (CO2, NO2, N2, O2, CH4, and water
vapor). The possible fluorescence mechanism was determined by using time-resolved
photoluminescence. Also, the limit of detection (LOD) was calculated to be 1.26 mM
(∼80.72 ppm) in a tetrahydrofuran (THF) solution of SO2.

1. INTRODUCTION Thus, many strategies have been developed for SO2

An undesirable consequence of the exponential growth of remediation, 11 such as alkaline solutions for flue gas
industrial activities is the generation of air pollution, which desulfurization (FGD),12 ionic liquids (ILs),13 and classical
porous materials such as metal oxides,14 activated carbons,15
considerably compromises the air quality of our planet.1
and zeolites.16 Unfortunately, these technologies need high
Reducing air pollution is a priority activity since the constant
reactivation temperatures, which cause a loss of structure
retention of such contaminant gases in the atmosphere, from
stability and, therefore, considerably decrease their capture
different emission sources, leads to negative effects. This relates
capacity over multiple cycles.17 Additionally, in some cases, the
not only to Earth’s temperature, e.g., CO2 is strongly associated
chemisorption of SO2 occurs, which adds to the energy penalty
with the greenhouse effect,2 but also to environmental health
for regeneration.16
as sulfur-containing gases have severely toxic effects on
Metal−organic frameworks (MOFs) are a class of porous
humans.3 The burning of fossil fuels produces sulfur oxides.4
materials formed by metal centers and organic linkers such as
The sectors responsible for the largest emission of these
carboxylates and nitrogen-containing ligands.18 Certain MOFs
polluting gases are the energy and the metallurgical industries.5
have shown high SO2 capacities at 298 K and 1 bar. For
In addition, nonanthropogenic emissions caused by volcanic
example, MFM-300(M) (M = Al3+, In3+, Sc3+),19 MIL-
eruptions constitute approximately 30% of emitted sulfur
101(Cr)-4F(1%),20 strongly adsorb SO2. More recently, the
oxides.6 When combined with water, which is present in the
uptake capacity of Mg2(dobpdc) (dobpdc = 4,4′-dioxido-3,3′-
atmosphere, these compounds can cause acid rain, which
biphenyldicarboxylate) was shown to be exceptionally high
causes severe damage to structures and buildings.7 Addition- (19.5 mmol g−1).21 It is worth noting that high SO2 uptakes
ally, acid rain is responsible for the alteration of the sulfur are not the only key consideration in the field of environmental
cycle, causing the adsorption of heavy metals by plants.8 remediation; MOF materials with moderate to low SO2
Additionally, when humans are exposed to sulfur dioxide
(SO2), it can cause breathing difficulties. At high concen-
trations, it can produce irreversible intoxication, leading to Received: October 23, 2023
death.9 The concentration of SO2 over periods of 10 min must Revised: February 19, 2024
not exceed about 10 ppm, and the maximum regulated Accepted: February 21, 2024
concentration limits to protect health are 0.075 ppm for a 1 h Published: March 5, 2024
limit. Safety guidelines recommend a maximum concentration
in the range of 0.025−0.04 ppm for SO2 exposure over 24 h.10
© 2024 The Authors. Published by
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2735 Chem. Mater. 2024, 36, 2735−2742
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adsorption provide valuable information, particularly in the 2. EXPERIMENTAL SECTION

context of SO2 detection.22 2.1. Synthesis of MUF-16. A mixture of Co(OAc)2·4H2O (0.625
Small and low-cost SO2 gas detectors are crucial for the g, 2.5 mmol), 5-aminoisophthalic acid (1.8 g, 10 mmol), methanol
safety of workers who are exposed to various industrial (80 mL), and water (5 mL) was sonicated for 25 min in a sealed 1000
processes. Optical methods including ultraviolet (UV) mL Schott bottle, which was then heated in a preheated oven at 85 °C
absorption spectroscopy,23 mass spectrometry,24 multiaxis for 2 h under autogenous pressure. After cooling the oven to room
differential optical absorption spectroscopy (MAX-DOAS),25 temperature, the resulting pink crystals were isolated by decanting off
and emission (photoluminescence) spectroscopy (PL) have the mother liquor, washed with methanol several times, and dried
under vacuum at 130 °C for 20 h. Yield: 0.98 g (94% based on cobalt)
been used in the detection of SO2, allowing for real-time SO2 of guest-free MUF-16.
monitoring.26 A remarkable example of an MOF-based SO2 2.2. Instruments. Further details related to instrumental
detector was elegantly provided by Eddaoudi and co- techniques are presented in Section S1.
workers.27 In the first case using the MOF MFM-300 as a 2.3. Gas Adsorption Isotherms. The CO2 and SO2 adsorption
system that selectively detected SO2 versus CH4, CO2, NO2, experiments to measure absorbance capacity were performed on the
and H2 electrochemically, the device showed a detection limit Advantage One Dynamic Vapor Sorption (DVS) equipment of
of 5 ppb and exceptional cyclability.27 In another case, they surface measurement systems (SMS). The gravimetric capture of the
reported that KAUST-7 and KAUST-8 materials could be used gases was measured by placing a 23 mg sample of the material in a
for the selective capture and detection of SO2, also electro- constant flow of ultrapure grade SO2 (99.9995%) and CO2 (99.9%)
purchased from INFRA.
chemically, reaching detection limits of 25 ppm.28 Later, Cao 2.4. Fluorescence Experiments. Fluorescence spectra were
and co-workers presented another MOF-based detector, which carried out in an Edinburgh Instruments FS5 Spectrofluorometer
relied on the photoluminescence response of MOF-5-NH2 to using a continuous wave 150 W ozone-free xenon arc lamp at room
SO2.29 Recently, we have demonstrated selective SO2 detection temperature coupled with the SC-10 solid-state sample holder. The
by a metal−organic polyhedron (MOP-CDC).30 samples were packed into quartz sample holders and positioned in the
We previously reported the synthesis, characterization, and instrument. Emission measurements were carried out using an
CO2 separation by a microporous cobalt-based MOF named excitation wavelength of 360 nm with an LP-395 filter on the
MUF-16 (MUF = Massey University Framework).31 MUF-16 detector side to remove any remaining light from the excitation
is built up from 5-aminoisophthalate (Haip) linkers and source. Emission and excitation measurements were collected with a
step size of 1 nm and a dwell time of 0.1 s. The excitation bandwidth
divalent cobalt centers, which adopt an octahedral coordina- was set at 3.00 nm, and the emission bandwidth for the detector was
tion geometry. Interestingly, MUF-16 adopts a three-dimen- set at 2.00 nm. Time-resolved photoluminescence (TRPL) experi-
sional (3-D) lattice, which is supported by hydrogen bonds ments were measured in an Edinburgh Instruments FS5 Spectro-
between carboxyl motifs (Figure 1). Due to the simple, fluorometer using a 375 nm EPL laser, with an excitation bandwidth
accessible, and scalable synthesis of MUF-16, we decided to of 0.01 nm and an emission bandwidth of 2.00 nm at an emission
investigate the SO2 adsorption and fluorescence properties of wavelength of 455 nm.
this MOF material. We establish the affinity of MUF-16 for
SO2 and determine its detection capacity by taking advantage 3. RESULTS AND DISCUSSION
of its luminescent properties,32 which may be employed for the 3.1. Characterization of MUF-16. The material MUF-16,
fabrication of SO2 detectors. [Co(Haip)2], was synthesized via the solvothermal reaction of
cobalt acetate (Co(OAc)2·4H2O) and 5-aminoisophthalic acid
(H2aip) in a mixture of MeOH/H2O/MeCN.31,33 The
resulting pink microcrystals were characterized by powder X-
ray diffraction, FT-IR spectroscopy, N2 adsorption experi-
ments, thermogravimetric analysis, and scanning electron
microscopy (SEM) images (Figures S1−S5), corroborating
the obtention of the desired crystalline phase; its thermal
stability is up to 400 °C and the Brunauer−Emmett−Teller
(BET) surface area was 217 g2 m−1. The average particle size
of 3.47 μm was determined with ImageJ software.34
3.2. SO2 Adsorption−Desorption Measurements.
Prior to the SO2 adsorption−desorption studies, the MUF-
16 sample was activated at 403 K under a vacuum (1 × 10−3
bar) for 8 h. Figure 2a shows the SO2 adsorption−desorption
isotherm at 298 K and up to 1 bar. Initially, a strong adsorption
of 1.40 mmol g−1 can be seen in the low-pressure region up to
0.03 bar, which would indicate an affinity of MUF-16 for SO2.
Beyond 0.2 bar, steady plateau adsorption is observed, leading
to a saturation capacity of 2.20 mmol g−1 at 1 bar. The
saturation capacity of MUF-16 is comparable to other MOFs
with a similar surface area, for example, KAUST-7 and −8,28
MIL-53-NO2,35 and UNAM-136 (Table 1).
The isosteric enthalpy of adsorption for the binding of SO2
Figure 1. (a) MUF-16 view along the crystallographic b axis. (b) to MUF-16 was calculated from adsorption isotherms at 298
Close-up view of the pore channel formed by four H2aip and two and 308 K employing the virial method at low coverage.37 It
octahedrally coordinated Co(II) centers. Atom labels: carbon = black, was calculated in the range of −43.7−51.5 kJ mol−1 (Figure
nitrogen = blue, oxygen = red, cobalt(II) = pink. S6), which corresponds to a strong physisorption process and
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water vapor (60% RH, during 24 h). Again, the PXRD pattern
and IR spectra did not change (Figures S7 and S8), which
demonstrates the robustness of MUF-16 and a high tolerance
to SO2 over a range of real-world conditions.
Additionally, the N2 adsorption isotherm was measured
(Figure S9), and the BET surface area was estimated, resulting
in 217 m2 g−1, and by using SEM images, an average particle
size of 3.06 μm (Figure S10) was determined with ImageJ
software,34 which shows that neither the porosity nor the
morphology of the material is affected by harsh conditions
such as SO2 in the presence of water vapor. The above
contrasts with MOFs made of Co, as for example, the material
Co-URJC-5,22 in which when exposed to SO2, the Co(II)
metal center changes in its coordination sphere from
octahedral to tetrahedral, destroying the crystal structure of
the material. Furthermore, it is shown that the hydrogen bonds
forming the structure of MUF-16 are robust enough to prevent
Co(II) from undergoing changes in its coordination sphere.
To identify the strongest SO2 adsorption site in MUF-16, we
carried out first-principles dispersion-corrected density func-
tional (DFT-D3)38 calculations using the VASP software
package (see the Supporting Information).39 In addition to a
range of favorable electrostatic and van der Waals contacts,
MUF-16 interacts with the SO2 molecule via two hydrogen
bonds (Figure 2b). In the first, the N−H functional group of
the framework acts as the H-bond donor, while an O atom
from the SO2 molecule is the acceptor. The −NH2···O�S�O
Figure 2. (a) Experimental SO2 adsorption−desorption isotherm at distance is 2.523 Å. In the second, multiple −CH groups from
298 k and up to 1 bar for activated MUF-16. Filled circles = the framework form an H-bond to the SO2 molecule with an
adsorption; hollow circles = desorption. (b) Main SO2 adsorption site O···H distance varying from 2.26, to 3.1 Å. The calculated
in MUF-16 identified by DFT-D3 calculation. The interaction enthalpy of adsorption for the binding of this SO2 was
distance varies from 2.27 to 3.1 Å, which is assigned to −CH···O� estimated to be −64 kJ mol−1.
S�O; meanwhile, the 2.52 Å belongs to −NH2···O�S�O. Atom To gain insights into the nature of SO2 binding in MUF-16
label; carbon: black, nitrogen: blue, oxygen: red, cobalt: pink, and
and its behavior, we performed grand canonical Monte Carlo
sulfur: yellow.
(GCMC) simulations using the RASPA software package (see
Table 1. SO2 Capture in mmol g−1 the Supporting Information).40 The experimental and
simulated SO2 isotherms are in close agreement at 298 and
material 1 bar 0.1 bar ppm level refs 308 K (Figures S12 and S13), although the simulated
MUF-16 (217 m g ) 2 −1
2.22 2.05 1.33 at 1000 ppm this work adsorption uptake is slightly higher than the experimental
KAUST-7 (280 m2 g−1) 2.2a - 1.4 at 500 ppm 28 data. A possible explanation is that the force field model
KAUST-8 (258 m2 g−1) 2.2a - - overestimates the uptake because it is an estimate and general
MIL-53-NO2 3.5 2.07 0.12 at 1000 ppm 35 approach to energy distribution in the framework. Also, the
UNAM-1 (522 m2 g−1) 3.5 1.6 - 36 presence of any defects and disorders in the synthesized
a
Measured in the SO2/N2:7/93 mixture. sample would reduce the amount of adsorption compared to
the defect-free crystal structure. A snapshot from the
simulation of SO2 in MUF-16 at 1 bar and 298 K is presented
whereby the strong capture at low pressures of SO2 is justified. in Figure S15.
This value is comparable with other MOFs with a similar Since the DFT studies point to a strong interaction between
surface area, for example, Co-URJC-522 and UNAM-1.36 MUF-16 and the SO2 guest molecules, to investigate this
Clearly, the adsorption and desorption branches coincide, experimentally, we carried out FT-IR spectroscopic measure-
excluding a possible hysteresis and confirming an SO 2 ments on MUF-16 and a sample that had been saturated with
physisorption process.36 The structural stability following SO2 (Figure 3). While most absorption bands do not shift
SO2 adsorption/desorption was assessed by powder X-ray upon SO2 uptake, some differences are observed in the range
diffraction (PXRD) (Figure S7) and IR (Figure S8). 3350−3260 cm−1 (Figure 3b). Two sharp intense bands
The unchanged nature of the PXRD pattern shows that the associated with the symmetric and asymmetric stretching
crystal structure of MUF-16 was retained, which is consistent vibrational mode of the −NH2 group,41 undergo an inversion
with the reversibility of the isotherm. Also, no significant in intensity.
changes were observed in the IR spectra, indicating that the Also, the classical overtone from the primary amine group at
bonds remained unchanged. This result represents, to the best 3173 cm−1 disappears when MUF-16 is exposed to SO2. In a
of our knowledge, the first example of a Co(II)-based MOF complementary way, the band at 1681 cm−1, which belongs to
material that demonstrates stability toward SO2. To further this the N−H bending vibrational mode, develops a shoulder after
analysis, the structural stability of MUF-16 was investigated SO2 exposure (Figure 3c). According to the literature, these
under harsher conditions involving SO2 in the presence of changes suggest that the −NH2 motifs inside the channels of
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pressure range. Thus, a relatively high selectivity of 27.38 was

obtained for a CO2/SO2:99.9/0.1 mixture and selectivity
values between 24 and 27 for mixtures from CO2/SO2:80/20
(Table S4). This estimated selectivity can be also correlated
with the reported adsorption enthalpy value for CO2, which is
−32 kJ mol−1, which is a lower value than the values for SO2 of
approximately −43.7 to −51.5 kJ mol−1, indicating that the
interaction of SO2 with the pore walls of MUF-16 is higher in
the case of CO2, at low coverages.
3.3. SO2 Detection Measurements. Taking advantage of
the strong SO2 uptake at low pressure presented by MUF-16
and its high structural stability in dry and wet SO2 conditions
previously discussed, we measured the photoluminescence
changes upon gas uptake. First, a UV−visible (UV−vis)
spectrum was recorded to identify the wavelength range in
which MUF-16 absorbs light (Figure S18), and it was found
that this occurs between 300 and 400 nm. It was therefore
decided to measure the emission of MUF-16 at different
excitation wavelengths within its absorption wavelength range
(Figure S19), and it was observed that, in all cases, the
maximum emission length was 455 nm and that the emission
spectrum was more intense when excited at 360 nm. To
corroborate the choice of excitation wavelength of MUF-16, an
excitation spectrum was performed at an emission wavelength
of 455 nm, and it was found that the maximum emission was
indeed at 360 nm (Figure S20). Subsequently, emission
spectra of as-synthesized, activated, and saturated MUF-16
samples were performed with the following gases: SO2, CO2,
H2S, NO2, N2, O2, CH4, and water vapor. Since SO2, H2S, and
NO2 are toxic gases that were generated from hazardous and
corrosive precursors (H2SO4, HCl, and HNO3), it is important
to emphasize that, for their generation of these gases and
handling of samples exposed to these, particular safety
measures were performed, such as the use of gloves, goggles,
and respiratory protection. The saturations were carried out in
our ex situ gas generation system (Figure S11), and prior to all
saturations, MUF-16 samples were activated at 403 K under
vacuum for 4 h. Figure 4a shows the MUF-16 emission spectra
that were obtained for each case, showing that only for SO2, a
considerable change in fluorescence was obtained, which
Figure 3. FT-IR spectra comparison of MUF-16 activated (pink line), corroborates the good selectivity of MUF-16 for SO2. Similar
saturated with SO2 (green line), and saturated with CO2 (blue line). effects have been observed in other fluorescent MOFs.
(a) Complete spectrum from 4000 to 500 cm−1, (b) range from 4000
Recently, we conducted an experimental and theoretical
to 2500 cm−1, and (c) range from 1900 to 1400 cm−1.
investigation on the photoluminescent quenching of a
copper−organic polyhedron with carbazole motifs (MOP-
MUF-16 form hydrogen bonds, as seen in the DFT CDC).30 Here, the −NHcarbazol and oxygen atoms from the
models.42,43 In contrast to the case of SO2, loading MUF-16 SO2 molecule were seen to interact strongly, leading to a
with CO2 does not bring about significant changes. photoluminescence change. We propose a similar behavior for
Since SO2 is usually present as a trace gas in gas mixtures in MUF-16: H-bonding between the amino groups of the
which CO2 is usually a major component, we decided to framework and the SO2 adsorbates that change the emission
investigate the SO2 selectivity by MUF-16, using the Python intensity.
package called pyIAST44 that predicts mixed-gas adsorption To explain the low changes in fluorescence for the other
isotherms in porous materials from pure-component gas molecules, we can look at their polarities and kinetic diameters.
adsorption isotherms using ideal adsorbed solution theory In general, the greater the electronegativity difference between
(IAST). For this purpose, a single-component CO2 adsorption the constituent atoms of a molecule and the greater the
isotherm was measured (Figure S16) in which a total capture asymmetry in the geometry, the greater the polarity of the
of 2.07 mmol g−1 at 1 bar and 298 K was obtained. Comparing molecule. In the case of N2 and O2, being diatomic molecules
this isotherm with the one obtained for SO2, it can be observed with identical atoms, there is no polarity. For CO2, the linear
that the total CO2 capture is like the value obtained for SO2 symmetry of the molecule and the similarity of electro-
adsorption (2.22 mmol g−1 at 1 bar and 298 K). However, negativities between C (3.15) and O (3.78) make it nonpolar.
substantial differences were observed in the low-pressure range CH4 is also nonpolar due to its tetrahedral symmetry and
(0 to 0.2 bar), where SO2 capture was considerably higher than uniform charge distribution. In the above cases of nonpolar
the CO2 capture, so we calculated such selectivity at that molecules, their interaction with the material is expected to be
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over nonradiative ones (with duration in the order of 10−12

s),50 which increases of the fluorescence lifetime. In this work,
we propose that the presence of SO2, which establishes
hydrogen bonds with MUF-16, induces a rigidification in the
framework of the material, generating changes in the electronic
structure of the system and disfavoring the nonradiative
dissipation pathways such as vibrational relaxation.
In addition, we tested the fluorescence of samples exposed
to 0.1 and 0.01 bar, observing that in both cases, MUF-16
shows a fluorescence response (Figure 4b). The effect that
water vapor and CO2 can potentially have on the response of
the fluorescence for the material when evaluating SO2, was also
evaluated. For this purpose, independent MUF-16 samples
were exposed to 0.1 bar of SO2 in the ex situ gas generation
system, and simultaneously, approximately 0.9 bar of water
vapor and CO2 were introduced into the system, and their
emission spectra were measured. It was found that there were
no significant changes in the intensity or shape of the
fluorescence spectra with respect to the spectrum of the
sample exposed to only 0.1 bar (Figure S22). On the other
hand, to test the durability of the material as a detector, five
cycles of reactivation and saturation with SO2 were performed
on the same sample of MUF-16, showing that, in all cases, the
intensity of the material changes in the same way (Figure S23),
demonstrating that MUF-16 is a recyclable material in the
context of the fluorescent detection of SO2.
To further analyze MUF-16 for the detection of SO2, the
Figure 4. (a) Comparison of solid-state emission spectra of MUF-16
limit of detection (LOD) was calculated using a solution of
exposed to different gases, and (b) comparison of solid-state emission
spectra of MUF-16 exposed to different SO2 pressures. SO2 dissolved in THF. The LOD value was calculated with the
following formula: LOD = 3σ/m, where σ represents the
standard deviation of the initial intensity of pristine MUF-16 in
limited or nonexistent. In contrast, H2O, H2S, NO2, and SO2 THF and m is the slope of the linear fit from the experimental
are polar molecules due to the differences in electronegativities data. Different solutions were measured in the range 1−250
between their atoms and their angular molecular geometries, mM (Figures S24 and S25). In this case, the LOD was
showing dipole moments of 1.85, 0.98, 0.31, and 1.63 D, calculated to be 1.26 mM (∼80.72 ppm) of SO2 in a THF
respectively.45−47 On the other hand, the kinetic diameter is a solution.
concept used in the kinetic theory of gases to describe the
interaction and collision of the molecules of a gas; in general
terms, a larger kinetic diameter suggests a higher probability of 4. CONCLUSIONS
collision in the hard-sphere model. The kinetic diameter values To summarize, we report the reversible experimental SO2
are 2.65, 3.60, 3.30, and 4.10 Å for H2O, H2S, NO2, and SO2, adsorption−desorption for MUF-16 with a total SO2 uptake of
respectively.48,49 Considering that SO2 is a highly polar 2.2 mmol g−1 and a highly competitive SO2 uptake of 2.1
molecule compared to its competitors and shows the largest mmol g−1 at only 0.1 bar. This relatively high SO2 adsorption
kinetic diameter among the tested molecules, it is under- at low pressure (∼0.1 bar) suggests that the material exhibits a
standable why MUF-16 can form more specific interactions preferential adsorption domain. To elucidate the SO 2
with this gas, leading to changes in fluorescence, while the adsorption mechanism, FT-IR experiments were performed,
other molecules, displaying lower dipole moments, are less observing that once an MUF-16 sample is saturated with SO2,
likely to interact with the material and therefore do not induce the bands related to the −NH2 group clearly change,
significant changes in fluorescence. corroborating an SO2−NH2 interaction. Complementary, this
To elucidate a possible fluorescence mechanism causing the
material shows selective detection of SO2 since the effect of the
observed emission change, time-resolved photoluminescence
SO2 molecule quenched its emission. These experimental
(TRPL) experiments were performed (Figure S21), and
quantum yields were measured for activated and SO2-saturated results were supported by DFT calculations that indicated that
MUF-16 samples. The fluorescence lifetime for the activated the SO2 molecule is located in the vicinity of the NH2
sample was found to be 1.71 ns, while the one for the saturated functional group. In addition, MUF-16 displays a high change
sample was equal to 2.29 ns. The quantum yields were 0.63 in its fluorescence performances for SO2 compared to other
and 7.89%, respectively, for the activated and saturated gases (SO2, CO2, NO2, N2, O2, CH4, and water vapor),
samples. These results show that the presence of SO2 changes demonstrating its high affinity for a possible detection
the fluorescence lifetime of MUF-16 and increases the application of SO2. The possible florescence mechanism was
efficiency for the material to convert the absorbed energy determined using time-resolved photoluminescence. Finally,
into light, indicating that the presence of SO2 favors radiative the LOD was calculated to be 1.26 mM (∼80.72 ppm) of SO2
dissipation mechanisms (with duration in the order of 10−9 s) in a THF solution.
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■
*
ASSOCIATED CONTENT
sı Supporting Information
Investigaciones en Materiales, Universidad Nacional
Autónoma de México, 04510 México D.F., México
Enrique Lima − Laboratorio de Fisicoquímica y Reactividad
The Supporting Information is available free of charge at de Superficies (LaFReS), Instituto de Investigaciones en
https://pubs.acs.org/doi/10.1021/acs.chemmater.3c02715. Materiales, Universidad Nacional Autónoma de México,
Experimental details; PXRD patterns after SO2 exposure; 04510 México D.F., México
isosteric heat of adsorption of SO2, SO2 adsorption− Elnaz Jangodaz − MacDiarmid Institute for Advanced
desorption cycles, and SO2 testing in humid conditions; Materials and Nanotechnology, School of Natural Sciences,
computational studies; and fluorescence details (PDF) Massey University, Palmerston North 4410, New Zealand;
orcid.org/0000-0003-4902-3273

■ AUTHOR INFORMATION
Corresponding Authors
Ravichandar Babarao − School of Science, RMIT University,
Centre for Advanced Materials and Industrial Chemistry,
Melbourne, Victoria 3001, Australia; orcid.org/0000-
Diego Solís-Ibarra − Laboratorio de Fisicoquímica y 0003-3556-495X
Reactividad de Superficies (LaFReS), Instituto de Complete contact information is available at:
Investigaciones en Materiales, Universidad Nacional https://pubs.acs.org/10.1021/acs.chemmater.3c02715
Autónoma de México, 04510 México D.F., México;
orcid.org/0000-0002-2486-0967; Email: diego.solis@ Author Contributions
unam.mx #
V.B.L.-C., A.L.-O., and J.L.O. contributed equally to this
Ilich A. Ibarra − Laboratorio de Fisicoquímica y Reactividad work.
de Superficies (LaFReS), Instituto de Investigaciones en Notes
Materiales, Universidad Nacional Autónoma de México,
The authors declare no competing financial interest.
04510 México D.F., México; On sabbatical as “Catedra Dr.
Douglas Hugh Everett” at Departamento de Química,
Universidad Autónoma Metropolitana-Iztapalapa, 09310
Ciudad de México, México; orcid.org/0000-0002-8573-
■ ACKNOWLEDGMENTS
V.B.L.-C. and J.L.O. thank CONAHCYT for the Ph.D.
8033; Email: [email protected] fellowship (1005649 and 1003953). I.A.I. thanks PAPIIT
Shane G. Telfer − MacDiarmid Institute for Advanced UNAM (IN201123), México, for financial support. The
Materials and Nanotechnology, School of Natural Sciences, authors thank U. Winnberg (Euro Health) for scientific
Massey University, Palmerston North 4410, New Zealand; discussions and G. Ibarra-Winnberg for scientific encourage-
orcid.org/0000-0003-1596-6652; Email: S.Telfer@ ment. R.B acknowledges the National Computing Infra-
massey.ac.nz structure for providing the computational resources.
Authors
Valeria B. López-Cervantes − Laboratorio de Fisicoquímica y
Reactividad de Superficies (LaFReS), Instituto de
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