Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant

Article abstract of DOI:10.1021/jacs.9b05952

Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag₁₂(S^tBu)₆

Full text of DOI:10.1021/jacs.9b05952

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Communication
Porphyrinic Silver Cluster Assembled Material for Simultaneous
Capture and Photocatalysis of Mustard-Gas Simulant
Man Cao, Rui Pang, Qian-You Wang, Zhen Han, Zhao-Yang Wang, Xi-
Yan Dong, Shun-fang Li, Shuang-quan Zang, and Thomas C. W. Mak
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b05952 • Publication Date (Web): 18 Aug 2019
Downloaded from pubs.acs.org on August 18, 2019
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Porphyrinic Silver Cluster Assembled Material for Simultaneous
Capture and Photocatalysis of Mustard-Gas Simulant
Man Cao,† Rui Pang,‡ Qian-You Wang,*,† Zhen Han,† Zhao-Yang Wang,† Xi-Yan Dong,† Shun-Fang
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Li,‡ Shuang-Quan Zang,*,† and Thomas C. W. Mak†,§
†College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
‡International Laboratory for Quantum Functional Materials of Henan and School of Physics and Engineering, Zhengzhou
University, Zhengzhou 450001, China
§
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China
Supporting Information Placeholder
connects silver clusters with organic linkers to form periodic
frameworks, yielding a class of silver cluster-assembled materials
(denoted as SCAMs) with greatly improved chemical stability.20-
29 Compared with discrete silver nanoclusters, the porous structure
of the framework not only facilitates substrate diffusion and en-
hances the accessibility of active sites,30-32 but also improves the
synergy between inorganic silver clusters and organic ligands and
increases catalytic activities, thus presenting SCAMs as promising
candidates for high-performance catalysts.33 More importantly,
the chemical stability of SCAMs is advantageous for their recov-
ery from the reaction mixture and reusability for continuous pro-
cessing. Nevertheless, the current study on the SCAMs mainly
focuses on their photophysical properties, while the exploration of
their catalytic functions is still in its infancy.
ABSTRACT: Silver cluster-assembled materials (SCAMs), by
virtue of their tunable structure, accessible surface area and excel-
lent stability, hold great promise as highly efficient catalysts.
Herein, we report a new SCAM [Ag12(StBu)6(CF3COO)3(TPyP)]n
(denoted as Ag12TPyP) composed of a Ag12 chalcogenolate clus-
ter core stabilized by porphyrinic ligands. Ag12TPyP showed su-
perior sulfur mustard simulant (2-chloroethyl ethyl sulfide, CEES)
degradation efficiency and achieved a half lifetime (t1/2) of 1.5
min with 100% selectivity. The experimental results demonstrated
that synergistic effects between the silver cluster and photosensi-
tizer ligand promote the efficiency of the generation of singlet
oxygen (1O2), which accelerates the decontamination rate. Addi-
tionally, benefiting from strong affinity between the silver cluster
and CEES, Ag12TPyP exhibits a CEES uptake of 74.2 mg g-1.
This work demonstrates that SCAMs offer a new route to the
rational design of novel materials for the detoxification of mustard
gas.
To demonstrate our conceptual approach, we selected the pho-
tosensitizer 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) as the
organic linker,34-35 which was successfully coordinated with the
twelve-core silver chalcogenolate cluster to produce the novel
SCAM
[Ag12(StBu)6(CF3COO)3(TPyP)]n,
(designated
as
Ag12TPyP) (Scheme 1a). Our results demonstrated that the inte-
gration of silver cluster with porphyrin moieties generate syner-
gistic effects, and Ag12TPyP can simultaneously capture and pho-
tooxidize CEES (Scheme 1b). To the best of our knowledge, the
degradation rate of CEES by Ag12TPyP outperformed the most
efficient MOF-based photocatalysts.7-8 This study highlights the
fact that SCAMs are a class of attractive heterogeneous catalysts.
Chemical warfare agents (CWAs) pose serious threats to the
global community.1-2 Sulfur mustard bis(2-chloroethyl)sulfide
(denoted as HD) is a noxious vesicant agent against human pro-
teins and DNA that causes skin blisters, irritation to the eyes and
respiratory tract, and even results in fatal damage.2 One of the
efficient methods to decontaminate HD is through the selective
oxidation of the sulfides into environmentally benign sulfoxides.3-
Dark-purple, block-shaped Ag12TPyP crystals were obtained
via the conventional slow solvent evaporation method at an ambi-
ent temperature over 48 h (Figure S1). The single-crystal X-ray
4
It should be noted that the overoxidation of HD results in the
generation of sulfones that are highly toxic. Among various oxi-
dants, singlet oxygen (1O2) is a mild yet active one.5-6 Several
pioneering studies have utilized Zr cluster-based metal organic
frameworks (MOFs) as photooxidation catalysts for degrading
sulfur mustard simulants (2-chloroethyl ethyl sulfide, CEES) via
diffraction analysis revealed that Ag12TPyP crystallizes in the
—
space group P1 (Table S1). The Ag12 cluster takes the form of an
empty cubo-octahedron held by argentophilic interactions36 with
AgI···AgI distances of 2.8670(4)-3.3159(5) Å. Each Ag12 chal-
cogenolate core is consolidated by six StBu¯ ligands, four
CF3COO¯auxiliary ligands and four TPyP ligands. Each StBu¯
ligands adopts the µ4-η1, η1, η1, η1 coordination mode to link with
four adjacent Ag(I) ions, and each CF3COO¯ ligand bidentately
chelates with two different Ag atoms. The Ag12 cluster functions
as a four-connected node in assembly with the µ4-TPyP linkers to
form a 2D network that exhibits the AB stacking mode (Figures
S2-S4).
1
the O2 oxidation route.7-8 Despite great advances in recent years,
the low degradation kinetics hamper the demands of practical
applications. Hence, the development of novel photocatalysts with
1
high O2 generation efficiency, as well as rapidly detoxify HD,
presents an urgent yet challenging endeavor.
Silver nanoclusters,9-13 with unique optical properties14 and
abundant active sites, have shown great potential as catalysts in
organic reactions15 and biological applications16. For example,
1
Ag13 and Ag32 nanoclusters have been used to photosensitize O2
and applied in photodynamic therapy.17-18 However, inherent ul-
trainstability impedes their further application in large scales.19 To
overcome such drawback, our group has developed a strategy that
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S17, Ag12bpy-2 can degrade DMA, thereby demonstrating that the
silver cluster is able to generate O2 under light irradiation. How-
Scheme 1. (a) Synthesis of Ag12TPyP. (b) Schematic illus-
tration of the capture and photodetoxification of CEES by
Ag12TPyP.
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ever, the production rate was much slower compared with
Ag12TPyP (Figure 1d), which may be attributable to the larger
band gap of Ag12bpy-2 (Figure S14). Under the same test condi-
tions, TPyP and Ag-TPP also exhibited a sluggish DMA degrada-
tion rate due to their inferior dissolubility and nonporous structure
(Figures S18-S20). Therefore, we conclude that the higher activi-
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ties of Ag12TPyP for the generation of O2 can account for the
synergistic effect of the porphyrin photosensitizer units and the
silver clusters.
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The powder X-ray diffraction (PXRD) pattern verified the
phase purity of Ag12TPyP (Figure S5). Notably, after exposure to
air over three months and soaking in various organic solvents for
36 h, the PXRD patterns remained unchanged, indicating its re-
markable structural stability (Figure S5). The porosity of the acti-
vated Ag12TPyP was evaluated by the N2 sorption isotherm meas-
urements at 77 K, showing a Brunauer-Emmett-Teller (BET)
surface area of 234.02 m2 g-1 (Figures S6-S8), which provides a
facile pathway for substrate diffusion to the reactive sites. The
excellent chemical stability and the well-developed porous struc-
ture prompted us to assess the potential photocatalytic perfor-
mance of Ag12TPyP.
Initially, we analyzed the photoactivity of Ag12TPyP by ultra-
violet-visible diffuse reflectance spectroscopy, which showed
strong absorption peaks ranging from 240 nm to 650 nm (Figure
S9). The corresponding band gap was calculated to be 1.756 eV,
revealing preferable light-harvesting capability of Ag12TPyP. In
addition, the O2 sorption isotherms suggested type-I behavior and
the sorption quantity attained 89.47 cm3 g-1 (Figure 1a). It is rea-
Figure 1. (a) O2 sorption isotherms of Ag12TPyP at 77 K. (b) EPR
spectra of Ag12TPyP mixed with 4-oxo-TMP under visible-light
irradiation or in the dark. (c) Fluorescence spectra of DMA in the
presence of Ag12TPyP upon light irradiation. (d) The degradation
of DMA using Ag12TPyP and Ag12bpy-2 as monitored by the
emission decay at 430 nm. (e) CEES uptake isotherms at 298 K. (f)
Cl 2p high-resolution XPS spectra of Ag12TPyP with CEES.
1
soned that Ag12TPyP is a promising candidate for O2 generation
1
via photosensitization of the ground-state O2 by an energy transfer
process.
Despite the fast O2 generation rate, Ag12TPyP also exhibited a
high CEES capture amount. The maximum CEES uptake capacity
reached 74.2 mg g-1 (Figure 1e). To determine the possible bind-
ing motif between the CEES molecules and the SCAM host, we
employed X-ray photoelectron spectroscopy (XPS) to analyze the
detailed chemical bonding situation (Figure S21). Upon CEES
loading, the peak at 197.8 eV in the high-resolution Cl 2p data of
Ag12TPyP can be assigned to Cl adsorption on the Ag complex
(Figure 1f). Elemental mapping based on SEM energy dispersive
X-ray spectrometry (SEM-EDS) also confirmed that CEES is
uniformly loaded in Ag12TPyP samples (Figure S22), and the bulk
crystallinity of Ag12TPyP remains intact after CEES vapor sorp-
tion as evidenced by the PXRD patterns (Figure S23). In addition,
we also performed CEES adsorption experiment on Ag12 cluster
(Figure S25),21 TPyP, Ag-TPP, and Ag12bpy-2 (Figure 1e and
Figure S24). For the Ag12 cluster, TPyP and Ag-TPP, almost no
absorption performance was noted. Interestingly, CEES adsorp-
tion performance of Ag12bpy-2 is comparable to that of Ag12TPyP,
which is probably due to the existence of open micropores in both
structures (Figure S13). Based on the aforementioned results, we
1
The photocatalytic property of Ag12TPyP to generate O2 was
monitored by electron paramagnetic resonance (EPR) spectrosco-
py with 4-oxo-TMP as the probe.6 Upon light irradiation,
Ag12TPyP clearly displayed the characteristic 1:1:1 triplet signal
of EPR spectra, while the signals dramatically decreased in the
dark (Figure 1b). In the presence of the 1O2 scavenger β-carotene,
the signals were almost fully quenched (Figure 1b), indicating that
1O2 is the main component of generated reactive oxygen species
by Ag12TPyP photosensitizers.5-6 Meanwhile, we also used 9,10-
dimethylanthracene (DMA) as the 1O2 indicator to further validate
1
the O2 generation ability of Ag12TPyP (Figure S15).6 The emis-
sion peaks rapidly decreased along with the DMA oxidation to
endoperoxide within 300 s by the generated 1O2 (Figure 1c).
Moreover, to assess the influence of the silver cluster and the
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porphyrin moiety on the O2 generation rate, control experiments
were subsequently performed using a previously reported SCAM
(Ag12bpy-2) (Figures S11 and S12),21 the TPyP ligand, and a sil-
ver-porphyrin complex (Ag-TPP). As shown in Figures S16 and
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speculate that the high CEES uptake capacity of Ag12TPyP can be
can benefit from the synergistic effect of the silver cluster and the
1
2
3
porphyrin moieties.
ascribed to two main factors: (a) the well-defined porous structure,
which allows preconcentration of CEES, and (b) binding interac-
tion between Ag12TPyP and CEES.
In summary, a novel porphyrin-based SCAM (Ag12TPyP) was
prepared, and we have demonstrated its excellent photocatalytic
activity by the efficient and selective oxidation of a mustard simu-
lant (CEES). Our results clearly showed that the chemical stability
of Ag12TPyP, coupled with photoactivity derived from the silver
cluster moieties and porphyrin ligands, dramatically increased 1O2
generation rates. In particular, Ag12TPyP exhibited high capture
amounts of CEES vapor owing to its well-defined porous struc-
ture and Cl-Ag interactions. The structural uniqueness enabled
Ag12TPyP to show exceptional CEES decomposition rates, sur-
passing the largely reported MOF-based photocatalysts for the
CEES degradation. More importantly, by virtue of the judicious
choice of the silver cluster and organic linkers, the SCAMs pro-
vide a potential platform for further advancement in the explora-
tion of novel photocatalysts.
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ASSOCIATED CONTENT
Supporting Information. The Supporting Information is availa-
ble free of charge on the ACS Publications website. Experimental
details and data (PDF).
Data for Ag12TPyP (CIF)
Figure 2. (a) 1H NMR analysis of the CEES photooxidation reac-
tion by Ag12TPyP. (b) Conversion of CEES in the presence of
Ag12TPyP under O2 (in blue) and air (in red). (c) Reusability test
of Ag12TPyP with four consecutive injections of CEES into the
same reaction. (d) Post and pre-catalysis PXRD patterns of
Ag12TPyP.
AUTHOR INFORMATION
Corresponding Author
zangsqzg@zzu.edu.cn; qianyouwang@zzu.edu.cn.
ORCID
Inspired by these results, we conducted the oxidative degrada-
tion reaction of CEES under white LED irradiation (light intensity,
80 mW/cm2). Remarkably, Ag12TPyP displayed high catalytic
activity, which needed only 4 min for the conversion of 98% of
CEES (1% loading) into the nontoxic oxidation product CEESO
under an O2 atmosphere (t1/2 = 1.5 min). The reaction process was
Qian-You Wang: 0000-0002-8892-7825
Xi-Yan Dong: 0000-0002-2429-546X
Shun-Fang Li: 0000-0003-4661-6188
Shuang-Quan Zang: 0000-0002-6728-0559
Thomas C. W. Mak: 0000-0002-4316-2937
Notes
1
monitored by both H and 13C NMR spectra that indicated new
The authors declare no competing financial interests.
peaks of CEESO appearing at 1.5 min, revealing the very fast
degradation rate (Figure 2a, Figures S26-S32). It is noted that no
toxic CEESO2 was detected throughout the detoxification process
even after a long reaction period (2 h), and selectivity of 100%
was achieved (Figure S33). For the practical application, we ex-
amined the photocatalytic activity of Ag12TPyP under air atmos-
phere, where it fully decomposed CEES into CEESO within 14
min, with a calculated half-life of 6 min (Figure 2b). Impressively,
the catalytic activity of Ag12TPyP is among the best of previously
reported MOF-based photocatalysts (Table S2). Furthermore, the
catalyst stability test indicated that the conversion remained 100%
for 4 cycles with consecutive addition of CEES, while no obvious
performance decay was observed (Figure 2c). The PXRD results
confirmed that the structural integrity of Ag12TPyP was fully re-
tained after completion of reaction cycles under photocatalytic
conditions (Figure 2d). Indeed, the recyclability of photocatalytic
SCAMs is rarely reported.
ACKNOWLEDGMENT
This work was supported by the National Science Fund for Dis-
tinguished Young Scholars (No. 21825106), the National Natural
Science Foundation of China (No. 21671175), the Program for
Science & Technology Innovation Talents in Universities of He-
nan Province (164100510005), the Program for Innovative Re-
search Team (in Science and Technology) in Universities of He-
nan Province (19IRTSTHN022) and Zhengzhou University.
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