Porphyrinic Silver Cluster Assembled Material for Simultaneous

connects silver clusters with organic linkers to form periodic frameworks, yielding a class of silver cluster-assembled materials. (denoted as SCAMs) ...
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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, XiYan 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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Journal of the American Chemical Society

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†,§ †

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 ABSTRACT: 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(StBu)6(CF3COO)3(TPyP)]n (denoted as Ag12TPyP) composed of a Ag12 chalcogenolate cluster core stabilized by porphyrinic ligands. Ag12TPyP showed superior 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 photosensitizer ligand promote the efficiency of the generation of singlet oxygen (1O2), which accelerates the decontamination rate. Additionally, 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.

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 proteins 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.34 It should be noted that the overoxidation of HD results in the generation of sulfones that are highly toxic. Among various oxidants, 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 the 1O2 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 high 1O2 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, Ag13 and Ag32 nanoclusters have been used to photosensitize 1O2 and applied in photodynamic therapy.17-18 However, inherent ultrainstability impedes their further application in large scales.19 To overcome such drawback, our group has developed a strategy that

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.2029 Compared with discrete silver nanoclusters, the porous structure of the framework not only facilitates substrate diffusion and enhances 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 recovery from the reaction mixture and reusability for continuous processing. 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. To demonstrate our conceptual approach, we selected the photosensitizer 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 integration of silver cluster with porphyrin moieties generate synergistic effects, and Ag12TPyP can simultaneously capture and photooxidize 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. Dark-purple, block-shaped Ag12TPyP crystals were obtained via the conventional slow solvent evaporation method at an ambient temperature over 48 h (Figure S1). The single-crystal X-ray 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 chalcogenolate 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).

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Scheme 1. (a) Synthesis of Ag12TPyP. (b) Schematic illustration of the capture and photodetoxification of CEES by Ag12TPyP.

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S17, Ag12bpy-2 can degrade DMA, thereby demonstrating that the silver cluster is able to generate 1O2 under light irradiation. However, 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 conditions, TPyP and Ag-TPP also exhibited a sluggish DMA degradation rate due to their inferior dissolubility and nonporous structure (Figures S18-S20). Therefore, we conclude that the higher activities of Ag12TPyP for the generation of 1O2 can account for the synergistic effect of the porphyrin photosensitizer units and the silver clusters.

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 remarkable structural stability (Figure S5). The porosity of the activated Ag12TPyP was evaluated by the N2 sorption isotherm measurements 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 structure prompted us to assess the potential photocatalytic performance of Ag12TPyP. Initially, we analyzed the photoactivity of Ag12TPyP by ultraviolet-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 reasoned that Ag12TPyP is a promising candidate for 1O2 generation via photosensitization of the ground-state O2 by an energy transfer process. The photocatalytic property of Ag12TPyP to generate 1O2 was monitored by electron paramagnetic resonance (EPR) spectroscopy 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 1 O2 is the main component of generated reactive oxygen species by Ag12TPyP photosensitizers.5-6 Meanwhile, we also used 9,10dimethylanthracene (DMA) as the 1O2 indicator to further validate the 1O2 generation ability of Ag12TPyP (Figure S15).6 The emission 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 porphyrin moiety on the 1O2 generation rate, control experiments were subsequently performed using a previously reported SCAM (Ag12bpy-2) (Figures S11 and S12),21 the TPyP ligand, and a silver-porphyrin complex (Ag-TPP). As shown in Figures S16 and

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. Despite the fast 1O2 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 binding 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 sorption 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 adsorption 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

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can benefit from the synergistic effect of the silver cluster and the porphyrin moieties. 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 simulant (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 structure and Cl-Ag interactions. The structural uniqueness enabled Ag12TPyP to show exceptional CEES decomposition rates, surpassing 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 provide a potential platform for further advancement in the exploration of novel photocatalysts.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available 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 reaction 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

Inspired by these results, we conducted the oxidative degradation 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 monitored by both 1H and 13C NMR spectra that indicated new 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 examined the photocatalytic activity of Ag12TPyP under air atmosphere, 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 retained after completion of reaction cycles under photocatalytic conditions (Figure 2d). Indeed, the recyclability of photocatalytic SCAMs is rarely reported.

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

In comparison, the analogue Ag12bpy-2 exhibited inferior catalytic performance with a conversion of only 20% after a long reaction time (60 min) (Figure S37), which may be attributed to the slow 1O2 generation rate. Since TPyP and Ag-TPP easily aggregated or deteriorated under light irradiation (Figure S34), the utilization efficiency of the active sites was greatly decreased. Thus, they showed a slower CEES photooxidation rate compared to Ag12TPyP (Figures S35-S37). Moreover, they did not exhibit advantages over the SCAMs as recoverable photocatalysts. These results verified that the very fast photocatalytic rate of Ag12TPyP

Corresponding Author [email protected]; [email protected].

ORCID

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by the National Science Fund for Distinguished Young Scholars (No. 21825106), the National Natural Science Foundation of China (No. 21671175), the Program for Science & Technology Innovation Talents in Universities of Henan Province (164100510005), the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (19IRTSTHN022) and Zhengzhou University.

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