Functionalizing MOF with Redox-Active Tetrazine Moiety for Improving the Performance as Cathode of Li–O ₂ Batteries

Abstract

Open AccessCCS ChemistryCOMMUNICATION1 Mar 2021Functionalizing MOF with Redox-Active Tetrazine Moiety for Improving the Performance as Cathode of Li–O2 Batteries Na Li, Ze Chang, Ming Zhong, Zi-Xuan Fu, Jun Luo, Yi-Fang Zhao, Guo-Bao Li and Xian-He Bu Na Li School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 , Ze Chang School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 , Ming Zhong School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 , Zi-Xuan Fu School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 , Jun Luo School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 , Yi-Fang Zhao Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 , Guo-Bao Li Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 and Xian-He Bu *Corresponding author: E-mail Address: [email protected] School of Materials Science and Engineering, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350 Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071 https://doi.org/10.31635/ccschem.020.202000284 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesTrack Citations ShareFacebookTwitterLinked InEmail A redox-active tetrazine moiety is immobilized within a metal-organic framework (MOF) aiming at targeted construction of a cathode with improved performance for lithium–oxygen batteries. A 1,2,4,5-tetrazine (Tz) functionalized ligand is used to construct a nanoporous MOF, Tz-Mg-MOF-74, in which the redox activity of the Tz moiety is retained. Combining the redox activity of Tz with the porous nature of a MOF produced a Tz-Mg-MOF-74-based cathode with significantly improved electrochemical performance. Specifically, the material has improved sustainable capacity with a lower overpotential compared with otherwise similar batteries without Tz and other reported MOF-based catalysts. The present approach productively integrates electrochemical activity derived from redox-active moieties and MOFs, and this combination opens a new avenue for the design of effective materials for energy storage and conversion. Download figure Download PowerPoint The urgent demand for renewable energy sources has prompted the development of high-performance electrical energy storage devices. Among the energy storage systems that have been developed,1–3 nonaqueous lithium–oxygen (Li–O2) batteries have garnered enormous interest due to their potentially superior specific energy density compared with that of traditional Li-ion batteries.4,5 Despite remarkable advancements in the past few years, there are still critical limitations on the performance of Li–O2 batteries, including: high overpotential, poor cycle life, limited rate capability, and poor round-trip efficiency.6,7 In general, these shortages are closely related to the chemistry of Li–O2 batteries, 2Li+ + O2 + 2e− ↔ Li2O2, with an oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring on the cathode electrode.8 Insulated Li2O2 products with low electrical conductivity create batteries with sluggish kinetics, thereby resulting in high overpotentials and poor electrochemical performance, especially in ORR processes.9 Therefore, cathode performance optimization is critical for the further development of Li–O2 batteries.10 Considering the cathode reaction of Li–O2 batteries, several features are desired for promising materials. Structurally, a porous architecture is necessary for the transport of electrolyte ions and oxygen molecules, the accommodation of Li2O2, and the buffering of material volume changes during a charge–discharge process.11–13 On the other hand, the presence of useful redox-active moieties as catalytic sites is preferable to facilitate the electrochemical reaction.14 Here, the goal is to combine the aforementioned features to accelerate the reaction kinetics for ORR and OER processes, reduce the overpotential, and improve the practical discharge capacity as well as the energy efficiency of the system. Aiming at optimizing the cathode for Li–O2 batteries via redox-active moieties, several kinds of materials have been extensively studied.15,16 Very recently, organic redox-active moieties have attracted much attention and have been applied in organic electrodes or homogeneous catalysts as a redox mediator in Li–O2 batteries.17 Electrolyte additives based on redox-active moieties can improve the capacity and reduce the charge overpotential in Li–O2 batteries due to their high reactivity and fast kinetics. 1,2,4,5-Tetrazine (Tz) is a promising redox-active moiety which shows good stability at room temperature and in common organic solvents.18 Based on their highly electron-deficient character, Tz derivatives can serve as remarkable redox-active constituents,19,20 leading to the formation of stable anion radicals by accepting one electron and accelerating the reaction kinetics of charge–discharge processes. Furthermore, Tz may provide suitable sites for adsorbing Li+ ions.21 Thus, these features endow Tz with the ability to improve the performance of Li–O2 batteries. All these characteristics make tetrazine a good candidate for Li-based energy storage systems. Furthermore, to avoid the dissolution of tetrazine-based small molecules in the electrolyte, which would reduce the capacity and sustainability of the cathode, the anchoring of redox-active moieties into a porous matrix is desirable.22 In this regard, metal-organic frameworks (MOFs) are a very promising porous matrix. MOFs are a family of inorganic–organic hybrids with great structural diversity and functional tenability.23 A variety of MOFs have been investigated as novel energy storage materials.24–26 Furthermore, their porous nature makes them a candidate for cathode materials in Li–O2 batteries.27,28 Note, the related studies mainly focus on the introduction of redox-active metal centers into the framework. Though the well-investigated redox nature of metal centers could be utilized for the rational design of cathode materials, there are still some tough issues (1) the redox activity from oxidation state changes of metal ions may result in poor structural stability of MOFs during the charge–discharge processes; (2) most redox activities of MOFs depend on transition metals, which could restrict the structural diversity of MOFs. In contrast, the hybrid nature of MOFs allows for the straightforward introduction of organic redox-active moieties and associated exposure of the redox-active sites via rational structure design. These advantages make MOFs a highly desirable platform for the investigation of cathode materials based on redox-active organic moieties. On the basis of the aforementioned considerations, we have proceeded to investigate tetrazine-functionalized MOFs. Herein, we for the first time demonstrate that it is possible to strategically immobilize a redox-active Tz moiety within a porous MOF to improve Li–O2 battery performance (Figure 1). Our design marries the promising redox-active attributes of the Tz moiety with the nanopore and dense packing organic linkers of MOFs, creating a Tz-functionalized MOF cathode (Tz-Mg-MOF-74, Tz-functionalized linker = 5,5'-(1,2,4,5-tetrazine-3,6-diyl)bis(2-hydroxybenzoic acid), abbreviated as TzHBA; see Supporting Information Figures S1 and S2). The anchoring of redox-active tetrazine moieties into porous MOF matrixes is desirable to avoid the solvation of small molecules in the electrolyte. Particularly, the electrochemical reaction kinetics for charge–discharge processes in Li–O2 batteries could be accelerated by combining the advantages of MOF structure with a redox-active moiety, thereby contributing to the improved electrochemical performance of MOF-based electrode materials. Strikingly, the as-designed Tz-Mg-MOF-74 features a high density of redox-active Tz sites, which could result in enhanced electrochemical performance in terms of sustainable discharge capacity and lower overpotential in comparison with cathode catalysts containing nonfunctionalized MOFs and other reported MOF-based cathode materials. The proof of concept demonstrates it to be an ideal platform for both large- and fine-scale targeted construction and performance control of Li–O2 cathodes via the design of its structure and composition. Figure 1 | Demonstration of the advantages of a Li–O2 battery equipped with a MOF-based cathode via the functionalization of redox-active Tz. Download figure Download PowerPoint The solvothermal reaction of TzHBA with Mg(NO3)2·6H2O in an N,N-dimethylformamide and ethanol mixed solvent system afforded the red microcrystalline powder of Tz-Mg-MOF-74 ( Supporting Information Figure S4). The high crystallinity of the sample was confirmed by its sharp powder X-ray diffraction (PXRD) peaks, and its crystal structure was analyzed using PXRD and Rietveld refinements (Figure 2a). The PXRD pattern is consistent with that from the models ( Supporting Information Section 5). No inconsistencies are observed, indicating high phase purity. Tz-Mg-MOF-74 features a similar structure—with expanding pore apertures—to that observed in MOF-74, in which the same rod secondary building units (SBUs) are present.29,30 The SBUs are interconnected by TzHBA to form a one-dimensional (1D) hexagonal nanopore with a pore aperture of 23 Å (Figure 2b and Supporting Information Figure S5). To gain more insight into the effect on the electrochemical behavior of Tz sites within the MOF, the isostructural Ben-Mg-MOF-74, with Tz moieties replaced with benzene, was also prepared for comparison. Its PXRD pattern is almost identical to that of Tz-Mg-MOF-74 ( Supporting Information Figure S6), indicating that Ben-Mg-MOF-74 exhibits similar pore structures, and serves as a control to identify the effect of Tz on the performance of Tz-Mg-MOF-74. Figure 2 | (a) Rietveld refinement of Tz-Mg-MOF-74. (The blue lines indicate the positions of Bragg reflections.) (b) Nanoporous structure of Tz-Mg-MOF-74 obtained by the linkage of rod-shaped Mg SBUs with TzHBA linkers. Download figure Download PowerPoint The stabilities of both Tz-Mg-MOF-74 and Ben-Mg-MOF-74 have been investigated to evaluate their applicability in Li–O2 batteries system. The results of PXRD analyses indicate that the frameworks of the obtained MOFs are stable after soaking in the electrolyte of Li–O2 batteries and in O2 atmosphere for over 48 h ( Supporting Information Figures S7 and S8), which could make them relatively suitable as cathode materials for Li–O2 batteries. Thermogravimetric analyses (TGA) demonstrate thermal stabilities up to 230 and 350 °C for Tz-Mg-MOF-74 and Ben-Mg-MOF-74, respectively ( Supporting Information Figure S9). The nitrogen sorption isotherms at 77 K for both Tz-Mg-MOF-74 and Ben-Mg-MOF-74 exhibit type-I sorption; the Brunauer–Emmett–Teller (BET) surface areas are listed in Supporting Information Table S2. Both Tz-Mg-MOF-74 and Ben-Mg-MOF-74 possess nanoporous structures featuring uniform 1D channels with a diameter of 23.0 Å, which could significantly assist the diffusion of lithium ions and O2 as well as accumulation of discharged products in MOF channels to enhance the performance of Li–O2 batteries. In addition, the low-pressure oxygen adsorptions of these materials were tested to investigate their O2 enrichment capabilities at 298 K. As shown in Figure 3e, the O2 adsorption capabilities of Tz-Mg-MOF-74, Ben-Mg-MOF-74, and Ketjen Black (KB) are ca. 3.63, 4.78, and 4.62 cm3/g (standard temperature and pressure [STP]) under 1 atm, each of which shows Henry's law behavior as a function of pressure. These unsaturated isotherms indicate relatively weak interaction between the samples and O2, which may not affect their battery performances from the perspective of O2 enrichment. Figure 3 | (a) Schematic representation of 1D nanopores of Tz-Mg-MOF-74 and Ben-Mg-MOF-74. (b) First discharge profiles of Tz-Mg-MOF-74, Ben-Mg-MOF-74, and KB-based cathodes. (c) Nyquist plots of the Tz-Mg-MOF-74 and Ben-Mg-MOF-74-based cathodes. (d) and (e) N2 isotherms at 77 K and O2 isotherms at 298 K for different samples. Download figure Download PowerPoint To investigate whether the redox-activity of Tz is retained in the MOF and further prove the suitability of Tz-functionalized MOFs as cathode materials for Li−O2 batteries, cyclic voltammetry (CV) measurements using a three-electrode setup were carried out. Acetonitrile solutions were used with 0.01 M AgCl/Ag as the reference electrode and a platinum wire as the counter electrode.31 The CV profile of Tz-Mg-MOF-74 under Ar atmosphere shows a reversible redox peak, corresponding to the Tz/Tz – redox couples. The redox potential versus Li+/Li is about 2.80 V by averaging the reduction and oxidation peaks (Figure 4a), suggesting its utility as a cathode in Li–O2 batteries. Taking into account that the SBUs of Tz-Mg-MOF-74 and Ben-Mg-MOF-74 are identical, the CV data of Ben-Mg-MOF-74 were collected to explore the influence of the Tz moieties on the electrocatalytic activity. In contrast, no obvious redox peak can be observed in Ben-Mg-MOF-74 under the same conditions, confirming the electroactivity of Tz moieties in Tz-Mg-MOF-74. Their electrocatalytic activities were further confirmed by additional CV tests in 1 M LiTFSI tetraethylene glycol dimethyl ether as the electrolyte (see Supporting Information S7). As shown in Supporting Information Figure S11, the CV profile of Ben-Mg-MOF-74 under O2 atmosphere shows reversible electrochemical redox reactions, which should be assigned to OER and ORR processes. It is obvious that the current peak of Tz-Mg-MOF-74 under O2 is significantly higher than that of Ben-Mg-MOF-74 under the same conditions. The quite similar potential of the peaks indicates that the increased current should be attributed to the promoted ORR/OER process.32 It should be noted that the reduction potential observed in Figure 4 is more positive than that in Supporting Information Figure S11, while the oxidation potential is more negative. This indicates that the redox of Tz should occur under O2. Then the promoted ORR/OER should be attributed to the presence of Tz in the framework. Figure 4 | (a) CV profiles of MOF samples in 0.1 M [NBu4][PF6] acetonitrile solutions under Ar atmosphere. (b) Charge–discharge profiles of the Tz-Mg-MOF-74 cathode at different current densities. (c) First six cycling responses of the Tz-Mg-MOF-74 cathode at a current density of 200 mA/g. (d) Cycling performance of the Tz-Mg-MOF-74 cathode at 200 mA/g under a specific capacity cutoff of 600 mAh/g. Download figure Download PowerPoint Next, the investigation of Tz-Mg-MOF-74 as a cathode material for Li–O2 batteries was performed. We incorporated KB into the MOF to enhance the electrical conductivity. During the testing process of the battery, both the applied current (mA/g) and the achieved capacity (mAh/g) were normalized to the combined weight of the Tz-Mg-MOF-74 sample. In a voltage range of 2.0–4.5 V, the full charge–discharge profiles of batteries with the MOF-KB composites as O2 cathodes are shown in Figure 4b. The as-prepared Tz-Mg-MOF-74 cathode shows a discharge capacity of 7700 mAh/g at a current density of 50 mA/g. When the current density is increased to 200 mA/g, the discharge capacity of the Tz-Mg-MOF-74 cathode decreases to 4907 mAh/g, suggesting a polarization with the higher current operation. Notably, the Tz-functionalized Tz-Mg-MOF-74-based cathode exhibits much higher discharge capacity than that of the reported Mg-MOF-74 (4560 mAh/g) at the same current density.27 Detailed performance comparisons of our study with other reported studies of MOF-based Li–O2 batteries are listed in Supporting Information Table S3. We infer that the improved performance of the Li–O2 batteries is likely due to the nanopore and Tz redox activity of Tz-Mg-MOF-74 compared with that of Ben-Mg-MOF-74, which was further evidenced by the following control experiments. The six cycles of charge–discharge profiles of batteries at a current density of 200 mA/g reveal that the cathode delivers high Coulombic efficiency (87.7%) in the first cycle (Figure 4c). Furthermore, the cycle stability of the battery was also estimated with a cutoff specific capacity of 600 mAh/g at a current density of 200 mA/g. The discharge voltage of the Li–O2 battery with Tz-Mg-MOF-74 cathode is still maintained at above 2.20 V after 28 cycles, indicating that the Tz-Mg-MOF-74 assembled Li–O2 battery could operate efficiently with a slightly lower voltage (Figure 4d). To evaluate the structural stability of the MOF-based cathode materials, the morphology of the Tz-Mg-MOF-74 was observed through scanning electron microscope (SEM) after 20 cycles at 200 mA/g under a specific capacity cutoff of 600 mAh/g. As seen from Supporting Information Figure S12, the morphology of Tz-Mg-MOF-74 is not significantly changed by 20 cycles, demonstrating the good structural stability. X-ray photoelectron spectroscopy (XPS) was performed to further confirm the promising electrocatalytic activity of Tz in the Tz-Mg-MOF-74-based cathodes. As shown in Figure 5a, the pristine electrode shows a signal of N 1s (400.48 eV) resulting from the nature of the bonding of the nitrogen atoms within Tz molecules. Notably, the down-shifted binding energy about 0.71 eV of N 1s (399.77 eV) can be observed after discharge, corresponding to the electrochemical reduction of the Tz (which accepts one electron to form the reduced Tz –, Figure 4a, inset).33 In the subsequent charging process, the peak is restored to its original position, demonstrating the reversibility of the redox process. This implies that the Tz moiety participates in the charge–discharge processes, promoting the ORR reaction as an activation site. Furthermore, the Li 1s XPS spectrum indicates that the discharge product is Li2O2. A Li 1s signal at 54.90 eV appears upon discharge and then disappears with charging (Figure 5a).34 Also, the C 1s XPS spectrum reveals no additional discharge products, such as Li2CO3, which are by-products in Li–O2 batteries ( Supporting Information Figure S13). PXRD was also used to identify discharge products. The corresponding characterization of the charge–discharge processes was limited to a specific capacity cutoff of 600 mAh/g with a current density of 200 mA/g. The PXRD pattern of the discharged sample shows three extra peaks located at 33°, 35°, and 59° compared with the pristine cathode (Figure 5b). These can be identified as diffraction from Li2O2. No other impurities are observed and the Li2O2 peaks disappear after the subsequent charging process,35 indicating a reversible process. The morphologies of the sample before and after the first cycle were directly observed using SEM (Figures 5c–5f). Considering the discharged Tz-Mg-MOF-74 cathode, Li2O2 with toroidal shapes are observed in the discharged state, in agreement with the previous results.34 After charging, the surface of Tz-Mg-MOF-74 restores to a clean pristine state, consistent with the XPS results. The SEM images of the cycled cathode indicate that the surface morphology of Tz-Mg-MOF-74 is retained in the discharged and charged states. Figure 5 | (a) Li 1s and N 1s XPS spectra of the pristine, first discharged and charged cathodes with Tz-Mg-MOF-74. (b) PXRD patterns of pristine, first discharged, and charged Tz-Mg-MOF-74-KB cathodes. (c) SEM images of the pristine Tz-Mg-MOF-74-KB cathode. (d) Energy dispersive spectrometer (EDS) mapping images of the first discharged cathode. (e) and (f) SEM images of the first discharged and charged cathodes. Download figure Download PowerPoint To gain insight into the electrocatalytic behavior of Tz-Mg-MOF-74 and illustrate the impact of the Tz moiety on the performance of the cathode, the performance of Ben-Mg-MOF-74 and KB was investigated under the same conditions for comparison. In identical test conditions, the discharge capacities of Tz-Mg-MOF-74, Ben-Mg-MOF-74, and KB at a current density of 200 mA/g are 4907, 2996, and 2920 mAh/g, respectively (Figures 3a and 3b). Notably, the discharge capacity of the Ben-Mg-MOF-74-based cathode is 40% less than that of the Tz-Mg-MOF-74-based cathode. Importantly, Tz-Mg-MOF-74 shows a higher discharge voltage and better cycling performance compared with Ben-Mg-MOF-74 ( Supporting Information Figure S14), illustrating the electroactivity of Tz to promote the electrochemical kinetics. Electrochemical impedance spectroscopy (Figure 3c) reveals that the Tz-Mg-MOF-74-based cathode has higher electrochemical activity compared with the Ben-Mg-MOF-74, which is attributed to the synergy of the redox activity and the close packing of the Tz moieties.36 Besides, the almost identical pore sizes and O2 capture capabilities of Ben-Mg-MOF-74 and Tz-Mg-MOF-74 (Figures 3d and 3e) imply that the presence of redox-active Tz is decisive for the enhanced performance of the corresponding cathode. In summary, a new strategy for the targeted construction of cathode materials utilizing a redox-active moiety embedded in a porous MOF to enhance the performance of Li–O2 batteries is demonstrated. A new Tz-functionalized mesoporous MOF was successfully designed with enhanced performance. The design takes advantages of the redox activity of Tz and structural feature of MOFs to accelerate the electrochemical kinetics toward lower overpotential and boost the reaction efficiency with high capacity. The overall performance gain is greater than that of the analogs MOF without Tz and other reported MOF-based catalysts. This system provides a proof of concept that motivates the exploration of future redox-active functionalized materials. There is clearly potential for improved performance for energy storage and conversion applications using this approach. Supporting Information Supporting Information is available. Conflict of Interest The authors declare no conflict of interest. Acknowledgments This study was supported by the NSFC (nos. 21421001, 21531005, 21905142, and 21671112), the Program of Introducing Talents of Discipline to Universities (no. B18030), and the Natural Science Fund of Tianjin (nos. 19JCZDJC37200 and 19JCQNJC02600), China. The authors thank Professor Brian Space (University of South Florida, Tampa, FL) for discussion and help. References 1. Zeng C.; Xie F.; Yang X.; Jaroniec M.; Zhang L.; Qiao S. Z.Ultrathin Titanate Nanosheets/Graphene Films Derived from Confined Transformation for Excellent Na/K Ion Storage.Angew. Chem. Int. Ed.2018, 57, 8540–8544. Google Scholar 2. Ye C.; Jiao Y.; Jin H.; Slattery A. D.; Davey K.; Wang H.; Qiao S. Z.2D MoN-VN Heterostructure to Regulate Polysulfides for Highly Efficient Lithium-Sulfur Batteries.Angew. Chem. Int. Ed.2018, 57, 16703–16707. Google Scholar 3. Kong L.; Zhu J.; Shuang Bu Derived from MOF for Energy Google Scholar S. J.; and Batteries with Energy Google Scholar H.; Wang H.; Qiao S. for Chem. Google Scholar D.; S. S. D.; X.; to and Energy Google Scholar Li F.; of Energy Google Scholar J.; Wang L.; D.; Zhang L.; Zhang and of and Google Scholar X.; Wang Batteries and Their Chem. Int. Google Scholar D.; D.; F.; in Google Scholar L.; Cathode via of in a Chem. Google Scholar H.; for Energy Google Scholar Zeng C.; Wang X.; Zhang L.; Qiao S. as an Efficient for Google Scholar of in of Chem. Google Scholar Y.; S. a a Google Scholar S. Y.; Y.; M.; the of the on in Chem. Google Scholar D.; Black Highly for of Google Scholar of and in Google Scholar as for and Molecular Google Scholar M.; C.; C.; and with Chem. Google Scholar K. L.; M.; and of a and Then Google Scholar S. H.; D.; for and Google Scholar and in Google Scholar A. and for Advanced Electrochemical Energy Google Scholar Li Y.; J.; Y.; Wang J.; X.; Y.; Wang in the for Performance in Google Scholar Zhao for Google Scholar D.; X.; Zhang L.; Wang Li as Cathode Materials for Google Scholar S. H.; J.; H.; as Efficient Cathode for Google Scholar L.; D.; A. C.; H.; H.; F.; in an Google Scholar J.; L.; K.; M.; with Excellent of and for Chem. Google Scholar J.; F.; S. as a Material for Google Scholar X.; Y.; L.; in Batteries Electrolyte Google Scholar J.; M.; H.; for Google Scholar Li F.; M.; D.; D.; Based on Highly Efficient Google Scholar M.; S. in Chem. Google Scholar K. C.; K.; J.; for with Chem. Google Scholar Information study was supported by the NSFC (nos. 21421001, 21531005, 21905142, and 21671112), the Program of Introducing Talents of Discipline to Universities (no. B18030), and the Natural Science Fund of Tianjin (nos. 19JCZDJC37200 and 19JCQNJC02600), China. The authors thank Professor Brian Space (University of South Florida, Tampa, FL) for discussion and help.

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