Fabrication and Electrochemical Performance of Polyoxometalate

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Functional Inorganic Materials and Devices

Fabrication and Electrochemical Performance of POM-based Threedimensional Metal Organic Frameworks Containing Carbene Nanocages Jing-Quan Sha, Xi-Ya Yang, Yanyan Chen, Pei-Pei Zhu, Yufei Song, and Jianzhuang Jiang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04009 • Publication Date (Web): 26 Apr 2018 Downloaded from http://pubs.acs.org on April 26, 2018

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ACS Applied Materials & Interfaces

Fabrication and Electrochemical Performance of POM-based Three-dimensional Metal Organic Frameworks Containing Carbene Nanocages ⊥

⊥

Jing-Quan Sha,†,‡ Xi-Ya Yang,† Yanyan Chen, Pei-Pei Zhu,† Yu-Fei Song,* and Jianzhuang Jiang*‡ †

Key Laboratory of Inorganic Chemistry in Universities of Shandong, Department of Chemistry

and Chemical Engineering, Jining University, Qufu, Shandong, 273155, China ‡

Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline

Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China ⊥

Beijing Advanced Innovation Center for Soft Matter Science and Engineering, State Key La-

boratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

ABSTRACT: Two new polyoxometalate-based three-dimensional metal organic carbene frameworks,

[Ag10(trz)4(H2O)2][HPW12O40]

(POMs@MCNCs-1)

and

[Ag10(trz)4(H2O)6][H2SiW12O40] (POMs@MCNCs-2), were hydrothermally synthesized, in which Keggin-type polyoxoanions as templates induce the formation of two different kinds of

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metal-carbene nanocages (MCNCs) for the first time. Combination of the reversible multielectron redox behavior and electron storage functions of POMs with the good electrical conductivity of the single-walled carbon nanotubes (SWNTs) renders the POMs@MCNCs-1/SWNT composite excellent electrochemical performance and good stability as anode materials of lithium-ion batteries (LIBs), with up to 2000 mAh g-1 for the first discharge capacity and ca. 859 mAh g-1 for the second cycle at a current density of 100 mA g-1. The successful fabrication of unprecedented metal-carbene nanocages into the POM-based three-dimensional metal-organic frameworks in the present work must initiate extensive research interests in diverse fields. KEYWORDS: Polyoxometalates, Carbene nanocage, Carbon nanotubes, Anode materials, Lithium-ion batteries


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INTRODUCTION Carbenes, defined as neutral compounds containing a divalent carbon atom with a six-electron valence shell, have been considered as important transient intermediates for a long time. However, due to the significant difficulty in controlling their reactivity, as late as in 1991 the first stable carbene, actually the Arduengo-type N-heterocyclic carbene (NHC), was isolated.1 In 1995, the Pd complex of NHC was found to exhibit efficient catalysis activity in the Heck coupling reactions.2 This resulted in the evolution of metal-carbene complexes (MCCs) into one of the most active topics in organometallic chemistry.3-6 As a consequence, many mono-/bidentate-carbenes in particular NHCs bearing N-alkyl or -aryl wingtips have been synthesized and isolated associated with their relatively good stability in order to explore their inherent performances and especially generate functional metal-carbene complexes (Scheme S1).7-9 However, MCCs constructed from NHCs generated in situ, in particular those with high reactivity and low stability and therefore hard to isolate, still remain unknown, to the best of our knowledge. For the purpose of yielding new functional materials, trials for developing the strategy towards forming and/or affording MCCs by means of NHCs generated in situ (without the necessary synthesis and isolation in a separate manner) is therefore of great significance. On the other hand, in the past two decades significant progress has been achieved over the application of metal organic frameworks (MOFs) in diverse fields such as gas storage and separation, catalysis, sensor, drug delivery etc.10-13 In particular, nanocage-containing MOFs14-16 have been emerging as a new hot direction and attracting increasing interest due to their potential application as molecular trap for the confined chemical reaction and as catalysis for organic reactions associated with their elegant structures.17-20 As can be expected, great effort then has been directed towards constructing metal-carbene nanocage organic frameworks with MCCs as sec-



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ondary building units. However, despite the efforts paid in this regard, metal-carbene nanocagecontaining MOF system still remains unreported, with [M10(H3trz)4(Htrz)4](HnXW12O40) (M = Ag, Cu, X = P, Si) even as the sole example of the three-dimensional metal-carbene organic framework.21 Considering the successful template role during the adamantane-like nanocage [Ag24(trz)18]6+ formation22 and effective catalysis activity for the C–C cleavage of viologen monomer,23 polyoxometalates (POMs) with abundant topologies and fascinating electronic properties24-26 might be selected as the suitable candidate to induce the fabrication of metal-carbene nanocage-containing metal-organic frameworks under certain reaction condition. Indeed, in the present work hydrothermal reaction between 1,2,3-triazole-4,5-dicarboxylic acid (H3tda) and Keggin-type POMs, [PW12O40]3-/[SiW12O40]4-, leads to the successful formation and isolation of two unprecedented POMs-based three-dimensional MOFs containing the metal-carbene nanocages,

[Ag10(trz)4(H2O)2][HPW12O40]

(POMs@MCNCs-1)

and

[Ag10(trz)4(H2O)6][H2SiW12O40] (POMs@MCNCs-2), via the in situ POM-aided generation of carbene and carbene nanocage, Scheme 1. Scheme 1. Schematic formation process of metal-carbene nanocage involved in the present work.

At the end of this section, it is worth noting that in recent years lithium ions batteries (LIBs) as one of major electrical energy storage materials have attracted intriguing interests.27-29 However, graphite, as commercial LIBs anode material, exhibits lower theoretical capacity (< 372 mAh g−1) and relatively poor rate performance.30 As a result, developing new alternative anode mate-


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rials for LIBs becomes highly desired. A wide range of investigations have demonstrated the great prospect of POMs for electrochemical energy storage associated with their reversible multielectron redox behavior and electron storage functions,31 of MOFs due to their advantages toward conversion-type reactions of LIBs provided by their appropriate metal centers and organic linkers,32 and in particular of POMOFs because of the combination of both POMs and MOFs advantages.33,34 However, practical application of these materials in LIBs is still hampered due mainly to their poor electronic conductivity, limited capacity, and poor cycling performance. Fortunately, fabrication of POM-based compounds into composites with carbon materials with good electric conductivity like carbon nanotubes (CNTs) and reduced graphene oxide (RGO) significantly improve their electrochemical performance as electrode materials of LIBs.35-37 As a consequence, herein the newly prepared polyoxometalates-based three-dimensional carbene nanocage-containing metal-organic framework POMs@MCNCs-1 was also integrated with SWNT into composite POMs@MCNCs-1/SWNT, which indeed shows excellent electrochemical performance. RESULTS AND DISCUSSION Synthesis. In 2010, the first adamantine-like [Ag24(trz)18]6+ nanocage-containing silver-triazole polycatenane framework was isolated with the help of Keggin-type polyoxoanion,22 which was followed by the isolation of another 28-nuclear [Zn28(trz)34] nanocage formed in the presence of the Keggin-type [SiW12O40]4- polyanion.38 Both examples demonstrate the effective template role of the POMs during the nanocage formation. Nevertheless, the -C–C- cleavage of viologen monomer catalyzed by Na9[EuW10O36]23 and the decarboxylation of H2pzdc catalyzed by AgSiW12O40/CuP2W18O6239 clearly revealed the effective catalysis activity of POMs for the stable C–C bonds. As a result, in the present case the saturated Keggin-type polyoxoanion, [PW12O40]3-



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/[SiW12O40]4-, was selected to aid the proceeding of the reaction between 1,2,3-triazole-4,5dicarboxylic and AgNO3 under hydrothermal condition, resulting in the successful isolation of the POM-based three-dimensional metal organic frameworks containing carbene nanocages [Ag10(trz)4(H2O)2][HPW12O40]

(POMs@MCNCs-1)

and

[Ag10(trz)4(H2O)6][H2SiW12O40]

(POMs@MCNCs-2). No targeted compounds could be isolated when the Keggin-type POMs are absent. In addition, replacement of 1,2,3-triazole-4,5-dicarboxylic acid by 1,2,3-triazole/1,2,3,4tetrazole led to the isolation of compound H[Ag27(trz)16(H2O)4][PW12O40]2·2H2O and [Ag10(ttz)4(H2O)2][HPW12O40], respectively, rather than the target POM-based three-dimensional metal organic frameworks containing carbene nanocages, please refer to Experimental Section 1.6, 1.7, and Tables S2 and S3 (Supporting Information). As a total result, most probably the C– C cleavage of H3tda molecules was achieved under the help of corresponding POMs at high temperature and pressure, leading to the formation of the 1,2,3-triazole-like intermediate with lone pair electrons, actually the NHC. Complexation of the NHC intermediate with Ag+ templated by the POM inorganic polyanion induces the formation of metal-carbene nanocage, which further packs into the targeted POM-based three-dimensional metal organic frameworks containing carbene nanocages (Scheme S2). Single crystal structure. Single crystal X-ray diffraction analysis reveals the isomorphous crystal structure of POMs@MCNCs-1 and POMs@MCNCs-2. As a consequence, Figures 1 and 2 show the structure of POMs@MCNCs-1 as a typical representative. The asymmetric unit cell of POMs@MCNCs-1 consists of one-eighth of a polyoxoanions [PW12O40]3- (PW12), half each of two independent Ag+ ion, one quarter of a third disorder Ag+ ion, half of an independent triazole ligand, one quarter of a water molecule, with their coordinated modes shown in Figure S1. There are two crystallographic independent 1,2,3-triazole-like NHC intermediates, both of which adopt


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the quadridentate coordination linking with neighboring NHC units through Ag ions to form the metal-carbene nanocage templated by PW12 polyoxoanion. Interestingly, two different types of carbene nanocages with free diameter of ca. 11.4 (nanocage A) and 7.1 Å (nanocage B), respectively, exist in the POMs@MCNCs-1. Each of which is composed of 20 Ag centers and 16 trz ligands (Figures 1 and S2a). In addition, both the nanocages A and B consist of 2 regular tetragonal windows and 8 quadrangular trapezium windows, forming 12 vertices, 20 edges, and 10 faces, meeting well with the Euler rule of “vertex + face - edge = 2”. Specifically, four Ag2 ions link with four triazole ligands in a imidazole-like bridging mode to give a space octagon polygon [Ag4(trz)4], which bonds with eight Ag(trz)2 units through eight Ag1 ions in both upward and downward patterns, resulting in the formation of [Ag20(trz)16] nanocage A. Different from nanocage A, carbene nanocage B is composed of two crown-like [Ag4(trz)4], eight Ag2 cations, and eight Ag(trz)2 subunits. The apical four trz ligands of nanocage B adopt the pyrazole-like coordination mode to complex with Ag1 ions, forming the crown-like [Ag4(trz)4] moiety. Two [Ag4(trz)4] rings and eight Ag(trz)2 fragments are then linked together using eight Ag2 ions as connector to form the [Ag20(trz)16] nanocage B, which contains two Ag atoms along a axis, Figure S3 (Supporting Information). Furthermore, by sharing their top and bottom [Ag4(trz)4] segments in adjacent nanocages, a 1D nanocage array along the c axis is formed from either nanocage A or nanocage B, respectively (Figure 2a). The two neighboring 1D nanocage arrays formed from nanocage A and B, respectively, then connect with each other via sharing half of their framework, Figure 2b, leading to the formation of the three-dimensional metal-carbene nanocage MOFs (Figures 2c and S2b). At the end of this paragraph, it is noteworthy that one PW12 polyoxoanion locates inside each carbene nancage A, which connects with the carbene nanocage shell through twenty O-Ag covalent bonds via eight Ag1, eight Ag2, and four Ag3 cations, Figu-



re S4a (Supporting Information). This however is not the case for the carbene nanocage B, which is filled by Ag3 ions and water molecules, Figures 2c and S4b (Supporting Information).

Figure 1. Ball/stick representation of the details of the metal-carbene nanocages A and B in POM@MCNC-1.


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Figure 2. (a) Representation of two kinds of one dimensional nanocage arrays constructed by nanocages A and B, respectively. (b) The connection pattern of nanocages A and B. (c) View of the whole framework of POMs@MCNCs-1 containing nanocage tubes occupied by PW12 polyanions and Ag3 ions, respectively. XPS, XPRD, SEM, EDS, FT-IR, and Raman spectroscopic characterization. The POMs@MCNCs-1, POMs@MCNCs-2, and POMs@MCNCs-1/SWNT composite were fully



characterized by XPS, XPRD, SEM, EDS, FT-IR, SEM, EDS, and Raman spectroscopic techniques, Figures 3 and S6-S11 (Supporting Information). XPS of POMs@MCNCs-1/SWNT composite shows the strong signals of C1s, Ag3d, W4f, and P2p, indicating the presence of POMs@MCNCs-1 in the nanocomposite, among which two peaks at 35.2 and 37.3eV should be attributed to W+6 and two peaks at 375.0 and 368.5 eV to Ag+. Observation of the signal at 285.45 eV due to -C-N- can be attributed to the POMs@MCNCs-1 in the POMs@MCNCs1/SWNT composite (Figure 3a), which was not found in pure SWNT.40 In the Raman spectrum of the POMs@MCNCs-1/SWNT composite (λex = 532 nm), Figure 3b, the tangential vibration mode (G-band), disorder-induced D-band, and 2D-band of SWNT appear at 1586, 1326, and 2670 cm-1, respectively, demonstrating the structural integrity of SWNT with POMs@MCNCs-1 in the composite. Additional evidence for this point comes from the FTIR spectroscopic and powder XRD measurement results of POMs@MCNCs-1/SWNT composite, Figures S10 and S11 (Supporting Information). Nevertheless, electron microscopy was also used to study the structural feature of the materials. For pristine SWNTs, scanning electron microscopy (SEM) showed a high degree of agglomeration. In contrast, the POMs@MCNCs-1/SWNT composite features a significantly lower degree of agglomeration, highlighting their increased dispersibility in ethanol (Figure 3c). Finally, EDX spectroscopy was employed to further explore the incorporation of POMs@MCNCs-1 with SWNT matrix in the composite. The presence of P, W, and Ag elements confirms the integration of the POMs@MCNCs-1 with SWNT in the composite (Figure 3d).


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Figure 3. (a) X-ray photoelectron spectra of C1s peak analysis of the POMs@MCNCs-1/SWNT composites. (b) Raman spectra of the SWNT, POMs@MCNCs-1 and POMs@MCNCs-1/SWNT composites. (c) SEM image and (d) EDX analysis of the POMs@MCNCs-1/SWNT hybrids. Electrochemical

performance.

The

battery

performances

of

POMs@MCNCs-1

and

POMs@MCNCs-1/SWNT composite as anode materials in LIBs were comparatively studied and evaluated by assembling it into coin cells with metallic lithium as counter electrode and cycled between 0-3 V vs Li+/Li, Figures 4a and S12a (Supporting Information). The first discharge capacity of POMs@MCNCs-1 is 1200 mAh g-1 at a current density of 100 mA g−1. Compared with (NBu4)3[PW12O40] (434 mAh g-1), Figure S13 (Supporting Information), fabrication of the POMs and carbene nanocages into the three-dimensional frameworks combine the advantages of POMs, MOFs, and in particular the carbenes for electrochemical energy storage, resulting in the quite good intrinsic electrochemical performance of POMs@MCNCs-1 anode. However, the second cycle capacity is reduced to 600 mAh g-1. The significant loss in capacity



during the initial cycles is attributed to the formation of solid electrolyte interphase (SEI) films, a common phenomenon in LIBs.41 After grafting POMs@MCNCs-1 on SWNT with high conductivity performance to give POMs@MCNCs-1/SWNT composite, Figure S5 (Supporting Information), the electrochemical performance was significantly enhanced, in terms of 2000 mAh g-1 for the first discharge capacity and ca. 859 mAh g-1 for the second cycle, in comparison with those for POMs@MCNCs-1, 1200 and 600 mAh g-1, under the same condition, indicating an enhanced conductivity of the POMs@MCNCs-1/SWNT composite due to the presence of SWNT. Even after 70 cycles, the reversible capacity can be stabilized at ca. 800 mAh g-1 for POMs@MCNCs-1/SWNT and ca. 400 mAh g-1 for POMs@MCNC-1, demonstrating the good cycling stability. Nevertheless, after the first few cycles, the coulombic efficiency (CE) of POMs@MCNCs-1/SWNT and POMs@MCNCs-1 could be quickly improved to above 99%, confirming the formation of stable SEI films, Figures 4b and S12b (Supporting Information). On the basis of the excellent electrochemical performance of the POMs@MCNCs-1/SWNT composite at 100 mA g-1 and for their future practical application, the cycling stability of this composite electrode was further tested at the current density of 100, 200, 400, 600, 800 to 1000 mA g-1, respectively, giving the discharge specific capacity of ca. 859, 620, 465, 390, 325, 285 mAh g-1 (Figure 4c). Nevertheless, when the current density resets to 100 mA g-1, the capacity can be restored to 850 mAh g-1. For comparative study, the rate performance of POMs@MCNCs-1 was also investigated under the same conditions, giving the discharge specific capacity of ca. 354, 335, 279, 237, 197, 177 mAh g-1, Figure S12c (Supporting Information). The results verify the high stability of the POMs@MCNCs-1 and POMs@MCNCs-1/SWNT composite as LIBs anode material.


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In order to further understand the inherent electrochemical behavior of as-fabricated electrodes derived from the POMs@MCNCs-1/SWNT and POMs@MCNCs-1, cyclic voltammograms (CV) were collected. An irreversible reduction peak at 0.7 V could be observed only in the first cycle for both POMs@MCNCs-1/SWNT and POMs@MCNCs-1 electrodes, Figures 4d and S12d (Supporting Information), indicating the formation of solid electrolyte interphase,41 which gets disappeared in the following cycles. Observation of the peak at ~1 V in the reduction process is attributed to the reduction of W during the insertion of Li+ into the POM for both electrodes.42 In addition, the oxidation states of W atoms in POMs@MCNCs-1/SWNT compound are confirmed by XPS measurements, Figure S14 (Supporting Information). After the insertion of Li+ into the POM, the most of the peaks of W6+ converted into the W4+. This result indicates that the W6+ is reduced to the W4+ during the intercalation.To unravel the internal resistance of the battery, the electrochemical impedance spectroscopy (EIS) was carried out to explore the electrochemical processes of the POMs@MCNCs-1/SWNT composite. As illustrated in Figure S15 (Supporting Information), the EIS measurement gives the interface information between the electrode and electrolyte. The electrolyte resistance (Re) and charge transfer resistance (Rct) are 2.63 and 73.51 Ω for the POMs@MCNCs-1, and 2.69 and 42.29 Ω for the POMs@MCNCs-1/SWNT composite electrode, respectively. As such, the POMs@MCNCs-1/SWNT composite shows much improved charge transfer than that of the POMs@MCNCs-1. In addition, a straight line with a slope of about 65o can be observed at the low frequency for the POMs@MCNCs-1/SWNT composite, indicating the potential as capacitance material.



Figure 4. Electrochemical performance of POMs@MCNCs-1/SWNT. (a) Charge/discharge profiles for the first and second cycle constantly at 100 mA g−1. (b) Cycling performance at a current density of 100 mA g−1. (c) Cycling at various current densities. (d) Cyclic voltammograms profiles in the range of 0.01–3 V at a scan rate of 0.1 mV/s. CONCLUSIONS In summary, we have developed a new general strategy towards the straightforward preparation of three-dimensional metal-organic carbene frameworks by means of the in situ generated Nheterocyclic carbene with POMs as template. The rare metal-carbene nanocages have also been constructed and revealed for the first time. The resultant compound especially after being fabricated into composite with SWNT shows excellent electrochemical performance as anode material of LIBs. The successful fabrication of metal-carbene nanocages into the POM-based metalorganic frameworks reported in the present work will initiate further research interests towards various application-driven functional studies in diverse fields.


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ASSOCIATED CONTENT Supporting Information. Tables of selected bond lengths and bond angles for compounds 1 and 2; IR and PXRD and part structural figures of compounds 1 and 2. This information is available free of charge via the Internet at http: //pubs.acs.org. AUTHOR INFORMATION

Corresponding Author * E-mail: [email protected] * E-mail: [email protected] Notes The authors declare no competing financial interests. ACKNOWLEDGMENT Financial support from the Natural Science Foundation of China (Nos. 21631003, 21671017, 21301017, 21401009), the Talent Culturing Plan for Leading Disciplines of University in Shandong Province, Beijing Municipal Commission of Education, and University of Science and Technology Beijing is gratefully acknowledged. REFERENCES (1) Arduengo, A. J.; Harlow, R. L.; Kline, M. A Stable Crystalline Carbine. J. Am. Chem. Soc. 1991, 113, 361-363. (2) Herrmann, W. A.; Elison, M.; Fischer, J.; Köcher, C.; Artus, G. R. J. Metal Complexes of NHeterocyclic Carbenes-A New Structural Principle for Catalysts in Homogeneous Catalysis. Angew. Chem. Int. Ed., 1995, 34, 2371-2374.



(3) Sierra, M. A.; Amo, J. C. D.; Mancheño, M. J.; Gallego, M. G. Pd-Catalyzed Inter- and Intramolecular Carbene Transfer from Group 6 Metal-Carbene Complexes. J. Am. Chem. Soc. 2001, 123，851-861. (4) Poyatos,M.; Mata, J. A.; Peris, E. Complexes with Poly (N-heterocyclic carbene) Ligands: Structural Features and Catalytic Applications. Chem. Rev. 2009, 109, 3677-3707. (5) Liu, Z. X.; Tan, H. C.; Fu, T. R.; Xia, Y.; Qiu, D.; Zhang, Y.; Wang, J. B. Pd-Catalyzed Carbene Insertion into Si-Si and Sn-Sn Bonds. J. Am. Chem. Soc. 2015, 137, 12800-12803. (6) Murauski, K. J. R.; Jaworskia, A. A.; Scheidt, K. A. A Continuing Challenge: N-heterocyclic Carbenecatalyzed Syntheses of γ-butyrolactones. Chem. Soc. Rev. 2018, 47, 1773-1782. (7) Crabtree, R. H. Abnormal, Mesoionic and Remote N-heterocyclic Carbene Complexes. Coord. Chem. Rev. 2013, 257, 755-766. (8) Lazreg, F.; Nahra, F.; Cazin, C. S. J. Copper-NHC Complexes in Catalysis. Coord. Chem. Rev. 2015, 293, 48-79. (9) Trose, M.; Lazreg, F.; Chang, T.; Nahra, F.; Cordes, D. B.; Alexandra, M. Z. S.; Catherine, J. C. Neutral Dinuclear Copper (I)-NHC Complexes: Synthesis and Application in the Hydrosilylation of Ketones, ACS Catal. 2017, 7, 238-242. (10) Long, J. R.; Yaghi, O. M. The Pervasive Chemistry of Metal-Organic Frameworks. Chem. Soc. Rev. 2009, 38, 1213-1214. (11) Lu, G.; Hupp J. T. Metal-Organic Frameworks as Sensors: A ZIF-8 Based Fabry-Pérot Device as A Selective Sensor for Chemical Vapors and Gases. J. Am. Chem. Soc. 2010, 132, 78327833.


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Page 17 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(12) Jiang, H. L.; Feng, D.; Wang, K.; Gu, Z. Y.; Wei, Z.; Chen, Y. P.; Zhou, H. C. An Exceptionally Stable, Porphyrinic Zr Metal-Organic Framework Exhibiting pH-dependent Fluorescence. J. Am. Chem. Soc. 2013, 135, 13934-13938. (13) Deria, P.; Gómez-Gualdrón, D. A.; Hod, I.; Snurr, R. Q.; Hupp, J. T.; Farha O. K. Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato) zinc (II) MOFs. J. Am. Chem. Soc. 2016, 138, 14449-14457. (14) Zheng, S. T.; Zhang, J.; Li, X. X.; Fang, W. H.; Yang, G. Y. Cubic PolyoxometalateOrganic Molecular Cage. J. Am. Chem. Soc. 2010, 132, 15102-15103. (15) Yoneya, M.; Tsuzuki, S.; Yamaguchi, T.; Sato, S.; Fujita M. Coordination-Directed SelfAssembly of M12L24 Nanocage: Effects of Kinetic Trapping on the Assembly Process. ACS Nano 2014, 8, 1290-1296. (16) Chen, S.; Li, K.; Zhao, F.; Zhang, L.; Pan, M.; Fan, Y. Z.; Guo, J.; Shi, J.; Su, C. Y. A Metal-Organic Cage Incorporating Multiple Light Harvesting and Catalytic Centres for Photochemical Hydrogen Production. Nat. commun. 2016, 7, 13169. (17) Yoshizawa, M.; Klosterman, J. K.; Fujita M. Functional Molecular Flasks: New Properties and Reactions within Discrete, Self-Assembled Hosts. Angew. Chem. Int. Ed. 2009, 48, 34183438. (18) Pluth, M. D.; Bergman, R. G.; Raymond, K. N. Acid Catalysis in Basic Solution: A Supramolecular Host Promotes Orthoformate Hydrolysis. Science 2007, 316, 85-88. (19) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The Chemistry and Applications of Metal-Organic Frameworks. Science 2013, 341, 1230444.



(20) Ji, P.; Feng, X.; Veroneau, S. S.; Song, Y.; Lin, W. Trivalent Zirconium and Hafnium Metal-Organic Frameworks for Catalytic 1, 4-Dearomative Additions of Pyridines and Quinolines. J. Am. Chem. Soc. 2017, 139, 15600-15603. (21) Zhu, P. P.; Sheng, N.; Li, M. T.; Li, J. S.; Liu, G. D.; Yang, X. Y.; Sha, J. Q.; Zhu, M. L.; Jiang J. Z. Fabrication and Electrochemical Performance of Unprecedented POM-Based MetalCarbene Frameworks. J. Mater. Chem. A 2017, 5, 17920-17925. (22) Kuang, X.; Wu, X.; Yu, R.; Donahue, J. P.; Huang, J.; Lu, C. Z. Assembly of A Metal– Organic Framework by Sextuple Intercatenation of Discrete Adamantane-like Cages. Nat. Chem. 2010, 2, 461-465. (23) Shen, D. F.; Li, S.; Liu, H.; Jiang, W.; Zhang, Q.; Gao, G. G. A Durable and FastResponsive Photochromic and Switchable Luminescent Polyviologen-Polyoxometalate Hybrid, J. Mater. Chem. C 2015, 3, 12090-12097. (24) Pope, M.; Müller, A. Polyoxometalate Chemistry: From Topology Via Self-Assembly to Applications. Kluwer: Dordrecht, The Netherlands 2001. (25) Zhang, Z. M.; Zhang, T.; Wang, C.; Lin, Z.; Long, L. S.; Lin, W. Photosensitizing MetalOrganic Framework Enabling Visible-Light-Driven Proton Reduction by A Wells–Dawson-type Polyoxometalate. J. Am. Chem. Soc. 2015, 137, 3197-3200. (26) Boyd, T.; Mitchell, S. G.; Gabb, D.; Long, D. L.; Song, Y. F.; Cronin, L. POMzites: A Family of Zeolitic Polyoxometalate Frameworks from A Minimal Building Block Library. J. Am. Chem. Soc. 2017, 139, 5930-5938. (27) Chen, J.; Mao, Z.; Zhang, L.; Wang, D.; Xu, R.; Bie, L.; Fahlman, B. D. Nitrogen-Deficient Graphitic Carbon Nitride with Enhanced Performance for Lithium Ion Battery Anodes. ACS Nano 2017, 11, 12650-12657.


Page 18 of 23

Page 19 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(28) Huang, Q.; Wei, T.; Zhang, M.; Dong, L. Z.; Zhang, A. M.; Li, S. L.; Liu, W. J.; Liu, J.; Lan, Y. Q. A Highly Stable Polyoxometalate-Based Metal-Organic Framework with π-π Stacking for Enhancing Lithium Ion Battery Performance. J. Mater. Chem. A. 2017, 5, 8477-8483. (29) Yang, J.; Wu, Q.; Yang, X.; He, S.; Khan, J.; Meng, Y.; Zhu, X.; Tong, S.; Wu, M. MesoCrystalline Zn-Doped Fe3O4 Hollow Submicrospheres: Formation Mechanism and Enhanced Photo-Fenton Catalytic Performance, ACS Appl. Mater. Interfaces 2017, 9, 354-361. (30) Naji, A.; Willmann, P.; Billaud, D. Electrochemical Intercalation of Lithium into Graphite: Influence of the Solvent Composition and of the Nature of the Lithium Salt. Carbon 1998, 36, 1347-1352. (31) Wang, H.; Hamanaka, S.; Nishimoto, Y.; Irle, S.; Yokoyama, T.; Yoshikawa, H.; Awaga, K. In Operando X-ray Absorption Fine Structure Studies of Polyoxometalate Molecular Cluster Batteries: Polyoxometalates as Electron Sponges. J. Am. Chem. Soc. 2012, 134, 4918-4924. (32) Choi, K. M.; Jeong, H. M.; Park, J. H.; Zhang, Y. B.; Kang, J. K.; Yaghi, O. M. Supercapacitors of Nanocrystalline Metal-Organic Frameworks, ACS Nano 2014, 8, 7451-7457. (33) Yue, Y. F.; Li, Y. C.; Bi, Z. H.; Veith, G. M.; Bridges, C. A.; Guo, B. K.; Chen, J.; Mullins, D. R.; Surwade, S. P.; Mahurin, S. M.; Liu, H. J.; Paranthaman, M. P.; Dai, S. A POM-Organic Framework Anode for Li-ion Battery. J. Mater. Chem. A. 2013, 5, 22989-22995. (34) Wei, T.; Zhang, M.; Wu, P.; Tang, Y. J.; Li, S. L.; Shen, F. C.; Wang, X. L.; Zhou, X. P.; Lan, Y. Q. POM-Based Metal-Organic Framework/Reduced Graphene Oxide Nanocomposites with Hybrid Behavior of Battery-Supercapacitor for Superior Lithium Storage. Nano Energy 2017, 34, 205-214.



(35) Hu, J.; Ji, Y.; Chen, W.; Streb, C.; Song, Y. F. “Wiring” Redox-Active Polyoxometalates to Carbon Nanotubes Using A Sonication-Driven Periodic Functionalization Strategy, Energy Environ. Sci. 2016, 9, 1095-1101. (36) Xie, J. J.; Zhang, Y.; Han, Y. L.; Li, C. L. High-Capacity Molecular Scale Conversion Anode Enabled by Hybridizing Cluster-Type Framework of High Loading with AminoFunctionalized Graphene, ACS Nano 2016, 10, 5304-5313. (37) Ding, Y. H.; Peng, J.; Khan, S. U.; Yuan, Y. A New Polyoxometalate (POM)-Based Composite Fabrication through POM-Assisted Polymerization of Dopamine and Properties as Anode Materials for High-Performance Lithium Ion Battery, Chem. Eur. J. 2017, 23, 10338-10343. (38) Zhou, E. L.; Qin, C.; Wang, X. L.; Shao, K. Z.; Su, Z. M. Steam-Assisted Synthesis of An Extra-Stable Polyoxometalate Encapsulating Metal Azolate Framework: Applications in Reagent Purification and Proton Conduction. Chem. Eur. J. 2015, 37, 13058-13064. (39) Fan, L.; Yu, K.; Lv, J.; Zhang, H.; Su, Z.; Wang, L.; Wang, C.; Zhou, B. Synthesis and Photo-/Electro-Catalytic Properties of A 3D POMOF Material Based on An Interpenetrated Copper Coordination Polymer Linked by In Situ Dual Ligands and Dawson-type Phosphotungstates. Dalton Trans. 2017, 46, 10355-10363. (40) Ji, Y; Hu, J; Huang, L; Chen, W; Streb, C; Song, Y. F. Covalent Attachment of AndersonType Polyoxometalates to Single-Walled Carbon Nanotubes Gives Enhanced Performance Electrodes for Lithium Ion Batteries. Chem. Eur. J. 2015, 21, 6469-6474. (41) Yuan, T. Z.; Jiang, Y. Z.; Sun, W. P.; Xiang, B.; Li, Y.; Yan, M.; Xu, B.; Dou, S. X. EverIncreasing Pseudocapacitance in RGO-MnO-RGO Sandwich Nanostructures for Ultrahigh-Rate Lithium Storage. Adv. Funct. Mater. 2016, 26, 2198-2206.


Page 20 of 23

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(42) Wang, S; Li, H; Li, S; Liu, F; Wu, D; Feng X; Wu, L. Electrochemi cal-Reduction-Assisted Assembly of a Polyoxometalate/Graphene Nanocomposite and Its Enhanced Lithium-Storage Performance. Chem Eur J, 2013, 19, 10895-10902.



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Table of Contents POM-based

three-dimensional

metal-carbene

nanocage-containing

organic

frameworks

POMs@MCNCs were prepared and isolated via the in situ POM-aided formation of carbene and in turn carbene nanocages under hydrothermal condition, which exhibit excellent electrochemical performance as anode materials of lithium-ion batteries after being fabricated into composite with SWNT.

22 ACS Paragon Plus Environment

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Fabrication and Electrochemical Performance of POM-based

Three-dimensional

Metal

Organic

Frameworks Containing Carbene Nanocages Jing-Quan Sha,†,‡ Xi-Ya Yang,† Yanyan Chen,⊥ Pei-Pei Zhu,† Yu-Fei Song,*⊥and Jianzhuang Jiang*‡

POM-based three-dimensional metal-carbene nanocage-containing organic frameworks POMs@MCNCs were prepared and isolated via the in situ POM-aided formation of carbene and in turn carbene nanocages under hydrothermal condition, which exhibit excellent electrochemical performance as anode materials of lithium-ion batteries after being fabricated into composite with SWNT.


Fabrication and Electrochemical Performance of Polyoxometalate

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