Subscriber access provided by - Access paid by the | UCSB Libraries
Increased Electrical Conductivity in Mesoporous Metal– Organic Framework Featuring Metallacarboranes Guests Chung-Wei Kung, Kenichi Otake, Cassandra T. Buru, Subhadip Goswami, Yuexing Cui, Joseph T. Hupp, Alexander M Spokoyny, and Omar K. Farha J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b00605 • Publication Date (Web): 04 Mar 2018 Downloaded from http://pubs.acs.org on March 4, 2018
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 6 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
Journal of the American Chemical Society
Increased Electrical Conductivity in Mesoporous Metal–Organic Framework Featuring Metallacarboranes Guests Chung-Wei Kung,1 Ken-ichi Otake,1 Cassandra T. Buru,1 Subhadip Goswami,1 Yuexing Cui,1 Joseph T. Hupp,1,2 Alexander M. Spokoyny3 and Omar K. Farha1,4* 1- Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States 2- Argonne National Laboratory, 9700 South Cass Ave., Argonne, Illinois, 60439, United States 3- Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90095, United States 4- Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia KEYWORDS: Atomic layer deposition, Carborane, Donor-acceptor interaction, Manganese oxide, Metal–organic frameworks ABSTRACT: Nickel (IV) bis(dicarbollide) is incorporated in a zirconium-based MOF, NU-1000, to create an electrically conductive MOF with mesoporosity. All the nickel bis(dicarbollide) units are located as guest molecules in the microporous channels of NU-1000, which permits the further incorporation of other active species in the remaining mesopores. For demonstration, manganese oxide is installed on the nodes of the electrically conductive MOF. The electrochemically addressable fraction and specific capacitance of the manganese oxide in the conductive framework are more than ten times higher than those of the manganese oxide in the parent MOF.
Metal–organic frameworks (MOFs) consist of a class of porous materials constructed from metal-rich nodes and organic linkers.1 Due to their desirable characteristics such as the periodic porosity and ultrahigh specific surface area,2 MOFs have attracted great attention in several applications over the past two decades.3 The periodic intra-framework functionality of MOFs may be utilized to install well-separated and accessible active sites within the entire framework, which renders MOFs attractive porous supports for a range of catalytic applications.4 Among all existing MOFs, zirconium-based MOFs are known for their high water stability in a wide range of pH;5 this feature provides the potential of using these MOFs in applications necessitating aqueous conditions such as hydrogen evolution catalysis6 and water adsorption from air.7 Since a high density of accessible active sites may be built into MOFs, we reasoned that MOF thin films grown on conductive substrates with proper intra-framework functionality for installing electroactive sites should be excellent supports for electrocatalysis and relevant electrochemical applications. Furthermore, due to their water stability, thin films of zirconium-based MOFs are potential candidates for energy-related electrochemical applications such as water splitting and CO2 reduction, which usually need to be operated in aqueous solutions. However, due to the electrically insulating nature of most MOFs, the performance of MOF-based materials in electrochemical applications is significantly limited.8 To design electrically conductive MOFs, various strategies have been proposed recently, including the formation of π-stacked pathways within three-dimensional MOFs,9 the design of twodimensional MOFs with π-conjugation,10 using sulfur-based
ligands to facilitate charge delocalization,11 making MOFpolymer composite,12 and the introduction of guest molecules.13 Although the electrical conductivity has been established or imparted in certain MOFs and some conductive MOFs have been utilized in electrochemical applications,8i, 10a, 14 most of these reported conductive MOFs do not possess mesoporosity, and the electrically conductive zirconium-based MOFs are still rare. In our recent study, the electrically conductive zirconium-based MOF was reported for the first time by electrochemical incorporation of polythiophene in a MOF thin film.15 However, the MOF can only be prepared as thin films and is only conductive in the potential region where the thiophene units oxidize. In this study, an electrically conductive and mesoporous zirconium-based MOF was synthesized by introducing nickel (IV) bis(dicarbollide) (Ni(C2B9H11)2, NiCB)16 into the mesoporous MOF, NU-1000.17 Constructed by pyrene-based linkers and hexa-zirconium nodes, NU-1000 crystallizes with onedimensional mesoporous hexagonal channels and microporous triangular channels and exhibits high water stability.5a, 17 Additionally, the pyrene units present in the linkers of NU-1000 have been reported as electron donors.18 On the other hand, the bis(dicarbollide) cages in NiCB can serve as electron-deficient moiety.19 Since the size of NiCB fits well within the triangular channels of NU-1000, and the lowest unoccupied molecular orbital (LUMO) of NiCB locates between the conduction bands and valence bands of both the pyrene-based linker and NU-1000 (see Section S2 in Supporting Information), we hypothesized that NiCB molecules can be incorporated in these channels as guests, between three pyrenes, to engender donor-
1 Environment ACS Paragon Plus
Journal of the American Chemical Society acceptor interactions through the whole framework and render the MOF electrically conductive. The introduction of NiCB in NU-1000 was confirmed by single-crystal X-ray diffraction (Figure 1). The obtained framework (NiCB@NU-1000) is still mesoporous with accessible aqua and hydroxyl ligands on hexa-zirconium nodes, allowing further installation of electrochemically active species by either atomic layer deposition in MOFs (AIM)4c, 8d, 17, 20 or solvothermal deposition in MOFs (SIM).4c, 20-21 As a demonstration, manganese oxide was deposited via AIM in NiCB@NU-1000. The manganese oxide installed in the conductive NiCB@NU-1000 exhibits a much higher capacitance than when installed in pristine NU-1000.
porosity of NiCB@NU-1000; the obtained isotherm and density functional theory (DFT) pore size distribution, compared with those of pristine NU-1000, are shown in Figures 2c and 2d, respectively. The Brunauer-Emmett-Teller (BET) surface area of NU-1000 decreases from 2215 m2/g to 1260 m2/g after installing NiCB, but the resulting NiCB@NU-1000 still exhibits mesoporosity. To elucidate the structural changes during the addition of NiCB, large NU-1000 crystals grown from diethylformamide17 for single-crystal XRD measurements were also infiltrated with NiCB. In solving the crystal structure, NiCB was present in all the triangular channels of NU-1000 at 100% occupancy, as illustrated in Figure 1 (see details in Section S4 in Supporting Information).
a Intensity (a.u.)
(iii) (ii) (i)
NiCB@NU-1000 NU-1000 Simulated NU-1000
b
(iii)
(ii)
(i)
2
3
4
5
6
7
8
9 10 11 12
2 Theta (degree) 1000
NU-1000 2 (2215 m /g)
3
800
c
Pore volume (cm /g)
3
Quantity adsorbed (cm /g STP)
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
Page 2 of 6
600
NiCB@NU-1000 2 (1260 m /g)
400 200 0 0.0
0.2
0.4
0.6
0.8
Relative pressure (P/P0)
1.0
0.6 0.5
NU-1000 NiCB@NU-1000
d
0.4 0.3 0.2 0.1 0.0
1
2
3
4
5
Pore size (nm)
Figure 2. a) XRD patterns of NU-1000 and NiCB@NU-1000, compared with the simulated pattern of NU-1000;17 b) SEM image of NiCB@NU-1000; c) nitrogen adsorption-desorption isotherms and d) DFT pore size distributions of NU-1000 and NiCB@NU-1000.
Figure 1. The crystal structure of NiCB@NU-1000 (100 K; only one orientation of NiCB in the triangular channels is shown for clarity). Triangular channels of NiCB@NU-1000 are also shown in space-filling model to present the close interaction between NiCB and three surrounding pyrenes. For simplicity hydrogen atoms are not shown in the structure of NiCB@NU-1000. The structure of NiCB is also presented. The synthetic procedures for NU-1000 and NiCB have been reported previously.19c, 22 NiCB@NU-1000 was prepared by immersing NU-1000 crystals in a solution of NiCB in DMF for 3 days followed by subsequent washing and drying (see experimental details in Supporting Information). Both the crystallinity and hexagonal rod-like morphology of NU-1000 are preserved after the installation of NiCB, as revealed in the powder X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) image (Figures 2a and 2b). From energy dispersive X-ray spectroscopy (EDS) elemental line scan, the overlapping distributions of Ni and Zr across a crystal of NiCB@NU-1000 indicate that NiCB was installed uniformly in the NU-1000 crystals (Figure S2).23 Inductively coupled plasma optical emission spectroscopy (ICP–OES) measurements of the digested NiCB@NU-1000 samples suggest a loading of 0.74 ± 0.07 NiCB per Zr6 node. Nitrogen adsorption-desorption experiments were utilized to investigate the
To investigate the conductivity of NiCB@NU-1000, thin films of NU-1000, NiCB, and NiCB@NU-1000 were deposited on interdigitated electrodes (IDEs) by drop-casting (see experimental details in Supporting Information). Currentvoltage (I-V) curves of the obtained IDEs were measured in air and compared with that of the bare IDE. As shown in Figure 3, the electrical conductivity of both the pristine NU-1000 and bulk NiCB is not measurable by the IDE, confirming the insulating nature of both. However, a remarkable slope appears in the I-V curve of the NiCB@NU-1000/IDE, which suggests that the NiCB@NU-1000 is electrically conductive. To estimate the electrical conductivity of NiCB@NU-1000, electrochemical impedance spectroscopy was utilized with a spincoated thin film of NiCB@NU-100015 (see Section S5 in Supporting Information for details); an electrical conductivity of 2.7 × 10-7 S/cm was achieved.24 Both the quenching of emission from the linker and the emergence of charge-transfer band in the diffuse reflectance UV-vis spectra suggest an efficient electron transfer from the excited pyrene-based linkers to NiCB25 (see Section S7 in Supporting Information); these observations imply that the obtained electrical conductivity of NiCB@NU-1000 may be attributed to the donor-acceptor charge transfer between the linker and NiCB presented uniformly within the entire framework. As revealed in the crystal structure of NiCB@NU-1000, NiCB is highly disordered with various orientations. We speculated that NiCB may not generate a new distinct band but behave as a p-type dopant to render the transport of charge carriers within the framework.26
2 Environment ACS Paragon Plus
0.10 0.05
1.4
1.0
E (V) vs. Ag/AgCl/KCl (3 M)
To demonstrate the potential use of the conductive NiCB@NU-1000 in electrochemical applications, manganese oxide was deposited in NiCB@NU-1000 to examine its redox activity and capacitance under electrochemical conditions (see experimental details in Supporting Information); the obtained material is designated as “Mn-AIM-NiCB@NU-1000”. For comparison, manganese oxide was also installed in NU-1000 (Mn-AIM-NU-1000) (see detailed characterizations in Section S8 in Supporting Information). Cyclic voltammetric (CV) curves of the spin-coated NU-1000, NiCB@NU-1000, MnAIM-NU-1000, and Mn-AIM-NiCB@NU-1000 thin films, measured in an aqueous solution of 0.1 M Na2SO4, are shown in Figure 4a. The enclosed areas in the CV curves of the NU1000 and NiCB@NU-1000 thin films are barely observable, which indicates that the capacitance originating from NU-1000 or NiCB@NU-1000 is negligible. Reversible redox peaks can be observed in the CV curve of the Mn-AIM-NU-1000 thin film, and the redox activity is significantly enhanced when the Mn-AIM-NiCB@NU-1000 thin film is used. Chronopotentiometric charge-discharge experiments reveal that both the MnAIM-NU-1000 and Mn-AIM-NiCB@NU-1000 thin films exhibit reversible redox activity (Figures 4b and 4c). Apparently, the redox behavior of manganese oxide occurring within the same potential window and in the same electrolyte is attributed to the reversible and successive Faradaic reactions between Mn(IV) and Mn(III) along with the surface adsorption/desorption of electrolyte cations.27 Since the capacitances from both the NU-1000 and NiCB@NU-1000 scaffolds are negligible (Figure 4a), the electrochemically addressable fraction of the installed manganese oxide in each thin film can be calculated from the charge estimated from Figure 4b or 4c and the loading of manganese per square centimeter of the film; the latter was obtained by the previously reported UV-vis approach (also see Section S9 in Supporting Information).8d, 21 As a result, only 1.4% of the entire Mn sites installed in the MnAIM-NU-1000 thin film are electrochemically addressable; the poor redox activity of manganese oxide may be attributed to the poor charge transport in the insulating NU-1000.8d However, in the Mn-AIM-NiCB@NU-1000 thin film, 16% of the Mn sites are electrochemically addressable, which indicates that the electrical conductivity of the NiCB@NU-1000 scaffold significantly improves the redox activity of the installed manganese oxide.28 The chronopotentiometric experiments were also conducted at various charge-discharge current densities, and the specific capacitance of the installed manganese oxide (F/gMnO2) can be calculated by assuming that two oxygens are present on each manganese atom (see the result shown in Fig-
300
100 150 200 250 300 350
Specific capacitance (F/gMnO2)
2
Figure 3. I-V curves of the bare IDE, NU-1000/IDE, NiCB/IDE, and NiCB@NU-1000/IDE.
ure 4d and Section S9 in Supporting Information for details). At a charge-discharge current density of 0.02 mA/cm2, the specific capacitance of manganese oxide in the Mn-AIMNiCB@NU-1000 thin film reaches 276 F/gMnO2,29, 10a, 14b which is more than ten times higher than that in the Mn-AIM-NU1000 thin film (21 F/gMnO2). Long-term chronopotentiometric experiment suggests that a better approach for film deposition is needed to achieve a better performance retention (see Section S10 in Supporting Information). It should be noted that although the electrical conductivity of the NiCB@NU-1000 scaffold is in the range of 10-7 S/cm, it is enough to electrochemically address ~25% of the installed Mn sites within the micrometer-thick film (at 0.02 mA/cm2), which results in an excellent specific capacitance (Table S3). The findings open the opportunity in designing electrically conductive waterstable MOFs with accessible intra-framework functionality for a range of electrochemical applications. Current density (mA/cm )
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
Journal of the American Chemical Society
a Tested in 0.1 M Na2SO4 (aq)
0.00 Mn-AIM-NiCB@NU-1000 Mn-AIM-NU-1000 NiCB@NU-1000 NU-1000
-0.05 -0.10 0.0
0.2
0.4
0.6
0.8
E (V) vs. Ag/AgCl/KCl (3 M)
E (V) vs. Ag/AgCl/KCl (3 M)
Page 3 of 6
1.4
c
1.2
Mn-AIM-NiCB@NU-1000 Tested in 0.1 M Na2SO4 (aq)
1.0 0.8 0.6 0.4 0.2 0.0
0
50
Time (s)
Mn-AIM-NU-1000
b
1.2
Tested in 0.1 M Na2SO4 (aq)
1.0 0.8 0.6 0.4 0.2 0.0
0
5
10
15
20
Time (s) 250
d
Mn-AIM-NU-1000 Mn-AIM-NiCB@NU-1000
200 150 100 50 0
0
2
4
6
8
10
12
14
16
Charge-discharge current (A/gMnO2)
Figure 4. a) CV curves of the spin-coated NU-1000, NiCB@NU-1000, Mn-AIM-NU-1000, and Mn-AIMNiCB@NU-1000 thin films, measured at 25 mV/s. Chargedischarge curves of b) Mn-AIM-NU-1000 and c) Mn-AIMNiCB@NU-1000 thin films, measured at 0.08 mA/cm2. d) Specific capacitance of the installed manganese oxide in MnAIM-NU-1000 and Mn-AIM-NiCB@NU-1000 thin films, measured at various charge-discharge current densities. In conclusion, nickel bis(dicarbollide) (NiCB) can be installed in a zirconium-based MOF, NU-1000. Single-crystal Xray diffraction confirms that all the NiCB units are solely located in the microporous triangular channels of NU-1000, which keeps the mesoporous hexagonal channels of the framework open and allows for further incorporation of other active species. The donor-acceptor interaction between the pyrene-based linker and NiCB imparts electrical conductivity to the resulting mesoporous zirconium-based MOF, with a conductivity of 2.7 × 10-7 S/cm. Manganese oxide can be then deposited in NiCB@NU-1000. With the help of electrical conductivity from the NiCB@NU-1000 scaffold, the installed manganese oxide exhibits a specific capacitance of 276 F/gMnO2 at a charge-discharge current density of 0.02 mA/cm2, which is more than ten times higher than that of manganese oxide in NU-1000 (21 F/gMnO2). Ongoing work focuses on utilizing the conductive NiCB@NU-1000 as a platform to incorporate a range of electrochemically active metal oxides or sulfides via SIM or AIM for various electrochemical applications.
3 Environment ACS Paragon Plus
Journal of the American Chemical Society 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
ASSOCIATED CONTENT Additional experimental details and data are included in Supporting Information.
AUTHOR INFORMATION Corresponding Author
[email protected] (O. K. F.)
ACKNOWLEDGMENTS ACKNOWLEDGMENTS We thank the support of this work from Toyota and the ANSER Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0001059. This work made use of the J. B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR1121262) at the Materials Research Center of Northwestern University, and the EPIC facility (NUANCE Center, Northwestern University) supported by the MRSEC program (NSF DMR1121262), the International Institute for Nanotechnology (IIN), and the State of Illinois, through the IIN. A.M.S. thanks 3M for a non-tenured faculty award and Alfred P. Sloan Foundation for chemistry research fellowship.
REFERENCES 1. (a) Ferey, G., Chem. Soc. Rev. 2008, 37 (1), 191-214; (b) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M., Science 2013, 341 (6149), 1230444. 2. (a) Farha, O. K.; Eryazici, I.; Jeong, N. C.; Hauser, B. G.; Wilmer, C. E.; Sarjeant, A. A.; Snurr, R. Q.; Nguyen, S. T.; Yazaydın, A. Ö.; Hupp, J. T., J. Am. Chem. Soc. 2012, 134 (36), 15016-15021; (b) Li, P.; Vermeulen, N. A.; Malliakas, C. D.; Gómez-Gualdrón, D. A.; Howarth, A. J.; Mehdi, B. L.; Dohnalkova, A.; Browning, N. D.; O’Keeffe, M.; Farha, O. K., Science 2017, 356 (6338), 624-627; (c) Alezi, D.; Belmabkhout, Y.; Suyetin, M.; Bhatt, P. M.; Weseliński, Ł. J.; Solovyeva, V.; Adil, K.; Spanopoulos, I.; Trikalitis, P. N.; Emwas, A.-H.; Eddaoudi, M., J. Am. Chem. Soc. 2015, 137 (41), 13308-13318. 3. (a) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T., Chem. Soc. Rev. 2009, 38 (5), 1450-1459; (b) Ma, L.; Falkowski, J. M.; Abney, C.; Lin, W., Nat. Chem. 2010, 2 (10), 838-846; (c) Mondloch, J. E.; Katz, M. J.; Isley Iii, W. C.; Ghosh, P.; Liao, P.; Bury, W.; Wagner, G. W.; Hall, M. G.; DeCoste, J. B.; Peterson, G. W.; Snurr, R. Q.; Cramer, C. J.; Hupp, J. T.; Farha, O. K., Nat. Mater. 2015, 14 (5), 512-516; (d) Farha, O. K.; Özgür Yazaydın, A.; Eryazici, I.; Malliakas, C. D.; Hauser, B. G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T., Nat. Chem. 2010, 2 (11), 944-948; (e) Li, J.-R.; Sculley, J.; Zhou, H.C., Chem. Rev. 2012, 112 (2), 869-932; (f) So, M. C.; Wiederrecht, G. P.; Mondloch, J. E.; Hupp, J. T.; Farha, O. K., Chem. Commun. 2015, 51 (17), 3501-3510; (g) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T., Chem. Rev. 2012, 112 (2), 1105-1125; (h) Cadiau, A.; Adil, K.; Bhatt, P. M.; Belmabkhout, Y.; Eddaoudi, M., Science 2016, 353 (6295), 137-140. 4. (a) Evans, J. D.; Sumby, C. J.; Doonan, C. J., Chem. Soc. Rev. 2014, 43 (16), 5933-5951; (b) Islamoglu, T.; Goswami, S.; Li, Z.; Howarth, A. J.; Farha, O. K.; Hupp, J. T., Acc. Chem. Res. 2017, 50 (4), 805-813; (c) Li, Z.; Peters, A. W.; Bernales, V.; Ortuño, M. A.; Schweitzer, N. M.; DeStefano, M. R.; Gallington, L. C.; Platero-Prats, A. E.; Chapman, K. W.; Cramer, C. J.; Gagliardi, L.; Hupp, J. T.; Farha, O. K., ACS Cent. Sci. 2017, 3 (1), 31-38. 5. (a) Mondloch, J. E.; Katz, M. J.; Planas, N.; Semrouni, D.; Gagliardi, L.; Hupp, J. T.; Farha, O. K., Chem. Commun. 2014, 50 (64), 8944-8946; (b) Kandiah, M.; Nilsen, M. H.; Usseglio, S.; Jakobsen, S.; Olsbye, U.; Tilset, M.; Larabi, C.; Quadrelli, E. A.; Bonino, F.; Lillerud, K. P., Chem. Mater. 2010, 22 (24), 6632-6640; (c) Jiang, H.-L.; Feng, D.; Wang, K.; Gu, Z.-Y.; Wei, Z.; Chen, Y.-P.; Zhou, H.-C., J. Am. Chem. Soc. 2013, 135 (37), 13934-13938. 6. Peters, A. W.; Li, Z.; Farha, O. K.; Hupp, J. T., ACS Appl. Mater. Interfaces 2016, 8 (32), 20675-20681. 7. (a) Burtch, N. C.; Jasuja, H.; Walton, K. S., Chem. Rev. 2014, 114 (20), 10575-10612; (b) Kim, H.; Yang, S.; Rao, S. R.; Narayanan, S.; Kapustin, E. A.; Furukawa, H.; Umans, A. S.; Yaghi, O. M.; Wang, E. N.,
Science 2017, 356 (6336), 430-432; (c) Rieth, A. J.; Yang, S.; Wang, E. N.; Dincă, M., ACS Cent. Sci. 2017, 3 (6), 668-672. 8. (a) Choi, K. M.; Jeong, H. M.; Park, J. H.; Zhang, Y.-B.; Kang, J. K.; Yaghi, O. M., ACS Nano 2014, 8 (7), 7451-7457; (b) Hod, I.; Sampson, M. D.; Deria, P.; Kubiak, C. P.; Farha, O. K.; Hupp, J. T., ACS Catal. 2015, 5 (11), 6302-6309; (c) Kung, C.-W.; Li, Y.-S.; Lee, M.-H.; Wang, S.-Y.; Chiang, W.-H.; Ho, K.-C., J. Mater. Chem. A 2016, 4 (27), 10673-10682; (d) Kung, C.-W.; Mondloch, J. E.; Wang, T. C.; Bury, W.; Hoffeditz, W.; Klahr, B. M.; Klet, R. C.; Pellin, M. J.; Farha, O. K.; Hupp, J. T., ACS Appl. Mater. Interfaces 2015, 7 (51), 28223-28230; (e) Sun, L.; Campbell, M. G.; Dincă, M., Angew. Chem. Int. Ed. 2016, 55 (11), 35663579; (f) Kornienko, N.; Zhao, Y.; Kley, C. S.; Zhu, C.; Kim, D.; Lin, S.; Chang, C. J.; Yaghi, O. M.; Yang, P., J. Am. Chem. Soc. 2015, 137 (44), 14129-14135; (g) Lin, S.; Pineda-Galvan, Y.; Maza, W. A.; Epley, C. C.; Zhu, J.; Kessinger, M. C.; Pushkar, Y.; Morris, A. J., ChemSusChem 2017, 10 (3), 514-522; (h) Johnson, B. A.; Bhunia, A.; Ott, S., Dalton Trans. 2017, 46 (5), 1382-1388; (i) Miner, E. M.; Fukushima, T.; Sheberla, D.; Sun, L.; Surendranath, Y.; Dincă, M., Nat. Comm. 2016, 7, 10942. 9. (a) Leong, C. F.; Chan, B.; Faust, T. B.; D'Alessandro, D. M., Chem. Sci. 2014, 5 (12), 4724-4728; (b) Narayan, T. C.; Miyakai, T.; Seki, S.; Dincă, M., J. Am. Chem. Soc. 2012, 134 (31), 12932-12935. 10. (a) Sheberla, D.; Bachman, J. C.; Elias, J. S.; Sun, C.-J.; ShaoHorn, Y.; Dincă, M., Nat. Mater. 2016, 16, 220-224; (b) Sheberla, D.; Sun, L.; Blood-Forsythe, M. A.; Er, S.; Wade, C. R.; Brozek, C. K.; AspuruGuzik, A.; Dincă, M., J. Am. Chem. Soc. 2014, 136 (25), 8859-8862; (c) Clough, A. J.; Skelton, J. M.; Downes, C. A.; de la Rosa, A. A.; Yoo, J. W.; Walsh, A.; Melot, B. C.; Marinescu, S. C., J. Am. Chem. Soc. 2017, 139 (31), 10863-10867; (d) Hmadeh, M.; Lu, Z.; Liu, Z.; Gándara, F.; Furukawa, H.; Wan, S.; Augustyn, V.; Chang, R.; Liao, L.; Zhou, F.; Perre, E.; Ozolins, V.; Suenaga, K.; Duan, X.; Dunn, B.; Yamamto, Y.; Terasaki, O.; Yaghi, O. M., Chem. Mater. 2012, 24 (18), 3511-3513. 11. (a) Kobayashi, Y.; Jacobs, B.; Allendorf, M. D.; Long, J. R., Chem. Mater. 2010, 22 (14), 4120-4122; (b) Takaishi, S.; Hosoda, M.; Kajiwara, T.; Miyasaka, H.; Yamashita, M.; Nakanishi, Y.; Kitagawa, Y.; Yamaguchi, K.; Kobayashi, A.; Kitagawa, H., Inorg. Chem. 2009, 48 (19), 9048-9050; (c) Sun, L.; Miyakai, T.; Seki, S.; Dincă, M., J. Am. Chem. Soc. 2013, 135 (22), 8185-8188. 12. Le Ouay, B.; Boudot, M.; Kitao, T.; Yanagida, T.; Kitagawa, S.; Uemura, T., J. Am. Chem. Soc. 2016, 138 (32), 10088-10091. 13. (a) Talin, A. A.; Centrone, A.; Ford, A. C.; Foster, M. E.; Stavila, V.; Haney, P.; Kinney, R. A.; Szalai, V.; El Gabaly, F.; Yoon, H. P.; Léonard, F.; Allendorf, M. D., Science 2014, 343 (6166), 66-69; (b) Shiozawa, H.; Bayer, B. C.; Peterlik, H.; Meyer, J. C.; Lang, W.; Pichler, T., Sci. Rep. 2017, 7 (1), 2439; (c) Sengupta, A.; Datta, S.; Su, C.; Herng, T. S.; Ding, J.; Vittal, J. J.; Loh, K. P., ACS Appl. Mater. Interfaces 2016, 8 (25), 16154-16159. 14. (a) Feng, D.; Lei, T.; Lukatskaya, M. R.; Park, J.; Huang, Z.; Lee, M.; Shaw, L.; Chen, S.; Yakovenko, A. A.; Kulkarni, A.; Xiao, J.; Fredrickson, K.; Tok, J. B.; Zou, X.; Cui, Y.; Bao, Z., Nat. Energy 2018, 3 (1), 30-36; (b) Li, W.-H.; Ding, K.; Tian, H.-R.; Yao, M.-S.; Nath, B.; Deng, W.-H.; Wang, Y.; Xu, G., Adv. Funct. Mater. 2017, 27 (27), 1702067; (c) Miner, E. M.; Gul, S.; Ricke, N. D.; Pastor, E.; Yano, J.; Yachandra, V. K.; Van Voorhis, T.; Dincă, M., ACS Catal. 2017, 7 (11), 7726-7731. 15. Wang, T. C.; Hod, I.; Audu, C. O.; Vermeulen, N. A.; Nguyen, S. T.; Farha, O. K.; Hupp, J. T., ACS Appl. Mater. Interfaces 2017, 9 (14), 12584-12591. 16. (a) Hawthorne, M. F.; Dunks, G. B., Science 1972, 178 (4060), 462-471; (b) Warren, L. F.; Hawthorne, M. F., J. Am. Chem. Soc. 1970, 92 (5), 1157-1173. 17. Mondloch, J. E.; Bury, W.; Fairen-Jimenez, D.; Kwon, S.; DeMarco, E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P. C.; Snurr, R. Q.; Farha, O. K.; Hupp, J. T., J. Am. Chem. Soc. 2013, 135 (28), 10294-10297. 18. (a) Goetz, K. P.; Vermeulen, D.; Payne, M. E.; Kloc, C.; McNeil, L. E.; Jurchescu, O. D., J. Mater. Chem. C 2014, 2 (17), 30653076; (b) Melby, L. R.; Harder, R. J.; Hertler, W. R.; Mahler, W.; Benson, R. E.; Mochel, W. E., J. Am. Chem. Soc. 1962, 84 (17), 3374-3387. 19. (a) Spokoyny, A. M.; Li, T. C.; Farha, O. K.; Machan, C. W.; She, C.; Stern, C. L.; Marks, T. J.; Hupp, J. T.; Mirkin, C. A., Angew. Chem. Int. Ed. 2010, 49 (31), 5339-5343; (b) Li, T. C.; Fabregat-Santiago, F.; Farha, O. K.; Spokoyny, A. M.; Raga, S. R.; Bisquert, J.; Mirkin, C. A.; Marks, T. J.; Hupp, J. T., J. Phys. Chem. C 2011, 115 (22), 1125711264; (c) Li, T. C.; Spokoyny, A. M.; She, C.; Farha, O. K.; Mirkin, C. A.; Marks, T. J.; Hupp, J. T., J. Am. Chem. Soc. 2010, 132 (13), 45804582.
4 Environment ACS Paragon Plus
Page 4 of 6
Page 5 of 6 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
Journal of the American Chemical Society 20. Ahn, S.; Thornburg, N. E.; Li, Z.; Wang, T. C.; Gallington, L. C.; Chapman, K. W.; Notestein, J. M.; Hupp, J. T.; Farha, O. K., Inorg. Chem. 2016, 55 (22), 11954-11961. 21. Kung, C.-W.; Audu, C. O.; Peters, A. W.; Noh, H.; Farha, O. K.; Hupp, J. T., ACS Energy Lett. 2017, 2 (10), 2394-2401. 22. Wang, T. C.; Vermeulen, N. A.; Kim, I. S.; Martinson, A. B. F.; Stoddart, J. F.; Hupp, J. T.; Farha, O. K., Nat. Protocols 2016, 11 (1), 149-162. 23. The EDS line scan indicates the uniform distributions of Ni and Zr in micrometer scale due to the resolution limit of EDS under SEM. 24. The pellets of NU-1000 and NiCB@NU-1000 were also prepared for conductivity measurements (see Section S6 in Supporting Information). 25. (a) Chetcuti, P. A.; Hofherr, W.; Liegard, A.; Rihs, G.; Rist, G.; Keller, H.; Zech, D., Organometallics 1995, 14 (2), 666-675; (b) Yan, Y.K.; Mingos, D. M. P., Chem. Soc. Rev. 1995, 24 (3), 203-213. 26. Erickson, K. J.; Léonard, F.; Stavila, V.; Foster, M. E.; Spataru, C. D.; Jones, R. E.; Foley, B. M.; Hopkins, P. E.; Allendorf, M. D.; Talin, A. A., Adv. Mater. 2015, 27 (22), 3453-3459.
27. (a) Simon, P.; Gogotsi, Y., Nat. Mater. 2008, 7, 845-854; (b) Wei, W.; Cui, X.; Chen, W.; Ivey, D. G., Chem. Soc. Rev. 2011, 40 (3), 1697-1721; (c) Subramanian, V.; Zhu, H.; Vajtai, R.; Ajayan, P. M.; Wei, B., J. Phys. Chem. B 2005, 109 (43), 20207-20214. 28. As the manganese oxide sites were functionalized on the hexazirconium nodes of the MOF via AIM, by assuming an average crystal length of 3 µm and crystal width of 1 µm, the fraction of manganese oxide presented on the external surface of MOF crystals was estimated to be 0.65%; this value is much lower than the electrochemically addressable fraction. 29. Taking account of the mass loading of the whole electrode material including the redox-inactive scaffold, the specific capacitance of Mn-AIM-NiCB@NU-1000 is 69 F/g; this value is comparable to those of reported MOF-based supercapacitors (about 50-200 F/g).
5 Environment ACS Paragon Plus
Journal of the American Chemical Society 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
TOC Image
6 Environment ACS Paragon Plus
Page 6 of 6
