ReviewELECTROCHEMISTRY

Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges

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Science Advances  01 Dec 2017:
Vol. 3, no. 12, eaap9252
DOI: 10.1126/sciadv.aap9252

Figures

  • Fig. 1 Schematic of MOF-related materials for renewable energy.

    MOF-based materials with different functionalities by tuning the constituent components: (left to right) electrochemical charge storage, electrocatalytic generation of fuels, and ionic conductivity. MOF-derived materials with different compositions, structures, and functionalities: (left to right) porous carbon with electric double-layer capacitance, hollow structure for charge storage, and carbon-supported composite for electrocatalysis. These MOF-related functional materials enable the storage and utilization of electricity from renewable energy sources.

  • Fig. 2 MOF-related materials for charge storage.

    (A to C) A redox-active MOF Cu(2,7-anthraquinonedicarboxylate) [Cu(2,7-AQDC)] for lithium batteries: (A) structural schematic, (B) charge-discharge profiles, and (C) cycling performance [(A) to (C), adapted with permission from Zhang et al. (25)]. (D) Schematic of electrochemical Na storage in Prussian blue crystal [(D), adapted with permission from You et al. (28)]. (E and F) Electrochemical capacitors fabricated with nanocrystals of MOFs (nMOFs): (E) structure of nMOF electrochemical capacitor and (F) comparison of energy and power densities for electrochemical capacitors made from nMOF-867 and activated carbon [(E) and (F), adapted with permission from Choi et al. (34)]. (G to I) Electronic conductive MOF for electrochemical capacitors: structural schematics of (G) conductive MOF Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 [Ni3(HITP)2] and (H) electrolyte components in Ni3(HITP)2; (I) cyclic voltammetry at a scan rate of 10 mV s−1 at different cell voltages [(G) to (I), adapted with permission from Sheberla et al. (36)]. (J to L) MOFs as sulfur host for lithium-sulfur (Li-S) batteries: (J) schematic showing the interaction between polysulfides and MOF scaffold, (K) comparison of binding energy of lithium polysulfides to Ni-MOF or Co-MOF, and (L) charge-discharge profiles of MOF/S composite cathodes [(J) to (L), adapted with permission from Zheng et al. (38)].

  • Fig. 3 MOF-related materials for electrocatalysis.

    (A) Schematic of a Zr-based MOF with FeIII porphyrin linkers as a heterogeneous catalyst for ORR [(A), adapted with permission from Usov et al. (42)]. (B) Polarization curves of Ni3(HITP)2 under N2 and O2 atmosphere in 0.1 M KOH aqueous electrolyte at a scan rate of 5 mV s−1 and a rotation rate of 2000 rpm [(B), adapted with permission from Miner et al. (45)]. (C to E) UMOFNs as an electrocatalyst for OER: (C) crystal structure and (D) transmission electron microscopy (TEM) image of NiCo-UMOFNs and (E) polarization curves of various OER catalysts in O2-saturated 1 M KOH solution at a scan rate of 5 mV s−1 [(C) to (E), adapted with permission from Zhao et al. (46)]. (F and G) A Co-based MOF, MAF-X27-OH, for OER: (F) structure of MAF-X27-OH and (G) polarization curves of various Co-based catalysts at pH = 14 [three MAF-X27-OH(Cu) samples refer to the MOF catalyst directly grown on the Cu substrate] [(F) and (G), adapted with permission from Lu et al. (53)]. (H and I) A Ni-S electrocatalyst deposited on the fluorine-doped tin oxide (FTO) substrate with an array of NU-1000 rods for HER: (H) schematic of the creation of NU-1000_Ni-S hybrid system and (I) polarization curves of various catalysts in 0.1 M HCl aqueous electrolyte [(H) and (I), adapted with permission from Hod et al. (54)]. GCE, glassy carbon electrodes; RHE, reversible hydrogen electrode.

  • Fig. 4 MOF-related materials for ionic conduction.

    (A) Schematic of postsynthetic oxidation modification to synthesize UiO-66(SO3H)2 [(A), adapted with permission from Phang et al. (58)]. (B and C) PCMOF-5 with uncoordinated diprotic phosphonic acid groups for proton conduction: (B) 1D hydrogen-bonding array formed between phosphonic acid groups and free water molecules and (C) Arrhenius plots for PCMOF-5 at 90 and 98% RH [(B) and (C), adapted with permission from Taylor et al. (60)]. (D and E) A Fe-based MOF with imidazole for proton conduction: (D) structures of pristine Fe-MOF, imidazole physically absorbed in Fe-MOF (Im@Fe-MOF), and imidazole chemically coordinated in Fe-MOF (Im-Fe-MOF), and (E) their Arrhenius plots at 98% RH [(D) and (E), adapted with permission from Zhang et al. (65)]. (F and G) A layered anionic framework with interlayer-embedded counter cations for anhydrous proton conduction: (F) sandwich-type structure with cations (Me2NH2)+ periodically aligned in the interlayers (left) and the strongly hydrogen-bonded chains (right) and (G) Arrhenius plot under anhydrous condition [(F) and (G), adapted with permission from Wei et al. (66)]. (H and I) A Mg-based MOF with lithium isopropoxide as a lithium-ion conductor: (H) schematic of the modified channel of Mg-based MOF and (I) Arrhenius plots of MOF with liquid electrolyte (black cubes), with lithium isopropoxide and solvent (red dots), and with both lithium isopropoxide and liquid electrolyte (blue triangles) [(H) and (I), adapted with permission from Wiers et al. (71)].

  • Fig. 5 Compositional control of MOF-derived materials.

    (A) Synthesis of porous carbon by carbonization of ZIF-8 with infiltrated furfuryl alcohol (FA) [(A), adapted with permission from Jiang et al. (74)]. (B) Synthesis of hybrid nanoporous carbon by carbonization of core-shell MOF particles [(B), adapted with permission from Tang et al. (78)]. (C) Synthesis of porous carbon-coated ZnO quantum dots by pyrolysis of IRMOF-1 [(C), adapted with permission from Yang et al. (86)]. (D and E) Various Ni-based inorganic compounds derived from NiNi-PBAs: (D) schematic of the synthesis strategy and (E) TEM images of the NiNi-PBAs (upper) and derived porous Ni-P (lower) [(D) and (E), adapted with permission from Yu et al. (96)]. (F) Synthesis of mesoporous MoCx octahedral particles derived from NENU-5 [(F), adapted with permission from Wu et al. (102)]. (G) Synthesis of MoO2-based composite (MoO2@PC/RGO) from a MOF precursor containing POMs [(G), adapted with permission from Tang et al. (103)]. (H and I) A composite of Fe3C@N-CNTs derived from a MOF-in-MOF composite: (H) schematic of the synthetic procedure and (I) microscope images of the composite precursor (left) and the derived Fe3C@N-CNTs assemblies (right) [(H) and (I), adapted with permission from Guan et al. (84)].

  • Fig. 6 Morphological and structural control of MOF-derived materials.

    (A) Synthesis of MOF-74-Rod, carbon nanorods, and graphene nanoribbons [(A), adapted with permission from Pachfule et al. (75)]. RT, room temperature. (B) TEM image of mesoporous Fe2O3 derived from MIL-88-Fe [(B), adapted with permission from Xu et al. (109)]. (C) High-resolution TEM image of mesoporous MoCx derived from NENU-5 [(C), adapted with permission from Wu et al. (102)]. (D) High-angle annular dark-field scanning TEM image of single iron atoms (red circles) on N-doped porous carbon [(D), adapted with permission from Chen et al. (104)]. (E) Synthesis of complex hollow structures with multishells (left route) or multicompositions (right route) from Prussian blue [(E), adapted with permission from Zhang et al. (90)]. (F) Schematic of formation of NiS nanoframes from Ni-Co PBA nanocubes (upper) and microscope images of NiS nanoframes (lower) [(F), adapted with permission from Yu et al. (92)]. (G) Fabrication of hybrid Co3O4-carbon porous nanowire arrays using Co-based MOF arrays [(G), adapted with permission from Ma et al. (118)]. (H) Photograph of a MOF aerogel monolith and derived carbon monolith [(H), adapted with permission from Xia et al. (121)].

  • Fig. 7 Functionalities and applications of MOF-derived materials.

    (A and B) Carbon nanorods and graphene nanoribbons derived from MOF-74-Rod for electrochemical capacitors: morphology illustrations and cyclic voltammograms (CVs) of (A) carbon nanorods and (B) graphene nanoribbons in 1 M H2SO4 electrolyte [(A) and (B), adapted with permission from Pachfule et al. (75)]. (C to E) Multishelled Ni-Co oxide hollow particles for charge storage: (C) TEM image and (D) CVs of Ni-Co oxide hollow particles and (E) in situ liquid-cell TEM observation of charge/discharge processes [(C) to (E), adapted with permission from Guan et al. (124)]. (F and G) Double-shelled hydroxide hollow particles (CH@LDH) as a sulfur host for Li-S batteries: (F) synthesis of sulfur-loaded double-shelled CH@LDH particles and (G) their cycling performance compared with a conventional mesoporous carbon/sulfur composite [(F) and (G), adapted with permission from Zhang et al. (91)]. (H) Polarization curves of various cobalt-based sulfide particles in 0.5 M H2SO4 [(H), adapted with permission from Huang et al. (129)]. (I) Polarization curve of isolated single Fe atoms on N-doped porous carbon (Fe-ISAs/CN) compared with N-doped carbon (CN) and Pt/C in O2-saturated 0.1 M KOH (inset: scheme of Fe-ISAs/CN) [(I), adapted with permission from Chen et al. (104)]. (J and K) Hollow particles of N-doped carbon nanotubes (NCNTs) as a bifunctional catalyst: polarization curves at a rotation rate of 1600 rpm in (J) O2-saturated 0.1 M KOH and (K) 1 M KOH [(J) and (K), adapted with permission from Xia et al. (82)].