Metal-Organic Framework-derived Materials and Their Applications in EnergyStorage Devices and Electrocatalysis
YE Shaofeng1, LIU Wenxian1, XU Xilian1, SHA Dongyong1, SHI Wenhui2, CAO Xiehong1,3
1 College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014; 2 Center forMembrane Separation and Water Science & Technology, Ocean College, Zhejiang University of Technology,Hangzhou 310014; 3 State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology,Zhejiang University of Technology, Hangzhou 310032
Abstract: Metal-organic frameworks (MOFs), a kind of porous materials constructed from metal ion/cluster and organic li-gands, have been a major focus of materials science over the past decades. MOFs possess high specific surface area and uniform cavities, as well as structural tunability, which are promising for a variety of applications. However, the poor conductivity and low stability of MOFs restrict their further development of applications. In recent years, MOF-derived materials, obtained by hydrothermal and/or calcining process, which possess relatively higher conductivity and better stability while maintaining the structural advantages of MOFs, have become a research hotspot. However, the single composition and structure of MOF-derived materials, which can provide limited performance (such as capacitive properties, catalytic properties), greatly limit the development of its related applications. Therefore, in addition to research and preparation of a variety of different MOF-derived materials in recent years, researchers mainly foucs on the composition and structure of MOF-derived materials to prepare a variety of materials with excellent performance in various applications (such as energy storage and conversion, catalysis). As applied materials with excellent performance, composition and structure of MOF-derived materials have been studied maturely, mainly include porous carbon, metal oxides, metal phosphides, metal hydroxides, and fibrous structures, hollow structures, core-shell structures, etc. MOF-derived materials with large specific surface area, uniformly distributed cavities, always combine the porous carbon with high conductivity and other derived materials (metal compounds or doped metal atoms and heteroatoms such as N, P, S, etc.) with excellent performance (such as capacitance, catalytic properties), to play a rather excellent performance. Among them, MOF-derived metal compounds have porous structure, which can provide excellent capacity and catalytic properties, and the properties are usually superior to the same materials prepared by other methods. In terms of structure, in recent years, the resear-chers have prepared a variety of MOF-derived materials with different structures by controlling the precursor structure or the reaction conditions. On the one hand, partially prepared structures (such as the core shell structure and the hollow structure) of MOF-derived materials can alleviate the impact in the process of use, thus it can show excellent cycling performance. On the other hand, by regulating the structure of MOF-derived materials, the active sites are fully exposed, so that their performance can be maximized. In this review,we summarizes the recent progress of MOF-derived materials, including its composition, structural regulation, as well as their applications in energy storage, catalysis and other fields. Finally, the future direction and challenge of MOF-derived materials are discussed.
叶绍凤, 刘文贤, 徐喜连, 沙东勇, 施文慧, 曹澥宏. 金属-有机框架(MOFs)衍生材料及其在储能器件和电催化领域的应用[J]. 材料导报, 2018, 32(13): 2129-2142.
YE Shaofeng, LIU Wenxian, XU Xilian, SHA Dongyong, SHI Wenhui, CAO Xiehong. Metal-Organic Framework-derived Materials and Their Applications in EnergyStorage Devices and Electrocatalysis. Materials Reports, 2018, 32(13): 2129-2142.
1 Zheng H Q, Zhang Y N, Liu L F, et al. One-pot synthesis of metal-organic frameworks with encapsulated target molecules and their applications for controlled drug delivery[J].Journal of the American Chemical Society,2016,138(3):962. 2 Wang L, Han Y Z, Feng X, et al. Metal-organic frameworks for energy storage: Batteries and supercapacitors[J].Coordination Chemistry Reviews,2016,307:361. 3 Liu J W, Chen L F, Cui H, et al. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis[J].Chemical Society Reviews,2014,43(16):6011. 4 Xia W, Mahmood A, Zou R Q, et al. Metal-organic frameworks and their derived nanostructures for electrochemical energy storage and conversion[J].Energy & Environmental Science,2015,8(7):1837. 5 Cao X, Tan C L, Sindoro M, et al. Hybrid micro-/nano-structures derived from metal-organic frameworks: Preparation and applications in energy storage and conversion[J].Chemical Society Reviews,2017,46(10):2660. 6 Nandasiri M I, Jambovane S R, McGrail B P, et al. Adsorption, separation, and catalytic properties of densified metal-organic frameworks[J].Coordination Chemistry Reviews,2016,311:38. 7 Morozan A, Jaouen F. Metal organic frameworks for electrochemical applications[J].Energy & Environmental Science,2012,5(11):9269. 8 He J R, Lv W Q, Chen Y F, et al. Three-dimensional hierarchical C-Co-N/Se derived from metal-organic framework as superior cat-hode for Li-Se batteries[J].Journal of Power Sources,2017,363:103. 9 Liu X Y, Zou F, Liu K W, et al. A binary metal organic framework derived hierarchical hollow Ni3S2/Co9S8/N-doped carbon composite with superior sodium storage performance[J].Journal of Materials Chemistry A,2017,5(23):11781. 10 Pan Y, Zhao Y X, Mu S J, et al. Cation exchanged MOF-derived nitrogen-doped porous carbons for CO2 capture and supercapacitor electrode materials[J].Journal of Materials Chemistry A,2017,5(20):9544. 11 Kaneti Y V, Zhang J, He Y B, et al. Fabrication of an MOF-derived heteroatom-doped Co/CoO/carbon hybrid with superior sodium storage performance for sodium-ion batteries[J].Journal of Materials Che-mistry A,2017,5(29):15356. 12 Liu Y Z, Li G R, Guo Y, et al. Flexible and binder-free hierarchical porous carbon film for supercapacitor electrodes derived from MOFs/CNT[J].ACS Applied Materials & Interfaces,2017,9(16):14043. 13 Wang F, Zhuo H Y, Han X G, et al. Foam-like CoO@N,S-codoped carbon composites derived from a well-designed N, S-rich Co-MOF for lithium-ion batteries[J].Journal of Materials Chemistry A,2017,5(44):22964. 14 Zhao R, Xia W, Lin C, et al. A pore-expansion strategy to synthesize hierarchically porous carbon derived from metal-organic framework for enhanced oxygen reduction[J].Carbon,2017,114:284. 15 Wang Y, Chen X T, Lin Q P, et al. Nanoporous carbon derived from a functionalized metal-organic framework as a highly efficient oxygen reduction electrocatalyst[J].Nanoscale,2017,9(2):862. 16 Shen K, Chen L, Long J L, et al. MOFs-templated Co@Pd core-shell NPs embedded in N-doped carbon matrix with superior hydrogenation activities[J].ACS Catalysis,2015,5(9):5264. 17 Ji D, Zhou H, Zhang J, et al. Facile synthesis of a metal-organic framework-derived Mn2O3 nanowire coated three-dimensional graphene network for high-performance free-standing supercapacitor electrodes[J].Journal of Materials Chemistry A,2016,4(21):8283. 18 Xu X L, Shi W H, Li P, et al. Facile fabrication of three-dimensional graphene and metal-organic framework composites and their deri-vatives for flexible all-solid-state supercapacitors[J].Chemistry of Materials,2017,29(14):6058. 19 Wu X, Meng G, Liu W X, et al. Metal-organic framework-derived, Zn-doped porous carbon polyhedra with enhanced activity as bifunctional catalysts for rechargeable zinc-air batteries[J].Nano Research,2017,11(1):163. 20 Yan L T, Cao L, Dai P C, et al. Metal-organic frameworks derived nanotube of nickel-cobalt bimetal phosphides as highly efficient electrocatalysts for overall water splitting[J].Advanced Functional Materials,2017,27(40):1703455. 21 Xia G L, Su J W, Li M S, et al. A MOF-derived self-template stra-tegy toward cobalt phosphide electrodes with ultralong cycle life and high capacity[J].Journal of Materials Chemistry A,2017,5(21):10321. 22 Liang X, Zheng B X, Chen L G, et al. MOF-derived formation of Ni2P-CoP bimetallic phosphides with strong interfacial effect toward electrocatalytic water splitting[J].ACS Applied Materials & Interfaces,2017,9(27):23222. 23 Wu R B, Wang D P, Kumar V, et al. MOFs-derived copper sulfides embedded within porous carbon octahedra for electrochemical capacitor applications[J].Chemical Communications,2015,51(15):3109. 24 Liu J, Wu C, Xiao D D, et al. MOF-derived hollow Co9S8 nanoparticles embedded in graphitic carbon nanocages with superior Li-ion storage[J].Small,2016,12(17):2354. 25 Yilmaz G, Yam K M, Zhang C, et al. In situ transformation of MOFs into layered double hydroxide embedded metal sulfides for improved electrocatalytic and supercapacitive performance[J].Advanced Materials,2017,29(26):1606814. 26 Zhang J T, Hu H, Li Z, et al. Double-shelled nanocages with cobalt hydroxide inner shell and layered double hydroxides outer shell as high-efficiency polysulfide mediator for lithium-sulfur batteries[J].Angewandte Chemie,2016,55(12):3982. 27 Chaikittisilp W, Ariga K, Yamauchi Y. A new family of carbon materials: Synthesis of MOF-derived nanoporous carbons and their promising applications[J].Journal of Materials Chemistry A,2013,1(1):14. 28 Salunkhe R R, Kaneti Y V, Kim J, et al. Nanoarchitectures for me-tal-organic framework-derived nanoporous carbons toward supercapacitor applications[J].Accounts of Chemical Research,2016,49(12):2796. 29 Salunkhe R R, Kaneti Y V,Yamauchi Y. Metal-organic framework-derived nanoporous metal oxides toward supercapacitor applications: Progress and prospects[J].ACS Nano,2017,11(6):5293. 30 Kaneti Y V, Tang J, Salunkhe R R, et al. Nanoarchitectured design of porous materials and nanocomposites from metal-organic frameworks[J].Advanced Materials,2017,29(12):1604898. 31 Zhao S N, Song X Z, Song S Y, et al. Highly efficient heterogeneous catalytic materials derived from metal-organic framework supports/precursors[J].Coordination Chemistry Reviews,2017,337:80. 32 Salunkhe R R, Kamachi Y, Torad N L, et al. Fabrication of symmetric supercapacitors based on MOF-derived nanoporous carbons[J].Journal of Materials Chemistry A,2014,2(46):19848. 33 Wang R T, Jin D D, Zhang Y B, et al. Engineering metal organic framework derived 3D nanostructures for high performance hybrid supercapacitors[J].Journal of Materials Chemistry A,2017,5(1):292. 34 Fan H S, Yu H, Wu X L, et al. Controllable preparation of square nickel chalcogenide (NiS and NiSe2) nanoplates for superior Li/Na ion storage properties[J].ACS Applied Materials & Interfaces,2016,8(38):25261. 35 Qi L Y, Xin Y L, Zuo Z C, et al. Grape-like Fe3O4 agglomerates grown on graphene nanosheets for ultrafast and stable lithium sto-rage[J].ACS Applied Materials & Interfaces,2016,8(27):17245. 36 Dang S, Zhu Q L, Xu Q. Nanomaterials derived from metal-organic frameworks[J].Nature Reviews Materials,2017,3(1):17075. 37 Fu Y, Huang Y, Xiang Z H, et al. Phosphorous-nitrogen-codoped carbon materials derived from metal-organic frameworks as efficient electrocatalysts for oxygen reduction reactions[J].European Journal of Inorganic Chemistry,2016,2016(13-14):2100. 38 Zhang L J, Su Z X, Jiang F L, et al. Highly graphitized nitrogen-doped porous carbon nanopolyhedra derived from ZIF-8 nanocrystals as efficient electrocatalysts for oxygen reduction reactions[J].Nanoscale,2014,6(12):6590. 39 Bao W Z, Mondal A K, Xu J, et al. 3D hybrid-porous carbon derived from carbonization of metal organic frameworks for high perfor-mance supercapacitors[J].Journal of Power Sources,2016,325:286. 40 Yan X L, Li X J, Yan Z F, et al. Porous carbons prepared by direct carbonization of MOFs for supercapacitors[J].Applied Surface Science,2014,308:306. 41 Li Z X, Zou K Y, Zhang X, et al. Hierarchically flower-like N-doped porous carbon materials derived from an explosive 3-fold interpenetrating diamondoid copper metal-organic framework for a supercapacitor[J].Inorganic Chemistry,2016,55(13):6552. 42 Liu B, Shioyama H, Akita T, et al. Metal-organic framework as a template for porous carbon synthesis[J].Journal of the American Chemical Society,2008,130(16):5390. 43 Li Z Q, Li C X, Ge X L, et al. Reduced graphene oxide wrapped MOFs-derived cobalt-doped porous carbon polyhedrons as sulfur immobilizers as cathodes for high performance lithium sulfur batteries[J].Nano Energy,2016,23:15. 44 Liang X H, Quan B, Ji G B, et al. Novel nanoporous carbon derived from metal-organic frameworks with tunable electromagnetic wave absorption capabilities[J].Inorganic Chemistry Frontiers,2016,3(12):1516. 45 Qian Y H, Hu Z G, Ge X M, et al. A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-air batteries[J].Carbon,2017,111:641. 46 Tan H L, Ma C J, Gao L, et al. Metal-organic framework-derived copper nanoparticle@carbon nanocomposites as peroxidase mimics for colorimetric sensing of ascorbic acid[J].Chemistry,2014,20(49):16377. 47 Xia W, Zhu J H, Guo W H, et al. Well-defined carbon polyhedrons prepared from nano metal-organic frameworks for oxygen reduction[J].Journal of Materials Chemistry A,2014,2(30):11606. 48 Yin P Q, Yao T, Wu Y, et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts[J].Angewandte Chemie,2016,55(36):10800. 49 Liu T, Zhang Y, Hou J K, et al. High performance mesoporous C@Se composite cathodes derived from Ni-based MOFs for Li-Se batte-ries[J].RSC Advances,2015,102(5):84038. 50 Liu T, Jia M, Zhang Y, et al. Confined selenium within metal-organic frameworks derived porous carbon microcubes as cathode for rechargeable lithium-selenium batteries[J].Journal of Power Sources,2017,341:53. 51 Wang X, Li Y W. Nanoporous carbons derived from MOFs as metal-free catalysts for selective aerobic oxidations[J].Journal of Materials Chemistry A,2016,4(14):5247. 52 Wu H B, Wei S Y, Zhang L, et al. Embedding sulfur in MOF-derived microporous carbon polyhedrons for lithium-sulfur batteries[J].Chemistry,2013,19(33):10804. 53 Zhang W, Wu Z Y, Jiang H L, et al. Nanowire-directed templating synthesis of metal-organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis[J].Journal of the American Chemical Society,2014,136(41):14385. 54 Li J S, Li S L, Tang Y J, et al. Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction[J].Scientific Reports,2014,4:5130. 55 Chen Y Q, Wu J F, Yang W S, et al. Zn/Fe-MOFs-derived hierarchical ball-in-ball ZnO/ZnFe2O4@carbon nanospheres with exceptional lithium storage performance[J].Journal of Alloys & Compounds,2016,688:211. 56 Huang G, Zhang F F, Zhang L L, et al. Hierarchical NiFe2O4/Fe2O3 nanotubes derived from metal organic frameworks for supe-rior lithium ion battery anodes[J].Journal of Materials Chemistry A,2014,2(21):8048. 57 Cao K Z, Jiao L F, Xu H, et al. Reconstruction of mini-hollow polyhedron Mn2O3 derived from MOFs as a high-performance lithium anode material[J].Advanced Science,2016,3(3):1500185. 58 Li X Z, Fang Y Y, Lin X Q, et al. MOF derived Co3O4 nanoparticles embedded in N-doped mesoporous carbon layer/MWCNT hybrids: Extraordinary bi-functional electrocatalysts for OER and ORR[J].Journal of Materials Chemistry A,2015,3(33):17392. 59 Khaletskaya K, Pougin A, Medishetty R, et al. Fabrication of gold/titania photocatalyst for CO2 reduction based on pyrolytic conversion of the metal-organic framework NH2-MIL-125(Ti) loaded with gold nanoparticles[J].Chemistry of Materials,2015,27(21):7248. 60 Zhang L, Wu H B, Lou X W. Metal-organic-frameworks-derived general formation of hollow structures with high complexity[J].Journal of the American Chemical Society,2013,135(29):10664. 61 Chen S R, Xue M, Li Y Q, et al. Rational design and synthesis of NixCo3-xO4 nanoparticles derived from multivariate MOF-74 for supercapacitors[J].Journal of Materials Chemistry A,2015,3(40):20145. 62 Zou K Y, Liu Y C, Jiang Y F, et al. Benzoate acid-dependent lattice dimension of Co-MOFs and MOF-derived CoS2@CNTs with tunable pore diameters for supercapacitors[J].Inorganic Chemistry,2017,56(11):6184. 63 Zhu C B, Wen Y R, van Aken P A, et al. High lithium storage performance of FeS nanodots in porous graphitic carbon nanowires[J].Advanced Functional Materials,2015,25(15):2335. 64 Liu Y, Zhou X L, Ding T, et al. 3D architecture constructed via the confined growth of MoS2 nanosheets in nanoporous carbon derived from metal-organic frameworks for efficient hydrogen production[J].Nanoscale,2015,7(43):18004. 65 Zhang X, Liu S W, Zang Y P, et al. Co/Co9S8 @S,N-doped porous graphene sheets derived from S, N dual organic ligands assembled Co-MOFs as superior electrocatalysts for full water splitting in alkaline media[J].Nano Energy,2016,30:93. 66 Xu X B, Nosheen F, Wang X. Ni-decorated molybdenum carbide hollow structure derived from carbon-coated metal-organic framework for electrocatalytic hydrogen evolution reaction[J].Chemistry of Materials,2016,28(17):6313. 67 Yu D B, Wu B, Ran J, et al. An ordered ZIF-8-derived layered double hydroxide hollow nanoparticles-nanoflake array for high efficiency energy storage[J].Journal of Materials Chemistry A,2016,4(43):16953. 68 Guan B Y, Yu L,Lou X W. A dual-metal-organic-framework derived electrocatalyst for oxygen reduction[J].Energy & Environmental Science,2016,9(10):3092. 69 Gao M, Zeng L W, Nie J, et al. Polymer-metal-organic framework core-shell framework nanofibers via electrospinning and their gas adsorption activities[J].RSC Advances,2016,6(9):7078. 70 Koo W T, Choi S J, Kim S J, et al. Heterogeneous sensitization of metal-organic framework driven metal@metal oxide complex catalysts on an oxide nanofiber scaffold toward superior gas sensors[J].Journal of the American Chemical Society,2016,138(40):13431. 71 Lai Q X, Zhao Y X, Liang Y Y, et al. In situ confinement pyrolysis transformation of ZIF-8 to nitrogen-enriched meso-microporous carbon frameworks for oxygen reduction[J].Advanced Functional Materials,2016,26(45):8334. 72 Liu C, Wang J, Li J S, et al. Electrospun ZIF-based hierarchical carbon fiber as an efficient electrocatalyst for the oxygen reduction reaction[J].Journal of Materials Chemistry A,2017,5(3):1211. 73 Wang C H, Liu C, Li J S, et al. Electrospun metal-organic framework derived hierarchical carbon nanofibers with high performance for supercapacitors[J].Chemical Communications,2017,53(10):1751. 74 Li Z, Tang B H J. Mn3O4/nitrogen-doped porous carbon fiber hybrids involving multiple covalent interactions and open voids as flexible anodes for lithium-ion batteries[J].Green Chemistry,2017,19(24):5862. 75 Han Y, Zhao M L, Dong L, et al. MOF-derived porous hollow Co3O4 parallelepipeds for building high-performance Li-ion batteries[J].Journal of Materials Chemistry A,2015,3(45):22542. 76 Sun C C, Yang J, Rui X H, et al. MOF-directed templating synthesis of a porous multicomponent dodecahedron with hollow interiors for enhanced lithium-ion battery anodes[J].Journal of Materials Chemistry A,2015,3(16):8483. 77 Yang J, Zhang F J, Lu H Y, et al. Hollow Zn/Co ZIF particles derived from core-shell ZIF-67@ZIF-8 as selective catalyst for the semi-hydrogenation of acetylene[J].Angewandte Chemie International Edition,2015,54(37):10889. 78 Yu H, Fan H S, Yadian B L, et al. General approach for MOF-derived porous spinel AFe2O4 hollow structures and their superior li-thium storage properties[J].ACS Applied Materials & Interfaces,2015,7(48):26751. 79 Zou F, Hu X L, Li Z, et al. MOF-derived porous ZnO/ZnFe2O4/C octahedra with hollow interiors for high-rate lithium-ion batteries[J].Advanced Materials,2014,26(38):6622. 80 Guan B Y, Yu L,Lou X W. Formation of single-holed cobalt/N-doped carbon hollow particles with enhanced electrocatalytic activity toward oxygen reduction reaction in alkaline media[J].Advanced Science,2017,4(10):1700247. 81 Bai X, Liu J Y, Liu Q, et al. In-situ fabrication of MOF-derived Co-Co layered double hydroxide hollow nanocages/graphene composite: A novel electrode material with superior electrochemical performance[J].Chemistry—A European Journal,2017,23(59):14839. 82 Tian T, Huang L, Ai L H, et al. Surface anion-rich NiS2 hollow microspheres derived from metal-organic frameworks as a robust electrocatalyst for the hydrogen evolution reaction[J].Journal of Mate-rials Chemistry A,2017,5(39):20985. 83 Ge X L, Li Z Q, Wang C X, et al. Metal-organic frameworks derived porous core/shell structured ZnO/ZnCo2O4/C hybrids as anodes for high-performance lithium-ion battery[J].ACS Applied Materials & Interfaces,2015,7(48):26633. 84 Wang Z J, Lu Y Z, Yan Y, et al. Core-shell carbon materials derived from metal-organic frameworks as an efficient oxygen bifunctional electrocatalyst[J].Nano Energy,2016,30:368. 85 Yang J, Ye H L, Zhao F Q, et al. A novel CuxO nanoparticles@ZIF-8 composite derived from core-shell metal-organic frameworks for highly selective electrochemical sensing of hydrogen peroxide[J].ACS Applied Materials & Interfaces,2016,8(31):20407. 86 Zhang G H, Hou S C, Zhang H, et al. High-performance and ultra-stable lithium-ion batteries based on MOF-derived ZnO@ZnO quantum dots/C core-shell nanorod arrays on a carbon cloth anode[J].Advanced Materials,2015,27(14):2400. 87 Huang G, Yin D M, Wang L M. A general strategy for coating me-tal-organic frameworks on diverse components and architectures[J].Journal of Materials Chemistry A,2016,4(39):15106. 88 Ge X L, Li Z Q, Yin L W. Metal-organic frameworks derived porous core/shell CoP@C polyhedrons anchored on 3D reduced graphene oxide networks as anode for sodium-ion battery[J].Nano Energy,2017,32:117. 89 Sikdar N, Konkena B, Masa J, et al. Co3O4@Co/NCNT nanostructure derived from a dicyanamide-based metal-organic framework as an efficient bi-functional electrocatalyst for oxygen reduction and evolution reactions[J].Chemistry,2017,23(71):18049. 90 Zhao Y C, Li X, Liu J D, et al. MOF-derived ZnO/Ni3ZnC0.7/C hybrids yolk-shell microspheres with excellent electrochemical performances for lithium ion batteries [J]. ACS Applied Materials & Interfaces,2016,8(10):6472. 91 Gu F B, Chen H H, Han D M, et al. Metal-organic framework derived Au@ZnO yolk-shell nanostructures and their highly sensitive detection of acetone[J].RSC Advances,2016,6(35):29727. 92 Qu F D, Jiang H F, Yang M H. MOF-derived Co3O4/NiCo2O4 double-shelled nanocages with excellent gas sensing properties[J].Materials Letters,2017,190:75. 93 Wu M K, Chen C, Zhou J J, et al. MOF-derived hollow double-shelled NiO nanospheres for high-performance supercapacitors[J].Journal of Alloys & Compounds,2018,734:1. 94 Su Y, Ao D, Liu H, et al. MOF-derived yolk-shell Cds microcubes with enhanced visible-light photocatalytic activity and stability for hydrogen evolution[J].Journal of Materials Chemistry A,2017,5(18):8680. 95 Li G C, Liu P F, Liu R, et al. MOF-derived hierarchical double-shelled NiO/ZnO hollow spheres for high-performance supercapacitors[J].Dalton Trans,2016,45(34):13311. 96 Wu H B, Lou X W. Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges[J].Science Advances,2017,3(12):eaap9252. 97 Huang M, Mi K, Zhang J H, et al. MOF-derived bi-metal embedded N-doped carbon polyhedral nanocages with enhanced lithium storage[J].Journal of Materials Chemistry A,2017,5(1):266. 98 Ji D, Zhou H, Tong Y L, et al. Facile fabrication of MOF-derived octahedral CuO wrapped 3D graphene network as binder-free anode for high performance lithium-ion batteries[J].Chemical Engineering Journal,2017,313:1623. 99 Mahmood A, Zou R Q, Wang Q F, et al. Nanostructured electrode materials derived from metal-organic framework xerogels for high-energy-density asymmetric supercapacitor[J].ACS Applied Materials & Interfaces,2016,8(3):2148. 100 Xia W, Qu C, Liang Z B, et al. High-performance energy storage and conversion materials derived from a single metal-organic framework/graphene aerogel composite[J].Nano Letters,2017,17(5):2788. 101 Zheng F C, Xia G L, Yang Y, et al. MOF-derived ultrafine MnO nanocrystals embedded in a porous carbon matrix as high-perfor-mance anodes for lithium-ion batteries[J].Nanoscale,2015,7(21):9637. 102 Li W H, Hu S H, Luo X Y, et al. Confined amorphous red phosphorus in MOF-derived N-doped microporous carbon as a superior anode for sodium-ion battery[J].Advanced Materials,2017,29(16):1605820. 103 Tong M Y, Liu S W, Zhang X, et al. Two-dimensional CoNi nanoparticles@S,N-doped carbon composites derived from S, N-containing Co/Ni MOFs for high performance supercapacitors[J].Journal of Materials Chemistry A,2017,5(20):9873. 104 Fu S F, Zhu C Z, Song J H, et al. Metal-organic framework-derived non-precious metal nanocatalysts for oxygen reduction reaction[J].Advanced Energy Materials,2017,7(19):1700363. 105 Ma B, Guan P Y, Li Q Y, et al. MOF-derived flower-like MoS2@TiO2 nanohybrids with enhanced activity for hydrogen evolution[J].ACS Applied Materials & Interfaces,2016,8(40):26794. 106 Mahmood A, Guo W H, Tabassum H, et al. Metal-organic framework-based nanomaterials for electrocatalysis[J].Advanced Energy Materials,2016,6(17):1600423. 107 Hao Y C, Xu Y Q, Liu J F, et al. Nickel-cobalt oxides supported on Co/N decorated graphene as an excellent bifunctional oxygen catalyst[J].Journal of Materials Chemistry A,2017,5(11):5594. 108 Yang Y, Lun Z Y, Xia G L, et al. Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst[J].Energy & Environmental Science,2015,8(12):3563.