Semiconductor@metal-organic framework core-shell heterostructures: a case of ZnO@ZIF-8 nanorods with selective photoelectrochemical response.

Metal-organic frameworks (MOFs) and related material classes are attracting considerable attention for their applications in gas storage/separation as well as catalysis. In contrast, research concerning potential uses in electronic devices (such as sensors) is in its infancy, which might be due to a great challenge in the fabrication of MOFs and semiconductor composites with well-designed structures. In this paper, we proposed a simple self-template strategy to fabricate metal oxide semiconductor@MOF core-shell heterostructures, and successfully obtained freestanding ZnO@ZIF-8 nanorods as well as vertically standing arrays (including nanorod arrays and nanotube arrays). In this synthetic process, ZnO nanorods not only act as the template but also provide Zn(2+) ions for the formation of ZIF-8. In addition, we have demonstrated that solvent composition and reaction temperature are two crucial factors for successfully fabricating well-defined ZnO@ZIF-8 heterostructures. As we expect, the as-prepared ZnO@ZIF-8 nanorod arrays display distinct photoelectrochemical response to hole scavengers with different molecule sizes (e.g., H(2)O(2) and ascorbic acid) owing to the limitation of the aperture of the ZIF-8 shell. Excitingly, such ZnO@ZIF-8 nanorod arrays were successfully applied to the detection of H(2)O(2) in the presence of serous buffer solution. Therefore, it is reasonable to believe that the semiconductor@MOFs heterostructure potentially has promising applications in many electronic devices including sensors.

[1]  Jianzhang Zhou,et al.  ZnO nanorod light-emitting diodes fabricated by electrochemical approaches , 2008 .

[2]  T. Akita,et al.  Synergistic catalysis of Au@Ag core-shell nanoparticles stabilized on metal-organic framework. , 2011, Journal of the American Chemical Society.

[3]  S. Qiu,et al.  "Twin copper source" growth of metal-organic framework membrane: Cu(3)(BTC)(2) with high permeability and selectivity for recycling H(2). , 2009, Journal of the American Chemical Society.

[4]  M. O'keeffe,et al.  Design and synthesis of an exceptionally stable and highly porous metal-organic framework , 1999, Nature.

[5]  Zu-Jin Lin,et al.  Palladium nanoparticles encapsulated in a metal-organic framework as efficient heterogeneous catalysts for direct C2 arylation of indoles. , 2011, Chemistry.

[6]  Yi Cui,et al.  Functionalization of silicon nanowire surfaces with metal-organic frameworks , 2012, Nano Research.

[7]  Peidong Yang,et al.  Nanowire dye-sensitized solar cells , 2005, Nature materials.

[8]  Christopher J. Chang,et al.  A FRET-based approach to ratiometric fluorescence detection of hydrogen peroxide. , 2006, Journal of the American Chemical Society.

[9]  Seung Jae Yang,et al.  Preparation and Enhanced Hydrostability and Hydrogen Storage Capacity of CNT@MOF-5 Hybrid Composite , 2009 .

[10]  Chengdu Liang,et al.  A microporous metal-organic framework for gas-chromatographic separation of alkanes. , 2006, Angewandte Chemie.

[11]  N. Phan,et al.  Expanding Applications of Metal−Organic Frameworks: Zeolite Imidazolate Framework ZIF-8 as an Efficient Heterogeneous Catalyst for the Knoevenagel Reaction , 2011 .

[12]  Jianzhang Zhou,et al.  White-Light-Emitting Diode Based on ZnO Nanotubes , 2009 .

[13]  T. Akita,et al.  Au@ZIF-8: CO oxidation over gold nanoparticles deposited to metal-organic framework. , 2009, Journal of the American Chemical Society.

[14]  Seth M. Cohen,et al.  Engineering a metal-organic framework catalyst by using postsynthetic modification. , 2009, Angewandte Chemie.

[15]  Fang Qian,et al.  Nitrogen-doped ZnO nanowire arrays for photoelectrochemical water splitting. , 2009, Nano letters.

[16]  Yongcai Qiu,et al.  Secondary branching and nitrogen doping of ZnO nanotetrapods: building a highly active network for photoelectrochemical water splitting. , 2012, Nano letters.

[17]  Yingwei Li,et al.  Multifunctional catalysis by Pd@MIL-101: one-step synthesis of methyl isobutyl ketone over palladium nanoparticles deposited on a metal-organic framework. , 2010, Chemical communications.

[18]  Xiaoping Zhou,et al.  Formation of ZnO hexagonal micro-pyramids: a successful control of the exposed polar surfaces with the assistance of an ionic liquid. , 2005, Chemical communications.

[19]  G. Majano,et al.  Scalable Room‐Temperature Conversion of Copper(II) Hydroxide into HKUST‐1 (Cu3(btc)2) , 2013, Advanced materials.

[20]  Omar M. Yaghi,et al.  Metal-organic frameworks: a new class of porous materials , 2004 .

[21]  Shinobu Fujihara,et al.  Enhanced photoelectrochemical performance of ZnO electrodes sensitized with N-719 , 2006 .

[22]  Randall Q. Snurr,et al.  Ultrahigh Porosity in Metal-Organic Frameworks , 2010, Science.

[23]  S. Turner,et al.  GaN@ZIF-8: selective formation of gallium nitride quantum dots inside a zinc methylimidazolate framework. , 2011, Journal of the American Chemical Society.

[24]  M. Carreon,et al.  Highly permeable zeolite imidazolate framework-8 membranes for CO2/CH4 separation. , 2010, Journal of the American Chemical Society.

[25]  Junfa Zhu,et al.  Fe3O4@MOF core–shell magnetic microspheres with a designable metal–organic framework shell , 2012 .

[26]  H. García,et al.  Catalysis by metal nanoparticles embedded on metal-organic frameworks. , 2012, Chemical Society reviews.

[27]  I. Kiricsi,et al.  Synthesis of Zinc Glycerolate Microstacks from a ZnO Nanorod Sacrificial Template , 2009 .

[28]  Zhong Lin Wang Nanostructures of zinc oxide , 2004 .

[29]  J. Jasinski,et al.  Structural evolution of zeolitic imidazolate framework-8. , 2010, Journal of the American Chemical Society.

[30]  Zhaoxiong Xie,et al.  The preparation of spiral ZnO nanostructures by top-down wet-chemical etching and their related properties , 2012 .

[31]  G. Tendeloo,et al.  ZnO@ZIF-8: stabilization of quantum confined ZnO nanoparticles by a zinc methylimidazolate framework and their surface structural characterization probed by CO2 adsorption , 2011 .

[32]  Xi-hong Lu,et al.  Vertically aligned In2O3 nanorods on FTO substrates for photoelectrochemical applications , 2011 .

[33]  Gunter Hagen,et al.  Metal-Organic Frameworks for Sensing Applications in the Gas Phase , 2009, Sensors.

[34]  Klaus Huber,et al.  Controlling Zeolitic Imidazolate Framework Nano- and Microcrystal Formation: Insight into Crystal Growth by Time-Resolved In Situ Static Light Scattering , 2011 .

[35]  Michael O'Keeffe,et al.  Secondary building units, nets and bonding in the chemistry of metal-organic frameworks. , 2009, Chemical Society reviews.

[36]  H. Su,et al.  Tuning the crystal morphology and size of zeolitic imidazolate framework-8 in aqueous solution by surfactants , 2011 .

[37]  T. Xu,et al.  Versatile fabrication of aligned SnO2nanotube arrays by using various ZnO arrays as sacrificial templates , 2009 .

[38]  Jingui Duan,et al.  Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups. , 2011, Journal of the American Chemical Society.

[39]  C. Téllez,et al.  Ordered mesoporous silica-(ZIF-8) core-shell spheres. , 2012, Chemical communications.

[40]  Z. Lai,et al.  Rapid synthesis of zeolitic imidazolate framework-8 (ZIF-8) nanocrystals in an aqueous system. , 2011, Chemical communications.

[41]  M. Oh,et al.  Growth-controlled formation of porous coordination polymer particles. , 2008, Journal of the American Chemical Society.

[42]  Guangjin Chen,et al.  A novel method to improve the gas storage capacity of ZIF-8 , 2012 .

[43]  M. Grätzel,et al.  Probing the photoelectrochemical properties of hematite (α-Fe2O3) electrodes using hydrogen peroxide as a hole scavenger , 2011 .

[44]  A. Karyakin,et al.  Prussian blue based nanoelectrode arrays for H(2)O(2) detection. , 2004, Analytical chemistry.

[45]  Guodong Qian,et al.  Metal-organic frameworks with functional pores for recognition of small molecules. , 2010, Accounts of chemical research.

[46]  Heng Jiang,et al.  MOF-5 decorated hierarchical ZnO nanorod arrays and its photoluminescence , 2011 .

[47]  M. Oh,et al.  Advanced fabrication of metal-organic frameworks: template-directed formation of polystyrene@ZIF-8 core-shell and hollow ZIF-8 microspheres. , 2012, Chemical communications.

[48]  M. van der Auweraer,et al.  Patterned film growth of metal-organic frameworks based on galvanic displacement. , 2010, Chemical communications.

[49]  S. Kitagawa,et al.  Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication. , 2012, Nature materials.

[50]  C. Mirkin,et al.  Amorphous Infinite Coordination Polymer Microparticles: A New Class of Selective Hydrogen Storage Materials , 2008, Advanced materials.

[51]  Guang Lu,et al.  Metal-organic frameworks as sensors: a ZIF-8 based Fabry-Pérot device as a selective sensor for chemical vapors and gases. , 2010, Journal of the American Chemical Society.

[52]  Guozhong Cao,et al.  ZnO Nanostructures for Dye‐Sensitized Solar Cells , 2009 .

[53]  Amy J. Cairns,et al.  Successful implementation of the stepwise layer-by-layer growth of MOF thin films on confined surfaces: mesoporous silica foam as a first case study. , 2012, Chemical communications.

[54]  D. Cao,et al.  Zeolitic imidazolate framework-8 as a luminescent material for the sensing of metal ions and small molecules , 2011 .

[55]  Qiang Xu,et al.  Porous metal-organic frameworks as platforms for functional applications. , 2011, Chemical communications.

[56]  Junfa Zhu,et al.  A rational self-sacrificing template route to metal-organic framework nanotubes and reversible vapor-phase detection of nitroaromatic explosives. , 2012, Small.

[57]  Qiang Xu,et al.  Immobilizing highly catalytically active Pt nanoparticles inside the pores of metal-organic framework: a double solvents approach. , 2012, Journal of the American Chemical Society.

[58]  Yi Wang,et al.  Imparting functionality to a metal-organic framework material by controlled nanoparticle encapsulation. , 2012, Nature chemistry.

[59]  Xiao-Ming Chen,et al.  Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. , 2006, Angewandte Chemie.

[60]  Yuanjing Cui,et al.  A luminescent metal-organic framework with Lewis basic pyridyl sites for the sensing of metal ions. , 2009, Angewandte Chemie.

[61]  Nathaniel L Rosi,et al.  Tuning MOF CO2 adsorption properties via cation exchange. , 2010, Journal of the American Chemical Society.

[62]  T. Akita,et al.  Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage. , 2011, Journal of the American Chemical Society.

[63]  Jinxiang Dong,et al.  Synthesis of ZIF-8 and ZIF-67 by steam-assisted conversion and an investigation of their tribological behaviors. , 2011, Angewandte Chemie.

[64]  C. Ahn,et al.  Photovoltaic device on a single ZnO nanowire p–n homojunction , 2012, Nanotechnology.

[65]  Cheng Wang,et al.  Isoreticular chiral metal-organic frameworks for asymmetric alkene epoxidation: tuning catalytic activity by controlling framework catenation and varying open channel sizes. , 2010, Journal of the American Chemical Society.