Pt nanoparticles@photoactive metal-organic frameworks: efficient hydrogen evolution via synergistic photoexcitation and electron injection.

Pt nanoparticles of 2-3 nm and 5-6 nm in diameter were loaded into stable, porous, and phosphorescent metal-organic frameworks (MOFs 1 and 2) built from [Ir(ppy)(2)(bpy)](+)-derived dicarboxylate ligands (L(1) and L(2)) and Zr(6)(μ(3)-O)(4)(μ(3)-OH)(4)(carboxylate)(12) secondary building units, via MOF-mediated photoreduction of K(2)PtCl(4). The resulting Pt@MOF assemblies serve as effective photocatalysts for hydrogen evolution by synergistic photoexcitation of the MOF frameworks and electron injection into the Pt nanoparticles. Pt@2 gave a turnover number of 7000, approximately five times the value afforded by the homogeneous control, and could be readily recycled and reused.

[1]  G. Tendeloo,et al.  Metals@MOFs – Loading MOFs with Metal Nanoparticles for Hybrid Functions , 2010 .

[2]  Omar K Farha,et al.  Metal-organic framework materials as catalysts. , 2009, Chemical Society reviews.

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

[4]  Ji Hyun Kim,et al.  Redox-active porous metal-organic framework producing silver nanoparticles from AgI ions at room temperature. , 2005, Angewandte Chemie.

[5]  Wenbin Lin,et al.  A series of isoreticular chiral metal-organic frameworks as a tunable platform for asymmetric catalysis. , 2010, Nature chemistry.

[6]  Jonas I. Goldsmith,et al.  Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production. , 2005, Journal of the American Chemical Society.

[7]  S. Bernhard,et al.  Robust photocatalytic water reduction with cyclometalated Ir(III) 4-vinyl-2,2'-bipyridine complexes. , 2010, Chemical communications.

[8]  M. S. El-shall,et al.  Metallic and bimetallic nanocatalysts incorporated into highly porous coordination polymer MIL-101† , 2009 .

[9]  S. Bernhard,et al.  Structure-activity correlations among iridium(III) photosensitizers in a robust water-reducing system. , 2009, Inorganic chemistry.

[10]  S. Bernhard,et al.  Visible light induced catalytic water reduction without an electron relay. , 2007, Chemistry.

[11]  Zhigang Xie,et al.  Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis. , 2011, Journal of the American Chemical Society.

[12]  Kazuhiko Maeda,et al.  Visible light water splitting using dye-sensitized oxide semiconductors. , 2009, Accounts of chemical research.

[13]  K. Tamaki,et al.  Size-selective Lewis acid catalysis in a microporous metal-organic framework with exposed Mn2+ coordination sites. , 2008, Journal of the American Chemical Society.

[14]  Daniel G Nocera,et al.  Hydrogen production by molecular photocatalysis. , 2007, Chemical reviews.

[15]  Zhigang Xie,et al.  Porous phosphorescent coordination polymers for oxygen sensing. , 2010, Journal of the American Chemical Society.

[16]  M. Muhler,et al.  Loading of MOF-5 with Cu and ZnO Nanoparticles by Gas-Phase Infiltration with Organometallic Precursors : Properties of Cu/ZnO@MOF-5 as Catalyst for Methanol Synthesis , 2008 .

[17]  D. Olson,et al.  A luminescent microporous metal-organic framework for the fast and reversible detection of high explosives. , 2009, Angewandte Chemie.

[18]  Wenbin Lin,et al.  Highly porous, homochiral metal-organic frameworks: solvent-exchange-induced single-crystal to single-crystal transformations. , 2005, Angewandte Chemie.

[19]  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.

[20]  Wenbin Lin,et al.  Nanoscale Metal–Organic Frameworks: Magnetic Resonance Imaging Contrast Agents and Beyond , 2010 .

[21]  Brian P. Mehl,et al.  Energy transfer dynamics in metal-organic frameworks. , 2010, Journal of the American Chemical Society.

[22]  H. R. Moon,et al.  A redox-active two-dimensional coordination polymer: preparation of silver and gold nanoparticles and crystal dynamics on guest removal. , 2006, Journal of the American Chemical Society.

[23]  Gérard Férey,et al.  Porous metal-organic-framework nanoscale carriers as a potential platform for drug delivery and imaging. , 2010, Nature materials.

[24]  Elsje Alessandra Quadrelli,et al.  Synthesis and Stability of Tagged UiO-66 Zr-MOFs , 2010 .

[25]  Younan Xia,et al.  Shape-Controlled Synthesis of Gold and Silver Nanoparticles , 2002, Science.

[26]  Cheng Wang,et al.  A chiral metal-organic framework for sequential asymmetric catalysis. , 2011, Chemical communications.

[27]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[28]  H. Furukawa,et al.  A multiunit catalyst with synergistic stability and reactivity: a polyoxometalate-metal organic framework for aerobic decontamination. , 2011, Journal of the American Chemical Society.

[29]  Guohua Cao,et al.  Iodinated nanoscale coordination polymers as potential contrast agents for computed tomography. , 2009, Angewandte Chemie.

[30]  T. Akita,et al.  Deposition of gold clusters on porous coordination polymers by solid grinding and their catalytic activity in aerobic oxidation of alcohols. , 2008, Chemistry.

[31]  Omar K Farha,et al.  Rational design, synthesis, purification, and activation of metal-organic framework materials. , 2010, Accounts of chemical research.

[32]  Wenbin Lin,et al.  Enantioselective catalysis with homochiral metal-organic frameworks. , 2009, Chemical Society reviews.

[33]  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.

[34]  Omar M Yaghi,et al.  Strategies for hydrogen storage in metal--organic frameworks. , 2005, Angewandte Chemie.

[35]  Seth M Cohen,et al.  Postsynthetic modification of metal-organic frameworks--a progress report. , 2011, Chemical Society reviews.

[36]  Wenbin Lin,et al.  Nanoscale coordination polymers for platinum-based anticancer drug delivery. , 2008, Journal of the American Chemical Society.

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

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

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

[40]  Wenbin Lin,et al.  Modular synthesis of functional nanoscale coordination polymers. , 2009, Angewandte Chemie.

[41]  A Alec Talin,et al.  Stress-induced chemical detection using flexible metal-organic frameworks. , 2008, Journal of the American Chemical Society.

[42]  C. Serre,et al.  Crystallized frameworks with giant pores: are there limits to the possible? , 2005, Accounts of chemical research.

[43]  S. Kaskel,et al.  Solution infiltration of palladium into MOF-5: synthesis, physisorption and catalytic properties , 2007 .

[44]  S. Bernhard,et al.  Orchestrated photocatalytic water reduction using surface-adsorbing iridium photosensitizers. , 2011, Journal of the American Chemical Society.

[45]  A. Jess,et al.  Pt@MOF-177: synthesis, room-temperature hydrogen storage and oxidation catalysis. , 2008, Chemistry.

[46]  Daniel L DuBois,et al.  Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation. , 2009, Accounts of chemical research.

[47]  Wenbin Lin,et al.  Light harvesting in microscale metal-organic frameworks by energy migration and interfacial electron transfer quenching. , 2011, Journal of the American Chemical Society.

[48]  Huanfeng Jiang,et al.  A highly active heterogeneous palladium catalyst for the Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides in aqueous media. , 2010, Angewandte Chemie.

[49]  Wenbin Lin,et al.  Crystal engineering of NLO materials based on metal--organic coordination networks. , 2002, Accounts of chemical research.

[50]  Susumu Kitagawa,et al.  Functional porous coordination polymers. , 2004, Angewandte Chemie.

[51]  J. Long,et al.  Hydrogen storage in microporous metal-organic frameworks with exposed metal sites. , 2008, Angewandte Chemie.

[52]  C. Serre,et al.  Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences. , 2009, Chemical Society reviews.

[53]  R. Schmid,et al.  Metal@MOF: loading of highly porous coordination polymers host lattices by metal organic chemical vapor deposition. , 2005, Angewandte Chemie.

[54]  L. Hammarström,et al.  Artificial photosynthesis and solar fuels. , 2009, Accounts of chemical research.