Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State.

The selectivity control toward aldehyde in the aromatic alcohol oxidation remains a grand challenge using molecular oxygen under mild conditions. In this work, we designed and synthesized Pt/PCN-224(M) composites by integration of Pt nanocrystals and porphyrinic metal-organic frameworks (MOFs), PCN-224(M). The composites exhibit excellent catalytic performance in the photo-oxidation of aromatic alcohols by 1 atm O2 at ambient temperature, based on a synergetic photothermal effect and singlet oxygen production. Additionally, in opposition to the function of the Schottky junction, injection of hot electrons from plasmonic Pt into PCN-224(M) would lower the electron density of the Pt surface, which thus is tailorable for the optimized catalytic performance via the competition between the Schottky junction and the plasmonic effect by altering the light intensity. To the best of our knowledge, this is not only an unprecedented report on singlet oxygen-engaged selective oxidation of aromatic alcohols to aldehydes but also the first report on photothermal effect of MOFs.

[1]  M. Deenadayalan,et al.  Visible-Light-Assisted Photocatalytic Reduction of Nitroaromatics by Recyclable Ni(II)-Porphyrin Metal-Organic Framework (MOF) at RT. , 2016, Inorganic chemistry.

[2]  Shuhong Yu,et al.  Pd Nanocubes@ZIF-8: Integration of Plasmon-Driven Photothermal Conversion with a Metal-Organic Framework for Efficient and Selective Catalysis. , 2016, Angewandte Chemie.

[3]  Omar K Farha,et al.  Dual-Function Metal-Organic Framework as a Versatile Catalyst for Detoxifying Chemical Warfare Agent Simulants. , 2015, ACS nano.

[4]  Z. Li,et al.  Fe-Based Metal–Organic Frameworks for Highly Selective Photocatalytic Benzene Hydroxylation to Phenol , 2015 .

[5]  Yadong Li,et al.  Platinum–nickel frame within metal-organic framework fabricated in situ for hydrogen enrichment and molecular sieving , 2015, Nature Communications.

[6]  Yi Xie,et al.  Ultrathin Black Phosphorus Nanosheets for Efficient Singlet Oxygen Generation. , 2015, Journal of the American Chemical Society.

[7]  J. Hupp,et al.  Selective Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic Metal-Organic Framework. , 2015, Angewandte Chemie.

[8]  Shuyan Song,et al.  Pt nanohelices with highly ordered horizontal pore channels as enhanced photothermal materials† †Electronic supplementary information (ESI) available: XPS and TEM of the Pt nanohelices. See DOI: 10.1039/c5sc01686j , 2015, Chemical science.

[9]  Yasuhiro Shiraishi,et al.  Hot-Electron-Induced Highly Efficient O2 Activation by Pt Nanoparticles Supported on Ta2O5 Driven by Visible Light. , 2015, Journal of the American Chemical Society.

[10]  R. Luque,et al.  Palladium Nanoparticles Supported in the Nanospaces of Imidazolium-Based Bifunctional PMOs: The Role of Plugs in Selectivity Changeover in Aerobic Oxidation of Alcohols , 2015 .

[11]  Suljo Linic,et al.  Photochemical transformations on plasmonic metal nanoparticles. , 2015, Nature materials.

[12]  Zhiyong Tang,et al.  Solar‐Light‐Driven Renewable Butanol Separation by Core–Shell Ag@ZIF‐8 Nanowires , 2015, Advanced materials.

[13]  Bao-hang Han,et al.  Metallophthalocyanine-based conjugated microporous polymers as highly efficient photosensitizers for singlet oxygen generation. , 2015, Angewandte Chemie.

[14]  S. Irle,et al.  Locking covalent organic frameworks with hydrogen bonds: general and remarkable effects on crystalline structure, physical properties, and photochemical activity. , 2015, Journal of the American Chemical Society.

[15]  Jihye Park,et al.  Photochromic metal-organic frameworks: reversible control of singlet oxygen generation. , 2015, Angewandte Chemie.

[16]  Wenbin Lin,et al.  Nanoscale Metal–Organic Framework for Highly Effective Photodynamic Therapy of Resistant Head and Neck Cancer , 2014, Journal of the American Chemical Society.

[17]  Chia‐Kuang Tsung,et al.  Core–Shell Catalysts of Metal Nanoparticle Core and Metal–Organic Framework Shell , 2014 .

[18]  Wen-Yang Gao,et al.  Metal-metalloporphyrin frameworks: a resurging class of functional materials. , 2014, Chemical Society reviews.

[19]  G. Qian,et al.  Methane storage in metal-organic frameworks. , 2014, Chemical Society reviews.

[20]  H. Zhou,et al.  Metal-organic frameworks (MOFs). , 2014, Chemical Society reviews.

[21]  Bin Liu,et al.  Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry. , 2014, Chemical Society reviews.

[22]  Xiaojun Wu,et al.  Tunable oxygen activation for catalytic organic oxidation: Schottky junction versus plasmonic effects. , 2014, Angewandte Chemie.

[23]  Chuande Wu,et al.  Porous metal-organic frameworks for heterogeneous biomimetic catalysis. , 2014, Accounts of chemical research.

[24]  Dawei Feng,et al.  Construction of ultrastable porphyrin Zr metal-organic frameworks through linker elimination. , 2013, Journal of the American Chemical Society.

[25]  V. Ozoliņš,et al.  Facet-selective adsorption on noble metal crystals guided by electrostatic potential surfaces of aromatic molecules. , 2013, Journal of the American Chemical Society.

[26]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[27]  S. Kitagawa,et al.  Integration of porous coordination polymers and gold nanorods into core-shell mesoscopic composites toward light-induced molecular release. , 2013, Journal of the American Chemical Society.

[28]  Huaiyong Zhu,et al.  Enhancing catalytic performance of palladium in gold and palladium alloy nanoparticles for organic synthesis reactions through visible light irradiation at ambient temperatures. , 2013, Journal of the American Chemical Society.

[29]  Huanjun Chen,et al.  Plasmonic harvesting of light energy for Suzuki coupling reactions. , 2013, Journal of the American Chemical Society.

[30]  Can Li,et al.  Roles of cocatalysts in photocatalysis and photoelectrocatalysis. , 2013, Accounts of chemical research.

[31]  Kai A. I. Zhang,et al.  Modification of conjugated microporous poly-benzothiadiazole for photosensitized singlet oxygen generation in water. , 2013, Chemical communications.

[32]  Wensheng Yan,et al.  Surface facet of palladium nanocrystals: a key parameter to the activation of molecular oxygen for organic catalysis and cancer treatment. , 2013, Journal of the American Chemical Society.

[33]  M. Antonietti,et al.  Surface area control and photocatalytic activity of conjugated microporous poly(benzothiadiazole) networks. , 2013, Angewandte Chemie.

[34]  H. R. Moon,et al.  Fabrication of metal nanoparticles in metal-organic frameworks. , 2013, Chemical Society reviews.

[35]  S. Kümmel,et al.  Ni/Pd@MIL-101: synergistic catalysis with cavity-conform Ni/Pd nanoparticles. , 2012, Angewandte Chemie.

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

[37]  B. Li,et al.  Investigation of size-dependent plasmonic and catalytic properties of metallic nanocrystals enabled by size control with HCl oxidative etching. , 2012, Small.

[38]  W. Choi,et al.  Simultaneous production of hydrogen with the degradation of organic pollutants using TiO2 photocatalyst modified with dual surface components , 2012 .

[39]  Zhaohui Li,et al.  An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction. , 2012, Angewandte Chemie.

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

[41]  J. Long,et al.  Introduction to metal-organic frameworks. , 2012, Chemical reviews.

[42]  K. Hwang,et al.  Metal nanoparticles sensitize the formation of singlet oxygen. , 2011, Angewandte Chemie.

[43]  M. Glasius,et al.  Singlet Oxygen Sensor Green®: Photochemical Behavior in Solution and in a Mammalian Cell , 2011, Photochemistry and photobiology.

[44]  Yongping Luo,et al.  Plasmon‐Driven Selective Oxidation of Aromatic Alcohols to Aldehydes in Water with Recyclable Pt/TiO2 Nanocomposites , 2011 .

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

[46]  Peter R Ogilby,et al.  Singlet oxygen: there is indeed something new under the sun. , 2010, Chemical Society reviews.

[47]  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.

[48]  Yasuhiro Shiraishi,et al.  One-pot synthesis of benzimidazoles by simultaneous photocatalytic and catalytic reactions on Pt@TiO2 nanoparticles. , 2010, Angewandte Chemie.

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

[50]  Seth M. Cohen,et al.  Postsynthetic modification of metal-organic frameworks. , 2009, Chemical Society reviews.

[51]  Omar M Yaghi,et al.  The pervasive chemistry of metal-organic frameworks. , 2009, Chemical Society reviews.

[52]  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.

[53]  T. Montagnon,et al.  Using singlet oxygen to synthesize polyoxygenated natural products from furans. , 2008, Accounts of chemical research.

[54]  C. Serre,et al.  Amine grafting on coordinatively unsaturated metal centers of MOFs: consequences for catalysis and metal encapsulation. , 2008, Angewandte Chemie.

[55]  Xiaohua Huang,et al.  Noble metals on the nanoscale: optical and photothermal properties and some applications in imaging, sensing, biology, and medicine. , 2008, Accounts of chemical research.

[56]  G. Hutchings,et al.  Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO2 Catalysts , 2006, Science.

[57]  Eduarda Fernandes,et al.  Fluorescence probes used for detection of reactive oxygen species. , 2005, Journal of biochemical and biophysical methods.

[58]  M. Fujii,et al.  Silicon Nanocrystals: Photosensitizers for Oxygen Molecules , 2005 .

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

[60]  A. Corma,et al.  A collaborative effect between gold and a support induces the selective oxidation of alcohols. , 2005, Angewandte Chemie.

[61]  G. Somorjai,et al.  Pt nanocrystals: shape control and Langmuir-Blodgett monolayer formation. , 2005, The journal of physical chemistry. B.

[62]  K. Ebitani,et al.  Hydroxyapatite-supported palladium nanoclusters: a highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen. , 2004, Journal of the American Chemical Society.

[63]  A. Baiker,et al.  Oxidation of alcohols with molecular oxygen on solid catalysts. , 2004, Chemical reviews.

[64]  D. Vos,et al.  Solid Materials as Sources for Synthetically Useful Singlet Oxygen , 2004 .

[65]  M. DeRosa.  Photosensitized singlet oxygen and its applications , 2002 .

[66]  R. Sheldon,et al.  Green, catalytic oxidations of alcohols. , 2002, Accounts of chemical research.

[67]  E. Kasahara,et al.  Irradiation of titanium dioxide generates both singlet oxygen and superoxide anion. , 1999, Free radical biology & medicine.

[68]  L. Packer,et al.  Hydroxyl and superoxide anion radical scavenging activities of natural source antioxidants using the computerized JES‐FR30 ESR spectrometer system , 1997, Biochemistry and molecular biology international.

[69]  W.Phillip Helman,et al.  Rate Constants for the Decay and Reactions of the Lowest Electronically Excited Singlet State of Molecular Oxygen in Solution. An Expanded and Revised Compilation , 1995 .

[70]  R P Mason,et al.  The horseradish peroxidase-catalyzed oxidation of 3,5,3',5'-tetramethylbenzidine. Free radical and charge-transfer complex intermediates. , 1982, The Journal of biological chemistry.

[71]  J. A. Badwey,et al.  Active oxygen species and the functions of phagocytic leukocytes. , 1980, Annual review of biochemistry.

[72]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure: I. Spectra of Diatomic Molecules , 1944 .