CO2 Hydrogenation over Pt-Containing UiO-67 Zr-MOFs—The Base Case

CO2 hydrogenation was carried out over Pt-containing UiO-67 Zr-MOFs at T = 220–280 °C and ambient pressure, with H2/CO2 = 0.2–9 and contact times, τ = 0.004–0.01 gcat·min·mL–1. The catalysts were characterized by XRD, N2 adsorption, FESEM, TEM and HRTEM, Pt L3-edge XANES and EXAFS, dissolution-NMR, CO chemisorption, IR spectroscopy, and TGA. A positive correlation was observed between the degree of Pt reduction and CO2 conversion. Contact time variation experiments showed that CO is a primary product of reaction, while CH4 is a secondary product. Testing of catalyst crystals with 0.15 and 2.0 μm crystal size, respectively, revealed no influence of diffusion on the reaction rate. Comparison to a conventional Pt/SiO2 catalyst showed very similar activation energy, with Eapp = 50 ± 3 kJ·mol–1. However, the turnover frequency over Pt/SiO2 was significantly lower, and Pt/SiO2 did not yield methane as a product. The Pt-containing UiO-67 Zr-MOF catalyst showed stable activity during 60 h of testing.

[1]  K. Lillerud,et al.  Tuning Pt and Cu sites population inside functionalized UiO-67 MOF by controlling activation conditions. , 2017, Faraday discussions.

[2]  Cheng Wang,et al.  Confinement of Ultrasmall Cu/ZnOx Nanoparticles in Metal-Organic Frameworks for Selective Methanol Synthesis from Catalytic Hydrogenation of CO2. , 2017, Journal of the American Chemical Society.

[3]  J. Hupp,et al.  Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks , 2017 .

[4]  Ping Liu,et al.  CO2 hydrogenation on Pt, Pt/SiO2 and Pt/TiO2: Importance of synergy between Pt and oxide support , 2016 .

[5]  Chongli Zhong,et al.  The Effect of N-Containing Support on Catalytic Activity of CO Oxidation over Highly Dispersed Pt/UiO-67 , 2016 .

[6]  Xiaolei Fan,et al.  On thermal stability and catalytic reactivity of Zr-based metal–organic framework (UiO-67) encapsulated Pt catalysts , 2016 .

[7]  J. Hupp,et al.  Probing the correlations between the defects in metal-organic frameworks and their catalytic activity by an epoxide ring-opening reaction. , 2016, Chemical communications.

[8]  Chongli Zhong,et al.  Enhancing CO2 adsorption and separation ability of Zr(IV)-based metal–organic frameworks through ligand functionalization under the guidance of the quantitative structure–property relationship model , 2016 .

[9]  Carlos A. Grande,et al.  UiO-67-type Metal-Organic Frameworks with Enhanced Water Stability and Methane Adsorption Capacity. , 2016, Inorganic chemistry.

[10]  G. Stucky,et al.  Supplementary Material for Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts , 2015 .

[11]  C. Henriques,et al.  Insight into CO2 methanation mechanism over NiUSY zeolites: An operando IR study , 2015 .

[12]  G. Somorjai,et al.  Chemical Environment Control and Enhanced Catalytic Performance of Platinum Nanoparticles Embedded in Nanocrystalline Metal-Organic Frameworks. , 2015, Journal of the American Chemical Society.

[13]  Y. Horiuchi,et al.  Immobilization of Cu Complex into Zr-Based MOF with Bipyridine Units for Heterogeneous Selective Oxidation , 2015 .

[14]  Jiajian Gao,et al.  Recent advances in methanation catalysts for the production of synthetic natural gas , 2015 .

[15]  J. Long,et al.  Single-crystal-to-single-crystal metalation of a metal-organic framework: a route toward structurally well-defined catalysts. , 2015, Inorganic chemistry.

[16]  K. Lillerud,et al.  Probing Reactive Platinum Sites in UiO-67 Zirconium Metal–Organic Frameworks , 2015 .

[17]  Zhiyong Guo,et al.  Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks , 2014 .

[18]  Ming Li,et al.  Tuning CO₂ selective adsorption over N₂ and CH₄ in UiO-67 analogues through ligand functionalization. , 2014, Inorganic chemistry.

[19]  Zhiyong Guo,et al.  Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation , 2014 .

[20]  O. Lemaire,et al.  Study of CO and Hydrogen Interactions on Carbon-Supported Pt Nanoparticles by Quadrupole Mass Spectrometry and Operando Diffuse Reflectance FTIR Spectroscopy , 2013 .

[21]  Anne-Cécile Roger,et al.  Catalytic CO2 valorization into CH4 on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy , 2013 .

[22]  M. Ozawa,et al.  Effect of platinum dispersion on the catalytic activity of Pt/Al2O3 for the oxidation of carbon monoxide and propene , 2013 .

[23]  Michael J. Katz,et al.  A facile synthesis of UiO-66, UiO-67 and their derivatives. , 2013, Chemical communications.

[24]  K. Lillerud,et al.  In Situ Infrared Spectroscopic and Gravimetric Characterisation of the Solvent Removal and Dehydroxylation of the Metal Organic Frameworks UiO-66 and UiO-67 , 2013, Topics in Catalysis.

[25]  Arnold J. Forman,et al.  UV-Vis Spectroscopy , 2013 .

[26]  M. Vandichel,et al.  Electronic effects of linker substitution on Lewis acid catalysis with metal-organic frameworks. , 2012, Angewandte Chemie.

[27]  Sung Su Kim,et al.  A study on the effect of support's reducibility on the reverse water-gas shift reaction over Pt catalysts , 2012 .

[28]  Kenji Sumida,et al.  Carbon dioxide capture in metal-organic frameworks. , 2012, Chemical reviews.

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

[30]  Wei Wang,et al.  Recent advances in catalytic hydrogenation of carbon dioxide. , 2011, Chemical Society reviews.

[31]  Bartolomeo Civalleri,et al.  Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory , 2011 .

[32]  P. Edwards,et al.  Turning carbon dioxide into fuel , 2010, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

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

[34]  C. Mirodatos,et al.  Propane dry reforming to synthesis gas over Ni-based catalysts : Influence of support and operating parameters on catalyst activity and stability , 2007 .

[35]  M. Mihaylov,et al.  Polycarbonyl species in Pt/H–ZSM-5: FTIR spectroscopic study of 12CO–13CO co-adsorption , 2005 .

[36]  M. Mihaylov,et al.  FTIR spectroscopic study of CO adsorption on Pt–H–ZSM-5 , 2005 .

[37]  F. Schüth,et al.  Parallel IR spectroscopic characterization of CO chemisorption on Pt loaded zeolites , 2005 .

[38]  Alexandre Goguet,et al.  Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO2 Catalyst , 2004 .

[39]  Enrique Iglesia,et al.  Mechanism and Site Requirements for Activation and Chemical Conversion of Methane on Supported Pt Clusters and Turnover Rate Comparisons among Noble Metals , 2004 .

[40]  J. Rasko.  CO-induced surface structural changes of Pt on oxide-supported Pt catalysts studied by DRIFTS , 2003 .

[41]  D. Ferri,et al.  Probing boundary sites on a Pt/Al2O3 model catalyst by CO2 hydrogenation and in situ ATR-IR spectroscopy of catalytic solid-liquid interfaces , 2002 .

[42]  James A. Anderson,et al.  Infrared study of crotonaldehyde and CO adsorption on a Pt/TiO2 catalyst , 1998 .

[43]  D. Cazorla-Amorós,et al.  Structure Sensitivity of CO2 Hydrogenation Reaction Catalyzed by Pt/Carbon Catalysts , 1996 .

[44]  D. Cazorla-Amorós,et al.  CO2 hydrogenation under pressure on catalysts PtCa/C , 1996 .

[45]  M. Hughes,et al.  The interpretation of CO adsorbed on Pt/SiO2 of two different particle-size distributions , 1993 .

[46]  D. Haaland.  Infrared studies of CO adsorbed on Pt/Al2O3: Evidence for CO bonded in 3-fold coordination , 1987 .

[47]  B. Hayden,et al.  An infrared study of the adsorption of CO on a stepped platinum surface , 1985 .

[48]  A. Bradshaw,et al.  The adsorption of CO on Pt(111) studied by infrared reflection—Absortion spectroscopy , 1983 .

[49]  H. J. Krebs,et al.  Evidence for two different adsorption sites of CO on Pt(111) from infrared reflection spectroscopy , 1977 .

[50]  D. King,et al.  Infrared spectra for co isotopes chemisorbed on Pt “111”: Evidence for strong absorbate coupling interactions , 1977 .

[51]  A. Bradshaw,et al.  IR reflection-absorption spectroscopy of CO adsorbed on platinum and palladium , 1976 .

[52]  D. King,et al.  Chemisorption of carbon monoxide on platinum {111}: Reflection-absorption infrared spectroscopy , 1976 .

[53]  J. Freel.  Chemisorption on supported platinum: I. Evaluation of a pulse method , 1972 .