Online citations, reference lists, and bibliographies.
← Back to Search

Selective Methane Oxidation Catalyzed By Platinum Salts In Oleum At Turnover Frequencies Of Large-Scale Industrial Processes.

Tobias Zimmermann, Mario Soorholtz, Marius Bilke, F. Schüth
Published 2016 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Share
Direct catalytic methane functionalization, a "dream reaction", is typically characterized by relatively low catalyst activities. This also holds for the η(2)-(2,2'-bipyrimidyl)dichloroplatinum(II) [(bpym)PtCl2, 1] catalyst which oxidizes methane to methyl bisulfate in sulfuric acid. Nevertheless, it is arguably still one of the best systems for the partial oxidation of methane reported so far. Detailed studies of the dependence of activity on the SO3 concentration and the interplay with the solubility of different platinum compounds revealed potassium tetrachloroplatinate (K2PtCl4) as an extremely active, selective, and stable catalyst, reaching turnover frequencies (TOFs) of more than 25,000 h(-1) in 20% oleum with selectivities above 98%. The TOFs are more than 3 orders of magnitude higher compared to the original report on (bpym)PtCl2 and easily reach or exceed those realized in commercial industrial processes, such as the Cativa process for the carbonylation of methanol. Also space-time-yields are on the order of large-scale commercialized processes.
This paper references
10.1016/S0920-5861(00)00263-7
High productivity methanol carbonylation catalysis using iridium
Glenn J Sunley (2000)
10.1021/CR000018S
Catalysis research of relevance to carbon management: progress, challenges, and opportunities.
H. Arakawa (2001)
10.1126/SCIENCE.280.5363.560
Platinum catalysts for the high-yield oxidation of methane to a methanol derivative
Periana (1998)
10.1021/ja404895z
Using reduced catalysts for oxidation reactions: mechanistic studies of the "Periana-Catalytica" system for CH4 oxidation.
O. Mironov (2013)
10.1021/OM00027A045
Oxidation of hydrocarbons by aqueous platinum salts: mechanism and selectivity
J. Labinger (1993)
10.1007/978-3-642-39709-7
Methanol: The Basic Chemical and Energy Feedstock of the Future
M. Bertau (2014)
10.1021/JA00002A063
Low-temperature, palladium(II)-catalyzed, solution-phase oxidation of methane to methanol derivative
L. C. Kao (1991)
10.1016/J.MOLCATA.2004.05.036
Perspectives on some challenges and approaches for developing the next generation of selective, low temperature, oxidation catalysts for alkane hydroxylation based on the CH activation reaction
R. Periana (2004)
10.1002/cssc.201200299
Oxidative methane upgrading.
C. Hammond (2012)
10.1016/J.MOLCATA.2006.02.035
Design and study of homogeneous catalysts for the selective, low temperature oxidation of hydrocarbons
Brian L. Conley (2006)
10.1016/J.MOLCATA.2006.06.059
Pt-catalyzed oxidative carbonylation of methane to acetic acid in sulfuric acid
M. Zerella (2006)
10.1007/BF02067738
Pt(II) complexes in activation of saturated hydrocarbons
N. Goldshleger (1977)
An Empirical Equation for the Solubility of Nonpolar Gases and Vapors in Concentrated Water-Acid and Water-Salt Solutions
A. Lutsyk (2002)
10.1016/J.JORGANCHEM.2015.07.043
Preface to Shilov special issue
G. B. Shul'pin (2015)
10.1002/anie.200902009
Solid catalysts for the selective low-temperature oxidation of methane to methanol.
R. Palkovits (2009)
10.1002/ANGE.19590710503
Katalytische Umsetzungen von Olefinen an Platinmetall‐Verbindungen Das Consortium‐Verfahren zur Herstellung von Acetaldehyd
J. Smidt (1959)
10.1021/OM0101691
Stability and thermodynamics of the PtCl2 type catalyst for activating methane to methanol: A computational study
J. Kua (2002)
10.1002/anie.201006424
Chemistry with methane: concepts rather than recipes.
H. Schwarz (2011)
10.1016/S0920-5861(00)00456-9
CATALYTIC CONVERSION OF METHANE TO MORE USEFUL CHEMICALS AND FUELS: A CHALLENGE FOR THE 21ST CENTURY
J. Lunsford (2000)
10.1021/OM060465J
A Detailed Theoretical Study of the Mechanism and Energetics of Methane to Methanol Conversion by Cisplatin and Catalytica
A. Paul (2007)
10.1039/c2cc36232e
Direct methane oxidation over Pt-modified nitrogen-doped carbons.
Mario Soorholtz (2013)
10.1126/science.1249357
Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters
B. Hashiguchi (2014)
World Patent WO / 1998 / 050333 , 1998 . ( 35 )
R. A. Periana
10.1039/c3cs60120j
Methane as raw material in synthetic chemistry: the final frontier.
Ana Caballero (2013)
Russ
A. I. Lutsyk (2002)
10.1002/anie.201108706
Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5.
C. Hammond (2012)
10.1016/J.APCATA.2006.04.006
The kinetics of homogeneous catalytic methane oxidation
B. Michalkiewicz (2006)
10.1002/chem.201402086
Oxidizing elemental platinum with oleum under harsh conditions: the unique tris(disulfato)platinate(IV) [Pt(S2O7)3]2- anion.
Joern Bruns (2014)
Superacid chemistry, 2nd edition
G. A. Olah (2009)
10.1038/417507a
Understanding and exploiting C–H bond activation
J. Labinger (2002)
10.1021/CS400420N
Effect of Solvent and Ancillary Ligands on the Catalytic H/D Exchange Reactivity of Cp*IrIII(L) Complexes
Matthew C. Lehman (2013)
10.1021/CR9411886
ACTIVATION OF C-H BONDS BY METAL COMPLEXES
Alexander E. Shilov and (1997)
10.1021/CR030710Y
Mechanistic aspects of C-H activation by Pt complexes.
Martin Lersch (2005)
10.1016/S0022-0728(77)80279-9
Utilisation des mélanges H2O−H2SO4−SO3 en tant que solvants: Partie III. Construction d'un diagramme potentiel-fraction molaire. Domaines d'électroactivité
P. Gaillochet (1977)
10.1021/jacs.5b08707
Evolution of C-H Bond Functionalization from Methane to Methodology.
J. Hartwig (2016)
10.1039/B610328F
Direct methane conversion to methanol by ionic liquid-dissolved platinum catalysts.
J. Cheng (2006)
10.1021/ja903930e
Product protection, the key to developing high performance methane selective oxidation catalysts.
Mårten S G Ahlquist (2009)
10.1007/978-90-481-3698-8_2
Alkane Functionalization via Electrophilic Activation
J. Labinger (2012)
10.1021/CS501620F
Proton or Metal? The H/D Exchange of Arenes in Acidic Solvents
Dominik Munz (2015)



This paper is referenced by
10.1007/s11157-017-9447-9
Low-temperature biological activation of methane: structure, function and molecular interactions of soluble and particulate methane monooxygenases
Sikai Zhang (2017)
10.1002/ANGE.201814313
Von Sonnenlicht zu Brennstoffen: aktuelle Fortschritte der C1‐Solarchemie
Guang-bo Chen (2019)
10.1002/ANGE.201710377
Steigerung der Katalysatoreffizienz in der C-H-Aktivierungskatalyse
Tobias Gensch (2018)
10.1039/C6CY01879C
Methane conversion into different hydrocarbons or oxygenates: current status and future perspectives in catalyst development and reactor operation
E. Kondratenko (2017)
10.1039/c9dt00922a
Direct conversion of methane to methanol with zeolites: towards understanding the role of extra-framework d-block metal and zeolite framework type.
Samuel Raynes (2019)
10.1007/s11172-019-2581-5
Homogeneous catalytic systems for the oxidative functionalization of alkanes: design, oxidants, and mechanisms
E. G. Chepaikin (2019)
10.1002/ANGE.201702550
Die direkte katalytische Oxidation von Methan zu Methanol – eine kritische Beurteilung
M. Ravi (2017)
10.1021/acscentsci.7b00469
When Electrochemistry Met Methane: Rapid Catalyst Oxidation Fuels Hydrocarbon Functionalization
K. J. Lee (2017)
10.1002/cctc.201900919
Aqueous‐Phase Selective Oxidation of Methane with Oxygen over Iron Salts and Pd/C in the Presence of Hydrogen
Jongkyu Kang (2019)
10.1002/9781119379256.CH8
Oxidative Functionalization of Methane on Heterogeneous Catalysts
M. Sanchez-Sanchez (2018)
10.1002/anie.201710377
Increasing Catalyst Efficiency in C-H Activation Catalysis.
T. Gensch (2018)
10.1016/j.mcat.2020.110886
Direct oxidation of methane to methanol over Cu-zeolites at mild conditions
M. Álvarez (2020)
10.1016/J.JCAT.2019.04.042
Pt black catalyzed methane oxidation to methyl bisulfate in H2SO4-SO3
H. W. Lee (2019)
10.1038/s41560-019-0491-2
Fuels and energy carriers from single-site catalysts prepared via surface organometallic chemistry
C. Copéret (2019)
10.1038/s41467-020-17494-w
Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer
Jiao Deng (2020)
10.1002/ANGE.201712405
Direkte Umwandlung von Methan zu protoniertem Formaldehyd bei Raumtemperatur in der Gasphase: Zur Rolle von Quecksilber unter den Oxidkationen der Zinktriade
Lei Yue (2018)
The Selective Oxidation of Hydrocarbons on Isolated Iron Active Sites under Ambient Conditions
Zhengliang Qi (2019)
10.1007/978-981-15-4132-2_3
Heterogeneous and Homogeneous Catalytic Partial Oxidations of Methane to Methanol and Its Derivatives
T. Baba (2020)
10.1021/acs.chemrev.6b00739
Homogeneous Functionalization of Methane.
N. Gunsalus (2017)
10.1002/cctc.201901175
Selective Photo‐Oxygenation of Light Alkanes Using Iodine Oxides and Chloride
Nichole S. Liebov (2019)
10.1038/s41929-018-0170-x
Highly selective oxidation of methane to methanol at ambient conditions by titanium dioxide-supported iron species
Jijia Xie (2018)
10.1002/anie.201814313
Solar-to-Fuels: Recent Advances in Light-driven C1 Chemistry.
Guangbo Chen (2019)
10.1126/science.aaw7738
Making more from methane
F. Schüth (2019)
10.3390/APP9142798
Combination of Chemo- and Biocatalysis: Conversion of Biomethane to Methanol and Formic Acid
Benny Kunkel (2019)
10.1021/acsami.7b07339
Facile Method for the Preparation of Covalent Triazine Framework coated Monoliths as Catalyst Support: Applications in C1 Catalysis.
A. Bavykina (2017)
10.1016/j.fuel.2020.117104
Visible-light-driven selective oxidation of methane to methanol on amorphous FeOOH coupled m-WO3
J. Yang (2020)
10.1002/9781119379256.CH17
Catalytic Borylation of Methane: Combining Computational and High‐Throughput Screening Approaches to Discover a New Catalyst
P. Zatsepin (2018)
10.1021/acsami.7b02195
Optimizing Open Iron Sites in Metal-Organic Frameworks for Ethane Oxidation: A First-Principles Study.
Peilin Liao (2017)
10.1016/J.MCAT.2018.11.008
Electrocatalytic Shilov chemistry for the oxidation of aliphatic groups
Liu Sophie (2019)
10.1021/acscentsci.7b00342
Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate
Matthew E. O’Reilly (2017)
10.1016/J.CHEMPR.2019.05.008
Direct Methane Conversion under Mild Condition by Thermo-, Electro-, or Photocatalysis
X. Meng (2019)
10.1002/AENM.202002154
Conversion of Methane into Liquid Fuels—Bridging Thermal Catalysis with Electrocatalysis
Shuai Yuan (2020)
See more
Semantic Scholar Logo Some data provided by SemanticScholar