2537-69-1

Upstream product

• 34557-54-5 methane 
• 32767-18-3 oxygen-18 
• 124-38-9 carbon dioxide 
• 14797-71-8 ¹⁸O-labeled water 
• 75-15-0 carbon disulfide 
• 201230-82-2 carbon monoxide 
• 55125-78-5 carbon monoxide 
• 41061-01-2 bis(2,2'-bipyridyl)(carbonyl)chlororuthenium(II) chloride 
• 80937-33-3 oxygen 
• 67-56-1 methanol 
• 64-19-7 acetic acid 
• 14742-23-5 ethanol-1-13C 
• 594-04-7 dichloroiodomethane 
• 78921-00-3 dichloro-deuterio-iodo-methane 

Downstream Products

• 17217-84-4 [¹⁸(O)₂]-benzoic acid 
• 18983-82-9 CO⁽¹⁸⁾O 
• 12504-93-7 NO⁽¹⁸⁾O 
• 14040-11-0 tungsten hexacarbonyl 
• 17594-12-6 W(⁽¹³⁾CO)(CO)5 
• 88057-32-3 K₂(CO₂) 
• 1111-72-4 carbon dioxide 
• 442910-53-4 ((C₆H₁₁)3P)2Ni(C⁽¹⁸⁾O₂) 
• 1445972-15-5 C₁₅H₁₁N⁽¹⁸⁾O₂ 

Relevant academic research and scientific papers

Water Oxidation by Mononuclear Ruthenium Complex with a Pentadentate Isoquinoline-Bipyridyl Ligand

Mononuclear ruthenium complexes with a pentadentate ligand, N,N-bis[(isoquinolin-1-yl)methyl][6-(pyridin-2-yl)pyridin-2-yl]methanamine (DIQ-Bpy), were synthesized and characterized by 1H NMR spectroscopy, elemental analysis, electrochemistry, and theoretical calculations. The oxidation of water by [Ru(DIQ-Bpy)(H2O)]2+ was observed in the presence of excess amounts of CeIV. Relative to [Ru(DPA-Bpy)(H2O)]2+ [DPA-Bpy = N,N-bis(2-pyridinylmethyl) -2,2-bipyridine-6-methanamine], the substitution of pyridine groups in DPA-Bpy with electron-withdrawing isoquinolines results in higher redox potential and lower activity for the oxidation of water by [Ru(DIQ-Bpy)(H2O)] 2+. A kinetic study of water oxidation by [Ru(DPA-Bpy)(H 2O)]2+ suggests a mononuclear pathway for the oxidation of water. The noncovalent interaction between isoquinoline groups in [Ru(DIQ-Bpy)(H2O)]2+, which favors the formation of dinuclear species, might account for the lower activity for water oxidation by [Ru(DIQ-Bpy)(H2O)]2+. Mononuclear Ru complexes with a pentadentate ligand, N,N-bis[(isoquinolin-1-yl)methyl][6-(pyridin-2-yl)pyridin- 2-yl]methanamine (DIQ-Bpy), were synthesized and characterized. The effects of isoquinoline groups on the electrochemistry and the activity of [Ru(DIQ-Bpy)(H2O)]2+ on water oxidation are discussed. Copyright

IR spectroscopic study of the dichloromethyl peroxyl radical and its deuterated analogs in the argon matrix

The dichloromethyl peroxyl radical (CHCl2OO?) and its deuterated analog formed in the reaction of the corresponding dichloromethyl radicals with O2 were studied by matrix IR spectroscopy. Dichloromethyl radicals are genera

Elucidation of the Reaction Mechanism for Higherature Water Gas Shift over an Industrial-Type Copper-Chromium-Iron Oxide Catalyst

The water gas shift (WGS) reaction is of paramount importance for the chemical industry, as it constitutes, coupled with methane reforming, the main industrial route to produce hydrogen. Copper-chromium-iron oxide-based catalysts have been widely used for the higherature WGS reaction industrially. The WGS reaction mechanism by the CuCrFeOx catalyst has been debated for years, mainly between a "redox" mechanism involving the participation of atomic oxygen from the catalyst and an "associative" mechanism proceeding via a surface formate-like intermediate. In the present work, advanced in situ characterization techniques (infrared spectroscopy, temperature-programmed surface reaction (TPSR), near-ambient pressure XPS (NAP-XPS), and inelastic neutron scattering (INS)) were applied to determine the nature of the catalyst surface and identify surface intermediate species under WGS reaction conditions. The surface of the CuCrFeOx catalyst is found to be dynamic and becomes partially reduced under WGS reaction conditions, forming metallic Cu nanoparticles on Fe3O4. Neither in situ IR not INS spectroscopy detect the presence of surface formate species during WGS. TPSR experiments demonstrate that the evolution of CO2 and H2 from the CO/H2O reactants follows different kinetics than the evolution of CO2 and H2 from HCOOH decomposition (molecule mimicking the associative mechanism). Steady-state isotopic transient kinetic analysis (SSITKA) (CO + H216O → CO + H218O) exhibited significant 16O/18O scrambling, characteristic of a redox mechanism. Computed activation energies for elementary steps for the redox and associative mechanism by density functional theory (DFT) simulations indicate that the redox mechanism is favored over the associative mechanism. The combined spectroscopic, computational, and kinetic evidence in the present study finally resolves the WGS reaction mechanism on the industrial-type higherature CuCrFeOx catalyst that is shown to proceed via the redox mechanism.

Rh/Ce0.25Zr0.75O2 Catalyst for Steam Reforming of Propane at Low Temperature

Solid oxide fuel cells (SOFCs) show high energy-conversion efficiency and thus emit less CO2 than conventional combustion engines. Although SOFCs can directly convert hydrocarbons such as liquefied petroleum gas, these fuels readily induce coking on the electrodes of fuel cell stacks. To avoid coking, hydrocarbons can be subjected to a preliminary endothermic steam-reforming step at a relatively low temperature using waste heat from the stack. Herein, we report that a Rh/Ce0.25Zr0.75O2 catalyst exhibited higher propane-steam-reforming activity than other Rh/Ce1?xZrxO2 catalysts and Rh/γ-Al2O3. Catalyst characterization revealed that Rh/Ce0.25Zr0.75O2 had excellent redox property and high H2O-adsorption activity, which contributed to the activation of steam and thus enhanced the propane-steam-reforming activity of this catalyst.

Confined Pt11+ Water Clusters in a MOF Catalyze the Low-Temperature Water–Gas Shift Reaction with both CO2 Oxygen Atoms Coming from Water

The synthesis and reactivity of single metal atoms in a low-valence state bound to just water, rather than to organic ligands or surfaces, is a major experimental challenge. Herein, we show a gram-scale wet synthesis of Pt11+ stabilized in a confined space by a crystallographically well-defined first water sphere, and with a second coordination sphere linked to a metal–organic framework (MOF) through electrostatic and H-bonding interactions. The role of the water cluster is not only isolating and stabilizing the Pt atoms, but also regulating the charge of the metal and the adsorption of reactants. This is shown for the low-temperature water–gas shift reaction (WGSR: CO + H2O → CO2 + H2), where both metal coordinated and H-bonded water molecules trigger a double water attack mechanism to CO and give CO2 with both oxygen atoms coming from water. The stabilized Pt1+ single sites allow performing the WGSR at temperatures as low as 50 °C.

A Structural Mimic of Carbonic Anhydrase in a Metal-Organic Framework

Metal-organic frameworks (MOFs) have exciting potential for biomimetic studies of enzymes, yet construction of high-fidelity models at the metal nodes is challenging. Nonetheless, biomimetic MOFs have significant advantages, such as increased stability and ease of separation, over their enzymatic and homogeneous counterparts, making them particularly attractive for industrial applications. Here, we demonstrate biomimetic behavior of Zn hydroxide moieties inside a MOF with structural and reactivity characteristics of carbonic anhydrase. Similar to the biological system, the MOF binds CO2 by an insertion mechanism into the Zn–OH bond, leading to significant adsorption of CO2 (3.41 mmol/g). In reactivity mimicking that of the enzyme, the material also catalyzes the oxygen isotope exchange between water and carbon dioxide. Overall, these results provide the strongest evidence yet of metal nodes in MOFs bearing high structural fidelity to enzymatic active sites. The nodes of metal-organic frameworks are attractive sites for mimicking metalloenzymes, primarily through their site isolation and similar ligand fields. In this article, the metal-organic framework MFU-4l is shown to mimic the active site of carbonic anhydrase with high structural fidelity and reactivity. The material adsorbs high quantities of carbon dioxide at low pressures and mimics critical features of carbonic anhydrase, such as isotopic exchange of oxygen atoms from water and carbon dioxide. Mimicking metalloenzymes at the node of a metal-organic framework (MOF) has the potential to impart enzyme-like catalytic activity within a heterogeneous material. Carbonic anhydrase, one of nature's fastest enzymes, catalyzes the hydrolysis of carbon dioxide into bicarbonate and protons. Notably, carbonic anhydrase mimics have been proposed as potential catalysts for carbon capture and sequestration from the environment. Here, we demonstrate that the metal node of MFU-4l, a MOF featuring a metal node with a N3ZnX coordination environment, can be functionalized to give a mimic of carbonic anhydrase. This work describes a well-defined example of a metal node within a MOF with high structural fidelity to an enzyme active site. It has potential applicability to applications such as CO2 capture and sequestration and also important gas separations involving CO2.

Mechanistic Insights into Catalytic Ethanol Steam Reforming Using Isotope-Labeled Reactants

The low-temperature ethanol steam reforming (ESR) reaction mechanism over a supported Rh/Pt catalyst has been investigated using isotope-labeled EtOH and H2O. Through strategic isotope labeling, all nonhydrogen atoms were distinct from one another, and allowed an unprecedented level of understanding of the dominant reaction pathways. All combinations of isotope- and non-isotope-labeled atoms were detected in the products, thus there are multiple pathways involved in H2, CO, CO2, CH4, C2H4, and C2H6product formation. Both the recombination of C species on the surface of the catalyst and preservation of the C?C bond within ethanol are responsible for C2product formation. Ethylene is not detected until conversion drops below 100 % at t=1.25 h. Also, quantitatively, 57 % of the observed ethylene is formed directly through ethanol dehydration. Finally there is clear evidence to show that oxygen in the SiO2-ZrO2support constitutes 10 % of the CO formed during the reaction.

Steady-State and Transient Kinetic Studies of the Acetoxylation of Toluene over Pd-Sb/TiO2

A combination of steady-state catalytic tests, transient studies with isotopic tracers, and kinetic modeling was used to derive detailed insights into the individual reaction pathways in the course of toluene acetoxylation over a Pd-Sb/TiO2 catalyst. This reaction can be considered as an environmentally friendly route for the production of benzyl alcohol. Benzyl acetate and benzaldehyde are the only products formed from toluene, while acetic acid gives CO2 in addition to benzyl acetate. The Arrhenius plots revealed apparent activation energies for formation of benzyl acetate and benzaldehyde of 24.9 and 27.5 kJ mol-1, respectively, thus, indicating that these products originate from the same surface intermediate, i.e. benzyl cation. The corresponding value for CO2 formation was 152.9 kJ mol-1. Transient isotopic studies and their kinetic evaluation demonstrated the participation of lattice oxygen and adsorbed oxygen species in activation of acetic acid, with the latter species favoring oxidation of the acid to CO2.

Formation of complex organic molecules in methanol and methanol-carbon monoxide ices exposed to ionizing radiation - A combined FTIR and reflectron time-of-flight mass spectrometry study

The radiation induced chemical processing of methanol and methanol-carbon monoxide ices at 5.5 K exposed to ionizing radiation in the form of energetic electrons and subsequent temperature programmed desorption is reported in this study. The endogenous formation of complex organic molecules was monitored online and in situ via infrared spectroscopy in the solid state and post irradiation with temperature programmed desorption (TPD) using highly sensitive reflectron time-of-flight (ReTOF) mass spectrometry coupled with single photoionization at 10.49 eV. Infrared spectroscopic analysis of the processed ice systems resulted in the identification of simple molecules including the hydroxymethyl radical (CH2OH), formyl radical (HCO), methane (CH4), formaldehyde (H2CO), carbon dioxide (CO2), ethylene glycol (HOCH2CH2OH), glycolaldehyde (HOCH2CHO), methyl formate (HCOOCH3), and ketene (H2CCO). In addition, ReTOF mass spectrometry of subliming molecules following temperature programmed desorption definitely identified several closed shell C/H/O bearing organics including ketene (H2CCO), acetaldehyde (CH3COH), ethanol (C2H5OH), dimethyl ether (CH3OCH3), glyoxal (HCOCOH), glycolaldehyde (HOCH2CHO), ethene-1,2-diol (HOCHCHOH), ethylene glycol (HOCH2CH2OH), methoxy methanol (CH3OCH2OH) and glycerol (CH2OHCHOHCH2OH) in the processed ice systems. Additionally, an abundant amount of molecules yet to be specifically identified were observed sublimating from the irradiated ices including isomers with the formula C3H(x=4,6,8)O, C4H(x=8,10)O, C3H(x=4,6,8)O2, C4H(x=6,8)O2, C3H(x=4,6)O3, C4H8O3, C4H(x=4,6,8)O4, C5H(x=6,8)O4 and C5H(x=6,8)O5. The last group of molecules containing four to five oxygen atoms observed sublimating from the processed ice samples include an astrobiologically important class of sugars relevant to RNA, phospholipids and energy storage. Experiments are currently being designed to elucidate their chemical structure. In addition, several reaction pathways were identified in the irradiated ices of mixed isotopes based upon the results of both in situ FTIR analysis and TPD ReTOF gas phase analysis. In general, the results of this study provide crucial information on the formation of a variety of classes of organics including alcohols, ketones, aldehydes, esters, ethers, and sugars within the bulk ices upon exposure to ionizing radiation that are relevant to the molecular clouds within the interstellar medium.

Constructing hierarchical interfaces: TiO2-supported PtFe-FeOx nanowires for room temperature CO oxidation

In this communication, we report a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFe-FeOx nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeOx within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeOx and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, the intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe-FeOx/TiO2 catalyst exhibits no activity decay. Our results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.