Selective oxidation of methane to formaldehyde by oxygen over silica-supported iron catalysts (Special column of methane transformation, Article)

FeO_x-SiO₂ catalysts prepared by a sol-gel method were studied for the selective oxidation of methane by oxygen. A single-pass formaldehyde yield of 2.0% was obtained over the FeO_x-SiO₂ with an iron content of 0.5 wt% at 898 K. This 0.5 wt% FeO_x-SiO₂ catalyst demonstrated significantly higher catalytic performances than the 0.5 wt% FeO_x/SiO₂ prepared by an impregnation method. The correlation between the catalytic performances and the characterizations with UV-Vis and H₂-TPR suggested that the higher dispersion of iron species in the catalyst prepared by the sol-gel method was responsible for its higher catalytic activity for formaldehyde formation. The modification of the FeO_x-SiO₂ by phosphorus enhanced the formaldehyde selectivity, and a single-pass formaldehyde yield of 2.4% could be attained over a P-FeO_x-SiO₂ catalyst (P/Fe = 0.5) at 898 K. Raman spectroscopic measurements indicated the formation of FePO₄ nanoclusters in this catalyst, which were more selective toward formaldehyde formation.     

Thermal Conversion of Methane to Formaldehyde Promoted by Gold in AuNbO3+ Cluster Cations

In addition to generation of a methyl radical, formation of a formaldehyde molecule was observed in the thermal reaction of methane with AuNbO₃⁺ heteronuclear oxide cluster cations. The clusters were prepared by laser ablation and mass‐selected to react with CH₄ in an ion‐trap reactor under thermal collision conditions. The reaction was studied by mass spectrometry and DFT calculations. The latter indicated that the gold atom promotes formaldehyde formation through transformation of an Au?O bond into an Au?Nb bond during the reaction.     

Chemoenzymatic Hydrogen Production from Methanol through the Interplay of Metal Complexes and Biocatalysts

Microbial methylotrophic organisms can serve as great inspiration in the development of biomimetic strategies for the dehydrogenative conversion of C₁ molecules under ambient conditions. In this Concept article, a concise personal perspective on the recent advancements in the field of biomimetic catalytic models for methanol and formaldehyde conversion, in the presence and absence of enzymes and co-factors, towards the formation of hydrogen under ambient conditions is given. In particular, formaldehyde dehydrogenase mimics have been introduced in stand-alone C₁-interconversion networks. Recently, coupled systems with alcohol oxidase and dehydrogenase enzymes have been also developed for in situ formation and decomposition of formaldehyde and/or reduced/oxidized nicotinamide adenine dinucleotide (NADH/ NAD⁺). Although C₁ molecules are already used in many industries for hydrogen production, these conceptual bioinspired low-temperature energy conversion processes may lead one day to more efficient energy storage systems enabling renewable and sustainable hydrogen generation for hydrogen fuel cells under ambient conditions using C₁ molecules as fuels for mobile and miniaturized energy storage solutions in which harsh conditions like those in industrial plants are not applicable.     

Plant-mediated fabrication of cobalt oxide nanoparticles and evaluation of their catalytic effects on electro-oxidation of formaldehyde

Cobalt oxide nanoparticles (Co₃O₄-NPs) were synthesized by aqueous extract of Artemisia vulgaris plant at 50°C. The biosynthesized extract mediated Co₃O₄-NPs were characterized through different methods containing FT-IR (Fourier transform infrared spectroscopy), FESEM (Field emission scanning electron microscopy), EDS (Energy-dispersive x-ray spectroscopy), and XRD (x-ray diffraction). Co₃O₄-NPs as an efficient and practical catalyst was employed for the electrochemical oxidation of formaldehyde; which was an irreversible charge transfer controlled by mass transfer. The coefficients of electron transfer and diffusion were 0.87 and 0.122 cm²/s for formaldehyde oxidation on Co₃O₄ electrode, respectively. The formation of the CoOOH species during potential sweeping appears to be involved in the catalytic activity of the Co₃O₄ toward formaldehyde oxidation.     

An Improved Liquid-Phase Synthesis of Simple Alkylpyridines

The synthesis of pyridines from mixtures of aldehydes or ketones NH₃ in the liquid phase has been reinvestigated, using continuous dosage of the carbonyl components to the reaction mixture. The main product from the reaction of acetaldehyde and formaldehyde is 3-methylpyridine ( 6 ), which is also the main product from the reaction of acrolein or a mixture of crotonaldehyde and formaldehyde under the same conditions. The reaction of other aldehydes with formaldehyde give 3,5-dialklypyridines, e.g. 10, 16 . Acetone reacts with either formaldehyde or acetaldehyde to give polysubstituted alkylpyridines. A mechanistic pathway is proposed which accounts for the formation of the observed products.     

Electrochemical reduction of CO2 and degradation of KHP on boron-doped diamond electrodes in a simultaneous and enhanced process

A BDD-BDD system was developed in the simultaneous conversion of CO₂ and wastewater purification in one electrochemical cell.     

Ab initio study on the mechanism of cycloaddition reaction between H<Subscript>2</Subscript>Si=Si: and formaldehyde

The mechanism of the cycloaddition reaction between singlet H₂Si=Si: and formaldehyde has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has three competitive dominant reaction pathways. The reaction rules presented is that the 3p unoccupied orbital of the Si: atom in H₂Si=Si: inserts the π orbital of formaldehyde from the oxygen side, resulting in the formation of an intermediate. Isomerization of the intermediate further generates a four-membered ring silylene (the H₂Si–O in the opposite position). In addition, the [2+2] cycloaddition reaction of the two π-bonds in H₂Si=Si: and formaldehyde also generates another four-membered ring silylene (the H₂Si–O in the syn-position). Because of the unsaturated property of the Si: atom in the two four-membered ring silylenes, the two four-membered ring silylenes could further react with formaldehyde, generating two silicic bis-heterocyclic compounds. Simultaneously, the ring strain of the four-membered ring silylene (the H₂Si–O in the syn-position) makes it isomerize to a twisted four-membered ring product.     

Heteropolyacid as an Efficient Catalyst for Synthesis of 3,4-Dihydro-1H-2,3-benzothiazine-2,2-dioxides

A facile and efficient method for the formation of 3,4-dihydro-1H-2,3-benzothiazine 2,2-dioxides 2, compounds from benzylsulfonamides and formaldehyde is described using heteropolyacids H₃PW₁₂O₄₀ and H₃PMo₁₂O₄₀ supported on silica as catalysts.     

Acidities of Hydrochloric Acid in Water/Acetic Acid and in Water/Acetic Acid/Formaldehyde Mixtures: Investigations with the indicator method and with the nmr method. 31st communication on investigations in textile chemistry

The NMR. chemical shift (δ_H) of the acidic proton in the systems HCl/H₂O and HCl/H₂O/HOAc was correlated with the acidity function (H_o)_I determined by the indicator method. By using three indicators it could be shown that, except for solutions with very low concentrations of hydrochloric acid, the acidity function (H_o)_I correlates with δ_H in a way which can be rationalized. Addition of 7,5% (W) formaldehyde to these systems changes (H_o)_I and δ_H very significantly, particularly in systems with low water content. Logarithmic rate constants of cellulose formal formation in HCl/H₂O/HOAc systems which do not show a linear relationship with (H_o)_I, measured without presence of formaldehyde, do so if (H_o)_I is measured with formaldehyde present. For these systems, however, δ_H is not a suitable acidity parameter.     

Mechanism of the chain process forming H2 in the photooxidation of formaldehyde

A mechanism for the formation in a chain of H₂, CO, and HCOOH in the photooxidation of formaldehyde is proposed. This mechanism is initiated by the addition of HO₂ to formaldehyde. Hydrogen atoms are produced by the thermal dissociation of the HOCH₂O radical: HOCH₂O → H + HCOOH; ΔH = + 3.2 kcal/mol [5]. Photolysis of CH₂O? O₂? NO mixtures and product analysis were carried out in conjunction with kinetic simulation yielding an estimate for the activation energy of the dissociation reaction : E₅ = 14.9 ± 1.0 kcal/mol. Previous observations of this chain process are considered in view of this mechanism.     

Kinetic Studies of Ethyl N-Hydroxymethyl Carbamate

Abstract

Kinetics of the dissociation of ethy1 N-hydroxymethylcarbamate, and monomethylolethylcarbamate (MMEC) at various temperatures and pH values have been studied by measuring the formaldehyde concentration in solution via an electrochemical technique. Formaldehyde and ethyl carbamate (EC) are the products of the dissociation. Formaldehyde concentration as a function of time has been used in a computer program designed to calculate the rate constant, k_f, for the formation of MMEC form formaldehyde and EC and the rate constant, k_r, for the dissociation of MMEC.     

2-nitroguanidine derivatives: X. Synthesis and nitration of 4-nitriminotetrahydro-1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their substituted derivatives

A new synthetic procedure was developed to obtain 1-hydroxymethyl-2-nitroguanidine from 2-nitroguanidine and formaldehyde without catalyst. Reactions of 2-nitroguanidine and its 1-methyl-and 1-phenylsubstituted derivatives with formaldehyde and urotropin under acid catalysis resulted in 4-nitriminotetrahydro-1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their methyl-and phenyl-substituted derivatives, whose nitration with concn. HNO₃ in the presence of acetic anhydride and concn. H₂SO₄ depending on the temperature conditions led to the formation of 4-nitrimino-3,5-dinitrotetrahydro-1,3,5-oxadiazine, 3-methyl-4-nitrimino-5-nitrotetrahydro-1,3,5-oxadiazine, 2-nitrimino-5-nitrohexahydro-1,3,5-triazine, and 1,3,5-trinitro-hexahydro-1,3,5-triazine-2-one.     

High-level ab initio calculations on CH+2(2A1) + PO(2II) reactions

We present ab initio calculations carried out in the framework of the G 2 theory on the singlet and triplet potential energy surfaces corresponding to the gas-phase between CH⁺₂ and PO. The global minimum of both potential energy surfaces is a cyclic singlet-state cation. Oxygen attachment of PO to CH⁺₂ in a triplet configuration is accompanied by a P(SINGLEBOND)O bond fission, with the result that the corresponding global minimum is an ion-dipole complex between P⁺(³P) and formaldehyde. This is also consistent with the fact that our results predict the formation of formaldehyde to be highly exothermic, either as a neutral or as radical cation. Both charge-transfer processes yielding CH₂(³B₁) or CH₂(¹A₁) are also exothermic. The formation of other carbon and oxygen containing species are endothermic. © 1996 John Wiley & Sons, Inc.     

Reaction of formaldehyde with the Wilkinson complex in the presence of carboxylic acid amides

N,N-Dimethylacetamide and N, N-dimethyformamide react with RhCl(PPh₃)₃ with displacement of PPh₃ and the formation of a complex with the amide. Formamide and N-propylacetamide do not form similar complexes under similar conditions. In contrast to the reaction of RhCl(PPh₃)₃, which leads to the formation of RhCl(CO)(PPh₃)₂ due to decarbonylation of CH₂O, stabilization of the ₂-CH₂O form of the CH₂O coordinated with rhodium is likely in the reaction of formaldehyde with a rhodium complex containing an N-bonded amide. Under the conditions of hydroformylation of CH₂O in a solution of the Wilkinson complex in an unsubstituted amide the dominating pathway of the transformation of formaldehyde is its reaction with the solvent or the ammonia formed via decarbonylation of the unsubstituted amide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2670–2673, December, 1989.     

Ab initio quantum-mechanical calculations of the propagation enthalpies for the radical and anionic polymerizations of formaldehyde and methanimine

The gas phase enthalpies of formation for oligomeric radicals and anions H(CH₂NH)_n^* and H(CH₂O)_n^* were theoretically determined by ab initio quantum-mechanical calculations with n in the range 1 to 6. From these results, the reaction enthalpies for each of the first five propagation steps of the polymerization were estimated for methanimine (H₂C = NH) and formaldehyde (H₂C = O). At the same step of oligomerization, enthalpies associated with anionic polymerizations are always more negative than enthalpies corresponding to radical polymerizations, but the difference between them decreases with increasing n. Both Delta;H (propagation) vs. n curves tend rapidly, particularly for radical polymerizations, towards an asymptotic value independent of the mode of polymerization and equal to - 12 kcal/mol for formaldehyde and - 14 kcal/mol for methanimine. Experimental data for the gas phase polymerization of formaldehyde are in good agreement with our theoretical value. These results demonstrate that heats of polymerization can be reasonably estimated by intensive calculation methods if a careful choice of the reaction mimicking the propagation step is done.     

Intermolecular complexes between sulfide radical cations from β-hydroxy sulfides and phosphate

Triplet-sensitized oxidation of 2-(methylthio)ethanol (2-MTE) and photosensitized formaldehyde formation from 2-MTE were measured in aqueous solutions. The formaldehyde quantum yields were measured in steady-state experiments; whereas the time-resolved detection of dimeric sulfur radical cations (S∴S)⁺ was followed in nanosecond laser flash photolysis. 4-Carboxybenzophenone was the triplet sensitizer in both types of experiments. It was found that the lifetimes of the (S∴S)⁺ radicals increased in the presence of phosphate buffer, sodium perchlorate, or D₂O. There were corresponding decreases in the formaldehyde yields for these same experimental factors. The phosphate case was discussed in some detail in terms of a new intermolecular complex between the sulfide radical cations and the oxyanions.     

The nature of autocatalysis in the Butlerov reaction

The effect of the nature of an initiator on the kinetics of formaldehyde consumption and on product composition in the Butlerov reaction was studied in a stirred flow reactor and a batch reactor. It was found that, under flow conditions, the kinetics and the product composition of this reaction are independent of the nature of the initiator. The reaction schemes proposed previously for an autocatalytic process mechanism based on the formation of glycolaldehyde from two formaldehyde molecules are incorrect. A correlation between the initiating activities of various monosaccharides and the rates of their conversion into an enediol form was found with the use of a batch reactor. Solid enediol complexes with Ca²⁺ ions were isolated for glucose, fructose, ribose, and sorbose; the initiating activity of these complexes was found to be much higher than the initiating activity of pure monosaccharides. A self-consistent mechanism was proposed for Butlerov reaction initiation. The formation of the enediol forms of monosaccharides followed by degradation to lower carbohydrates plays a key role in this mechanism. In turn, the initiating activity depends on the position of the carbonyl group in the monosaccharide molecule. The condensation reactions of glycolaldehyde, glyceraldehyde, and dihydroxyacetone with each other were studied. Based on data on the condensation products of lower carbohydrates, a scheme was proposed for the Butlerov reaction. According to this reaction scheme, C₂ and C₃ carbohydrates mainly undergo an aldol condensation reaction with formaldehyde, whereas the formation of higher monosaccharides occurs by the aldol condensation of lower C₂–C₃ carbohydrates with each other.     

Formaldehyde in Super Acids: A Succession of Products from Carbenium through Oxonium Ion to Hydroxymethyl(methylidene)oxonium Salts

An oxonium ion with hydroxymethyl and methylidene substituents is found in the salts 1 -MF₆ (M=As, Sb), which can be isolated from solutions of formaldehyde in superacids HF/MF₅. Their formation was at first surprising, since NMR spectroscopy indicates that protonated monofluoromethanol is present in solution.     

Laser activation of ethylene and formaldehyde quenching

A novel method is described for oxidizing ethylene with molecular oxygen to give formaldehyde under normal conditions in the presence of the beam from a continuous wave low-power CO₂ laser (943 cm^–1), which is in resonance with the ethylene vibrational mode p(CH₂) = 949 cm^–1; the method involves activating the CH₂-CH₂ bonds to failure with the formation of biradicals and then quenching the formaldehyde, which is out of equilibrium as regards temperature.Institute for General and Inorganic Chemistry, Academy of Sciences of The Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Eksperimental'naya Khimiya, No. 2, pp. 220–223, March–April, 1991. Original article submitted April 19, 1990.     

Towards a Sustainable Synthesis of Oxymethylene Dimethyl Ether by Homogeneous Catalysis and Uptake of Molecular Formaldehyde

Oxymethylene dimethyl ethers (OME_n; CH₃(‐OCH₂‐)_nO‐CH₃, n=3–5) are a novel class of sustainable synthetic fuels, which are of increasing interest due to their soot‐free combustion. Herein a novel anhydrous OME_n synthesis route is presented. Catalyzed by trimethyloxonium salts, dimethoxymethane takes up monomeric gaseous formaldehyde instantaneously and forms high purity OME_n at temperatures of 25–30 °C. This new anhydrous approach using molecular formaldehyde and catalytic amounts of highly active trimethyloxonium salts represents a promising new step towards a sustainable formation of OME_n emanating from CO₂ and H₂.