1664-98-8Relevant articles and documents
Stepwise photocatalytic dissociation of methanol and water on TiO 2(110)
Guo, Qing,Xu, Chenbiao,Ren, Zefeng,Yang, Wenshao,Ma, Zhibo,Dai, Dongxu,Fan, Hongjun,Minton, Timothy K.,Yang, Xueming
, p. 13366 - 13373 (2012)
We have investigated the photocatalysis of partially deuterated methanol (CD3OH) and H2O on TiO2(110) at 400 nm using a newly developed photocatalysis apparatus in combination with theoretical calculations. Photocatalyzed products, CD2O on Ti5c sites, and H and D atoms on bridge-bonded oxygen (BBO) sites from CD3OH have been clearly detected, while no evidence of H2O photocatalysis was found. The experimental results show that dissociation of CD3OH on TiO2(110) occurs in a stepwise manner in which the O-H dissociation proceeds first and is then followed by C-D dissociation. Theoretical calculations indicate that the high reverse barrier to C-D recombination and the facile desorption of CD2O make photocatalytic methanol dissociation on TiO2(110) proceed efficiently. Theoretical results also reveal that the reverse reactions, i.e, O-H recombination after H2O photocatalytic dissociation on TiO2(110), may occur easily, thus inhibiting efficient photocatalytic water splitting.
Olofson,Zimmermann
, p. 5057 (1967)
Concerted Grob Fragmentation in N-Halo-α-amino Acid Decomposition
Armesto, X. L.,Canle L., M.,Losada, M.,Santaballa, J. A.
, p. 4659 - 4664 (1994)
The Grob fragmentation of N-halo-α-amino acids in aqueous solution has been studied, being first order in N-halo-α-amino acid and pH-independent.The substituents on the C2 and N atoms strongly affect the reaction rate.Structure reactivity correlations for C2 substituents provide ρ* values of -3.9 and -4.1 for N-Cl and N-Br compounds, respectively.The same correlations for N substituents lead to ρ* values of -2.1 and -1.9 for N-Cl and N-Br compounds.The transition state (TS) can be generally described as product-like, its structure and characteristics being significantly affected by the substituents on the C2 and on the N atoms.In conclusion, the reaction is a DEDN concerted and slightly nonsynchronous two-stage process.
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Bannard et al.
, p. 351,358 (1953)
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Hydrogen atom abstraction reactions independent of C-H bond dissociation energies of organic substrates in water: Significance of oxidant-substrate adduct formation
Ishizuka, Tomoya,Ohzu, Shingo,Kotani, Hiroaki,Shiota, Yoshihito,Yoshizawa, Kazunari,Kojima, Takahiko
, p. 1429 - 1436 (2014)
Detailed kinetic studies on the oxidation reactions of organic substrates such as methanol with RuIVO complexes as oxidants, formed electrochemically in water, have been conducted to elucidate the reaction mechanism. The rate constants of the oxidation reactions exhibited saturation behaviours relative to the substrate concentration, regardless of the oxidants and the substrates employed. This indicates the existence of a pre-equilibrium process based on the adduct formation between the RuIVO oxidant and the substrate. Herein, we have experimentally confirmed that the driving force of the adduct formation is the hydrogen bonding between the oxidants and alcohols even in water. In addition, we have investigated the kinetic isotope effects (KIE) on the oxidation reaction using methanol and its deuterated derivatives and as a result observed moderate KIE values for the C-H bond of methanol. We have also revealed the independency of the reaction rates from the bond dissociation enthalpies of the C-H bonds of the substrates. This independency is probably derived from the tightly condensed transition state, whose energy level is strongly controlled by the activation entropy but less sensitive to the activation enthalpy.
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Breuer et al.
, p. 452 (1970)
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Formaldehyde O-Methylide, +-C--H2>: The Parent Carbonyl Ylide
Prakash, G. K. Surya,Ellis, Robert W.,Fellberg, Jeff D.,Olah, George A.
, p. 1341 - 1342 (1986)
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Photodecomposition of Methyl Nitrite Trapped in Solid Argon
Jacox, Marilyn E.,Rook, Frederick L.
, p. 2899 - 2904 (1982)
The threshold wavelength for the photolysis of methyl nitrite isolated in solid argon at 14 K has been determined to be near 370 nm.Photolyzed samples show prominent infrared absorptions of H2CO and HNO, which are perturbed by the hydrogen-bonding interac
Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules
Rauch, Michael,Strater, Zack,Parkin, Gerard
supporting information, p. 17754 - 17762 (2019/11/05)
The conversion of carbon dioxide to formaldehyde is a transformation that is of considerable significance in view of the fact that formaldehyde is a widely used chemical, but this conversion is challenging because CO2 is resistant to chemical transformations. Therefore, we report here that formaldehyde can be readily obtained from CO2 at room temperature via the bis(silyl)acetal, H2C(OSiPh3)2. Specifically, formaldehyde is released from H2C(OSiPh3)2 upon treatment with CsF at room temperature. H2C(OSiPh3)2 thus serves as a formaldehyde surrogate and provides a means to incorporate CHx (x = 1 or 2) moieties into organic molecules. Isotopologues of H2C(OSiPh3)2 may also be synthesized, thereby providing a convenient means to use CO2 as a source of isotopic labels in organic molecules.
Accessing the Nitromethane (CH3NO2) Potential Energy Surface in Methanol (CH3OH)-Nitrogen Monoxide (NO) Ices Exposed to Ionizing Radiation: An FTIR and PI-ReTOF-MS Investigation
Góbi, Sándor,Crandall, Parker B.,Maksyutenko, Pavlo,F?rstel, Marko,Kaiser, Ralf I.
, p. 2329 - 2343 (2018/03/21)
(D3-)Methanol-nitrogen monoxide (CH3OH/CD3OH-NO) ices were exposed to ionizing radiation to facilitate the eventual determination of the CH3NO2 potential energy surface (PES) in the condensed phase. R