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1.
ChemSusChem ; 12(7): 1381-1389, 2019 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-30698350

RESUMO

Glutamic acid, an abundant nonessential amino acid, was converted into 2-pyrrolidone in the presence of a supported Ru catalyst under a pressurized hydrogen atmosphere. This reaction pathway proceeded through the dehydration of glutamic acid into pyroglutamic acid, subsequent hydrogenation, and the dehydrogenation-decarbonylation of pyroglutaminol into 2-pyrrolidone. In the conversion of pyroglutaminol, Ru/Al2 O3 exhibited notably higher activity than supported Pt, Pd, and Rh catalysts. IR analysis revealed that Ru can hydrogenate the formed CO through dehydrogenation-decarbonylation of hydroxymethyl groups in pyroglutaminol and can also easily desorb CH4 from the active sites on Ru. Furthermore, Ru/Al2 O3 showed the highest catalytic activity among the tested catalysts in the conversion of pyroglutamic acid. Consequently, the conversion of glutamic acid produced a high yield of 2-pyrrolidone by using the supported Ru catalyst. This is the first report of this one-pot reaction under mild reaction conditions (433 K, 2 MPa H2 )" which avoids the degradation of unstable amino acids above 473 K.

2.
ChemCatChem ; 10(17): 3806-3812, 2018 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-30546494

RESUMO

Cobalt-loaded MFI zeolite showed distinct activity for direct methylation of benzene with methane into toluene. High activity was found at around 0.6 of Co/Al molar ratio. Incorporation of carbon from methane into the methyl group of toluene was confirmed with isotope tracer experiments and mass spectroscopy. Ammonia infrared-mass spectroscopy temperature-programmed desorption, transmission electron microscopy, X-ray absorption near edge spectroscopy and extended X-ray absorption fine structure indicated that Lewis acidic divalent (+II of oxidation state) Co species mono-atomically dispersed on the ion exchange site of MFI zeolite was the active species.

3.
J Am Chem Soc ; 139(32): 11197-11206, 2017 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-28735530

RESUMO

The oxygen storage capability and related defect structure of tetrahedral orthochromite(V) compound YCr1-xPxO4 (x = 0, 0.3, 0.5, and 0.7) were investigated by employing thermal gravimetry and in situ X-ray spectroscopy for reversible oxygen store/release driven by heating-cooling cycles in the temperature range from 50 to 600 °C. YCr1-xPxO4 started releasing oxygen as heated from 50 °C under ambient atmosphere, with reduction of CrV to CrIV, while the reduced YCr1-xPxO4-δ phase was significantly reoxidized via absorbing oxygen by cooling to 50 °C under ambient atmosphere, recovering the original stoichiometric phase. Operando X-ray adsorption spectroscopy and first-principles calculations demonstrate that nonstoichiometric YCr1-xPxO4-δ phases were stabilized by forming linking polyhedral CrIV2O76- via corner sharing between oxygen-deficient CrIVO32- and adjacent CrIVO44-. YCr1-xPxO4 was found to have an extremely low reduction enthalpy of about 20 kJ mol-1 probably due to the relatively high reduction potential of high-valence-state Cr(V)/Cr(IV) redox pairs, thereby resulting in reversible oxygen storage in such a low-temperature region.

4.
ChemSusChem ; 10(14): 2864-2868, 2017 07 21.
Artigo em Inglês | MEDLINE | ID: mdl-28544652

RESUMO

Here, we report remarkable oxygen evolution reaction (OER) catalytic activity of brownmillerite (BM)-type Ca2 FeCoO5 . The OER activity of this oxide is comparable to or beyond those of the state-of-the-art perovskite (PV)-catalyst Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ (BSCF) and a precious-metal catalyst RuO2 , emphasizing the importance of the characteristic BM structure with multiple coordination environments of transition metal (TM) species. Also, Ca2 FeCoO5 is clearly advantageous in terms of expense/laboriousness of the material synthesis. These facts make this oxide a promising OER catalyst used in many energy conversion technologies such as metal-air secondary batteries and hydrogen production from electrochemical/photocatalytic water splitting.


Assuntos
Cobalto/química , Compostos de Ferro/química , Óxidos/química , Oxigênio/química , Catálise , Modelos Moleculares , Conformação Molecular
5.
Faraday Discuss ; 180: 479-93, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25893229

RESUMO

Conducting polymers (CPs), including polypyrrole, have attracted attention for their potential in the protection of metals against corrosion; however, CP coatings have the limitation of poor adhesion to metal substrates. In this study, a composite coating, comprising a self-organized porous anodic oxide layer and a polypyrrole layer, has been developed on iron. Because of electropolymerization in the pores of the anodic oxide layer, the composite coating showed improved adhesion to the substrate along with prolonged corrosion protection in a NaCl aqueous corrosive environment. The anodic oxide layers are formed in a fluoride-containing organic electrolyte and contain a large amount of fluoride species. The removal of these fluoride species from the oxide layer and the metal/oxide interface region is crucial for improving the corrosion protection.

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