@article {42828,
	title = {C-H activation of methane to formaldehyde on Ce1-xZrxO2 thin films: a step to bridge the material gap},
	journal = {ChemCatChem},
	volume = {8},
	year = {2016},
	month = {DEC},
	pages = {3650{\textendash}3656},
	type = {Article},
	abstract = {<p>Ce1-xZrxO2 (CZ) thin films were prepared by a combination of sol{\textendash}gel and spin-coating methods and were evaluated for the C-H activation of methane by using a molecular beam set-up with the aim to bridge the material gap. The C-H activation of methane begins at 950 K, and a Ce-rich CZ composition displays a high selectivity (4{\textendash}12 \%) to the partially oxidised product, formaldehyde. A 10{\textendash}12 \% selectivity towards HCHO with 1.6 \% methane conversion was observed with methane-rich CH4/O2 reactant compositions at 1050 K. Short contact times, prevalent under molecular beam conditions, could be a possible reason for HCHO formation. Although combustion products were observed instantly upon shining the mixture of reactants on CZ surfaces, up to 20 s delay was observed before formaldehyde generation, which indicates that the oxygen vacancy migration contributes to the rate-determining step and the diffusion-controlled nature of the reaction. A burst in HCHO generation at the point of molecular beam opening, after beam-closed conditions, suggests that the diffusion of oxygen vacancies to the surface is the reason for HCHO formation. Kinetics results also indicate the necessity of reduction sites for HCHO generation.</p>},
	doi = {10.1002/cctc.201600670},
	author = {Dubey, Anjani and Kolekar, Sadhu K. and Gopinath, Chinnakonda S.}
}
@article {42856,
	title = {C-H activation of methane to syngas on MnxCe1-x-yZryO2 - a molecular beam study},
	journal = {Chemcatchem},
	volume = {8},
	year = {2016},
	month = {JUL},
	pages = {2296-2306},
	type = {Article},
	abstract = {<p>Mn-doped ceria zirconia thin films (MnxCe1-x-yZryO2, MCZ) were employed as flat model catalyst surfaces for CH4 activation. MCZ films exhibit characteristics of single crystal and powder materials, such as smooth surfaces and porosity. From molecular-beam studies, it has been identified that the oxygen storage capacity increases with Mn content. Mutually exclusive observation of H2O or a mixture of products (CO2+ CO + H-2) occurs, when the reactants was allowed to react directly on MCZ, underscoring their formation or prevention (and consumption), respectively. The results suggest that there is competition and cooperation among different elementary reactions under complementary conditions. From a significant partial oxidation of CH4 through C-H activation, it is found that formation of syngas begins at 700 K and the reaction rate increases with increasing temperature. Kinetic evidences indicate that the reaction proceeds through a combustion-reformation pathway.</p>},
	doi = {10.1002/cctc.201600365},
	author = {Dubey, Anjani and Kolekar, Sadhu K. and Gopinath, Chinnakonda S.}
}
