Nanostructured doped ceria is a prospective material for catalytic applications such as the construction of membranes with mixed electronic and ionic conductivity for effective syngas production. In this article, the surface properties of nanostructured ceria doped with praseodymium have been studied by X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and Fourier transform infrared spectroscopy of adsorbed carbon monoxide. The effects of supporting 1.4 wt % Pt as well as structural changes upon the reduction of the samples with methane have been investigated. While in samples without supported platinum, mainly praseodymium cations are reduced in a methane atmosphere; stronger reduction of cerium cations was found in the case of surface modification with Pt. The structural differences correlate with results from temperature-programmed reaction experiments with methane. Explanations are discussed in terms of different reaction mechanisms.

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The electron nuclear dipolar interactions responsible for some dynamic nuclear polarization (DNP) mechanisms also are responsible for the presence formally in CW EPR spectra of forbidden satellite lines in which both the electron spin and a nuclear spin flip. Such lines arising from 1H nuclei are easily resolved in CW EPR measurements of trityl radicals, a popular family of DNP reagents. The satellite lines overlap some of the hyperfine features from 13C in natural abundance in the trityl radical, but their intensity can be easily determined by simple simulations of the EPR spectra using the hyperfine parameters of the trityl radical. Isotopic substitution of 2H for 1H among the hydrogens of the trityl radical and/or the solvent allows the dipolar interactions from the 1H on the trityl radical and from the solvent to be determined. The intensity of the dipolar interactions, integrated over all the 1H in the system, is characterized by the traditional parameter called reff. For the so-called Finland trityl in methanol, the reff values indicate that collectively the 1H in the unlabeled solvent have a stronger integrated dipolar interaction with the unpaired electron spin of the Finland trityl than do the 1H in the radical and consequently will be a more important DNP route. Although reff has the dimensions of distance, it does not correspond to any simple physical dimension in the trityl radical because the details of the unpaired electron spin distribution and the hydrogen distribution are important in the case of trityls.