N-Containing graphenes obtained either by simultaneous amination and reduction of graphene oxide or by pyrolysis of chitosan under an inert atmosphere have been found to act as catalysts for the selective wet oxidation of glucose to succinic acid. Selectivity values over 60% at complete glucose conversion have been achieved by performing the reaction at 160 °C and 18 atm O2 pressure for 20 h. This activity has been attributed to graphenic-type N atoms on graphene. The active N-containing graphene catalysts were used four times without observing a decrease in conversion and selectivity of the process. A mechanism having tartaric and fumaric acids as key intermediates is proposed.
We investigate the effect of the nature of the substrate and the bottom interface on the out-of-plane polarization orientation of ultrathin (10-nm) lead zirconate titanate (PZT) thin films of (001) orientation by photoelectron spectroscopy of samples without surface contamination. The substrate nature is varied between insulator (strontium titanate, STO) and semiconductor (-doped STO, STON) and finally to a metal with a work function lower than that of PZT (strontium ruthenate, SRO). Outward polarization is obtained for PZT/STON(001) and inward polarization is obtained for PZT/STO(001) and PZT/SRO(001). Explanations are given for all these typical cases, the main elements being charge accumulation for compensation of the depolarization field, self-doping of PZT films, and the interface electric field driving the orientation of the polarization of the ferroelectric films. We find p-type self-doping is correlated with the inward polarization, and the driving field is formed between a negatively charged region with negatively ionized acceptors near the interface with the substrate and the p-type degenerate region with holes accumulated inside, toward the surface. This mechanism may be reversed under the assumption of n-type self-doping, positively ionized donors near the interface, and accumulated electrons toward the surface in the case of an interface with a substrate with a higher work function, being in line with recent data (PZT/ or ).