A new carbon-nitrogen organic semiconductor has been synthesized by pyrolysis of uric acid. This layered carbon-nitrogen material contains imidazole-, pyridine (naphthyridine)- and graphitic-like nitrogen, as evinced by infrared and X-ray photoelectron spectroscopies. Quantum chemistry calculations support that it would consist of a 2D polymeric material held together by hydrogen bonds. Layers are stacked with an interplanar distance between 3.30 and 3.36 Å, as in graphite and coke. Terahertz spectroscopy shows a behavior similar to that of amorphous carbons, such as coke, with non-interacting layers. This material features substantial differences from polymeric carbon nitride, with some characteristics closer to those of nitrogen-doped graphene, in spite of its higher nitrogen content. The direct optical band gap, dependent on the polycondensation temperature, ranges from 2.10 to 2.32 eV. Although in general the degree of crystallinity is low, the material synthesized at 600 °C is composed of globular hollow particles, in which spots with a certain degree of crystallinity can be found.Junta de Castilla y León Grant VA089U1
1 November 2014 in Journal of Solid State Chemistry
Polymeric carbon nitride doped with copper through a solid-state reaction was characterized by several techniques, among them are UV-visible spectroscopy, infrared spectroscopy, X-ray photoelectron spectroscopy, etc. The material is a semiconductor with a wide band gap of 2.74 eV. Sites of both Cu(I) and Cu(II) were detected, apparently only coordinated by the polymer. The material comprises crumpled nanosheets, and is substantially an amorphous layered material with a prevalent 2D structure with low inter-planar interactions, as shown by X-ray diffractometry and TeraHertz spectroscopy. Photo-oxidation of benzyl alcohol was used to probe the active sites of the material, comparing them with the non-doped material. The higher activity and selectivity toward salicylic alcohol of the non-doped material can be due to both a more localized electron transfer and a longer lifetime of the hole–electron pair. Cu-CN favored the oxidation of hydroxymethyl group. Therefore, the presence of copper can favor different reaction pathways with respect to the non-doped material.