Dissociation of Cyanogen Azide:  An Alternative Route to Synthesis of Carbon Nitride

Abstract

Solid films composed principally of carbon and nitrogen were grown on a variety of substrates at ambient temperature in a flow-tube reactor by upstream mixing of cyanogen azide, cyanogen, or cyanogen halides with active nitrogen obtained from an electrical discharge. Ab initio calculations and dependence of deposition rates on both choice of donor and N atom production suggests that NCN radicals are a critical growth species. The films obtained are electrically insulating with a refractive index of 2.3 at visible wavelength and are optically transparent from 550 nm out to at least 14 µm with the exception of two broad absorption bands centered at 1550 and 3250 cm -1 , the latter band growing in upon exposure of the film to atmospheric moisture. Film analysis by X-ray photoelectron spectroscopy revealed comparable concentrations of both carbon-tonitrogen bonds (with approximate C 3 N 4 stoichiometry) and diamond-like carbon-to-carbon bonds as well as minority bonding of carbon to impurities.

Polymeric Graphitic Carbon Nitride as a Heterogeneous Organocatalyst: From Photochemistry to Multipurpose Catalysis to Sustainable Chemistry

“…It is however interesting to note here that this polymeric semiconductor is mainly composed of carbon and nitrogen, and its organic chemistry provides ways to modify its reactivity without having to change the overall composition too much. Indeed, reports on approaching the synthesis of different modifications and the elucidation of the composition and structure of carbon nitride materials abound in the literature 15–28. Potential applications in energy conversion,29, 30 hydrogen31–33 and carbon dioxide storage,34 purification of contaminated water,35 in solar cells,36–38 as humidity and gas sensors39, 40 have also been reported.…”

A consistent model for the thermal decomposition of NCN3 and the singlet– triplet relaxation of NCN

“…Besides the photolysis of diazomethane (CH 2 N 2 ) in the presence of cyanogen (C 2 N 2 ), the photolysis or pyrolysis of NCN 3 served as a source of NCN radicals. The decomposition of NCN 3 in a microwave discharge has also been used for the synthesis of carbon nitride (C 3 N 4 ) [18], a very hard material. The mechanism of this synthesis is also believed to proceed via NCN radicals.…”

Polymeres graphitisches Kohlenstoffnitrid als heterogener Organokatalysator: von der Photochemie über die Vielzweckkatalyse hin zur nachhaltigen Chemie

“…Tatsächlich findet man mittlerweile eine Vielfalt von Arbeiten, die die Synthese verschiedener Modifikationen und die Ausarbeitung von Zusammensetzung und Struktur von Kohlenstoffnitrid-Materialien zum Inhalt haben. [15][16][17][18][19][20][21][22][23][24][25][26][27][28] Potentielle Anwendungen in der Energieumwandlung, [29,30] Wasserstofferzeugung [31][32][33] Kohlendioxidspeicherung, [34] Reinigung von kontaminiertem Wasser, [35] in Solarzellen, [36][37][38] als Gas-und Feuchtigkeitssensor [39,40] und Vieles mehr wurden ebenfalls beschrieben. Das sogenannte g-C 3 N 4 ist das stabilste Allotrop des Kohlenstoffnitrids und findet weltweit das meiste Interesse.…”