PNNL

Abstract

Hydrogen peroxide is a valuable chemical commodity whose production relies on expensive methods. If an efficient, sustainable, and inexpensive solar-mediated production method could be developed from the reaction between dioxygen and water then its use as a fuel may be possible and gain acceptance. Hydrogen peroxide at greater than 10 M possesses a high specific energy, is environmentally clean, and is easily stored. However, the current method of manufacturing H2O2 via the anthraquinone process is environmentally unfriendly making the unexplored nature of its photochemical production from solar irradiation of interest. Here the concentration and quantum yield of hydrogen peroxide produced in an ultraviolet (UV-B) irradiated environment using aromatic and nitrogen-heterocyclic ring complexes of zinc(II) as solid substrates was studied. The amino-substituted isomers of the substrates indazole, pyridine, and phenylenediamine solid polymer complexes are examined. Samples exposed to the ambient atmosphere (e.g., aerated) were irradiated with a low power lamp with emission from 280-360 nm. Irradiation of various zinc complexes revealed Zn-5-aminoindazole to have the greatest first-day production of 63 mM/day with a 37% quantum yield. Para-phenylenediamine (PPAM) showed the greatest long-term stability and thus suggests H2O2 is produced photocatalytically. Isomeric forms of the catalyst’s organic components (e.g., amino groups) did have an effect on the production. Irradiation of diaminopyridine isomers indicated 2,3-diamino and 3,4-diamino structures were the most productive, each generating 32 mM/day hydrogen peroxide. However, the 2,5-diamino isomer showed no peroxide production. A significant decrease in hydrogen peroxide production in all but PPAM was noticed in the samples, suggesting the possibility of a catalyst poisoning mechanism. The samples ability to produce H2O2 is rationalized by proposing a reaction mechanism and examining the stability of the resonance structures of the different isomers.