ABSTRACT
A "pseudo photocatalysis" process, being initiated between plasma and N-type semiconductors in the absence of light, was investigated for NO removal for the first time via dynamic probing of reaction processes by FT-IR spectra. It was demonstrated that N-type semiconductor catalysts could be activated to produce electron-hole (e--h+) pairs by the collision of high-energy electrons (e*) from plasma. Due to the synergy of plasma and N-type semiconductors, major changes were noted in the conversion pathways and products. NO can be directly converted to NO2- and NO3- instead of toxic NO2, owing to the formation of O2- and ·OH present in catalysts. New species like O3 or ·O may be generated from the interaction between catalyst-induced species and radicals in plasma at a higher SIE, leading to deep oxidation of existing NO2 to N2O5. Experiments with added trapping agents confirmed the contribution of e- and h+ from catalysts. A series of possible reactions were proposed to describe reaction pathways and the mechanism of this synergistic effect. We established a novel system and realized an e*-activated "pseudo photocatalysis" behavior, facilitating the deep degradation of NO. We expect that this new strategy would provide a new idea for in-depth analysis of plasma-activated catalysis phenomenon.
Subject(s)
Electrons , Semiconductors , Catalysis , Oxidation-Reduction , Spectroscopy, Fourier Transform InfraredABSTRACT
TiO2 and Ce/TiO2 were synthesized and subsequently used for the catalytic combustion of DCM. TiO2 had abundant Lewis acid sites and was responsible for the adsorption and the rupture of C-Cl bonds. However, TiO2 tended to be inactivated because of chloride poisoning due to the adsorption and accumulation of Cl species over the surface. While, Ce/TiO2 obtained total oxidation of CH2Cl2 at 335°C and exhibited stable DCM removal activity on 100h long-time stability tests at 330°C without any catalyst deactivation. The doped cerium generated Ce(3+) chemical states and surface active oxygen, and therefore played important roles from two aspects as follows. First of all, the poisoning of Cl for Ce/TiO2 was inhibited to some extent by CeO2 due to the rapid removal of Cl on the surface of CeO2, which has been verified by NH3-IR characterization. In the other hand, CeO2 enhanced the further deep oxidation of C-H from byproducts and retained the certain oxidation of CO to CO2. Based on the DRIFT characterization and the catalysts activity tests, a two-step reaction pathway for the catalytic combustion of DCM on Ce/TiO2 catalyst was proposed.
