Low-temperature NH3 abatement via selective oxidation over a supported copper catalyst with high Cu+ abundance.

Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.

Highly efficient adsorptive removal of toluene using silicon-modified activated carbon with improved fire resistance.

Activated carbons (ACs) are widely applied in the removal of volatile organic compounds (VOCs) emitted from industrial processes, because of their high adsorption capacity, low cost and reusability. Their poor thermal stability under oxidative conditions is a limiting factor and often leads to fire risk in real applications. Here, Si-modification was performed over a wood-derived AC material, and a series of modified ACs with different Si/C mass ratios (0.1-0.9) were prepared via a hydrothermal route. Physicochemical characteristics of Si/C samples was examined by XRD, SEM, TEM, XPS, FTIR and N2-physisorption measurements. As compared to pristine AC, Si-modified ACs showed enhanced fire resistance, and an increase of ignition temperature by 79 â„ƒ was achieved at a Si/C mass ratio of 0.9. A combination of TEM, XPS and FTIR characterization suggests that the formation of amorphous SiO2 nanoparticles and SiC species on the surface was responsible for the enhanced fire resistance of Si-modified ACs. By increasing microporosity, Si-modification also significantly improved the adsorption capacity of toluene as a model VOC molecule. Static and dynamic adsorption experiments were performed to understand the adsorption kinetics of the Si-modified ACs. Reusability tests showed that the desorption rate of the modified AC remained at nearly 80% even after five cycles of repeated adsorption-desorption, indicating that the modified AC has a great potential for industrial applications.