John D. Atkinson

Sustainable and hierarchical porous Enteromorpha prolifera based carbon for CO2 capture.

Nitrogen-containing porous carbon was synthesized from an ocean pollutant, Enteromorpha prolifera, via hydrothermal carbonization and potassium hydroxide activation. Carbons contained as much as 2.6% nitrogen in their as-prepared state. Physical and chemical properties were characterized by XRD, N(2) sorption, FTIR, SEM, TEM, and elemental analysis. The carbon exhibited a hierarchical structure with interconnected microporosity, mesoporosity and macroporosity. Inorganic minerals in the carbon matrix contributed to the development of mesoporosity and macroporosity, functioning as an in situ hard template. The carbon manifested high CO(2) capacity and facile regeneration at room temperature. The CO(2) sorption performance was investigated in the range of 0-75°C. The dynamic uptake of CO(2) is 61.4 mg/g and 105 mg/g at 25°C and 0°C, respectively, using 15% CO(2) (v/v) in N(2). Meanwhile, regeneration under Ar at 25°C recovered 89% of the carbons initial uptake after eight cycles. A piecewise model was employed to analyze the CO(2) adsorption kinetics; the Avrami model fit well with a correlation coefficient (R(2)) of 0.98 and 0.99 at 0°C and 25°C, respectively.

Adsorption and destruction of PCDD/Fs using surface-functionalized activated carbons

Activated carbon adsorbs polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) from gas streams but can simultaneously generate PCDD/Fs via de novo synthesis, increasing an already serious disposal problem for the spent sorbent. To increase activated carbons PCDD/F sorption capacity and lifetime while reducing the impact of hazardous waste, it is beneficial to develop carbon-based sorbents that simultaneously destroy PCDD/Fs while adsorbing the toxic chemicals from gas streams. In this work, hydrogen-treated and surface-functionalized (i.e., oxygen, bromine, nitrogen, and sulfur) activated carbons are tested in a bench-scale reactor as adsorbents for PCDD/Fs. All tested carbons adsorb PCDD/F efficiently, with international toxic equivalent removal efficiencies exceeding 99% and mass removal efficiencies exceeding 98% for all but one tested material. Hydrogen-treated materials caused negligible destruction and possible generation of PCDD/Fs, with total mass balances between 100% and 107%. All tested surface-functionalized carbons, regardless of functionality, destroyed PCDD/Fs, with total mass balances between 73% and 96%. Free radicals on the carbon surface provided by different functional groups may contribute to PCDD/F destruction, as has been hypothesized in the literature. Surface-functionalized materials preferentially destroyed higher-order (more chlorine) congeners, supporting a dechlorination mechanism as opposed to oxidation. Carbons impregnated with sulfur are particularly effective at destroying PCDD/Fs, with destruction efficiency improving with increasing sulfur content to as high as 27%. This is relevant because sulfur-treated carbons are used for mercury adsorption, increasing the possibility of multi-pollutant control.

Simple dimer containing dissociatively stable mono-imidazole ligated ferrohemes

In weakly coordinating solvents FeII meso-(N-methylimidazol-2-yl)porphine Fe exists as a stable dimer (Kd=50+/-30 nM) that binds ligands without undergoing dissociation and is presently the simplest complex in which the mono-imidazole ligation of a ferroheme is enforced without excess imidazole in solution.