A novel Mg-based bimetal reagent(Mg/Cu)was used as an enhanced reductive system to degrade insensitivemunition 2,4-dinitroanisole(DNAN),a contaminant found in energeticladenwaste.Degradation ofDNANwas significantly im...A novel Mg-based bimetal reagent(Mg/Cu)was used as an enhanced reductive system to degrade insensitivemunition 2,4-dinitroanisole(DNAN),a contaminant found in energeticladenwaste.Degradation ofDNANwas significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems(i.e.,purging with N2,air,or O_(2) gas).Degradation occurred through sequential nitroreduction:first one nitro group was reduced(ortho or para)to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole(2-ANAN or 4-ANAN),and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole(DAAN).The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN;Regioselectivity was also impacted by the anoxic/oxic environment.Under O_(2)-purging DNAN degradation rate was slightly enhanced,but most notably O_(2) significantly accelerated DAAN generation.DAAN also further degraded only in the oxygenated Mg/Cu system.Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition,resulting in a partition of carbon mass between the adsorbed phase(27%-35%)and dissolved phase(59%-72%).Additional surface techniqueswere applied to investigate contaminant interaction with Cu.Density functional theory(DFT)calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups.X-ray absorption spectroscopy(XAS)measurements determined the oxidation state of catalyticmetal Cu and formation of a Cu-O-N bond during treatment.Laser desorption ionization mass spectrometry(LDI-MS)measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.展开更多
基金This work was supported by the Army Corps of Engineers,Industrial Base Resilience Initiative under Contract No.:W91278-16-D-0007,Delivery Order W9127820F0125.
文摘A novel Mg-based bimetal reagent(Mg/Cu)was used as an enhanced reductive system to degrade insensitivemunition 2,4-dinitroanisole(DNAN),a contaminant found in energeticladenwaste.Degradation ofDNANwas significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems(i.e.,purging with N2,air,or O_(2) gas).Degradation occurred through sequential nitroreduction:first one nitro group was reduced(ortho or para)to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole(2-ANAN or 4-ANAN),and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole(DAAN).The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN;Regioselectivity was also impacted by the anoxic/oxic environment.Under O_(2)-purging DNAN degradation rate was slightly enhanced,but most notably O_(2) significantly accelerated DAAN generation.DAAN also further degraded only in the oxygenated Mg/Cu system.Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition,resulting in a partition of carbon mass between the adsorbed phase(27%-35%)and dissolved phase(59%-72%).Additional surface techniqueswere applied to investigate contaminant interaction with Cu.Density functional theory(DFT)calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups.X-ray absorption spectroscopy(XAS)measurements determined the oxidation state of catalyticmetal Cu and formation of a Cu-O-N bond during treatment.Laser desorption ionization mass spectrometry(LDI-MS)measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.
