Manganese Oxide Nanoarchitectures for Broad-Spectrum Removal of Toxic Gases in Air-Filtration Applications

Abstract

A high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders comprising a manganese oxide nanoarchitecture comprising an interior surface area >200 m 2 g −1 , wherein the MnOx gel has a void structure comprising pores that are sized from 2-150 nm, and wherein the manganese oxide nanoarchitecture removes toxic gas from a toxic gas and air mixture at room temperature via an oxidative mechanism that converts the toxic gas to an innocuous adsorbed substance. These high-surface-area, ultraporous manganese oxide (MnOx) xerogels and aerogels exhibit outstanding filtration performance for multiple, chemically distinct toxic gases, including ammonia, sulfur dioxide and hydrogen sulfide. These MnOx materials use multiple mechanisms for small molecule capture/catalysis including molecular sieving and oxidative decomposition, and function in a wide range of humidity conditions.

What we claim is: 
     
         1 . A high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders comprising:
 a manganese oxide nanoarchitecture comprising an interior surface area >200 m 2  g −1 ;
 wherein the MnOx gel has a void structure comprising pores that are sized from 2-150 nm; 
 wherein the manganese oxide nanoarchitecture removes toxic gas from a toxic gas and air mixture at room temperature via an oxidative mechanism that converts the toxic gas to an innocuous adsorbed substance; and 
 wherein the manganese oxide nanoarchitecture removes ammonia from a contacting gas mixture at sorption capacities >1.0 mol NH 3  kg −1  MnOx for H—MnOx compositions and >1.5 mol NH 3  kg −1  MnOx for Na—MnOx compositions under dry conditions. 
   
     
     
         2 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders of  claim 1   wherein the manganese oxide nanoarchitecture removes sulfur dioxide from a contacting gas mixture at sorption capacities >2 mol SO 2  kg −1  MnOx for H—MnOx compositions and >3 mol SO 2  kg −1  MnOx for Na—MnOx compositions under wet conditions or wherein the humidity is about 80% relative humidity.   
     
     
         3 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders of  claim 1   wherein the manganese oxide nanoarchitecture removes hydrogen sulfide from a contacting gas mixture at sorption capacities >0.3 mol H 2 S kg −1  MnOx for H—MnOx compositions and >1.5 mol H 2 S kg −1  MnOx for Na—MnOx compositions under dry conditions or under wet conditions or wherein the humidity is about 80% relative humidity.   
     
     
         4 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders of  claim 1  wherein the manganese oxide nanoarchitecture removes >35% of HD mustard agent from a liquid-phase application. 
     
     
         5 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders of  claim 1  wherein the MnOx gel has an average manganese oxidation state between +3 and +4. 
     
     
         6 . A high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders for filtering toxic gases made from the steps of:
 adding fumaric acid to an aqueous solution of NaMnO 4  in a 1:3 mole ratio to form a fluid-filled porous gel of MnOx in which the oxide domains also contain Na +  and thereby form Na—MnOx;   rinsing the Na—MnOx gel with an acid solution to protonate the oxide and form H—MnOx and remove Na + ; and   rinsing the gel in water to remove residual acid;   drying the fluid-filled porous gel under ambient-pressure conditions to generate a densified xerogel MnOx material;
 wherein the manganese oxide nanoarchitecture has an interior surface area >200 m 2  g −1 ; 
 wherein the MnOx gel has a void structure comprising pores that are sized from 2-150 nm; 
   exchanging the fluid in the pores of the fluid-filled porous gel for CO 2 ; and   removing said CO 2  under supercritical conditions to render a dry, low-density MnOx aerogel;   wherein the low-density MnOx aerogel with a manganese oxide nanoarchitecture is exposed to a toxic gas and air mixture;   wherein the toxic gas is removed from a toxic gas and air mixture at room temperature via an oxidative mechanism that converts the toxic gas to an innocuous adsorbed substance; and   wherein the low-density MnOx aerogel with a manganese oxide nanoarchitecture removes ammonia from a contacting gas mixture at sorption capacities >1.0 mol NH 3  kg −1  MnOx for H—MnOx compositions and >1.5 mol NH 3  kg −1  MnOx for Na—MnOx compositions under dry conditions.   
     
     
         7 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders for filtering toxic gases of  claim 6   wherein the low-density MnOx aerogel with a manganese oxide nanoarchitecture removes sulfur dioxide from a contacting gas mixture at sorption capacities >2 mol SO 2  kg −1  MnOx for H—MnOx compositions and >3 mol SO 2  kg −1  MnOx for Na—MnOx compositions under wet conditions or wherein the humidity is about 80% relative humidity.   
     
     
         8 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders for filtering toxic gases of  claim 6   wherein the low-density MnOx aerogel with a manganese oxide nanoarchitecture removes hydrogen sulfide from a contacting gas mixture at sorption capacities >0.3 mol H 2 S kg −1  MnOx for H—MnOx compositions and >1.5 mol H 2 S kg −1  MnOx for Na—MnOx compositions under dry conditions or under wet conditions or wherein the humidity is about 80% relative humidity.   
     
     
         9 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders for filtering toxic gases of  claim 6   wherein the low-density MnOx aerogel with a manganese oxide nanoarchitecture removes >35% of HD mustard agent from a liquid-phase application.   
     
     
         10 . The high-surface-area, highly porous manganese oxide (MnOx) in the form of xerogel or aerogel monoliths or powders for filtering toxic gases of  claim 6   wherein the MnOx gel has an average manganese oxidation state between +3 and +4.