Porous multi-metal oxide compositions and methods of use for the conversion of carbon dioxide to carbon-containing products

Abstract

A porous multi-metal oxide composition comprising at least two metal elements interconnected with oxygen atoms, wherein the at least two metal elements are selected from at least one transition metal element and at least one other element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements, and wherein the composition contains micropores and/or mesopores. A method of producing the oxide composition is also described. Methods of using the oxide composition as a catalyst to convert carbon dioxide to carbon-containing products, such as carbon monoxide, methane and other hydrocarbons, are also described.

What is claimed is: 
     
         1 . A porous multi-metal oxide composition comprising at least two metal elements interconnected with oxygen atoms, wherein the at least two metal elements are selected from at least one transition metal element and at least one other element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements, and wherein the composition contains micropores and/or mesopores. 
     
     
         2 . The composition of  claim 1 , wherein the composition contains defect sites corresponding to oxygen vacant sites. 
     
     
         3 . The composition of  claim 1 , wherein the at least one transition metal element is selected from one or more of Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Pd, Pt, and Zn. 
     
     
         4 . The composition of  claim 1 , wherein the at least one transition metal element is selected from Cu, Ni, Mn, and/or Fe. 
     
     
         5 . The composition of  claim 1 , wherein said at least one other element comprises at least one lanthanide element. 
     
     
         6 . The composition of  claim 5 , wherein said at least one lanthanide element is selected from one or more of La, Ce, Pr, Nd, and Sm. 
     
     
         7 . The composition of  claim 1 , wherein the composition comprises said at least one transition metal element and at least one lanthanide element or at least one alkaline earth metal, wherein the at least one transition metal element is selected from one or more of Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Pd, Pt, and Zn; the at least one lanthanide element is selected from one or more of La, Ce, Pr, Nd, and Sm; and the at least one alkaline earth metal is selected from Mg, Ca, Sr, and Ba. 
     
     
         8 . The composition of  claim 1 , wherein the composition has the following formula:
   M a   2-x M b   x M c O 4   (1)
   wherein:   M a  is selected from one or more lanthanide elements;   M b  is selected from one or more alkaline earth elements;   M c  is selected from one or more first-row transition metal elements; and   x is a value between 0 and 2, expressed as 0≤x≤2.   
     
     
         9 . The composition of  claim 8 , wherein 0<x<2. 
     
     
         10 . The composition of  claim 8 , wherein M a  is selected from one or more of La, Ce, Pr, Nd, and Sm. 
     
     
         11 . The composition of  claim 8 , wherein M c  is selected from one or more of Cr, Mn, Fe, Co, Ni, Cu, and Zn. 
     
     
         12 . The composition of  claim 8 , wherein M c  is selected from Cu and/or Fe. 
     
     
         13 . The composition of  claim 8 , wherein the composition has the following formula:
   La 2-x M b   x CuO 4   (1c)
   wherein 0<x<0.5.   
     
     
         14 . A method of producing a porous multi-metal oxide composition, the method comprising:
 (i) impregnating a sacrificial mesoporous template with a solution containing an organic acid and at least two metal salts comprising: (a) a first metal salt containing at least one transition metal element and (b) a second metal salt containing at least one other metal element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements;   (ii) subjecting the impregnated sacrificial mesoporous template to a temperature of 500-1000° C. to calcine the metal salts and convert them to metal oxides; and   (iii) removing the sacrificial mesoporous template;   wherein the resulting porous multi-metal oxide composition comprises at least two metal elements interconnected with oxygen atoms, wherein the at least two metal elements are selected from at least one transition metal element and at least one other element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements, and wherein the composition contains micropores and mesopores.   
     
     
         15 . The method of  claim 14 , wherein the composition contains defect sites corresponding to oxygen vacant sites. 
     
     
         16 . The method of  claim 14 , wherein the at least one transition metal element is selected from one or more of Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Pd, Pt, and Zn. 
     
     
         17 . The method of  claim 14 , wherein the at least one transition metal element is selected from Cu, Ni, Mn, and/or Fe. 
     
     
         18 . The method of  claim 14 , wherein said at least one other metal element comprises at least one lanthanide element. 
     
     
         19 . The method of  claim 18 , wherein said at least one lanthanide element is selected from one or more of La, Ce, Pr, Nd, and Sm. 
     
     
         20 . The method of  claim 14 , wherein the composition comprises said at least one transition metal element and at least one lanthanide element, wherein the at least one transition metal element is selected from one or more of Cr, Mn, Fe, Co, Ni, Cu, Zr, Ag, Pd, Pt, and Zn and the at least one lanthanide element is selected from one or more of La, Ce, Pr, Nd, and Sm. 
     
     
         21 . A method of converting carbon dioxide gas to one or more carbon-containing products, the method comprising contacting the carbon dioxide gas with a porous multi-metal oxide catalyst at a temperature of 25-1000° C., while the porous multi-metal oxide catalyst is disposed on an electrically charged cathode, to result in conversion of the carbon dioxide to said one or more carbon-containing products;
 wherein the porous catalyst comprises: a porous multi-metal oxide composition comprising at least two metal elements interconnected with oxygen atoms, wherein the at least two metal elements are selected from at least one transition metal element and at least one other element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements, and wherein the composition contains micropores and mesopores. 
 
     
     
         22 . The method of  claim 21 , wherein the composition contains defect sites corresponding to oxygen vacant sites. 
     
     
         23 . A method of converting carbon dioxide gas to one or more carbon-containing products, the method comprising contacting the carbon dioxide gas with an electrolyte solution in which the carbon dioxide remains soluble in the solution, and contacting the solution with a porous multi-metal oxide catalyst, while the porous multi-metal oxide catalyst is disposed on an electrically charged cathode, to result in reductive conversion of the carbon dioxide to said one or more carbon-containing products;
 wherein the porous catalyst comprises: a porous multi-metal oxide composition comprising at least two metal elements interconnected with oxygen atoms, wherein the at least two metal elements are selected from at least one transition metal element and at least one other element selected from transition metal elements, lanthanide elements, alkaline earth elements, and main group elements, and wherein the composition contains micropores and mesopores.   
     
     
         24 . The method of  claim 23 , wherein the composition contains defect sites corresponding to oxygen vacant sites.