Nanoparticle catalysts for conversion of cyclohexanol to cyclohexanone

Abstract

Methods for converting an alcohol, such as cyclohexanol to a ketone, such as cyclohexanone, include reacting the alcohol in the presence of a catalyst and oxygen to produce the ketone. In one exemplary embodiment, the catalyst comprises a microporous copper chloropyrophosphate framework including a plurality of noble metal nanoparticles. In one exemplary embodiment, the noble metal nanoparticles include at least one metal selected from the group consisting of platinum, palladium, and gold.

What is claimed is: 
     
         1 . A catalyst comprising a microporous copper chloropyrophosphate framework comprising a plurality of noble metal nanoparticles, the catalyst activated in a reducing atmosphere. 
     
     
         2 . The catalyst of  claim 1 , wherein the microporous copper chloropyrophosphate framework has the general formula:
   [A 9 Cu 6 (P 2 O 7 ) 4 Cl].[MX 4 ]Cl y      where: A is selected from K, Rb, Cs, and NH 4 ;
 M is selected from Cu, Au, Pt, and Pd; 
 X is selected from Cl and Br; and 
 y is 2 when M is Pt, Pd, or Cu and y is 3 when M is Au. 
   
     
     
         3 . The catalyst of  claim 2 , wherein the microporous copper chloropyrophosphate framework has a general formula selected from the group consisting of:
 Rb 9 Cu 6 (P 2 O 7 ) 4 Cl 4 (AuCl 4 ), Rb 9 Cu 6 (P 2 O 7 ) 4 Cl 3 (PtCl 4 ), and Rb 9 Cu 6 (P 2 O 7 ) 4 Cl 3 (PdCl 4 ).   
     
     
         4 . The catalyst of  claim 1 , wherein the catalyst comprises precursor complexes that result in isolated noble metal nanoparticle sites upon activation. 
     
     
         5 . The catalyst of  claim 4 , wherein the precursor complexes are selected from the group consisting of [PtCl 4 ] 2− , [PdCl 4 ] 2− , and [AuCl 4 ] − . 
     
     
         6 . The catalyst of  claim 1 , wherein the noble metal nanoparticles include at least one metal selected from the group consisting of platinum, palladium, and gold. 
     
     
         7 . The catalyst of  claim 6 , wherein the microporous copper chloropyrophosphate framework includes a plurality of mono-metallic platinum nanoparticles. 
     
     
         8 . The catalyst of  claim 7 , wherein the catalyst has been activated at a temperature of about 200° C. 
     
     
         9 . The catalyst of  claim 1 , wherein the microporous copper chloropyrophosphate framework includes a plurality of mono-metallic palladium nanoparticles. 
     
     
         10 . The catalyst of  claim 1 , wherein the reducing atmosphere includes hydrogen and nitrogen. 
     
     
         11 . A catalyst comprising a microporous copper chloropyrophosphate framework including a plurality of mono-metallic platinum nanoparticles, the microporous copper chloropyrophosphate framework having a general formula of Rb 9 Cu 6 (P 2 O 7 ) 4 Cl 3 (PtCl 4 ), the catalyst activated in a reducing atmosphere. 
     
     
         12 . The catalyst of  claim 11 , wherein the catalyst is activated at a temperature of about 200° C. 
     
     
         13 . The catalyst of  claim 11 , wherein the reducing atmosphere includes hydrogen and nitrogen. 
     
     
         14 . A catalyst comprising a microporous copper chloropyrophosphate framework having the general formula:
   [(NH 4 ) 9 Cu 6 (P 2 O 7 ) 4 Cl].[MX 4 ]Cl 2      wherein:
 M is selected from Pt, and Pd; and 
 X is selected from Cl and Br. 
   
     
     
         15 . The catalyst of  claim 14 , wherein the microporous copper chloropyrophosphate framework has a general formula selected from the group consisting of: (NH 4 ) 9 Cu 6 (P 2 O 7 ) 4 Cl 3 (PtCl 4 ) and (NH 4 ) 9 Cu 6 (P 2 O 7 ) 4 Cl 3 (PdCl 4 ). 
     
     
         16 . The catalyst of  claim 14 , wherein the catalyst comprises precursor complexes selected from the group consisting of [PtCl 4 ] 2−  and [PdCl 4 ] 2− , that result in isolated noble metal nanoparticle sites upon activation. 
     
     
         17 . The catalyst of  claim 14 , wherein the noble metal nanoparticles include at least one metal selected from the group consisting of platinum and palladium. 
     
     
         18 . The catalyst of  claim 17 , wherein the microporous copper chloropyrophosphate framework includes a plurality of mono-metallic platinum nanoparticles. 
     
     
         19 . The catalyst of  claim 14 , wherein the microporous copper chloropyrophosphate framework includes a plurality of mono-metallic palladium nanoparticles. 
     
     
         20 . The catalyst of  claim 14 , wherein the catalyst is activated in a reducing atmosphere, the reducing atmosphere including hydrogen and nitrogen.