NANOPARTICLE CATALYSTS FOR CONVERSION OF CYCLOHEXANOL TO CYCLOHEXANONE
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.
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.