Intermediate precursor compositions used to make supported catalysts having a controlled coordination structure and methods for preparing such compositions
View Patent ↗Intermediate precursor compositions for use in manufacturing supported reactive catalysts having a controlled coordination structure, and methods for manufacturing such precursor compositions are disclosed. The precursor compositions include a catalyst complex formed from catalyst atoms and a control agent that is applied to a substrate. Reduction of the catalyst complex yields supported reactive catalyst in which a preponderance of the top or outer layer of atoms of the catalyst particles exhibit a controlled coordination number of 2. The supported catalysts are useful for a variety of chemical reactions, including the preparation of hydrogen peroxide with high selectivity.
1. An intermediate precursor composition for use in manufacturing a supported catalyst having a controlled coordination structure, comprising:
a plurality of catalyst atoms comprising at least one member selected from the group comprising noble metals, rare earth metals, and transition metals, and optionally one or more non-metals; and
a control agent comprising a plurality of complexing molecules selected from the group comprising polymers, oligomers, and organic compounds, each complexing molecule having a plurality of functional groups disposed along a backbone for complexing the catalyst atoms to the complexing molecules,
at least about 50% of the complexing molecules being straight-chained molecules that include at least four functional groups per molecule, and at least a portion of the complexing molecules forming a catalyst complex between the catalyst atoms and the complexing molecules,
wherein the catalyst complex, after being applied to a support, forms a supported reactive catalyst comprising a support and a plurality of reactive catalyst particles formed from the catalyst complex,
wherein the complexing molecules and catalyst atoms interact in such a way that a preponderance of catalyst atoms on an upper surface of supported reactive catalyst particles formed from the catalyst complex will have a nearest neighbor coordination number of 2.
2. An intermediate precursor composition as defined in claim 1 , wherein at least a portion of the catalyst atoms comprise at least one noble metal selected from the group comprising palladium, platinum, iridium, gold, osmium, ruthenium, rhodium, and rhenium.
3. An intermediate precursor composition as defined in claim 1 , wherein at least a portion of the catalyst atoms comprise at least one transition metal.
4. An intermediate precursor composition as defined in claim 3 , wherein the transition metal comprises at least one member selected from the group comprising chromium, manganese, iron, cobalt, nickel, copper, zirconium, tin, zinc, tungsten, titanium, molybdenum, and vanadium.
5. An intermediate precursor composition as defined in claim 1 , wherein at least a portion of the catalyst atoms comprise at least one rare earth metal.
6. An intermediate precursor composition as defined in claim 5 , wherein the rare earth metal comprises at least one member selected from the group comprising lanthanum and cerium.
7. An intermediate precursor composition as defined in claim 1 , wherein a portion of the catalyst atoms comprise at least one non-metal.
8. An intermediate precursor composition as defined in claim 1 , further comprising at least one of an alkali metal or alkaline earth metal.
9. An intermediate precursor composition as defined in claim 1 , wherein at least a portion of the functional groups comprise a carbon atom bonded to at least one electron-rich atom that is more electronegative than the carbon atom and that is able to donate one or more electrons so as to form a bond or attraction with at least one of the catalyst atoms.
10. An intermediate precursor composition as defined in claim 9 , wherein the electron-rich atom comprises at least one of oxygen or nitrogen.
11. An intermediate precursor composition as defined in claim 9 , wherein the electron-rich atom has a negative charge and the catalyst atoms have a positive charge.
12. An intermediate precursor composition as defined in claim 1 , wherein at least about 60% of the complexing molecules are straight-chained.
13. An intermediate precursor composition as defined in claim 1 , wherein at least about 75% of the complexing molecules are straight-chained.
14. An intermediate precursor composition as defined in claim 1 , wherein at least about 90% of the complexing molecules are straight-chained.
15. An intermediate precursor composition as defined in claim 1 , wherein at least about 95% of the complexing molecules are straight-chained.
16. An intermediate precursor composition as defined in claim 1 , wherein about 100% of the complexing molecules are straight-chained.
17. An intermediate precursor composition as defined in claim 1 , further comprising a solvent or carrier into which the catalyst complex and any remaining catalyst atoms and control agent are mixed.
18. An intermediate precursor composition as defined in claim 17 , wherein the solvent or carrier comprises water.
19. An intermediate precursor composition as defined in claim 17 , wherein the solvent or carrier comprises at least one aqueous acid.
20. An intermediate precursor composition as defined in claim 17 , wherein the solvent or carrier comprises at least one organic solvent.
21. An intermediate precursor composition as defined in claim 17 , further comprising at least one support material.
22. An intermediate precursor composition as defined in claim 21 , wherein the catalyst complex is impregnated within, but not chemically bonded to, the support material.
23. An intermediate precursor composition as defined in claim 21 , wherein the catalyst complex is chemically bonded to the support material.
24. An intermediate precursor composition as defined in claim 1 , further comprising at least one support material to which the catalyst complex is chemically bonded.
25. An intermediate precursor composition as defined in claim 1 , wherein the control agent has a number average molecular weight in a range of about 300 to about 15,000 Daltons.
26. An intermediate precursor composition as defined in claim 1 , wherein the control agent has a number average molecular weight in a range of about 600 to about 6,000 Daltons.
27. An intermediate precursor composition as defined in claim 1 , wherein a substantial portion of the control agent includes from about 4 to about 200 of the functional groups per complexing molecule.
28. An intermediate precursor composition as defined in claim 1 , wherein a substantial portion or the control agent includes from about 8 to about 80 functional groups per complexing molecule.
29. An intermediate precursor composition as defined in claim 1 , wherein a substantial portion of the control agent includes from about 10 to about 20 functional groups per complexing molecule.
30. An intermediate precursor composition as defined in claim 1 , wherein the intermediate precursor composition includes a molar ratio of control agent functional groups to catalyst atoms in a range of about 0.5:1 to about 40:1.
31. An intermediate precursor composition as defined in claim 1 , wherein the intermediate precursor composition includes a molar ratio of control agent functional groups to catalyst atoms in a range of about 1:1 to about 35:1.
32. An intermediate precursor composition as defined in claim 1 , wherein the intermediate precursor composition includes a molar ratio of control agent functional groups to catalyst atoms in a range of about 3:1 to about 30:1.
33. An intermediate precursor composition as defined in claim 1 , wherein the control agent comprises at least one of polacrylic acid or a polyacrylic acid salt.
34. An intermediate precursor composition as defined in claim 1 , wherein the control agent comprises at least one member selected from the group comprising polyvinylbenzoates, polyvinyl sulfate, polyvinyl sulfonates including sulfonated styrene, polybisphenol carbonates, polybenzimidizoles, polypyridine, sulfonated polyethylene terephthalate, polyvinyl alcohol, polyethylene glycol, and polypropylene glycol.
35. An intermediate precursor composition as defined in claim 1 , wherein the catalyst complex comprises a random distribution of at least two different types of catalyst atoms.
36. An intermediate precursor composition as defined in claim 35 , wherein the catalyst complex forms a supported reactive catalyst in a manner so that reactive catalyst particles formed from the catalyst complex will also include a random distribution of at least two different types of catalyst atoms.
37. An intermediate precursor composition for use in manufacturing a supported catalyst having a controlled coordination structure, comprising:
a plurality of catalyst atoms comprising at least one member selected from the group comprising noble metals, rare earth metals, and transition metals, and optionally one or more non-metals; and
a control agent comprising a plurality of complexing molecules selected from the group comprising polymers and oligomers, each complexing molecule having a plurality of functional groups disposed along a backbone for complexing the catalyst atoms to the complexing molecules,
at least about 50% of the complexing molecules being straight-chained and at least a portion of the complexing molecules forming a catalyst complex between the catalyst atoms and the complexing molecules,
wherein the catalyst complex, after being applied to a support, forms a supported reactive catalyst comprising a support and a plurality of reactive catalyst particles formed from the catalyst complex,
wherein the complexing molecules and catalyst atoms interact in such a way that a preponderance of catalyst atoms on an upper surface of supported reactive catalyst particles formed from the catalyst complex will have a nearest neighbor coordination number of 2.
38. An intermediate precursor composition as defined in claim 37 , wherein at least about 75% of the complexing molecules are straight-chained.
39. An intermediate precursor composition as defined in claim 37 , wherein at least about 90% of the complexing molecules are straight-chained.
40. An intermediate precursor composition as defined in claim 37 , further comprising a solvent or carrier into which the catalyst complex and any remaining catalyst atoms and control agent are dissolved or dispersed.
41. An intermediate precursor composition as defined in claim 40 , further comprising at least one support material.
42. An intermediate precursor composition as defined in claim 41 , wherein the catalyst complex is impregnated within, but not chemically bonded to, the support material.
43. An intermediate precursor composition as defined in claim 41 , wherein the catalyst complex is chemically bonded to the support material.
44. An intermediate precursor composition as defined in claim 37 , further comprising at least one support material to which the catalyst complex is chemically bonded.
45. An intermediate precursor composition as defined in claim 37 , wherein the control agent comprises at least one of polacrylic acid or a polyacrylic acid salt.
46. An intermediate precursor composition as defined in claim 37 , wherein the control agent comprises at least one member selected from the group comprising polyvinylbenzoates, polyvinyl sulfate, polyvinyl sulfonates including sulfonated styrene, polybisphenol carbonates, polybenzimidizoles, polypyridine, sulfonated polyethylene terephthalate, polyvinyl alcohol, polyethylene glycol, and polypropylene glycol.
47. An intermediate precursor composition as defined in claim 37 , wherein the catalyst complex comprises a random distribution of at least two different types of catalyst atoms.
48. An intermediate precursor composition as defined in claim 47 , wherein the catalyst complex forms a supported reactive catalyst in a manner so that reactive catalyst particles formed from the catalyst complex will also include a random distribution of at least two different types of catalyst atoms.
49. A method of preparing an intermediate precursor composition for use in manufacturing a supported catalyst having a controlled coordination structure, the method comprising:
providing a plurality of catalyst atoms comprising at least member selected from the group comprising noble metals, rare earth metals, and transition metals, and optionally one or more non-metals;
providing a control agent comprising a plurality of complexing molecules selected from the group comprising polymers, oligomers, and organic compounds, each complexing molecule having a plurality of functional groups disposed along a backbone for complexing the reactive catalyst atoms to the complexing molecules, wherein at least about 50% of the complexing molecules are straight-chained molecules that include at least four of the functional groups per molecule;
mixing together the catalyst atoms and control agent in a liquid to form a mixture; and
reacting at least a portion of the catalyst atoms with at least a portion of the control agent to yield a catalyst complex that, after being applied to a support, forms a supported reactive catalyst comprising a support and a plurality of reactive catalyst particles formed from the catalyst complex,
wherein the complexing molecules and catalyst atoms interact in such a way that a preponderance of catalyst atoms on an upper surface of supported reactive catalyst particles formed from the catalyst complex will have a nearest neighbor coordination number of 2.
50. A method of preparing an intermediate precursor composition as defined in claim 49 , further comprising contacting the catalyst complex with a support.
51. A method of preparing an intermediate precursor composition as defined in claim 50 , wherein the catalyst complex is impregnated within, but not bonded to, the support.
52. A method of preparing an intermediate precursor composition as defined in claim 50 , further comprising reacting the catalyst complex with the support so that a portion of the control agent chemically bonds the catalyst complex to the support.
53. A method of preparing an intermediate precursor composition as defined in claim 52 , wherein the portion of the control agent that bonds the catalyst complex to the support does so by means of a condensation reaction.
54. A method of preparing an intermediate precursor composition as defined in claim 52 , wherein the portion of the control agent that bonds the catalyst complex to the support comprises an anchoring agent.
55. A method of preparing an intermediate precursor composition as defined in claim 52 , further comprising removing the liquid so as to yield a supported catalyst precursor composition comprising the catalyst complex bonded to the support.
56. A method of preparing an intermediate precursor composition as defined in claim 49 , wherein the catalyst complex includes a random distribution of at least two different types of catalyst atoms.
57. A method of preparing an intermediate precursor composition for use in manufacturing a supported catalyst having a controlled coordination structure, the method comprising:
providing a plurality of catalyst atoms comprising at least member selected from the group comprising noble metals, rare earth metals, and transition metals, and optionally one or more non-metals;
providing a control agent comprising a plurality of complexing molecules selected from the group comprising polymers and oligomers, each control agent molecule having a plurality of functional groups disposed along a backbone for complexing the reactive catalyst atoms to the complexing molecules, wherein at least about 50% of the complexing molecules arc straight-chained;
mixing together the catalyst atoms and control agent in a liquid to form a mixture; and
reacting at least a portion of the catalyst atoms with at least a portion of the control agent to yield a catalyst complex that, when applied to a support, forms a supported reactive catalyst comprising a support and a plurality of reactive catalyst particles formed from the catalyst complex,
wherein the complexing molecules and catalyst atoms interact in such a way that a preponderance of catalyst atoms on an upper surface of supported reactive catalyst particles formed from the catalyst complex will have a nearest neighbor coordination number of 2.
58. A method of preparing an intermediate precursor composition as defined in claim 57 , further comprising contacting the catalyst complex with a support.
59. A method of preparing an intermediate precursor composition as defined in claim 58 , wherein the catalyst complex is impregnated within, but not bonded to, the support.
60. A method of preparing an intermediate precursor composition as defined in claim 58 , further comprising reacting the catalyst complex with the support so that a portion of the control agent chemically bonds the catalyst complex to the support.
61. A method of preparing an intermediate precursor composition as defined in claim 60 , wherein the portion of the control agent that bonds the catalyst complex to the support does so by means of a condensation reaction.
62. A method or preparing an intermediate precursor composition as defined in claim 60 , wherein the portion of the control agent that bonds the catalyst complex to the support comprises an anchoring agent.
63. A method of preparing an intermediate precursor composition as defined in claim 60 , further comprising removing the liquid so as to yield a supported catalyst precursor composition comprising the catalyst complex bonded to the support.
64. A method of preparing an intermediate precursor composition as defined in claim 57 , wherein the catalyst complex includes a random distribution of at least two different types of catalyst atoms.