The societal significance of catalysis and the growing practical importance of single-site...

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The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A Volume 468(2143):1884-1903 July 8, 2012 ©2012 by The Royal Society

Transcript of The societal significance of catalysis and the growing practical importance of single-site...

Page 1: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

The societal significance of catalysis and the growing practical importance of single-site heterogeneous

catalysts

by John Meurig Thomas

Proceedings AVolume 468(2143):1884-1903

July 8, 2012

©2012 by The Royal Society

Page 2: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

An archetypal single-site heterogeneous catalyst (SSHC), (a) high-resolution electron micrograph of H-ZSM-5, and a Brønsted acid catalyst, empirical formula Hm+Sin−m Alm O2n

where the Si/Al ratio (n–m)/m is ca 25/1.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 3: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

A single-site, multinuclear nanocluster, Ru10Pt2C2 (bound to a mesoporous silica surface, right) catalyses the hydrogenation of muconic acid (derived from biological sources) into adipic acid,

which is one of the building blocks of nylon 6,6.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 4: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

Computed energy levels of outermost electrons in a nanocluster Pt3 compared with the corresponding computed levels in a much larger cluster Pt309.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 5: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

High-resolution electron micrograph of silicalite SiO2, which has the same framework structure as that of ZSM-5.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 6: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

The catalytic cycle, including density functional theory calculated energies, for the epoxidation of an alkene R CH=CH2 to its epoxide by a four-coordinated TiIV active site at a mesoporous

silica surface.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 7: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

In situ X-ray absorption fine structure spectroscopy (XAFS), shown at the extreme left, coupled with in situ FTIR (not shown), can trace the conversion of the precursor organometallic

titanocene dichloride (whose entry into a single mesopore of the silica i...

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 8: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

All three of these microporous SSHC, composed of framework-substituted aluminium phosphates, exhibit high Brønsted acid catalytic activity in the dehydration of ethanol and

methanol to produce ethylene and other light olefins.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 9: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

An outline of the mechanistic details involved in the use of a trifunctional SSHC for the production of propylene from ethylene.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 10: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

A summary of sequence of conversions that produce ε-caprolactam (and its linear polymer, nylon 6) from cyclohexanone (1) via its oxime (2).

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society

Page 11: The societal significance of catalysis and the growing practical importance of single-site heterogeneous catalysts by John Meurig Thomas Proceedings A.

Illustration of the supremacy of the bifunctional nanoporous catalyst, composed of CoIII (redox) and MgII (Brønsted) active centres for the solvent-free production of caprolactam and nylon 6

without generating unwanted solid products.

John Meurig Thomas Proc. R. Soc. A 2012;468:1884-1903

©2012 by The Royal Society