Catalysis and Green Chemistry

Thermodynamics vs Kinetics

2
Transition State

3
Catalysis

ΔG does
not change

4
Catalysis

5
Using Catalyst Increases Atom Efficiency

6
Using Catalyst Decreases Wastes

7
Using Catalyst Decreases Wastes

8
Using Catalyst Decreases Wastes

E > 10 (MnSO4,
FeCl2, NaCl,
Na2SO4)

E<1

9
 Homogeneous vs Heterogeneous

10
Lianjie Zhu, Ph.D thesis, TU Delft, 2005
 Heterogeneous Catalysis
Reaction commonly occurs on the surface of the solid
catalyst.

11
E. Marshall, Green Chem. Lecture, ICL
 Remove Homogeneous Catalysts
If solubilities of catalyst and product are different,
“purification” would be feasible.

Recoverability is a problem!
12
Y. Liu, C. E. Hobbs, Polymer 2018, 135, 25.
 Purification of Organic Compounds

Distillation

Extraction

Column
chromatography
13
Remove and Recover Heterogeneous Catalysts

Vacuum filtration

Centrifugation

14
Remove and Recover Heterogeneous Catalysts
Use inert atmosphere and strong vacuum to regenerate
the solid catalyst.

N2/Argon

Air-free Schlenk lines

15
Remove and Recover Heterogeneous Catalysts

16
 Homogeneous vs Heterogeneous

17
E. Marshall, Green Chem. Lecture, ICL
 Single-Site Catalyst

18
E. Marshall, Green Chem. Lecture, ICL
Zeolite

19
Using Zeolite to Replace Conventional Catalysts
Commonly, zeolites are used for replacing “homogeneous”
Lewis acids.

20
Using Zeolite to Replace Conventional Catalysts

21
Using Zeolite to Replace Conventional Catalysts

22
E. Marshall, Green Chem. Lecture, ICL
 “Shape” Selectivity in Zeolite

23
E. Marshall, Green Chem. Lecture, ICL
Heteropoly Acids

24
Heteropoly Acids

25
 Catalyst Immobilization
Defined as “the transformation of a homogeneous catalyst
into a heterogeneous one”

26
B. Plugin, Top. Catal. 2010, 53, 953.
 Catalyst Immobilization

Pt/mesoporous Al2O3
27
N. Yan, Nat. Commun. 2017, 8, 16100.
 Catalyst Immobilization
Use of Pt/mesoporous Al2O3 in selective 1,3-butadiene hydrogenation
and CO oxidation.

28
N. Yan, Nat. Commun. 2017, 8, 16100.
 Catalyst Immobilization

R. L. Augustin, Appl. Catal. A: Gen. 2003, 256, 69.

29
R. A. Sheldon, J. Catal. 2006, 239, 212.
Catalyst Immobilization

30
 Soluble Polymer-Supported Catalysts
Thermomorphic solvent mixtures are biphasic at low
temperature but a single phase when heating.
Ex: heptane/90% aq. EtOH (1/1 v/v) is biphasic at 25 °C but
is a single phase at 70 °C.

31
D. E. Bergbreiter, S. D. Sung, Adv. Synth. Catal. 2006, 348, 1352.
 Soluble Polymer-Supported Catalysts
Latent biphasic solvent mixtures are that a single phase
regardless of temperature, but is biphasic upon the addition
of a solute/another solvent/water or the formation of a
“different” product.

32
D. E. Bergbreiter, S. D. Sung, Adv. Synth. Catal. 2006, 348, 1352.
Nanocatalysis

33
 Nanoparticles and Superparamagnetic
Nanoparticles

difficult to remove/recover

34
F. Glorius, Catal. Sci. Technol. 2011, 1, 13.
 Superparamagnetic Nanoparticle Catalysis

Fe3O4 are superparamagnetic, thus “recoverable”.

35
L. M. Rossi, Green Chem. 2014, 16, 2906.
 Superparamagnetic Nanoparticle Catalysis

36
F. Glorius, Angew. Chem. Int. Ed. 2010, 49, 7786.
 Superparamagnetic Nanoparticle Catalysis

37
L. M. Rossi, App. Catal. A: Gen. 2008, 338, 52.
Biocatalysis

Stereoselective! 38
Biocatalysis

39
 Biocatalysis

40
F. Rudoff, Green Chem. 2017, 19, 367.
 Biocatalysis

treatment of
diabetes mellitus type 2

41
C. K. Savile, J. M. Janey, Science 2010, 329, 305.
 Concurrent Tandem Catalysis (CTC)

42
G. C. Bazan, Chem. Rev. 2005, 105, 1001.
 Concurrent Tandem Catalysis

43
Z.-B. Han, Inorg. Chem. 2018, 57, 2193.
 Concurrent Tandem Catalysis
Conversion of glucose to hydroxymethylfurfural

Hydrogenation of CO2 to methanol

T. L. Lohr, T. J. Marks, Nature Chem. 2015, 7, 477. 44