The Petrochemical Industry: A 20th Century Success Story

fuel

InterestingMaterials

Catalysis Enabling 21st Century E2

Catalysis

Energy

Environment

Reactions of chlorine oxyanions Biomass conversion Kinetics of olefin polymerization

Perchlorate: Rocket Science

Cl OO

O-

O

Interferes with the functioning of the thyroid.

Rocket fuel, missiles, and fireworks.

Water Contaminant

Uses Toxicity

Peter Waldman, The Wall Street Journal- Online (WSJ.com), December 16, 2002.

Reduction Via Oxygen Atom Transfer (OAT)

O

NOReO

ON

O

Solv

O

ClO

OO R

SR4 Cl- R

SR4

O

O

NOReO

ON

O

OH2

O

ClO

OO

RS

RR

SR

O

ReO OO

N NOO

O

O

ClO O

f ast

rds

Abu-Omar, Chem. Comm. 2003, 2102.Abu-Omar et al Inorg. Chem. 2004, 43, 4036.

Mechanism

John Shapley (UICU)

Environ. Sci. Tech. 2007, 41, 2044.

Perchlorate-Reducing Bacteria (PRB)

Coates et al, Nature Reviews Microbiology 2005, 2, 596.

1-1000 per g soil or water

Fe

Chlorite Dismutase

Cl- + O2

ClO2-ClO4

-

ClO2-

Fe

Perchlorate Reductase

Pcr B Pcr A

Pcr DPcr C

Cytoplasm

Periplasm

Organic carbon

CO2 + H2O

ClO3-

e -

Chlorite Dismutase

ClO2- O2 + Cl -

• Homotetramer, 100 -120 kDa• 1 heme b per monomer• Histidine ligated heme • No sequence homology with other proteins• Km ~ 215 µM• kcat ~ 7500 s-1

• kcat/Km = 3.5 x 107 M-1s-1

N

NN

N

COOHHOOC

FeFeIII

ClO2-

Cl-

ClO3-

HPO42- Compound Ci

mM

C∞ Recovery % Yield

O2 0 4.6 mL 4.6 mL 41

Cl- 2.8 25.7 mM 22.9 mM 49

ClO3- 1.6 1.4 mM 0 0

ClO2- 46.7 26.4 mM 26.4 mM 51

ClO2- cld O2 + Cl-

85 nM

0.050 M

MikeAmanda

19th Century mass spectrometry

MASS ANALYSER

Stirred not shaken

Carrier gas(N2)

Inject catalyst

Isotope Labeling

ClO2- Cld

H218O

O2 + Cl-

16O2

N2H2ON

H2

No incorporation of 18O from H2

18O into O2 product

log

inte

nsity

Both O atoms in the evolved O2derive from chlorite

Cl18O2- Cld

H2O O2 + Cl-

77%

ClO2_enriched_18O_2 #115-139 RT: 0.68-0.83 AV: 25 NL: 2.39E2T: ITMS - p ESI Full ms [50.00-100.00]

50 55 60 65 70 75 80 85 90 95 100m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

71

93

69

95

7353

9985

5589 9779

816751

8775 9177

Cl18O2-

Cross Over Experiment

O2

OO

O2

Freeze-Quench EPR

FeIII

NHis

(OH2)

heme bClO2

-

HN

NNH

N

COOHHOOC

FeIV

NHis

O

heme b FeIV

NHis

O

heme b

TrpH

a

b

c

b-c

Sim.

Mechanistic Insight

FeIII

NHis

ClO2-

FeIV

NHis

O

O Cl

FeIII

NHis

OO Cl

Cl- + O2

kr ~ 107 s-1

OH2

FeIII

NHis

O OCl

FeIV

NHis

O

Trp189k2 = 170 s-1

Deactivation

Proc. Natl. Acad. Sci. USA 2008, 105, 15654–15659.

Structural Confirmation

Daniël C. de Geus et al J. Mol. Biol. 2009, 387, 192-206.

• “The heme active-site pocket is solvent accessible both from the inside and the outside of the ring. Moreover, a second anion binding site that could accommodate the assumed reaction intermediate ClO‾ for further transformation has been identified near the active site.The current crystal structure confirms and complements a recently proposed catalytic mechanism that proceeds via a ferryl species and a ClO‾ anion.”

•Azospira oryzae Cld

Density Functional Theory

With Derat, Submitted for publication.

QM/MMB3LYP

ClO2-

Fe(Por)1 mol%pH = 7.1H2O

O2 + Cl- + ClO3-

First Generation Cld Model Complexes

N

NN

N

Ar

Ar

ArAr Fe

[Fe(TF4TMAP)]5+[OTf-]5

[Na+]3[Fe(TPPS)]3-

[Fe(TMAP)]5+[Cl-]5 NMe3

NMe3

F F

FF

SO3

Ar =

Ar =

Ar =

20 – 30%

Catalysis via Two Pathways

Angew. Chem. Int. Ed. 2008, 47, 7697-7700.Inorg. Chem. 2009, 48, 2260-68.

Mn versus Fe pH = 5.0

TOF = 670 h-1

ClO2-

Cl-

ClO3-

Scott

ClO2 gas even at pH 7

Mechanism

Angew. Chem. Int. Ed. 2011, 50, 699.

Groves Angew. Chem. Int. Ed. 2011, 50, 695.

Global Energy Consumption

0

5

10

15

20

25

30

35

40

Oil Coal Gas Nuclear HydroRenew

% G

loba

l prim

ary

ener

gy c

onsu

mpt

ion

BP Energy Year in Review

Planes, Trains, & Automobiles

US Oil Imports in 2009

Country/Region Million tons Percent (%)

South America 119 19

Middle East 120 19Canada 122 20

Mexico 65 11Norway 43 7Africa 124 20Old Russia 24 4Total 617 100

But Where is the Proven Oil Reserves

Proven Oil Reserves

Country Reserves (109 bbl)

Saudi Arabia 260Canada 179Iraq 115Iran 105Kuwait 99UAE 97Venezuela 80Russia 60Libya 42Nigeria 36U.S. 21

5 out of the top 6 countries are in the Middle East.

The agronomic footprint of biofuel feedstock to displace 30% gasoline by 2030 with ethanol

Biological conversion of biomass to biofuel

Phenylpropanoid metabolism is critical for plant survival

http://givingspace.org/benlomond/up%20redwoods.jpg

Hatfield and Vermerris Plant Physiol. 2001, 126, 1351-1357.

• UV resistance• structural support• water transport

wild type

ref3-1

Catalytic Conversion Processes

Apply and optimize catalytic transformations to a range of biomass components and genetic variants.

Biomass

HydrocarbonLiquid Fuels

f ast hydropyrolysis polysaccharides

lignin componentsfururals

biomass-derived compounds

High-ValueOrganics

Controlling reaction selectivity towards hydrolysis and dehydration vs degradation critical to biofuel production

Leaving lignin unmodified

O

R

OH

OH OO

R

OH

HO O

n

R: -CH2OH Cellulose

R: -OH Hemicellulose

HydrolysisO

H

HO

H

HO

H

H

OHH

R

OH

Degradation

O

O

H

R

R: -CH2OH

R: -H

HMF

FurfuralR: -CH2OH

R: -OH

Glucose

XyloseR: - CH2OH CelluloseR: - OH Hemicellulose

R: - CH2OH GlucoseR: - OH Xylose

R: - CH2OH HMFR: - H Furfural

Hydrolysis Dehydration

Simple Sugars AldehydesCellulosic Biomass

H+ H+

The Acid Route Dilemma

Unusable “Tar”

Degradation

Selective Hydrolysis and Conversion

OOH

OHO

OHO

HO OH

OH

170 °C, 10 min+

Biomass Lignin & CelluloseXylose

filterAcid catalyst~200 °C, 4 min

OO

With Prof. Nate Mosier

furfural> 80% yield

Eurick & Shuo

> 90% yield

Pd/C~ 10 min

Me-THF

O

Biomass variants

Biomass Glucan

(Cellulose)

Xylan

(Hemi-cellulose)

Other Structural Carbo-hydrates

Lignin Extractives Other

(Ash, protein, etc.)

Switchgrass 35% 21% 3% 20% 10% 11%

Lodgepole Pine 25% 18% 2% 28% 12% 15%

Hybrid Poplar 45% 18% 4% 21% 8% 4%

One-pot furfural from biomass

Sample Reagent/ Catalyst T (@ 200 °C)/ min

Xylose % conversion

% Yield furfural

Pure xylose (10 g/L)

ZnCl2

Maleic acid

Maleic acid + ZnCl2

H2SO4

10

10

10

5

100

100

100

100

50

90

90

65

Switchgrass Maleic acid

Maleic acid + ZnCl2

H2SO4

10

10

5

100

100

100

85

80

55

Poplar Maleic acid

Maleic acid + ZnCl2

H2SO4

10

10

5

55

100

100

93

85

57

Pine Maleic acid + ZnCl2

H2SO4

10

5

100

97

53

34

Tandem hydrogenation of acetal products from Ff

Ether hydrocarbon products including isomers

GC1H NMR

Cyclic ethers

O O

HOH

OHHO O

O

O

O

O

O

O

O

OHOH

OH OH

O O

OO

Lewis Acid Cat.neat, 100 oC

Pd/CH2 (500 psi)room temp.

O

OO

OO O

Lignin Structure

O

O OH

OH

O

O

O

OH

OH

OH

OO

OH

HO

OH

O

O

OOH

OHO

O

OH

O

OH

O

OH

OH

O

OH

O

O

OH

OO

OH

OH

O

OH

OH

OH

Hardwood lignin

Sinapyl alcohol conifryl alcohol p-coumaryl alcohol

• UV resistance• structural support• water transport

0

200

400

600

800

1000

1200

1400

4 8 12 16 20

pA

Time (min)

Vanillyl Alcohol (a lignin monomer model)

OH

O

OH

O

O

OH

~63%

~23%

~7%

~7%

Trenton

HO

OOH

1 mol% MTO/Pd/C300 psi H2, 150 oC

THF, 2 h

0

500

1000

1500

2000

4 8 12 16 20

pA

Time (min)

Preserving the aromatic group!

OH

O

BHT

>99%

HO

OOH

1 mol% Zn/Pd/C300 psi H2, 150 oC

THF, 2 h

0 5 10 15 20 25

pA

time (s)

Lignin dimer

BHT

OH

O

OH

O

OH

O

OH

O

O

HO

1 mol% Zn/Pd/C300 psi H2, 150 oC

THF, 2 hlignin dimer

MS of oak lignin

400 800 1200 1600 2000

inte

nsity

m/z

With Profs. Joe Bozell and Hilkka Kenttämaa

Degradation of oak lignin

400 800 1200 1600 2000

inte

nsity

m/z

195

297

427

1 mol% Zn/Pd/C300 psi H2, 200 oC

THF, 2 hOak lignin

Degradation of oak lignin

0

20

40

60

80

100

400 800 1200 1600 2000

rela

tive

inte

nsity

m/z

195

297

427

Tailored biomass

With Clint Chapple

Acknowledgments Postdocs

Dr. Michael Zdilla Dr. Trenton Parsell

Graduate Students Dr. Amanda Lee Dr. Jennifer Petersen Scott Hicks Dr. Jeanette Zeigler Andrew Evans Ben Wegenhart Shuo Liu

Collaborators Jennifer DuBois (Cld, Notre Dame) Etienne Derat (DFT, Paris VI) Hilkka Kenttämaa (MS on lignin,

Purdue) Joe Bozell (Lignin samples, UT) Clint Chapple (Engineered biomass,

Purdue) $upport

The National Science Foundation (ClO2

- chemistry) DOE-BES-EFRC (Biomass

conversion)