1. coal, biomass, CH4, (CHxOy) = X
Catalytic Routes for C-H Bond Activation in Light Paraffins
Cathy Chin
Kazu Takanabe
Olefins,
aromatics,
H2 …
C-H activation
and conversion
olefins
paraffins,
alcohols
gasoline
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

2. coal, biomass, CH4, (CHxOy) = X
C-C Bond Formation: Homologation, Carbonylation,
and COx Hydrogenation
Brett Loveless
Carlo Visconti
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
John Ahn
Dante
Simonetti
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

3. coal, biomass, CH4, (CHxOy) = X
C-C Bond Formation: Homologation, Carbonylation,
and COx Hydrogenation
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
Maria E. Sad
De Chen
Eva Diaz
Konstantinos Goulas
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
removing O with C instead of H
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

4. coal, biomass, CH4, (CHxOy) = X
C-C Bond Formation: Homologation, Carbonylation,
and COx Hydrogenation
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
Matt Neurock, et al.
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
removing O with C instead of H
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

5. Catalytic Routes for Conversion of “X” and its Intermediates
Premises and Context:
a shift to X = (CHxOy) with low H/(C,O) ratios … imbalance in
feedstocks vs. products
synthesis gas and its first products (e.g. CH3OH/DME) as intermediates
upgrading of by-products from X and syngas conversion
Proposed Catalytic Strategies:
C-H bond activation in alkanes (Takanabe, Chin)
C-C bond formation in conversion of synthesis gas
and homologation/carbonylation of oxygenates
(Ahn, Loveless, Simonetti)
Selective removal of oxygen by carbon/CO
instead of hydrogen (Sad, Diaz, Chen, Goulas)
A ten year program with emphasis on fundamental chemistries underlying relevant catalysis

6. Selective Removal of O by C instead of H
Premises and Context:
……….. feedstocks and streams have low H/(C,O) ratios … a problem
best addressed by reacting C and O
CO/H2O mixtures as sources of “H” CO O*
H2O O* O* O* O*
… concentrated
… but unavoidable
CO2 H* O* H2 H*
Selective removal of oxygen using carbon monoxide instead of hydrogen
This is a new research thrust in which we pose and propose to address broad and fundamental questions about how oxygen atoms within molecules can be removed via (i) intermolecular reactions with CO or ii) reactions of C-atoms within oxygenates or within co-reactant molecules. These activities reflect the premise that X-to-liquids scenarios are evolving into H-poorer and C/O-richer contexts, as coal and biomass are increasingly introduced into carbon feedstock pools; they also reflect an expected benefit of forming concentrated CO2 streams, for conversion or sequestration purpose, in the economics of conversion processes within carbon-constrained scenarios. We stress that forming CO2 is unavoidable for the conversion of these H-deficient feedstock pools, whether by the selective use of excess C and CO directly or indirectly or by the production of H2 required for stoichiometric balance via endothermic gasification of carbon-rich feedstocks.
One component of the proposed research addresses the use of CO to extract oxygen from H2O with H2 as the desired by-product, a process that in its conventional catalytic context is known as the water-gas shift reaction. Our initial studies will address the mechanism for this reaction –widely studied but yet unclear- and the specific role of O2-assisted pathways in increasing rates and improving the thermodynamics of H2 generation from CO/H2O mixtures. We propose to then transfer these insights and knowledge into novel strategies for the removal of oxygen and/or the in situ regeneration of H2. Some of these proposed strategies are:
in-situ formation of H2 or hydrogen-rich transfer species from H2O/CO mixtures during the upgrading of molecules with high C or O content derived from coal or biomass
direct use of CO to remove oxygen from biomass-derived oxygenates (e.g. glycerol, carbohydrates) and the use of C atoms within these molecules (instead of their H atoms) to remove excess oxygen while preserving hydrogen
use of CO to remove O directly or to form H2 in situ during methanol/DME homologation via direct routes or intervening water-gas shift pathways
exploit redox water-gas shift routes by decoupling these elementary steps into thermochemical cycles that form separate high-purity H2 and CO2 streams via temporal cycling of H2O and CO reactants
direct or indirect (via in situ water-gas shift) reactions of CO with excess O atoms in coal of lignite origin
These projects share a need for precise understanding of the catalyst requirements and pathways by which O atoms are removed intermolecularly and intramolecularly by carbon versus hydrogen active species Our previous elucidation of the mechanism and site requirements for selective oxidation of CO in the presence of excess H2 and for removal of H2 via selective reaction with O2 during alkane dehydrogenation have led to precedents for our ability to design catalysts to control the selectivity of oxygen removal. Our on-going collaborations with Matt Neurock in theoretical studies of reactions of chemisorbed oxygen with diverse reactants provide also essential foundations for rapid progress in an area critical to address the severe H/C/O imbalances prevalent in conversion scenarios tackling alternate sources of carbon. O*
“CHxOy”
catalytic water-gas shift (or the thermochemical cycle analogs)
in situ generation of “H” during upgrading of aromatics
and oxygenates (methanol/DME/biomass/glycerol)

7. Selective Removal of O by C instead of H
Premise and Context:
……….. feedstocks and streams have low H/(C,O) ratios … a problem
best addressed by reacting C and O
“Direct” Reactions of CO with O CO O* O* O* O* O*
Selective removal of oxygen using carbon monoxide instead of hydrogen
This is a new research thrust in which we pose and propose to address broad and fundamental questions about how oxygen atoms within molecules can be removed via (i) intermolecular reactions with CO or ii) reactions of C-atoms within oxygenates or within co-reactant molecules. These activities reflect the premise that X-to-liquids scenarios are evolving into H-poorer and C/O-richer contexts, as coal and biomass are increasingly introduced into carbon feedstock pools; they also reflect an expected benefit of forming concentrated CO2 streams, for conversion or sequestration purpose, in the economics of conversion processes within carbon-constrained scenarios. We stress that forming CO2 is unavoidable for the conversion of these H-deficient feedstock pools, whether by the selective use of excess C and CO directly or indirectly or by the production of H2 required for stoichiometric balance via endothermic gasification of carbon-rich feedstocks.
One component of the proposed research addresses the use of CO to extract oxygen from H2O with H2 as the desired by-product, a process that in its conventional catalytic context is known as the water-gas shift reaction. Our initial studies will address the mechanism for this reaction –widely studied but yet unclear- and the specific role of O2-assisted pathways in increasing rates and improving the thermodynamics of H2 generation from CO/H2O mixtures. We propose to then transfer these insights and knowledge into novel strategies for the removal of oxygen and/or the in situ regeneration of H2. Some of these proposed strategies are:
in-situ formation of H2 or hydrogen-rich transfer species from H2O/CO mixtures during the upgrading of molecules with high C or O content derived from coal or biomass
direct use of CO to remove oxygen from biomass-derived oxygenates (e.g. glycerol, carbohydrates) and the use of C atoms within these molecules (instead of their H atoms) to remove excess oxygen while preserving hydrogen
use of CO to remove O directly or to form H2 in situ during methanol/DME homologation via direct routes or intervening water-gas shift pathways
exploit redox water-gas shift routes by decoupling these elementary steps into thermochemical cycles that form separate high-purity H2 and CO2 streams via temporal cycling of H2O and CO reactants
direct or indirect (via in situ water-gas shift) reactions of CO with excess O atoms in coal of lignite origin
These projects share a need for precise understanding of the catalyst requirements and pathways by which O atoms are removed intermolecularly and intramolecularly by carbon versus hydrogen active species Our previous elucidation of the mechanism and site requirements for selective oxidation of CO in the presence of excess H2 and for removal of H2 via selective reaction with O2 during alkane dehydrogenation have led to precedents for our ability to design catalysts to control the selectivity of oxygen removal. Our on-going collaborations with Matt Neurock in theoretical studies of reactions of chemisorbed oxygen with diverse reactants provide also essential foundations for rapid progress in an area critical to address the severe H/C/O imbalances prevalent in conversion scenarios tackling alternate sources of carbon.
CO2 H* O*
-(CHx)- H* O*
“CHxOy”

8. Selective Removal of O by C instead of H
Premise and Context:
……….. feedstocks and streams have low H/(C,O) ratios … a problem
best addressed by reacting C and O O* O* O* O* O*
CO2 H* O*
-(CHx)- H* O*
Selective removal of oxygen using carbon monoxide instead of hydrogen
This is a new research thrust in which we pose and propose to address broad and fundamental questions about how oxygen atoms within molecules can be removed via (i) intermolecular reactions with CO or ii) reactions of C-atoms within oxygenates or within co-reactant molecules. These activities reflect the premise that X-to-liquids scenarios are evolving into H-poorer and C/O-richer contexts, as coal and biomass are increasingly introduced into carbon feedstock pools; they also reflect an expected benefit of forming concentrated CO2 streams, for conversion or sequestration purpose, in the economics of conversion processes within carbon-constrained scenarios. We stress that forming CO2 is unavoidable for the conversion of these H-deficient feedstock pools, whether by the selective use of excess C and CO directly or indirectly or by the production of H2 required for stoichiometric balance via endothermic gasification of carbon-rich feedstocks.
One component of the proposed research addresses the use of CO to extract oxygen from H2O with H2 as the desired by-product, a process that in its conventional catalytic context is known as the water-gas shift reaction. Our initial studies will address the mechanism for this reaction –widely studied but yet unclear- and the specific role of O2-assisted pathways in increasing rates and improving the thermodynamics of H2 generation from CO/H2O mixtures. We propose to then transfer these insights and knowledge into novel strategies for the removal of oxygen and/or the in situ regeneration of H2. Some of these proposed strategies are:
in-situ formation of H2 or hydrogen-rich transfer species from H2O/CO mixtures during the upgrading of molecules with high C or O content derived from coal or biomass
direct use of CO to remove oxygen from biomass-derived oxygenates (e.g. glycerol, carbohydrates) and the use of C atoms within these molecules (instead of their H atoms) to remove excess oxygen while preserving hydrogen
use of CO to remove O directly or to form H2 in situ during methanol/DME homologation via direct routes or intervening water-gas shift pathways
exploit redox water-gas shift routes by decoupling these elementary steps into thermochemical cycles that form separate high-purity H2 and CO2 streams via temporal cycling of H2O and CO reactants
direct or indirect (via in situ water-gas shift) reactions of CO with excess O atoms in coal of lignite origin
These projects share a need for precise understanding of the catalyst requirements and pathways by which O atoms are removed intermolecularly and intramolecularly by carbon versus hydrogen active species Our previous elucidation of the mechanism and site requirements for selective oxidation of CO in the presence of excess H2 and for removal of H2 via selective reaction with O2 during alkane dehydrogenation have led to precedents for our ability to design catalysts to control the selectivity of oxygen removal. Our on-going collaborations with Matt Neurock in theoretical studies of reactions of chemisorbed oxygen with diverse reactants provide also essential foundations for rapid progress in an area critical to address the severe H/C/O imbalances prevalent in conversion scenarios tackling alternate sources of carbon.
“CHxOy”
…… or intramolecular reactions of C with O in CHxOy
……… carbohydrates are “containers” for C + H2O

9. Selective Removal of O by C instead of H
Premises and Context:
……….. feedstocks and streams have low H/(C,O) ratios … a problem
best address by reacting C and O
Hydrogenation/Oxygen Scavenging O* O* H2
CO/H2O CO
none O* O* O* H* O*
-(CHx)- H*
Selective removal of oxygen using carbon monoxide instead of hydrogen
This is a new research thrust in which we pose and propose to address broad and fundamental questions about how oxygen atoms within molecules can be removed via (i) intermolecular reactions with CO or ii) reactions of C-atoms within oxygenates or within co-reactant molecules. These activities reflect the premise that X-to-liquids scenarios are evolving into H-poorer and C/O-richer contexts, as coal and biomass are increasingly introduced into carbon feedstock pools; they also reflect an expected benefit of forming concentrated CO2 streams, for conversion or sequestration purpose, in the economics of conversion processes within carbon-constrained scenarios. We stress that forming CO2 is unavoidable for the conversion of these H-deficient feedstock pools, whether by the selective use of excess C and CO directly or indirectly or by the production of H2 required for stoichiometric balance via endothermic gasification of carbon-rich feedstocks.
One component of the proposed research addresses the use of CO to extract oxygen from H2O with H2 as the desired by-product, a process that in its conventional catalytic context is known as the water-gas shift reaction. Our initial studies will address the mechanism for this reaction –widely studied but yet unclear- and the specific role of O2-assisted pathways in increasing rates and improving the thermodynamics of H2 generation from CO/H2O mixtures. We propose to then transfer these insights and knowledge into novel strategies for the removal of oxygen and/or the in situ regeneration of H2. Some of these proposed strategies are:
in-situ formation of H2 or hydrogen-rich transfer species from H2O/CO mixtures during the upgrading of molecules with high C or O content derived from coal or biomass
direct use of CO to remove oxygen from biomass-derived oxygenates (e.g. glycerol, carbohydrates) and the use of C atoms within these molecules (instead of their H atoms) to remove excess oxygen while preserving hydrogen
use of CO to remove O directly or to form H2 in situ during methanol/DME homologation via direct routes or intervening water-gas shift pathways
exploit redox water-gas shift routes by decoupling these elementary steps into thermochemical cycles that form separate high-purity H2 and CO2 streams via temporal cycling of H2O and CO reactants
direct or indirect (via in situ water-gas shift) reactions of CO with excess O atoms in coal of lignite origin
These projects share a need for precise understanding of the catalyst requirements and pathways by which O atoms are removed intermolecularly and intramolecularly by carbon versus hydrogen active species Our previous elucidation of the mechanism and site requirements for selective oxidation of CO in the presence of excess H2 and for removal of H2 via selective reaction with O2 during alkane dehydrogenation have led to precedents for our ability to design catalysts to control the selectivity of oxygen removal. Our on-going collaborations with Matt Neurock in theoretical studies of reactions of chemisorbed oxygen with diverse reactants provide also essential foundations for rapid progress in an area critical to address the severe H/C/O imbalances prevalent in conversion scenarios tackling alternate sources of carbon. O*
“CHxOy”
……… carbohydrates are “containers” for C + H2O

10. coal, biomass, CH4, (CHxOy) = X
Catalytic Routes for “X” and Methanol/DME Conversion
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
CH3OH/DME carbonylation
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
removing O with C instead of H
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

11. coal, biomass, CH4, (CHxOy) = X
Collaborations with Matt Neurock (UVa): Existing and Planned
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Guidance from theory:
Active site structures and
reaction pathways
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
CH3OH/DME carbonylation
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
removing O with C instead of H
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..

12. coal, biomass, CH4, (CHxOy) = X
Planned Collaborations with Mark Davis (Caltech)
Olefins,
aromatics,
H2 …
C-H activation
and conversion
COx hydrogenation
olefins
methanol/DME
homologation
paraffins,
alcohols
gasoline
Synthesis and
characterization of
micropororous solids
Forming
C-C bonds
CH3OH
DME
(CH3O)2CO
(DMC)
CH3OH/DME carbonylation
HCHO
CH3OCH2OCH3
(DMM)
HCOOCH3
(MF)
oxygenates, ...
removing O with C instead of H
Synthesis gas (CO/H2)
coal, biomass, CH4, (CHxOy) = X
Olefins, aromatics,..