3.4 Photocatalytic Production of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
4 Carbon Dioxide Reduction Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.1 Structural Models of CODHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.2 Functional Models of CODH: Molecular Electrocatalysts for Reduction of CO 2
to CO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
5 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
Abbreviations
adt
Bn
(SCH 2 ) 2 NBn
bdt
benzene-1,2-dithiolate
bpy
bipyridyl
CB
conduction band
CODH
carbon monoxide dehydrogenase
Cy
cyclohexyl
DFT
density functional theory
dmg
dimethylgloxime
dppe
1,2-bis(diphenylphosphino)ethane
dppf
1,1
0 -bis(diphenylphosphino)ferrocene
dppv
cis-1,2-bis(diphenylphosphino)ethylene
EXAFS
Extended X-ray Absorption Fine Structure
FDH
formate dehydrogenase
Gly
glycine
HER
hydrogen evolution reaction
HOMO
highest occupied molecular orbital
LUMO
lowest unoccupied molecular orbital
MeCN
acetonitrile
pdt
1,3-propanedithiol
PFc
*Et
2
Et 2 PCH 2 C 5 Me 4 FeCp*
P
R N
Ph
2
1,5-diaza-3,7-diphosphaoctane
RHE
reversible hydrogen electrode
TD-DFT time-dependent density functional theory
TFA
trifluoroacetic acid
VB
valence band
1 Introduction
Enzymes have long been known to be efficient catalysts [1–3]. In particular, they
are admired for selectivity, fast rates, and low activation energies. When considering applications that require sustainability and scalability, enzymes also have the
advantage of being constructed exclusively from earth-abundant, bioavailable
materials. Thus metalloenzymes typically employ only earth-abundant metals
234
L. Gan et al.
4 Carbon Dioxide Reduction Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.1 Structural Models of CODHs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.2 Functional Models of CODH: Molecular Electrocatalysts for Reduction of CO 2
to CO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
5 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
Abbreviations
adt
Bn
(SCH 2 ) 2 NBn
bdt
benzene-1,2-dithiolate
bpy
bipyridyl
CB
conduction band
CODH
carbon monoxide dehydrogenase
Cy
cyclohexyl
DFT
density functional theory
dmg
dimethylgloxime
dppe
1,2-bis(diphenylphosphino)ethane
dppf
1,1
0 -bis(diphenylphosphino)ferrocene
dppv
cis-1,2-bis(diphenylphosphino)ethylene
EXAFS
Extended X-ray Absorption Fine Structure
FDH
formate dehydrogenase
Gly
glycine
HER
hydrogen evolution reaction
HOMO
highest occupied molecular orbital
LUMO
lowest unoccupied molecular orbital
MeCN
acetonitrile
pdt
1,3-propanedithiol
PFc
*Et
2
Et 2 PCH 2 C 5 Me 4 FeCp*
P
R N
Ph
2
1,5-diaza-3,7-diphosphaoctane
RHE
reversible hydrogen electrode
TD-DFT time-dependent density functional theory
TFA
trifluoroacetic acid
VB
valence band
1 Introduction
Enzymes have long been known to be efficient catalysts [1–3]. In particular, they
are admired for selectivity, fast rates, and low activation energies. When considering applications that require sustainability and scalability, enzymes also have the
advantage of being constructed exclusively from earth-abundant, bioavailable
materials. Thus metalloenzymes typically employ only earth-abundant metals
234
L. Gan et al.