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SYN
CH
RO
TRO
N R
AD
IATI
ON
FO
R E
LUC
IDA
TIN
G
STR
UC
TUR
ES O
F C
ATA
LYST
S
NA
NO
PO
RO
US
CA
TALY
TIC
MA
TER
IALS
–SY
NTH
ESIS
, C
HA
RA
CTE
RIS
ATI
ON
AN
D C
ATA
LYTI
C P
RO
PER
TIES
GO
PIN
ATH
AN
SA
NK
AR
DA
VY F
AR
AD
AY
RES
EAR
CH
LA
BO
RA
TOR
YTH
E R
OYA
L IN
STIT
UTI
ON
OF
GB
21 A
LBEM
AR
LE S
TREE
TLO
ND
ON
W1S
4B
S ICM
R –
JNC
WIN
TER
SC
HO
OL
OU
T LI
NE
•C
ATA
LYSI
S A
ND
CA
TALY
TIC
M
ATE
RIA
LS•
CH
AR
AC
TER
ISA
TIO
N B
Y X-
RA
Y TE
CH
NIQ
UES
–SY
NC
HR
OTR
ON
R
AD
IATI
ON
•ST
RU
CTU
RE
–C
ATA
LYTI
C P
RO
PER
TY
REL
ATI
ON
SHIP
S
Func
tiona
l mat
eria
ls
Bio
-m
ater
ials
Elec
tron
ic a
nd
Mag
netic
m
ater
ials
Opt
ical
Mat
eria
lsPo
lym
eric
mat
eria
ls
Am
orph
ous
mat
eria
ls
Nan
om
ater
ials
Cat
alyt
ic
Mat
eria
ls
Solid
-sta
te m
ater
ials
•80%
of p
roce
sses
in th
e ch
emic
al
indu
stry
use
cat
alys
ts.
•Cat
alys
t sal
es in
200
4 w
ere
wor
th
betw
een
8 an
d 10
mill
ion
dolla
rs.
•Gro
wth
in c
atal
yst s
ales
is in
crea
sing
at
bet
wee
n 5%
and
10%
per
yea
r.
•Tur
nove
r in
indu
stri
es u
sing
cat
alys
ts
was
abo
ut 1
4 tr
illio
n do
llars
whi
ch is
eq
ual t
o th
e gr
oss d
omes
tic p
rodu
ct o
f It
aly.
CA
TALY
SIS
SO
ME
MIL
E S
TON
ES
IN T
HE
20
TH C
EN
TUR
Y•
1900
-M
ETH
AN
E FR
OM
CO
+H2
-Ni C
ATA
LYST
S•
1910
-A
MM
ON
IA S
YNTH
ESIS
•19
36 –
CA
TALY
TIC
CR
AC
KIN
G O
F PE
TRO
LEU
M•
1950
-PO
LYM
ERIS
ATI
ON
OF
ETH
YLEN
E TO
PO
LYET
HYL
ENE
ZIEG
LER
-NA
TA, P
HIL
IPS
PRO
CES
S et
c•
1970
-M
ETH
AN
OL
FRO
M C
O +
H2
-Cu/
ZnO
; USE
OF
H-
ZSM
5 FO
R IS
OM
ERIS
ATI
ON
, DEW
AXI
NG
etc
.; A
UTO
-EX
HA
UST
CA
TALY
STS
BA
SED
ON
Pt-R
h-Pd
ON
OXI
DES
•19
72 -
PHO
TOC
ATA
LYSI
S –
TITA
NIA
FO
R W
ATE
R
SPLI
TTIN
G•
1980
-M
ETH
AN
OL
TO G
ASO
LIN
E -H
-ZSM
5•
1990
-O
XID
ATI
ON
OF
ALK
ENES
-TI
TAN
IUM
SIL
ICA
LITE
Am
mon
ia S
ynth
esis
–th
e im
porta
nce
100
80 60 40 20 019
7519
5019
2519
000123456
Worldpopulation (billions)
Consumptionofnitrogen fertilizer(megaton)
Year
Hab
er &
Bos
ch
CA
TALY
SIS
AN
D D
AIL
Y L
IFE
Bul
k or
gani
c ch
emic
als
influ
ence
our
dai
ly li
fe to
an
exte
nt th
at m
ay
go b
eyon
d ou
r sim
ple,
eve
ryda
y co
mpr
ehen
sion
. Th
ey h
ave
been
, and
will
con
tinue
to b
e, e
ssen
tial i
n nu
mer
ous
appl
icat
ions
that
are
indi
spen
sabl
e to
enh
ance
qua
lity
of li
fe a
nd
soci
ety.
Th
ey to
uch
alm
ost e
very
phy
sica
l asp
ect o
f it,
e.g.
in c
loth
es, c
ars,
co
nstr
uctio
n m
ater
ials
, pai
nts,
car
pets
, ele
ctric
al a
pplia
nces
, de
terg
ents
, sol
vent
s, fu
rnitu
re, e
tc.
Qua
ntum
leap
in c
atal
ytic
effe
ctiv
enes
s ai
ms
to d
evel
op n
ovel
pr
oces
ses
or to
sub
stan
tially
impr
ove
exis
ting
proc
esse
s in
term
s of
ene
rgy
and
raw
mat
eria
ls u
tilis
atio
n, th
eref
ore,
mak
ing
prog
ress
to
a m
ore
sust
aina
ble
bulk
che
mic
al in
dust
ry in
the
med
ium
tim
e fr
ame.
C
hem
istr
y In
tens
ifica
tion
CA
TALY
SIS
–C
UR
REN
T K
EY
AR
EAS
•EN
ERG
YH
YDR
OG
EN P
RO
DU
CTI
ON
(SPL
ITTI
NG
OF
WA
TER
-PH
OTO
C
ATA
LYSI
S)H
YDR
OG
EN S
TOR
AG
E (M
ETA
LS, A
LLO
YS, O
PEN
FR
AM
EWO
RK
MA
TER
IALS
….)
HYD
RO
GEN
TO
EN
ERG
Y(F
UEL
CEL
LS)
•O
RG
AN
IC T
RN
SFO
RM
ATI
ON
SPH
AR
MA
CEU
TIC
AL
PETR
O-C
HEM
ICA
LFI
NE-
CH
EMIC
AL
•C
LEA
N E
NVI
RO
NM
ENT
(CO
NVE
RSI
ON
OF
TOXI
C P
RO
DU
CTS
, UTI
LISA
TIO
N O
F TO
XIC
/GR
EEN
HO
USE
PR
OD
UC
TS)
•IN
SIT
U P
RO
DU
CTI
ON
OF
HA
ZAR
DO
US
INTE
RM
EDIA
TES
(CO
RR
OSI
VE A
ND
TO
XIC
INTE
RM
EDIA
TES)
OR
GA
NIC
TR
AN
SFO
RM
ATI
ON
SA
KEY
AR
EA IN
CA
TALY
SIS
•C
HEM
ICA
L IN
DU
STR
IES
–PO
LYET
HYL
ENE,
PLA
STIC
S,
TEXT
ILES
, FR
AG
RA
NC
E et
c…•
PHA
RM
AC
EUTI
CA
L IN
DU
STR
IES
DR
UG
S, S
PEC
IFIC
ISO
MER
S et
c..
Cat
alys
is F
undam
enta
ls
•St
eps
in c
atal
ytic
reac
tions
1.A
dsor
ptio
n of
reac
tant
s2.
Surf
ace
diffu
sion
of
reac
tant
s3.
Surf
ace
reac
tion
4.Su
rfac
e di
ffusi
on o
f pr
oduc
ts5.
Des
orpt
ion
of p
rodu
cts
•C
atal
ysis
requ
ires
bala
nce
of
adso
rptio
n, re
actio
n, a
nd
deso
rptio
nC
atal
yst s
tron
gly
adso
rbin
g –
–> n
o re
actio
nC
atal
yst w
eakl
y ad
sorb
ing
––>
no re
actio
n
Ads
orpt
ion
CO
O2
Sur
face
diffu
sion
Pre
curs
or
Sur
face
reac
tion
Des
orpt
ion
2C
O
GA
S PH
ASE
RE
AC
TIO
N
Cat
alyt
ic R
eact
ion S
teps
Act
ive
site
O
H2O
2
CA
TA
LY
ST
LIQ
UID
PH
ASE
RE
AC
TIO
N
LIQ
UID
LIQ
UID
LIQ
UID
SOL
ID
H2O
Cat
alyt
ic M
ater
ials
HO
MO
GE
NE
OU
S C
AT
AL
YST
S(E
g. c
obal
t ace
tate
solu
tion
for
cycl
ohex
ane
oxid
atio
n)H
ET
ER
OG
EN
EO
US
CA
TA
LY
STS
SOL
ID-S
TA
TE
MA
TE
RIA
LS
BIS
MU
TH
MO
LY
BD
AT
ES,
VA
NA
DIU
M P
HO
SPH
AT
ES,
IR
ON
PH
OSP
HA
TE
S, A
LL
OY
S e
tc.
MIC
RO
AN
D M
ESO
POR
OU
S C
AT
AL
YST
SZE
OLI
TES,
ALU
MIN
OPH
OSP
HA
TES,
MC
M-4
1 et
c
SUPP
OR
TE
D C
AT
AL
YST
SM
ETA
L C
LUST
ERS
SUPP
OR
TED
ON
HIG
H-S
UR
FAC
E A
REA
CA
RR
IER
S et
c
SO
LID
STA
TE C
ATA
LYS
TSD
EN
SE F
RA
ME
WO
RK
SO
LID
SC
LO
SE-P
AC
KE
D S
TR
UC
TU
RE
S
TY
PIC
AL
EX
AM
PLE
SB
ISM
UT
H M
OL
YB
DA
TE
SV
AN
AD
IUM
PH
OSP
HA
TE
SIR
ON
PH
OSP
HA
TE
SPE
RO
VSK
ITE
S SP
INE
LS
TIT
AN
IA
SEV
ER
AL
OT
HE
RS…
...A
dsor
ptio
nC
OO 2
Pre
curs
or
Sur
face
reac
tion
Des
orpt
io
2C
O
SU
PP
OR
TED
CA
TALS
YTS
SEV
ER
AL
CA
TA
LY
STS
HA
VE
FO
UN
D IN
DU
STR
IAA
L
APP
LIC
AT
ION
-SO
ME
EX
AM
PLE
S
ME
TA
L C
LU
STE
RS
SUPP
OR
TE
D O
N S
ILIC
AO
R A
LU
MIN
A -
HY
DR
OG
EN
AT
ION
RE
AC
TIO
NS
Cr/
SIL
ICA
-PH
ILL
IPS
CA
TA
LSY
TS
FOR
ET
HY
LE
NE
POL
YM
ER
ISA
TIO
N R
EA
CT
ION
S
Co-
Mo/
Al 2O
3-H
YD
RO
DE
SUL
PHU
RIS
AT
ION
CA
TA
LY
ST
OXI
DA
TIO
N O
F C
AR
BO
N M
ON
OXI
DE
ON
SU
PPO
RTE
D G
OLD
NA
NO
PA
RTI
CLE
SFT
-IR s
pect
ra fo
r CO
ads
orpt
ion
at 9
0K o
ver
Au/
TiO
2 ca
lcin
ed in
air
at d
iffer
ent t
empe
ratu
res.
Th
e m
ost a
ctiv
e sa
mpl
e (2
.5 n
m) h
as th
e la
rges
t in
tens
ities
of t
he p
eaka
t211
0~21
20cm
-1, w
hich
ca
n be
ass
igne
d to
CO
line
arly
ads
orbe
d on
the
met
allic
Au
site
s.
Whe
n A
u pa
rtic
les
are
larg
er th
an 1
0 nm
in
diam
eter
the
inte
nsity
of t
his
peak
is m
arke
dly
redu
ced,
indi
catin
g th
at C
O a
dsor
ptio
n m
ay ta
ke
plac
e on
ly o
n st
eps,
edg
es a
nd c
orne
rs o
f Au
part
icle
s, n
ot o
n th
e sm
ooth
sur
face
s.
No
dire
ct e
xper
imen
tal e
vide
nce
has
yet b
een
pres
ente
d w
here
oxy
gen
is a
ctiv
ated
for r
eact
ing
with
CO
ads
orbe
d on
the
Au
surf
aces
, and
w
heth
er th
e ox
ygen
mol
ecul
e is
dis
soci
ativ
ely
or
non-
diss
ocia
tivel
yad
sorb
ed.
Har
uta
and
co-w
orke
rs
1.7n
m M
oS2
PAR
TIC
LES
AR
E PR
ESEN
T O
N T
HE
ALU
MIN
A S
UR
FAC
ED
ECO
RA
TED
BY
CO
BA
LT A
T TH
E ED
GES
AN
D A
NC
HO
R T
HES
E SM
ALL
SULP
HID
ED P
AR
TILC
ES T
O A
LUM
INA
SU
RFA
CE
Wha
t are
thes
e m
icro
poro
us
mat
eria
ls•
Sili
cate
s•
Alu
min
opho
spha
tes
•G
allo
phos
phat
es•
Met
al-O
rgan
ic
Fram
ewor
ks a
nd
rela
ted
syst
ems
AlP
O-5
(7.3
Å) A
LU
MIN
OPH
OPH
AT
E
LA
RG
E P
OR
E
NA
NO
PO
RO
US
MA
TER
ILA
S -
MIC
RO
AN
D M
ESO
PO
RO
US
CA
TALY
STS
AlP
O-5
(7.3
Å) A
LU
MIN
OPH
OPH
AT
E
LA
RG
E P
OR
EM
CM
-41
ME
SOPO
RO
US
SIL
ICA
SMA
LL
POR
EZ
SM-5
M
ED
IUM
PO
RE
(5.3
x5.6
Å)
AL
UM
INO
SIL
ICA
TE
SILI
CA
TES
and
ALU
MIN
OPH
OSP
HA
ES
Me2+
OP5+
H
Mn2+
, Co2+
, Fe2+
etc
RED
OX
CA
TALY
STS
Mn3+
, Co3+
, Fe3+
Si4+
, Ti4+
etc
Al3+
, Ga3+
, Fe3+
Aci
d C
atal
yst
Ti4+
OSi
4+
Ti4+
, V4+
RE
DO
X
CA
TA
LY
ST
Si4+
OSi
4+1.
6
Neu
tral f
ram
ewor
kA
l3+O
p5+1.
73A
1.51
A
Neu
tral f
ram
ewor
k
In 1
756,
the
Swed
ish
min
eral
ogis
t Axe
l Fre
dric
k C
rons
tedt
disc
over
ed th
at st
ilbite
, a n
atur
al
min
eral
,vis
ibly
lost
wat
er w
hen
heat
ed, a
nd h
e na
med
the
clas
s of m
ater
ials
zeo
lites
from
the
clas
sica
l Gre
ek w
ords
mea
ning
'boi
ling
ston
es.'
Zeo
lites
wer
e co
nsid
ered
an
obsc
ure
grou
p of
m
iner
als w
ith u
niqu
e pr
oper
ties f
or a
lmos
t 200
yea
rs, a
nd C
rons
tedt
was
rem
embe
red
prim
arily
fo
r di
scov
erin
g th
e el
emen
t nic
kel.
GA
S SO
RPT
ION
SEPE
RA
TIO
N
cycl
ohex
anon
e+
NH
3
oxim
e +
capr
olac
tam
keto
ne +
be
nzal
dehy
de
lact
one
+ be
nzoi
c ac
id
cycl
ohex
anol
, cy
cloh
exan
one,
ad
ipic
aci
d
cycl
ohex
ane
epox
ide,
dio
l +be
nzoi
c ac
id
alke
ne +
benz
alde
hyde
MA
PO
-36
n-al
kane
sC
ATA
LYSI
S
C3
+ C
2fu
nctio
nalis
edpr
oduc
tsM
=C
o,M
nO
PA
l
ION
-EX
CH
AN
GE
ZEO
LITE
S
HO
W D
O Y
OU
PR
EPA
RE
THEM
?Sy
nth
esis
H3P
O4
+ H
2O
Al(O
H) 3
Me
sour
ce
Tem
plat
e
Fina
l gel
Hyd
roth
erm
alco
nditi
ons
Fina
l cry
stal
s
Cal
cina
tion
Silic
a +
H2O
Me
sour
ce
NaO
H
Tem
plat
e
HO
W D
O Y
OU
KN
OW
YO
U H
AVE
FO
RM
ED A
SP
ECIF
IC M
ATE
RIA
LC
HA
RA
CTE
RIS
ATI
ON
MET
HO
DS
PHO
TOEL
ECTR
ON
SPEC
TRO
SCO
PY
NEU
TRO
N S
CA
TTER
ING
X-R
AY
TEC
HN
IQU
ESX-
RA
Y D
IFFR
AC
TIO
NX-
RA
Y A
BSO
RPT
ION
OPT
ICA
L SP
ECTR
OSC
OPY
UV-
vis,
Ram
an, I
R
Nuc
lear
Mag
netic
Res
onan
ce
(MA
INLY
EX
SITU
, BU
TSO
ME
POSS
IBIL
ITIE
S FO
R IN
SIT
U
MIC
RO
SCO
PY(L
IMIT
ED T
O E
X SI
TU)
CH
AR
AC
TER
ISA
TIO
N
OF
CA
TALY
STS
RE
DO
X C
HE
MIS
TR
Y –
AC
TIV
AT
ION
OF
CH
3G
RO
UP
TE
RM
INA
L O
XID
AT
ION
CoA
lPO
-18
–4%
cob
alt
Oxi
datio
nR
educ
tion
O2
n-H
EXA
HE
XA
NO
IC A
CID
100C
Sin
gle
Cry
stal
X-R
ay D
iffra
ctio
n
Sel
ect s
uita
ble
crys
tal
and
mou
nt it
Obt
ain
Rep
eat’s
Uni
t G
eom
etry
& S
ymm
etry
Mea
sure
Inte
nsity
to d
educ
t at
om ty
pes
& p
ositi
ons
Sol
ve S
truct
ure
with
the
help
of d
ata
colle
cted
Inte
rpre
t the
resu
lts fo
r su
itabi
lity
Ref
ine
the
Stru
ctur
e M
odel
obt
aine
d
010
2030
4050
6070
80
0
1000
2000
3000
4000
5000
6000
INTENSITY
2 TH
ETA
(DE
GR
EE
S)
DA
F-5
(CoA
lPO
) CH
AB
AZI
TE
30µ
Tem
plat
e 4,
Pip
erid
inop
iper
idin
e
Sank
ar, W
yles
, Lew
is, C
atlo
w, a
nd T
hom
as
xy
zU(
eq) Å
2
Al(1
)0.2
3474
-0.00
518
0.597
730.0
1825
Co(1
)0.2
3474
-0.00
518
0.597
730.0
1825
P(1)
0.233
840.0
0325
0.399
550.0
1825
O(1)
0.311
65-0
.0115
00.3
3568
0.059
98
O(2)
0.280
260.0
0083
0.490
920.0
5998
O(3)
0.110
06-0
.0956
80.3
8818
0.059
98
O(4)
0.244
220.1
1391
0.376
520.0
5998
Bond
Dista
nce(Å
)Bo
nd A
ngle
Degr
ees
Al(1
)-O(1
)1.7
2786
(3)
O(1)
-Al(1
)-O(2
)11
0.497
(2)
Al(1
)-O(2
)1.7
6006
(5)
O(1)
-Al(1
)-O(3
)10
5.705
(1)
Al(1
)-O(3
)1.7
9906
(3)
O(1)
-Al(1
)-O(4
)11
0.433
(1)
Al(1
)-O(4
)1.7
1001
(3)
O(2)
-Al(1
)-O(3
)10
7.468
(1)
P(1)
-O(1
)1.5
2946
(3)
O(1)
-P(1
)-O(2
)10
5.874
(2)
P(1)
-O(2
)1.5
6219
(4)
O(1)
-P(1
)-O(3
)10
9.323
(1)
Cob
alt S
ubst
itute
d (in
pla
ce o
f alu
min
ium
) al
umin
opho
spha
te c
atal
ysts
Whe
re a
re C
obal
t ion
s?
Spac
e gr
oup
: R3
X-R
AY
AB
SO
RP
TIO
N
SP
EC
TRO
SC
OP
Y(X
-RA
Y A
BSO
RPT
ION
NEA
R E
DG
E ST
RU
CTU
RE
(XA
NES
) A
ND
EXT
END
ED X
-R
AY
AB
SOR
PTIO
N F
INE
STR
UC
TUR
E (E
XAFS
))
AT
OM
SPE
CIF
IC
DO
ES
NO
T
DE
PEN
D O
N
LO
NG
-RA
NG
E
OR
DE
R
APP
LIC
AB
LE
TO
A
NY
TY
PE O
F SO
LID
S82
0084
0086
0088
0090
0092
0094
00
012345
ln (Io/I)
Ener
gy (e
V)
Pre-
Edge
Edge EX
AFS
X-r
ay a
bsor
ptio
n ne
ar e
dge
stru
ctur
e (X
AN
ES
)
4900
4950
5000
5050
0.00.20.40.60.81.01.2Pr
e-edg
e1s
3d t
ransit
ion
EDGE
Normalised Absorption coefficient
Ener
gy (e
V)
Dip
ole
Sele
ctio
n ru
le∆l
= ±
1
How
1s-
>3d
tran
sitio
n is
allo
wed
?
Inte
nsity
is p
ropo
rtio
nal t
o tr
ansi
tion
prob
abili
ty
And
de
nsity
of u
nocc
upie
d st
ate
1.D
ue to
lack
of s
pher
ical
sy
mm
etry
in te
trah
edra
l coo
rdin
atio
n2.
d0
syst
em3.
p c
hara
cter
on
the
d-st
ate
due
to o
rbita
l mix
ing
In p
artic
ular
whe
n sh
ort o
xyge
n ne
ighb
ours
1s
2p1/
22s3d 3p 3s4p 4s
OX
IDA
TIO
N S
TATE
FR
OM
X
AN
ES
•N
EAR
ED
GE
STR
UC
UTR
E IS
A
PP
RO
PR
IATE
IN
DE
TER
MIN
ING
TH
E
OXI
DA
TIO
N S
TATE
AN
D L
OC
AL
CO
OR
DIN
ATI
ON
G
EOM
ETR
Y49
0049
5050
0050
50
0.00.20.40.60.81.01.2Tit
anium
meta
lTi4+
in
Tetra
hedr
al ge
ometr
y
Ti4+
Normalised Absorption coefficient
Ener
gy (e
V)
4920
4960
5000
5040
5080
Ti-(
OS
i(Ph)
3)4
JDF-
L1
ETS
-10
Normalised Absorption
EN
ER
GY
(eV
)
Ti-O
4
x 1.
79Å
Ti=O
1.7
0Å
Ti-O
4
x 1.
96Å
Ti-O
Dis
tanc
es1
x 1.
73Å
4 x
2.02
Å1
x 2.
11 Å
Si O Ti
Effe
ct o
f coo
rdin
atio
n ge
omet
ry o
n th
e X
AN
ES
X-r
ay a
bsor
ptio
n sp
ectru
m
8200
8400
8600
8800
9000
9200
9400
012345
ln (Io/I)
Ene
rgy
(eV
)
Pre-
Edge
Edge
EX
AFS
SE
CO
ND
NEA
R N
EIG
HBO
UR
S
FIR
ST N
EAR
NEI
GH
BOU
RS
TO
TAL
EXAF
S
010
020
030
040
050
060
070
0
CEN
TRAL
ATO
M (N
O N
EIG
HBO
UR
S)
EXAFS χ(k)
ENER
GY
(eV)
EX
TE
ND
ED
X-R
AY
AB
SOR
PTIO
N F
INE
ST
RU
CT
UR
EE
XA
FS
χ(k)
= Σ
(Nj/R
j2 k) e
xp (-
2σ2 k
2 ) F
j(k) S
IN (2
Rjk
+φj(k
))j
EX
AFS
•D
ETE
RM
INA
TIO
N
OF
PR
EC
ISE
LO
CA
L S
TRU
CTU
RA
L G
EO
ME
TRY
, IN
P
AR
ITC
ULA
R B
ON
D
DIS
TAN
ES
Fe-O
=1.8
4Å
Fe-P
=3.3
Å
24
68
1012
14
-8-4048
k3χ(k)
k (Å-1 )
01
23
45
60.00.20.40.60.81.01.21.41.6 FT Magnitude
R (Å)
Insi
de a
syn
chro
tron
•A
n el
ectro
n gu
n pr
oduc
es a
stre
am o
f fre
e el
ectro
ns.
•Th
e el
ectro
n st
ream
is th
en p
asse
d in
to th
e lin
ear a
ccel
erat
or (L
INA
C)
•Th
e LI
NA
C a
ccel
erat
es th
e el
ectro
ns to
nea
r lig
ht s
peed LI
NA
C
Ele
ctro
n G
un
Insi
de a
syn
chro
tron
•Th
e LI
NA
C th
en fe
eds
the
elec
trons
into
the
boos
ter r
ing.
•R
adio
freq
uenc
y w
aves
add
eve
n m
ore
spee
d an
d en
ergy
to th
e el
ectro
ns
Insi
de a
syn
chro
tron
•Th
e el
ectro
n be
am is
then
inje
cted
into
the
stor
age
ring.
•A
t th
e po
ints
w
ere
the
bend
ing
mag
nets
de
flect
th
e be
am
‘whi
te’
sync
hrot
roni
clig
ht is
giv
en o
f tan
gent
ially
.
The
pow
er o
f X-r
ays
X-ra
y So
urce
:W
ater
-coo
led
Ano
deR
otat
ing
Ano
deS
ynch
rotro
n
Dat
e in
vent
ed:
1918
1930
s
x
X Th
e su
n’s
brilli
ance
in c
ompa
rison
is 1
.5 x
101
0
1950
s
Insi
de a
syn
chro
tron
•Th
e w
hite
ligh
t is
then
use
d to
per
form
exp
erim
ents
.
•A
n op
tics
cabi
n (o
r ‘hu
tch’
) is
used
to m
anip
ulat
e th
e w
hite
ligh
t.
•sa
mpl
es a
re th
en p
lace
d in
the
expe
rimen
tal h
utch
.
•ex
perim
ents
are
con
trolle
d fro
m th
e co
ntro
l cab
in.
Whi
te L
ight
Syn
chro
trons
aro
und
the
wor
ld
•Muc
h of
thes
e ex
perim
ents
are
per
form
ed u
sing
X-r
ays
•lab
base
d X
-ray
diff
ract
ion
mac
hine
s ar
e st
anda
rd e
quip
men
t
•Mat
eria
ls s
cien
ce m
akes
up
70%
of a
nnua
l usa
ge
•Syn
chro
tron
radi
atio
n is
use
d ar
ound
the
wor
ld
•X-r
ays
are
used
con
tinua
lly in
the
wor
ld o
f mat
eria
ls s
cien
ce
In s
itu s
tudi
es b
y S
R te
chni
que
POW
DE
R
XR
PD
Act
ive
site
fo
rmat
ion
DE
NSE
MA
TE
RIA
L
EX
AFS
BO
ND
DIS
TA
NC
E
R (Å
)
HY
DR
OT
HE
RM
AL
SYN
TH
ESI
S
C6H
12
CA
TA
LY
SIS
CO
OH
CO
OH
CR
YST
AL
SIN
GL
E
CR
YST
AL
DIF
FRA
CT
ION
Stru
ctur
alSt
abili
ty
EXA
MPL
E O
F A
CA
TALY
TIC
REA
CTI
ON
–
USE
OF
AD
IPIC
AC
ID
A k
ey r
aw m
ater
ial o
f pol
yam
ides
and
pol
yure
than
es, a
dipi
c ac
id is
one
of t
he
mos
t im
port
ant p
rodu
cts o
f the
che
mic
al in
dust
ry.
Adi
pic
acid
was
ori
gina
lly m
ade
for
the
prod
uctio
n of
nylo
n 6,
6,
But
is n
ow in
crea
sing
ly u
sed
in a
wid
e ar
ray
of in
dust
ries
for
a br
oad
rang
e of
app
licat
ions
. *A
dhes
ives
*T
extil
e tr
eatm
ent
*Ure
than
e fo
ams,
elas
tom
ers,
coat
ings
, adh
esiv
es, f
iber
s*U
nsat
urat
ed p
olye
ster
res
ins ,
etc
Adi
pic
Aci
d(o
r Hex
aned
ioic
acid
or
1,4-
But
aned
icar
boxy
lic a
cid
C6H
10O
4/HO
OC
(CH
2) 4C
OO
HC
OO
H
HO
OC
Cat
alys
ts g
ener
ally
use
d -C
obal
t Ace
tate
TR
AN
SIT
ION
ME
TA
L IO
NS
ASS
IST
ED
C
AT
AL
YSI
S - R
OU
TE
TO
PR
OD
UC
E A
DIP
IC A
CID
Ozo
ne d
eple
tion
H2
O2
HN
O3
OOH
+N2O
CO
OH
CO
OH
MnA
lPO
•RE
CY
CL
AB
LE
(SO
LID
) CA
TA
LY
ST•N
O N
ITR
OG
EN
OX
IDE
FO
RM
AT
ION
O2
MnA
lPO
CO
OH
CO
OH
OH
O2
O
TA
RG
ET
TE
D P
RO
CE
DU
RE
USI
NG
HE
TE
RO
GE
NE
OU
S C
AT
AL
YST
S
Why
Cob
alt S
ubst
itute
d S
yste
ms?
•H
omog
eneo
us c
obal
t sys
tem
s ar
e kn
own
to
cata
lyse
the
form
atio
n of
adi
pic
acid
and
redo
xch
emis
try is
bel
ieve
d to
be
invo
lved
•C
an w
e id
entif
y a
hete
roge
neou
s co
balt
syst
em to
re
plac
e th
e ex
istin
g ho
mog
eneo
us c
atal
yst?
Het
erog
enis
edco
balt
acet
ate
(gra
fted
on s
ilica
)?Fr
amew
ork
subs
titut
ed C
o(II)
RE
DO
X C
HE
MIS
TR
Y –
AC
TIV
AT
ION
OF
CH
3G
RO
UP
TE
RM
INA
L O
XID
AT
ION
CoA
lPO
-18
–4%
cob
alt
Oxi
datio
nR
educ
tion
O2
n-H
EXA
HE
XA
NO
IC A
CID
100C
10.0
713
.09
16.1
219
.14
22.1
625
.19
25
370
2-T
HE
TA
(D
EG
RE
ES
)
Co
AP
SO
-44
25 530
EN
ER
GY
(e
V)
(b)
CA
TA
LY
ST A
CT
IVA
TIO
NC
OM
BIN
ED
XR
D/X
AS
RE
SUL
TS
OF
CoA
PSO
-44
XR
D
Co
K -e
dge
XA
S
HEA
TIN
GIN
O2
SUIT
AB
LE M
ATE
RIA
LSR
EDO
X R
EAC
TIO
N
Cat
alys
tC
o-O
dis
tanc
e Å
As-
prep
ared
m
ater
ial
Co-
O d
ista
nce
Cal
cine
d (o
xidi
sed)
m
ater
ial
CoA
lPO
51.
941.
91
CoA
lPO
-36
1.93
1.86
CoA
lPO
-18
1.93
1.82
CoA
lPO
-34
1.93
1.82
Co
K-e
dge
EXA
FS re
sults
Typi
cal C
o(II
)-O
dis
tanc
e in
tetra
hedr
al g
eom
etry
is 1
.94Å
as i
n C
oAl 2O
4A
s men
tione
d ea
rlier
Co(
III)
-O d
ista
nce
is 1
.79Å
X-R
AY-A
BSO
RP
TIO
N
SPE
CTR
OS
CO
PIC
ST
UD
Y O
F BR
ON
STED
, LE
WIS
, AN
D
RE
DO
X C
EN
TER
S IN
CO
BAL
T-S
UBS
TITU
TED
ALU
MIN
UM
PH
OSP
HA
TE C
ATA
LYS
TSBA
RR
ETT.
PA,
SA
NK
AR
. G, C
ATLO
W. C
RA,
TH
OM
AS. J
MJO
UR
NA
L O
F PH
YSIC
AL
CH
EMIS
TRY,
199
6, V
ol.1
00, N
o.21
, pp.
8977
-898
5
Stru
ctur
e of
cob
alt s
peci
es in
act
ivat
ed (c
alci
ned)
st
ate
OX
IDIS
ED
UN
-OX
IDIS
ED
Cat
alys
tC
o-O
dis
tanc
e Å
As-
prep
ared
m
ater
ial
Co-
O d
ista
nce
Cal
cine
d (o
xidi
sed)
m
ater
ial
Frac
tion
of
Co(
III)
x
CoA
lPO
51.
941.
910.
25
CoA
lPO
-36
1.93
1.86
0.56
CoA
lPO
-18
1.93
1.82
0.8
CoA
lPO
-34
1.93
1.82
0.8
RE
XA
FS =
R3+
x +
R2+
(1-x
)x-
frac
tion
of C
o(II
I)R
3+ -
Co(
III)
-O d
ista
nce
from
Co(
III)
het
erop
oly
tung
stat
e1.
79Å
R2+
-C
o(II
) –O
dis
tanc
e fr
om th
e as
-pre
pare
d m
ater
ials
1.93
Å
X-R
AY-A
BSO
RP
TIO
N
SPE
CTR
OS
CO
PIC
ST
UD
Y O
F BR
ON
STED
, LE
WIS
, AN
D
RE
DO
X C
EN
TER
S IN
CO
BAL
T-S
UBS
TITU
TED
ALU
MIN
UM
PH
OSP
HA
TE C
ATA
LYS
TSBA
RR
ETT.
PA,
SA
NK
AR
. G, C
ATLO
W. C
RA,
TH
OM
AS. J
MJO
UR
NA
L O
F PH
YSIC
AL
CH
EMIS
TRY,
199
6, V
ol.1
00, N
o.21
, pp.
8977
-898
5
How
doe
s th
is re
late
to c
atal
ytic
act
ivity
for
oxid
atio
n re
actio
n
CA
TALY
TIC
PER
FOR
MA
NC
E O
F C
oALP
O’s
FOR
TH
E
CO
NVE
RSI
ON
OF
CYC
LOH
EXA
NE
012345678910F
ract
ion
ofC
o(II
I) fo
rmed
% C
onve
rsio
n
Por
e Si
ze
CoAlPO-5
CoAlPO-18
CoAlPO-36
3.8X3.8Å
6.5 X 7.5Å
7.3X 7.3Å
RE
DO
X
SOLI
D
CA
TALY
STS
FO
R
THE
SELE
CTI
VE
OXI
DAT
ION
O
F C
YCLO
HEX
ANE
IN A
IRSA
NK
AR
_G, R
AJA_
R, T
HO
MAS
_JM
CAT
ALYS
IS L
ETTE
RS,
199
8, V
OL.
55, N
O.1
, PP
.15-
23
OTH
ER
TR
AN
SIT
ION
ME
TAL
ION
S?
•M
AN
GA
NES
E, IR
ON
, VA
NA
DIU
M
CH
RO
MIU
M S
UB
STI
TUTE
D A
lPO
’SH
AV
E B
EE
N S
YN
THE
SIS
ED
BY
US
AN
D
SE
VE
RA
L O
THE
RS
•R
ED
OX
CH
EM
ISTR
Y?
•S
TAB
ILIT
Y O
F TH
E IO
NS
IN T
HE
FR
AM
EW
OR
K?
Com
paris
ion
of la
rge
pore
AlP
O-5
co
ntai
ning
diff
eren
t met
al io
ns fo
r the
ox
idat
ion
cycl
ohex
ane
Frac
tion
ofM
e(II
I)
Co
–25
%
Mn
–60
%
Fe –
100
%
Pow
erfu
l Red
ox M
olec
ular
Sie
ve C
atal
ysts
for t
he S
elec
tive
Oxi
datio
n of
Cyc
lohe
xane
in
Air
Raj
a_R
, San
kar_
G, T
hom
as_J
M
Jour
nalo
fthe
Am
eric
anC
hem
ical
Soc
iety
;199
9V
OL
121
PP
1192
6-11
927
SE
LEC
TIV
E P
AR
TIA
L O
XID
ATI
ON
OF
ALK
AN
ES
CA
TALY
SIS
LE
TTE
RS
, 199
8, V
OL.
55, N
O.1
, PP
.15-
23N
ATU
RE
, 199
9, V
OL.
398,
PP
.227
-230
Jour
nal o
f the
Am
eric
an C
hem
ical
Soc
iety
; 199
9, V
OL.
121
PP
. 11
926-
1192
7A
NG
EW
AN
DT
E C
HE
MIE
-IN
TE
RN
AT
ION
AL
ED
ITIO
N39
: (13
) 231
0-23
13 2
000
AN
GE
WA
ND
TE
CH
EM
IE-I
NT
ER
NA
TIO
NA
L
ED
ITIO
N39
: (13
) 231
3-23
16 2
000
AC
CO
UN
TS
OF
CH
EM
ICA
L R
ESE
AR
CH
34 (3
): 19
1-20
0 M
AR
200
1
Adi
pic
Aci
dC
yclo
hexa
ne
n-H
exan
e
A P
romising
Reac
tion
•One
ste
p on
ly•
No
high
ly r
eact
ive
inte
rmed
iate
s•
No
acet
one
bypr
oduc
t•
Low
capita
l ex
pens
es•
uses
N2O
as
a va
luab
le r
aw
mat
erial inst
ead
of
spen
ding
eff
orts
and
mon
ey
on N
2O n
eutr
alizat
ion
Direc
t ox
idat
ion
of b
enze
ne t
o ph
enol w
ith
N2O
Our
obj
ective
s:
Cata
lytic
evalua
tion
of
othe
r mat
erials
Mec
hanist
ic u
nder
stan
ding
of
active
sites
Iron
subs
titut
ed s
yste
ms
•Fe
sili
calit
eFe
(III)
in te
trah
edra
l coo
rdin
atio
nun
like
Ti(IV
) Fe(
III) i
s in
tetr
ahed
ral
coor
dina
tion
in s
ilica
lite
in a
s-sy
nthe
sise
d an
d ca
lcin
ed s
tate
CA
LCIN
ATI
ON
AT
HIG
H (8
00C
) TE
MPE
RA
TUR
E TO
EXT
RA
CT
Fe S
PEC
IES
•Fe
alu
min
opho
spha
tes
Fe(II
I) in
oct
ahed
ral c
ordi
natio
nsu
rrou
nded
by
4 fr
amew
ork
oxyg
en a
nd 2
w
ater
mol
ecul
es
SIM
PLE
CA
LCIN
ATI
ON
AT
550C
Sili
calit
e
Coo
rdin
atio
n ex
pans
ion
Oxi
dation
of
benz
ene
to p
heno
l
Direc
t ox
idat
ion
of b
enze
ne
with
N2O
T= 6
53 K
, Be
nzen
e/N
2O =
1/4
(mol/m
ol)
Dilu
ent
= He
•W
itho
ut F
e, n
o sign
ifican
t ac
tivity
•M
axim
um b
enze
ne c
onve
rsion
and
Phen
ol Y
ield w
ith
1% F
e
Shiju
et a
l. C
hem
. Com
mn.
(20
06)
Fe
Targ
ets
for o
xida
tion
reac
tions
•M
any
com
mer
cial
oxi
datio
ns d
o no
t use
ca
taly
sts,
hen
ce im
men
se s
cope
for
gree
n/en
viro
nmen
tal i
mpr
ovem
ents
•C
urre
nt in
tere
st:
alka
nes
to a
lken
esal
kene
s to
epo
xide
s•
Dre
am re
actio
ns:
dire
ct o
xida
tion
met
hane
to m
etha
nol
dire
ct o
xida
tion
of h
ydro
gen
to h
ydro
gen
pero
xide
dire
ct o
xida
tion
of a
lkan
es to
alc
ohol
s
OTH
ER
AP
PLI
CA
TIO
NS
OF
ZEO
TYP
E M
ATE
RIA
LS•
SOFT
ENIN
G O
F W
ATE
R -
DET
ERG
ENT
•PR
OD
UC
TIO
N O
F SM
ALL
CER
AM
IC A
RTI
CLE
S•
TRA
PPIN
G M
OLE
CU
LES
FOR
SLO
W R
ELEA
SE -
FER
TILI
SER
SN
ITR
IC O
XID
E R
ELEA
SE –
MED
ICA
L A
PPLI
CA
TIO
NS
HYD
RO
CA
RB
ON
TR
AP
–A
UTO
MO
BIL
E•
TRA
PPIN
G N
UC
LEA
R W
AST
ES
•LO
W k
DIE
LEC
TRIC
S
The
Roy
al In
stitu
tion
Dr P
. A. B
arre
ttD
r N.R
. Shi
juD
r R. R
aja
Dr A
.M. B
eale
Dr C
. Zen
onos
Dr J
. K W
yles
Pro
fess
or R
icha
rd C
atlo
wP
rofe
ssor
Joh
n Th
omas
FUN
DIN
GD
ares
bury
Labo
rato
ry
Roy
al S
ocie
ty
EP
SR
C
Dar
esbu
ryLa
bora
tory
Pro
f Nev
ille
Gre
aves
Dr A
.J. D
ent
Dr I
. Har
vey
Dr S
. Fid
dy
912)
at t
he U
nive
rsity
of T
oulo
use
star
ted
wor
k on
his
met
hod
of h
ydro
gena
ting
orga
nic
mo
Nob
el P
rize
1932
) at G
ener
al E
lect
ric la
id d
own
the
scie
ntifi
c fo
unda
tions
for t
he o
xida
tion
ofn
Pin
es a
t UO
P d
evel
oped
a p
roce
ss to
mak
e hi
gh-o
ctan
e ga
solin
e th
at w
as s
hipp
ed ju
st in
Forc
e in
the
Bat
tle o
f Brit
ain.
arl Z
iegl
er a
nd G
iulio
Nat
ta (N
obel
Priz
e 19
63) i
nven
ted
proc
esse
s to
mak
e ne
w p
last
ican
dw
les
at M
onsa
nto
Com
pany
obt
aine
d a
pate
nt fo
r a b
ette
r way
to m
ake
the
drug
L-D
opa
to t
n an
d Fo
rd M
otor
Com
pany
intro
duce
d ne
w d
evic
es in
car
s to
cle
an a
utom
otiv
e ex
haus
t. Th
Cat
alys
is L
ooks
to th
e Fu
ture
(1
992)
prod
uctio
n is
thro
ugh
nitri
c ac
id o
xida
tion
of a
cyc
lohe
xano
ne-c
yclo
hexa
nolm
ixtu
re c
alle
d K
deriv
e K
A o
il fro
m c
yclo
hexa
nefe
edst
ock,
whi
le In
olex
uses
phe
nol a
s a
star
ting
mat
eria
l.A
lliedS
igna
l’s a
dipi
cac
id b
usin
ess,
and
last
yea
r exp
ande
d pr
oduc
tion
in H
opw
ell,
Va.
, to
6s
publ
icat
ion,
Sol
utia
has
deb
ottle
neck
edth
e P
ensa
cola
pla
nt tw
ice,
brin
ging
cap
acity
to a
tad
d m
ore
than
330
milli
on p
ound
s of
adi
pic
capa
city
at i
ts th
ree
Nor
th A
mer
ican
pla
nts
at M
The
expa
nsio
n pr
ogra
m is
exp
ecte
d to
be
com
plet
e in
200
3.P
rofil
e la
st p
ublis
hed
6/15
/98;
this
revi
sion
7/9
/01.
DEM
AN
D
llion
pou
nds;
200
4: 2
240
mill
ion
poun
ds, p
roje
cted
. Dem
and
equa
ls p
rodu
ctio
n pl
us
21 m
illio
n po
unds
) les
s ex
port
s (1
999:
147
mill
ion
poun
ds; 2
000:
154
mill
ion
poun
ds)
GR
OW
TH
His
toric
al (1
995
-200
0): 3
.2 p
erce
nt p
er y
ear;
futu
re: 2
.6 p
erce
nt p
er y
ear t
hrou
gh 2
004
CA
TALY
SIS
“It m
ay a
ppea
r tha
t a fi
eld
or e
ven
the
who
le o
f ca
taly
tic te
chno
logy
is re
lativ
ely
mat
ure.
Thi
s is
, ho
wev
er, a
mis
conc
eptio
n be
caus
e hi
stor
y te
ache
s us
that
fiel
ds w
hich
app
ear m
atur
e ar
e su
dden
ly
revi
taliz
ed b
y a
maj
or d
isco
very
.”