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SYNCHROTRON RADIATION FOR ELUCIDATING STRUCTURES OF CATALYSTS NANO POROUS CATALYTIC MATERIALS – SYNTHESIS, CHARACTERISATION AND CATALYTIC PROPERTIES GOPINATHAN SANKAR DAVY FARADAY RESEARCH LABORATORY THE ROYAL INSTITUTION OF GB 21 ALBEMARLE STREET LONDON W1S 4BS ICMR – JNC WINTER SCHOOL

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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

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Y(F

UEL

CEL

LS)

•O

RG

AN

IC T

RN

SFO

RM

ATI

ON

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AR

MA

CEU

TIC

AL

PETR

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HEM

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LFI

NE-

CH

EMIC

AL

•C

LEA

N E

NVI

RO

NM

ENT

(CO

NVE

RSI

ON

OF

TOXI

C P

RO

DU

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, UTI

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N O

F TO

XIC

/GR

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USE

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OD

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TS)

•IN

SIT

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RO

DU

CTI

ON

OF

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DO

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RM

EDIA

TES

(CO

RR

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TO

XIC

INTE

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TES)

OR

GA

NIC

TR

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KEY

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EA IN

CA

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DU

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, FR

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PHA

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L IN

DU

STR

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S, S

PEC

IFIC

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MER

S et

c..

SO

ME

OX

IDA

TIO

N R

EA

CTI

ON

S

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.

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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

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OR

TE

D C

AT

AL

YST

SM

ETA

L C

LUST

ERS

SUPP

OR

TED

ON

HIG

H-S

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FAC

E A

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S et

c

SO

LID

STA

TE C

ATA

LYS

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EN

SE F

RA

ME

WO

RK

SO

LID

SC

LO

SE-P

AC

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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

Ran

dom

ly o

rient

ed c

ryst

allit

es

22 θθ

Diff

ract

ion

from

an

"idea

l" po

wde

r

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

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

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)

NE

ED

FO

R S

YN

CH

RO

TRO

N

RA

DIA

TIO

N•

TUN

AB

ILIT

Y –

VAR

IAB

LE

WA

VELE

NG

TH•

INTE

NSI

TY

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

SR

SIT

ES

ESR

F, G

reno

ble

SRS

Dar

esbu

ry

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

STR

UC

TUR

E A

ND

CA

TALY

TIC

P

RO

PE

RTI

ES

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

NY

LON

PR

OD

UC

TIO

N

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

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HE

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-IN

TE

RN

AT

ION

AL

ED

ITIO

N39

: (13

) 231

0-23

13 2

000

AN

GE

WA

ND

TE

CH

EM

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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

.”

CO

MP

LEX

ITIE

S O

F C

HE

MIC

AL

RE

AC

TIO

NS

EX

AM

PLE

–R

EA

CTI

ON

BE

TWE

EN

E

THY

LEN

E A

ND

AC

ETI

C A

CID

TO F

OR

M V

INY

LAC

ETA

TE A

ND

WA

TER

RE

LEV

AN

T A

DS

OR

BA

TES

PR

ES

EN

T –

A T

HE

OR

ETI

CA

L D

ES

CR

IPTI

ON