Seminar Nasional Kimia KALTIM (Prof. Dr. Hadi Nur)

Seminar Nasional Kimia Kalimantan Timur 3 Desember 2011
The Design and Synthesis of

Heterogeneous Catalyst
Hadi Nur
Ibnu Sina Institute for Fundamental Science Studies
Universiti Teknologi Malaysia
Towards an Entrepreneurial University
1
1
Location of UTM
Main campus in Johor Bahru
350 km from Kuala Lumpur
25 km from Singapore
1904
Treacher Technical School, KL
1975
Universiti Teknologi Malaysia
Location1946
of UTM
Technical College, KL (1946)
1972
National Institute of Technology, KL
1,148
hectares of beauty
5
Kuala Lumpur International Campus (35 hectares)

Expected date of completion 2011
Ibnu Sina Institute for Fundamental Science Studies

7
Catalytic Science and Technology Research Group (2010)
PhD students (2011)
10
Definition of catalyst
A catalyst is a substance that increases the
rate of a reaction remaining itself unchanged
11
Importance of Catalysis
The production of 80 % industrially important chemicals involves
catalysis
Catalysts are involved in more than USD 10 trillion in goods &
services of the Global GDP annually
Catalyst industry contributes around 2% of total investment in a
chemical process
Catalyst make chemical processes possible and more efficient
The use of catalyst in chemical processes contributes to
environmental preservation
The key factor for sustainable development of industrial society
12
12 National Key Result Areas

Source: Economic Transformation Programme (ETP)
Oil and gas
Palm oil
Financial
services
Tourism
Business
services
Electronics &
Electrical
Wholesale &
retail
Education
Healthcare
Communication,
content,
infrastructure
Agriculture
Greater Kuala
Lumpur
Contribution of catalysis
13
Importance of Catalysis
Example: methyl metacrylate (MMA)
Old process: 2.5 kg waste / kg product
New catalytic process: 50 g waste / kg product
14
Energy profile of a reaction
15
Heterogeneous catalysis in action
substrates
reactor
product
16
substrates
reactor
product
17
substrates
catalyst
reactor
product
18
substrates
reactor
product
19
Catalytic process
Adsorption
Desorption
Catalyst surface
Chemical reaction at
the catalytic active
site
Issues:
How to improve the efficiency of adsorption, chemical reaction and
desorption in catalytic cycle processes?
How to design catalytic active site?
20
Classification of our research in heterogeneous catalysis
21
Phase-boundary catalysis
Synergytic catalysis
Bifunctional catalysis
Chiral catalysis
My note book on phase-boundary catalysis (1999)
22
Chiral catalysis
Chemical Communications, 2000, 2235-2236.
23
Chiral catalysis
What is the phase-boundary catalysis ?
1-Octene
Aqueous H2O2
catalyst located at
liquid-liquid boundary
24
phase-boundary catalysis
Heterogeneous catalytic system
No need stirring
H. Nur, S. Ikeda and B. Ohtani, Chemical

Communications, 2000, 2235-2236.
H. Nur, S. Ikeda and B. Ohtani, Journal of
Catalysis, 204, 2001, 402-408.
S. Ikeda, H. Nur, T. Sawadaishi, K. Ijiro, M.
Shimomura and B. Ohtani, Langmuir, 17,
2001, 7976-7979.
S. Ikeda, H. Nur, P. Wu, T. Tatsumi and B.
Ohtani, Stud. Surf. Sci. Catal., 145, 2003,
251-254.
H. Nur, S. Ikeda and B. Ohtani, (2004).
React. Kinet. Catal. Lett. 82: 255-261.
H. Nur, S. Ikeda and B. Ohtani, (2004). J.
Braz. Chem. Soc. 15: 719-724.
Chiral catalysis
phase transfer catalysis

Homogeneous catalytic system
Need vigorous stirring
(to form emulsion)
This concept was developed by Starks,
Liotta, Dehmlow and Makosza in the
1970s.
Inverse Phase Transfer Catalysis principle involving a surfactant as catalyst.
25
Chiral catalysis
Synthesis of phase boundary catalyst

NaY zeolite
Impregnation of Ti(OPr)4
NaY zeolite
Ti-NaY
Addition of
Water to make
aggregation
Attachment of
ODS
Attachment of
ODS
o-Ti-NaY
w/o-Ti-NaY
26
Chiral catalysis
NaY
Fluorescence and optical micrographs

of fluorescent dye-modified NaYs
Phase-boundary catalyst
fluorescent dye
S. Ikeda, H. Nur, T. Sawadaishi, K. Ijiro, M. Shimomura

and B. Ohtani, Langmuir, 17, 2001, 7976-7979.
27
Chiral catalysis
Phase boundary catalysis in action

H2 O2
1-octene
RT, 20h
1,2-epoxyoctane
30
20
10
0
organic
phase
aqueous
phase
catalyst at
phase-boundary
w-Ti-N aY
w/o-T i-N aY
o-Ti-NaY
Phase boundary catalyst
28
Chiral catalysis
Conventional Catalytic System

active site
organic phase
catalyst in
aqueous H2O2
phase
Phase Boundary Catalytic System

solid catalyst at
phase-boundary
hydrophobic
alkylsilane
hydrophobic
organic phase
aqueous H2O2
phase
hydrophilic
active site
29
Chiral catalysis
Conventional Catalytic System
active site
organic-aqueous
interphase
(phase boundary)
solid phase
organic phase
aqueous phase
Phase-Boundary Catalytic System

organic-aqueous
interphase
(phase boundary)
active site
organic phase
solid phase
aqueous phase
30
Chiral catalysis
Amphiphilic particle in adsorption of organic compounds

Paraquat (hydrophilic)
Dye (hydrophobic)
w-NaY
w/o-NaY
o-NaY
No steric hindrance !
No competitive adsorption !
H. Nur, A. F. N. A. Manan, L. K. Wei, M. N. M. Muhid and H. Hamdan. Journal of
Hazardous Materials, 117 (2005) 35-40.
31
Chiral catalysis
Phase Boundary Catalyst System

Source of
hydrophobicity
Octadecyltrichlorosilane
Fluorine
Active site
Titanium
Niobic acid
Titanium
Reaction
Oxidation
(oxidation of
alkene with
H2O2)
Chemical Communications,
(2000) 2235-2236; Journal of
Catalysis, 204 (2001) 402-408.
Langmuir, 17 (2001) 79767979; Stud. Surf. Sci. Catal.
145 (2003) 251-254.
React. Kinet. Catal. Lett. 82

Acid (hydration (2004) 255-261; Journal of
of epoxide)
Brazilian Chemical Society,
15 (2004) 719-724.
Oxidation
(oxidation of
alkene with
H2O2)
Journal of Fluorine
Chemistry, 128 (2007) 12-16;
Materials Letters, 60 (2006)
2274-2277.
32
Chiral catalysis
Floating catalyst in liquid-gas system
Gas phase
Aqueous phase
catalyst located at
liquid-gas boundary
33
Chiral catalysis
Polystyrene-coated hollow titania

carbon
Sucrose
Hydrothermal
synthesis
Carbon spheres
polystyrene
coating with titania

and removal of carbon
titania
Polystyrene-coated
hollow titania
coating with
polystyrene
Hollow titania
34
Chiral catalysis
Hollow titania
5 m
0.5 m
100 nm
Diameter ~1.4 m
Wall thickness ~138 nm
Carbon size average ~1.45 m
35
Chiral catalysis
Polystyrene coated hollow titania
3.56
2 nm
Wall thickness : ~ 3 nm
SEM image of polystyrenecoated titania
Crack prove
there is holllow
inside the
sphere
36
Chiral catalysis
Gold/Polystyrene-coated hollow titania as phase boundary catalyst

gold as
catalytic
active site
polystyrene
1. 0 m
IMG1
1. 0 m
C K
1. 0 m
O K
1. 0 m
Ti K
1. 0 m
Au M
sputtering
with gold
1. 0 m
Si K
Gold/Polystyrenecoated hollow titania
Polystyrene-coated
hollow titania
oxygen
benzyl alcohol
benzoic acid
37
Chiral catalysis
Brnsted acid
H+
Synergistic role of Lewis

and Brnsted acidities in
Friedel-Crafts alkylation of
resorcinol over galliumzeolite beta
O
Al
O
Ga
Si
OO
OO
Si
OO
~3 wt% Ga loading on BEA

Lewis acid
(GaOx)
+
O
Al
O
Al
Si
OO
OO
Ga
loading
Si
OO
O
Ga
O
Al
Si
OO
Ga
O
Al
Lewis acid
OO
Si
OO
38
50%
H. Nur et al. Catalysis Communications, 12 (2011) 822-825.
Chiral catalysis
50%
39
Chiral catalysis
Friedel-Crafts alkylation of resorcinol
H. Nur et al. Catalysis Communications, 12 (2011) 822-825.
40
Chiral catalysis
Our Approach
More hydrophilic
O
OH
OH
H2O2
epoxidation
hydrolysis
Titanosilicalite
(TS-1)
Cluster or atomic oxidative active site (eq. TiO2)

Cluster or atomic acidic active site (eq. Nb2O5, sulfated ZrO2)
41
Chiral catalysis
Bifunctional Catalyst ---- Sulfated ZrO2/TS-1

O
OH
HO
H
O
Ti
Atomic oxidative active site
Zr O
O
S
O
O
Zr
Zr
Cluster acidic active site

42
Chiral catalysis
The oxidation and hydrolysis rates

70
1400
Hydrolysis of 1,2epoxyoctane
Epoxidation of 1-octene
60
TS-1
1200
Sulfated
ZrO2/TS-1
TS-1-HZSM-5
50
1,2-octanediol / mmol
1,2-epoxyoctane / mmol
1000
800
Sulfated
ZrO2/TS-1
600
40
30
20
400
200
TS-1-HZSM5
10
Sulfated ZrO2
Sulfated ZrO2
0
10
20
Time / h
30
40
50
TS-1
0
0
10
20
30
40
50
Time / h
D. Prasetyoko, Z. Ramli, S. Endud and H. Nur, Journal of Molecular Catalysis A: Chemical, 241 (2005) 118-125.
43
Chiral catalysis
Bifunctional catalyst systems

Oxidative active site
Titanium
(TS-1)
Acid active site
Sulfated zirconia
D. Prasetyoko, Z. Ramli, S.
Endud and H. Nur, Journal
of Molecular Catalysis A:
Chemical, 241 (2005) 118125.
Endud and H. Nur,
Reaction Kinetics and
Catalysis Letters, 86
(2005) 83-89
Titanium
(TS-1)
Niobic acid
Endud and H. Nur,
Materials Chemistry and
Physics, 93 (2005) 443-449.
44
2011
Chiral catalysis
45
Chiral catalysis
What chirality means?
46
Chiral catalysis
The important of chirality
(S)-(+)-thalidomide
( S ) thalidomide was
responsible for many birth
defects such as phocomelia
(R)-(+)-thalidomide
( R ) thalidomide contained
the properties that made it
useful as a sedative and
antinausea drug
47
Chiral catalysis
Previous approaches
48
Chiral catalysis
Our approach
hydrophilic
hyrophobic
Amino
acid
Wash with
water in order
to remove
free amino
acid
49
Chiral catalysis
Interaction
50
13C
Chiral catalysis
CP/MAS NMR
H. Nur, L. K. Wei, S. Endud,

Catalysis Letters, 98 (2009)
157-164.
51
13C
Chiral catalysis
CP/MAS NMR
H. Nur, L. K. Wei, S. Endud,

Catalysis Letters, 98 (2009)
157-164.
52
Chiral catalysis
53
Chiral catalysis
54
Acknowledgements
Catalytic Science and Technology Research Group (2010)

55
Acknowledgements
Ministry of Higher
Education, Malaysia
(MOHE)
Ministry of Science,
Technology & Innovation,
Malaysia (MOSTI)
Academy of Sciences for

the Developing World
(TWAS)
56
Acknowledgements
Research officers, PhD, MSc and BSc students
Research officers: Leiw Sook Fun, Amelia Boon Hoo, Sheela Chandren and
Nur Izzati Abu Bakar. Ph.D. students: Dr. Didik Prasetyoko, Dr. Fitri Hayati, Dr.
Eriawan Rismana, Dr. Amin Eisazadeh Otaghsaraei, Surya Lubis, Umar Kalmar
Nizar, Nursyafreena Attan, Nur Hidayah Mohd Ran, Pratama Jujur Wibawa,
Syamsi Aini, Lai Sin Yuan, Noorfatimah Yahaya, Mohammed Salisu Musa,
Fatemeh Yaghoubi Doust, Shafiyah Pondi, Mita Rilyanti, Mukhamad Nurhadi
and Shohoh Parham. M.Sc. students: Norizah Abdul Rahman, Helda Hamid,
Dr. Ng Yun Hau, Lim Kheng Wei, Gui Lee Kee, Izan Izwan Misnon, Yong Khun
Fong, Sheela Chandren, Amelia Boon Hoo, Farizan Mohamad, Nor Rashidah
Md Juremi, Syaiful Akhmal Saadon, and Ghani Ur Rehman. B.Sc. students:
Amir Faizal Naidu Abdul Manan, Izan Izwan Misnon, Shahmeen Ismail,
Nurulashikin Mohd Ariffin, Chua Yew Hean, Farah Hannan Anuar, Sim Sau
Teing, Nur Hajarul Aswani Moamail, Norazlizan Abul Rashid, Noor Ayu Ismail,
Jessie Jessica Anak Robin, Raazatul Aidah Abd Latif, Norshahida Zamahsari,
Intan Dayana Samsuri, Ng Kar Fai, Ang Wai Leong, Salmi Fathiyah Sheikh
Salim, Siti Shahidaanis Abdul Aziz, Noorulsyahidaini Golbaha, Lai Sin Yuan,
Hidayati Mohamad Mukhair, Wan Faizal Wan Ahmad, Mohd Hayrie Mohd Hatta,
Shazliana Mohamad @ Mat Yasin, Teoh Leong Shen, Noor Hidayah Mohd
Jusoh, Siti Noramallina Nazri, Lim Chai Sin, and Ahmad Fahmi Abdullah.
57
Thank You !
58

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Seminar Nasional Kimia Kalimantan Timur 3 Desember 2011

The Design and Synthesis of

Towards an Entrepreneurial University

Treacher Technical School, KL

Universiti Teknologi Malaysia

Technical College, KL (1946)

National Institute of Technology, KL

Kuala Lumpur International Campus (35 hectares)

Ibnu Sina Institute for Fundamental Science Studies

Catalytic Science and Technology Research Group (2010)

PhD students (2011)

12 National Key Result Areas

Oil and gas

New catalytic process: 50 g waste / kg product

Energy profile of a reaction

Heterogeneous catalysis in action

Heterogeneous catalysis in action

Heterogeneous catalysis in action

Heterogeneous catalysis in action

Classification of our research in heterogeneous catalysis

My note book on phase-boundary catalysis (1999)

Chemical Communications, 2000, 2235-2236.

What is the phase-boundary catalysis ?

H. Nur, S. Ikeda and B. Ohtani, Chemical

phase transfer catalysis

Inverse Phase Transfer Catalysis principle involving a surfactant as catalyst.

Synthesis of phase boundary catalyst

Fluorescence and optical micrographs

S. Ikeda, H. Nur, T. Sawadaishi, K. Ijiro, M. Shimomura

Phase boundary catalysis in action

Phase boundary catalyst

Conventional Catalytic System

Phase Boundary Catalytic System

Conventional Catalytic System

Phase-Boundary Catalytic System

Amphiphilic particle in adsorption of organic compounds

Phase Boundary Catalyst System

React. Kinet. Catal. Lett. 82

Floating catalyst in liquid-gas system

Polystyrene-coated hollow titania

coating with titania

Polystyrene coated hollow titania

Gold/Polystyrene-coated hollow titania as phase boundary catalyst

Gold/Polystyrenecoated hollow titania

Synergistic role of Lewis

~3 wt% Ga loading on BEA

~7 wt% Ga loading on BEA

~25 wt% Ga loading on BEA

H. Nur et al. Catalysis Communications, 12 (2011) 822-825.

Friedel-Crafts alkylation of resorcinol

H. Nur et al. Catalysis Communications, 12 (2011) 822-825.

Cluster or atomic oxidative active site (eq. TiO2)

Bifunctional Catalyst ---- Sulfated ZrO2/TS-1

Atomic oxidative active site

Cluster acidic active site

The oxidation and hydrolysis rates

Bifunctional catalyst systems

Acid active site