Carbon Dioxide Reduction with Hydrogen

Using Photonanocatalyst
Nor Aishah Saidina Amin
Chemical Reaction Engineering Group (CREG)
N01-Faculty of Chemical Engineering
Universiti Teknologi Malaysia
UTM 81310 Johor Bahru, Johor Malaysia.
noraishah@cheme.utm.my
www.cheme.utm.my

Presentation Outline

Background of Study
Research Scope
Methodology
Results and Discussions
Conclusions
Acknowledgement

Background

Majour
contribu
tors

Global anthropogenic greenhouse gas emissions broken down into 8 different sectors.
[http://en.wikipedia.org/wiki/Greenhouse_gas]

Background
Energy consumption has
been increasing with world
population
Fossil fuels are the main
source of energy supply
Reserves of fossil fuel is
fossil depleting
Combustion of fossil fuels
generates greenhouse CO2

Greenho
use Gas
CO2

Fossil
fuel
Combusti
on
Energy
Crisis
and
Global
Warmin
g

Mitigation of
Greenhouse Gas
CO2

How?
(i) How CO2 can be re-utilized easily and efficiently
(ii) How CO2 can be recycled or converted to fuels

Recycling of CO2 to Fuels

Conversion of
Carbon Dioxide

Reforming
(CO, H2)

Plasma
reforming

Thermal
reforming

Required higher
temperature and
pressure
Thus, instability of
catalysts and
uneconomical

Electrochemical

Biological

(EtOH, HCOOH,
CO)

(EtOH, sugar,
CH3COOH)

Required
electricity for
the process
Required
high voltage
and cause
fouling on
electrode
surface

Required
biocatalyst
Required
very specific
conditions
Specific
bioreactors
Short life
time of
biocatalyst

Photocatalysis
(CO, CH4, HC,
MeOH, HCOOH)

Workable
under solar
energy
Economical
process
Required
normal temp
and pressure
Sustainable
process
High
6
stability of6

Photocatalysis
System
Reducing
Agent

Semiconductor
Material

Photocatalytic
Reactor

Can easily be oxidized Have good photoactivity

Higher photonic
Higher charger production
Can reduced CO2
Efficiency,

Lower
charges
recombination
Can help to produce
higher illumination area
desire products

Efficient
Phototechnolo
gy for CO2
Reduction

What we are Offering

Hydroge
n
Reducta
nt

Plasmonic
PhotoCatal
ysts

Monolith
Photoreac
tor

Hydrogen Reducing Agent

CO2 H 2
hv, catalyst

CO + H 2O

Hydrogen is good
reducing agent for
CO2 conversion via
(RWGS reaction)
RWGS reaction
Syngas (CO and
H2) can be used for
Single step
F-T process F-T process
CO2 reduction with
H2 can also be
produced
hydrocarbons in
single step.
9
H for CO

Monolith Photoreactor
It has microchannels of

Monolith
Honeycomb, foam or fibers structure
Channels have square, circular, and
triangular
Density varies from 9 to 600 cells per square inch
(CPSI)
Higher void fraction (65 to 91 %) compared to
packed bed catalyst (36 to 45 %)

different shape and sizes

Light
distribution
is
effective over the catalyst
surface.
Larger surface area to
reactor volume.
Catalyst loading is higher
with enhanced stability.
Very suitable for systems
operating in gas- solids.
Larger conversion with
improved selectivity.
Higher
quantum
efficiency
Higher light distribution
over the catalyst
10

Plasmonic Au/TiO2 Photonanocatalyst

LSPR of Au

(a)

(b)

TiO2

When the incident light is (in

the range of LSPR) absorbed
by Au- metal NPs, electric
filed (e-/h+ ) is produced (Fig.
a)
Plasmonic electrons are transferred
to TiO2 CB band for its activation
B)
(Fig.
Efficient separation of
electrons
Efficient CO2 reduction via
SPR effect
Higher efficiency for
trapping electrons
Au can enhance efficiency
11
under UV and visible light

Experimental Setup

Monoliths

Schematic of Monolith Reactor

Experimental Rig

Catalyst Preparation and Coat

Ti (C3H7O)4
+ isopropanol

Aging

Hydrolysis
Au-loading

Dip-coating
Dried at 80 oC
for 24 h

Drying and
Calcination

Acetic acid
+ isopropanol

Gold chloride
+ isopropanol

Monolith

Calcined at 500oC
for 5h @ 5oC/min

SEM and TEM Analysis

TEM (Au/TiO2)

SEM
Front view

TiO2

Side View

Au/TiO2

Uniform coating of catalysts

over the monolith surface
TiO2 particles are spherical in
shape and uniform size
Au/TiO2 have mesoporous

TEM images of Au/TiO2 exhibit

uniform particle size and
mesoporous structure of TiO2
TiO2 d-spacing confirmed

XRD, BET and UV-Vis Analys

XRD
A

(a)

(b)

A=anatase
A

A A

(c)
Plasmon effect
UV-Vis

BET

(a)Anatase phase in TiO2 and

Au/TiO2 samples
(b)N2 adsorption-desoprtion plots
show isothersms of type IV,
confirming mesoporous
materials of TiO2 and Au/TiO2
(c)UV-Visible analysis confirmed
Plasmonic effect in Au/TiO2

Summar
y of
Analysis

Table 1

Catalysts

TiO2
0.3
wt.%
Au- TiO2
0.5
wt.%
Au-TiO2

BET
BJH
surface adsorption
area
surface
(m2/g)
area
(m2/g)

BJH
pore
volume
(cm3/g)

Nanocataly
st
Crystallite Band
size
(nm)

gap
energy
(eV)

43
46

52
58

0.134
0.23

19
17

3.12
3.03

47

74

0.24

18

2.93

Table 2

Element
Ti2p

B.E (eV)
459.50

State
Ti4+

Au4f

465.20
83.86

Au

O1s

88.12
530.72

O-O

C1s

532.94
284.60

O-H
C-C

286.05

C-O

Au has no effect on
BET surface area
Au has no effect on
Crystallite size
Band gap energy
shifted to visible
region
in Au/TiO
Gold
was
present
2
over TiO2 in metal
state

Photoactivity Test of Continuous

CO2 Reduction to CO
(a)CO production

(a)CH4 production

Fig. Effects of Au-loading and irradiation time on CO2 reduction with H2 at CO2/H2 ratio
1.0, molar flow rate 20 mL/min, and temperature 100oC; (a) CO production, (b) CH4
Plasmonic Au/TiO
registered significantly
(a) Maximum production of CH initially
production.
2

enhanced CO production activity over irradiation

time
Optimum Au-loading of 0.5%Au was determined
Maximum yield of CO was 12445 mole g-catal.1

Steady sate process achieved after 2h

of irradiation time.

(b) CH4 production decreased due to photooxidation back into CO2 by O2 produced over
catalyst surface
(c) Saturation of catalyst sites with intermediate
species or deactivation of catalyst
(d) photo-reduction of products back to CO2.

Summary of Results
0.5% Au/TiO2

318
fold

CO selectivity
92% to 99%

TiO2

Fig. (a ) Yield rates of products over Au/TiO2

catalysts

Fig. (b) Selectivity of products over

Au/TiO2 catalysts.

Catalyst Stability Test

a= CO production

b= hydrocarbons production
CH4

C2H6

(a) In the cyclic runs over prolonged irradiation time, higher stability of
catalysts
(b) In second and third cycles, photoactivity slightly reduced
(c) Decreased in photoactivity of Au/TiO2 catalyst was possibly due to active
sites blockage with intermediate species.

Conclusions
Enhanced efficiency of monolith photoreactor for CO 2

reduction to fuels
Efficient CO2 reduction with H2 to CO and HCs over
Au/TiO2.
Yield of CO production over Au/TiO2 increased to 318
times higher than TiO2
Selectivity of CO production reached above 99% by Au
Enhanced Au/TiO2 activity was due to plasmonic effect
Efficient trapping of electrons and inhibited charges
recombination by Au-metal
Tests revealed prolonged stability of Au/TiO2 in cyclic
runs.

Acknowledgements
Ministry of Higher Education (MOHE) Malaysia for financial
support under NanoMite LRGS (Long-term Research Grant
Scheme , Vot 4L839),
Universiti Teknologi Malaysia (UTM) for the RUG (Research
University Grant, Vot 02G14) and
FRGS (Fundamental Research Grant Scheme, Vot 4F404).

THANK YOU FOR YOUR

ATTENTION

Chemical Reaction Engineering Group (CREG)

N01-Faculty of Chemical Engineering
Universiti Teknologi Malaysia
UTM 81310 Johor Bahru, Johor Malaysia.
noraishah@cheme.utm.my
www.cheme.utm.my/staff/noraishah