LEE KONG CHIAN FACULTY OF

ENGINEERING AND SCIENCE

HENG ZENG WEI

SUPERVISOR : DR. CHONG WOON CHAN
CO-SUPERVISOR : DR. PANG YEAN LING

ENHANCED PHOTOCATALYTIC
MEMBRANE USING CARBON DOTS/
TITANIUM OXIDE FOR DEGRADATION
OF PHARMACEUTICALS
INTRODUCTION

 Use of semiconductor in photocatalysis to treat pollutants is largely limited

under solar irradiation.
 Modification of semiconductor is needed to extend the absorption range
from UV to visible range.
 The integration of photocatalysis with membrane processes may degrade
the pollutant and retain the photocatalyst on the membrane.
1
PROBLEM STATEMENTS

Poor solar energy absorption Post-reaction separation step

 Due to large band gap of TiO2
& rapid recombination of
electron-hole pairs
 Sunlight contains only a small
fraction of UV light
 Long term exposure to UV
radiation can cause adverse
effect to human
 Unremoved photocatalyst may
result in secondary pollution
 Low reutilization rate
 Agglomeration of photocatalyst
suspended in pollutant solution
2
 OBJECTIVES

To investigate the
degradation efficiency of the
To prepare hybrid N- photocatalytic membrane on

01 03
CD/TiO2 with different pharmaceutical pollutant
N-CD content via in-situ under different operating
hydrothermal method. parameters.
To develop nitrogen To fabricate visible light-
doped carbon dots
(N-CD) from
oil palm frond using
02 responsive photocatalytic
membrane through the
coupling of the N-CD/TiO2
04
02
hydrothermal method. with ultrafiltration
membrane.

3
SYNTHESIS METHOD OF NANOHYBRID COMPOSITES
EX-SITU SYNTHESIS APPROACH
 CD and photocatalyst TiO2 were prepared
separately beforehand
 Pre-made CD then disperse into TiO2
nanoparticles through mixing to form
composites
 Key challenge : Particles agglomeration can
significantly reduce the photocatalytic
activity of nanocomposite
 Simple and effective route to prepare
nanocomposites.
 All starting materials for CD and photocatalyst
are added together to obtain a co-
synthesized hetero-structure
 Adv.: Prevents particle agglomeration while
maintaining a good spatial distribution
 Disadv: Unreacted materials might influence
the properties of the final material
IN-SITU SYNTHESIS APPROACH
45
N-CD/TIO2 IMMOBILIZED ON MEMBRANE
BLENDING WITHIN MEMBRANE MATRIX
 Facile membrane preparation, only blending
of catalyst into polymer solution is required
before membrane fabrication.
 Membranes consisted of more porous
structure
 Low possibility of catalyst leaching
 The entrapment of TiO2 in the inner layer
shielded the penetration of light, thus
compromised photocatalytic activities
 Complicated procedure involving multi-steps
(coating solution preparation, membrane
surface activation, and surface coating)
 Membrane morphology (porosity) may not
greatly affected
 Detach of catalyst from membrane
 High photocatalytic activity due to the high
accessibility of the catalysts to light
irradiation
COATING ON MEMBRANE SURFACE
56
RESEARCH METHODOLOGY

7
 Synthesis of N-CD

Ultrasonication
Hydrothermal
180 ℃, 12 h

Isopropanol Centrifugation
Ethylenediamine

Oil Palm
Frond

N-CD
8 7
Stir under room temperature
 Synthesis of N-CD/ TiO2

Age for 2 h
Titanium (IV)
Isopropoxide
+ Isopropanol
N-CD +
Distilled water

Stir under room temperature

Hydrothermal
180 ℃, 12 h

Dried N-CD/ TiO2 Wash and filter with ethanol 8

Photocatalytic test of N-CD/ TiO2

Visible light

N-CD/ TiO2
photocatalyst

Dichlorofenac
Sodium (DCF) UV-Vis Spectrophotometer

Stir under room temperature 9

 PES ultrafiltration membrane fabrication
4 Casting at 200 μm thick
Degassed for 24 h

Polymer blend solution

Coagulation bath
83 wt% NMP
16 wt% PES
1 wt% PVP

Soak PES
Stir at 60 ℃ for 6 h membrane in DI
prior to use
1011
 Deposition of N-CD/TiO2 on PES membrane
(Chemical grafting and photo-induced polymerisation)
5
Dip PES support membrane in
After polymerisation the polymer solution for 2 min

Dried at
75 ℃ for 4 h

N-CD photocatalyst
Acrylic acid monomer
Ethylene glycol
Potassium persulfate

Irradiate grafted
membrane with UV light
Stir for 20 min for 15 min
1112
 METHODOLOGY FLOWCHART

SYNTHESIS OF CHARACTERISATION PHOTOCATALYTIC CHARACTERISATION MEMBRANE

N-CD/TIO2 OF N-CD/TiO2 MEMBRANE OF MEMBRANE PHOTOCATALYTIC
PHOTOCATALYST FABRICATION PERFORMANCE TEST

1 2 3 4 5
• Hydrothermal TEM • N-CD/TiO2 SEM • pH of solution
duration XRD loading EDX (3,5,7,9,11)
(4h, 8h, 12h, 16h) FTIR on membrane XPS • Initial DCF
RAMAN (0.1g, 0.5g, concentration
• Volume ratio of UV-Vis 1g, 2g) (2, 3, 4, 5 ppm)
N-CD to TTIP PL • Light intensity
(0.5, 1, 1.5, 2 :5) (10W, 20W, 30W,
40W)

1213
 EXPECTED OUTCOME

N-CD/TiO2 catalyst Photocatalytic membrane Establish the optimum

synthesized from OPF exhibit enhanced operating conditions to
exhibited enhanced performance in achieve the desired
photocatalytic activity photodegradation of DCF degradation efficiency

14
REFERENCES
Al-Odaini, N., Zakaria, M., Yaziz, M., Surif, S. and Abdulghani, M. (2013). The occurrence of human pharmaceuticals in
wastewater effluents and surface water of Langat River and its tributaries, Malaysia. International Journal of
Environmental Analytical Chemistry, 93(3), pp.245-264.

Athanasekou, C., Romanos, G., Katsaros, F., Kordatos, K., Likodimos, V. and Falaras, P. (2012). Very efficient composite
titania membranes in hybrid ultrafiltration/photocatalysis water treatment processes. Journal of Membrane Science,
392-393, pp.192-203.

Bagheri, S., TermehYousefi, A. and Do, T. (2017). Photocatalytic pathway toward degradation of environmental
pharmaceutical pollutants: structure, kinetics and mechanism approach. Catalysis Science & Technology, 7(20),
pp.4548-4569.

DaSilva Souza, D.R., Caminhas, L.D., deMesquita, J.P. and Pereira, F.V., 2018. Luminescent carbon dots obtained from
cellulose. Materials Chemistry and Physics, 203, pp. 148–155.

Jiang, Z., Wan, W., Wei, W., Chen, K., Li, H., Wong, P. and Xie, J. (2017). Gentle way to build reduced titanium dioxide
nanodots integrated with graphite-like carbon spheres: From DFT calculation to experimental measurement. Applied
Catalysis B: Environmental, 204, pp.283-295. 1415
REFERENCES
Ke, J., Li, X., Zhao, Q., Liu, B., Liu, S. and Wang, S. (2017). Upconversion carbon quantum dots as visible light responsive
component for efficient enhancement of photocatalytic performance. Journal of Colloid and Interface Science, 496,
pp.425-433.

Ke, Y., Garg, B. and Ling, Y.-C., 2014. Waste chicken eggshell as low-cost precursor for efficient synthesis of nitrogen-
doped fluorescent carbon nanodots and their multi-functional applications. RSC Advances, 4(102), pp. 58329–58336.

Lin, Y., Tung, K., Tzeng, Y., Chen, J. and Chang, K. (2012). Rapid atmospheric plasma spray coating preparation and
photocatalytic activity of macroporous titania nanocrystalline membranes. Journal of Membrane Science, 389, pp.83-90.

Méricq, J., Mendret, J., Brosillon, S. and Faur, C. (2015). High performance PVDF-TiO 2 membranes for water
treatment. Chemical Engineering Science, 123, pp.283-291.

Molinari, R., Lavorato, C. and Argurio, P. (2017). Recent progress of photocatalytic membrane reactors in water
treatment and in synthesis of organic compounds. A review. Catalysis Today, 281, pp.144-164.

Pires, N., Santos, C., Sousa, R., Paula, R., Cunha, P. and Feitosa, J. (2015). Novel and Fast Microwave-Assisted Synthesis of
Carbon dots from Raw Cashew Gum. Journal of the Brazilian Chemical Society. 1516
THANK YOU
 Membrane photocatalytic performance test
6

1218
 EXPECTED OUTCOME

N-CD/TiO2 catalyst Photocatalytic membrane Establish the optimum

synthesized from OPF exhibit enhanced conditions to achieve
exhibited enhanced performance in the desired degradation
photocatalytic activity photodegradation of DCF efficiency

13
LITERATURE REVIEW

WHY NITROGEN DOPING IS NEEDED?

Bare surface of CD exposed to contaminants and
react with organic molecules resulted in low
fluorescent efficiency.
Surface passivation forms a thin insulating capping
layer that shields CD from the adhesion of impurities
Nitrogen doped CD can induce charge delocalization,
lower work function of carbon and enhance
photoluminescence

420