8th CAS Student Faculty Research Conference

16 November 2015

Visible light
Photocatalytic
activity of ZnO-CuO
composites
Dustin Loren V. Almanzaa*, Maria Carmela T. Garciaa, Alenn D. Prodigalidadb, Marvin U.
Herreraa

a
Institute of Mathematical Sciecnes and Physics, Universtiy of the Philippines Los Baos
College, Los Baos Laguna, Philippines 4031
b
San Pablo City Science High School, San Pablo City, Laguna, Philippines 4000
*dvalmanza@up.edu.ph

PHOTOCATALYSIS
Light energy

Air treatment
Water
treatment

h+
p

Semiconductor-based
material

+ H 2O

OH

+H

Sterilization

Degrades
organic
molecules
+

e-

h+

image of methyl orange

Source: Sigma Aldrich website

SEMICONDUCTOR: electron-hole
pair

OH
Source: H. Park, Y. Park, W. Kim, W. Choi, Journal of Photochemistry and
Photobiology C: Photochemistry Reviews 15, 1 20 (2013)

OH

: High oxidation potential

Source: S.-Y. Lee, S.-J. Park, Journal of Industrial and

Engineering Chemistry 19, 17611769 (2013)

ADVANTAGES
More sustainable
Non-biodegradable / does not deplete
(it is the OH radicals that are being used)

Low operational and installation cost

Simple pre-processing

DISADVANTAGE
Relay on illumination

WHY OXIDE Semicondutor?

Cheaper than conventional
semiconductor (e.g., Si, Ge)
Intrinsic state is dope state
n-type
TiO2, ZnO, Fe2O3, SnO2, WO3, and In2O3

p-type
CuO, NiO, Co3O4, Cr2O3 and Mn3O4

CHALLENGES
1) lower the energy of light needed
to activate photocatalysis
Classical approach: Choose a material with
lower band gap.
Oxide
Semiconductor

Intrinsic state

Band gap

Electromagnetic
radiation needed
for
photoactivation

Titanium dioxide,
TiO2
Zinc oxide, ZnO

n-type

3.2 eV

Ultraviolet

n-type

3.0 eV

Ultraviolet

Hematite, Fe2O3

n-type

2.2 eV

Visible light

Copper oxide, CuO

p-type

1.7 eV

Visible light

CHALLENGES
2. Increase efficiency (photocatalytic)
increase the rate of degrading
organic molecules

Increase production of

OH

Increase OH production
1) Increase e-/h+ production
Increase light intensity (up to some level only)
Increase quantum efficiency (nature of
material)

Increase surface area (e.g., nanosize)

h+
+
O
H2

e-

Interest :

2) Increase e-/h+ lifetime

higher probability to react
with water to produce OH
radical

OH

+ H+

e /h
lifetime
-

e comes back to
valence band,
h+ will disappear

Return
back!

Source: H. Park, Y. Park, W. Kim, W. Choi, Journal of

Photochemistry
and
Photobiology
C:
Photochemistry Reviews 15, 1 20 (2013)

We need h+ to
interact with water to
produce OH radical
longer lifetime
higher chance to
produce OH radical.

Increase e-/h+ lifetime*

Create surface charge region (+)
h
lig

Ec
EF
Ev

n-type

repel

prolong lifetime

H 2O

OH

+ H+

Creation of free holes Longer

time

Positive Space charge region

(SCR)
*at the (near the) interface

Repels the
photogenerated holes
out the semiconductor

to recombine

Crucial!

Lower Gap at the interface

Lower gap

Band gap

Source: L. J. Brillson , Surfaces and Interfaces of Electronic Materials WILEYVCH Verlag GmbH & Co. KGaA, Weinheim (2010)

Surface charge region of

semiconductor interfaces
(Semiconductor-vacuum
Kronik and Shapira (1999)
interface)

(Semiconductor-gas
Li Yang, et al (2013)
interface)

(Semiconductor-liquid
Michalak, et. al.
interface)
(2007)

(Semiconductor-metal
Schroder (2006)
interface)

(p-n junction)
Ng (2002)

How to make a surface region?

Create diode structure !

Ec
EF

pnjunction

Ev

ntype

repel

PositiveSpacechargeregion(SCR)

ZnO-CuO junction (p-n junction) from

various literatures

Schematic showing proposed energy band structure diagram for

flower-like p-CuO/n-ZnO heterojunction nanorods.
Source:

Ya-Bin Zhang, et al. (2014)

SOURCE: Hyo-Joong Kim, Jong-Heun Lee (2013)

OBJECTIVES
To fabricate oxide semiconductor-

based composites with p-n junction

type-interfaces.
To determine the amount of methyl

orange that were degraded with

respect to time in the presence of
illumination.

Methodology
(Heterogeneous mixing)

pressure

mixing

Sintering (100OC for 30mins)

breaking
n

p
p

n
n

n
p

Methodology
(degradation of methyl orange)

Light Sensor

Beaker w/ MO
solution (0.1mg/mL)

Vernier
LabQuest

UV Filter

Light Source

Methodology
(Data Processing)

Degradation

AVERAGE
15min, 30min,
45min, 60min,
75min

% Degradation
Transmittance Minimum Transmittance

X 100

Minimun Transmittance

Results

Pure ZnO

o Degrades methyl orange Low up to

75mins
Natural degradation of MO
Catalytic activity of ZnO
Some UV from the environment

Pure CuO
o Degrades methyl orange Low up to
75mins
o Band Gap of CuO corresponds to visible
light but p-type

Electrons went to the surface instead of holes

OH

Results

o In 25:75 volume fraction of ZnO-CuO, the percent

degradation of MO slightly improved through time
o In 75:25, volume fraction of ZnO-CuO the percent
degradation of MO slightly improved through time
This is due to the formation of p-n junction
interfaces

o In 50:50 volume fraction of ZnO-CuO, the percent

degradation of MO is maximum and increases
through time.
This is due to the formation of p-n junction
interfaces
50:50 volume fraction more interfaces

Results

Source: Ya-Bin Zhang, et al. (2014)

The ZnO-CuO composites

triggered
photocatalysis

visible light-

Conclusions
We have successfully fabricated visible
light-triggered photocatalyst material
from a p-CuO and UV-triggered n-ZnO.
The 50:50 Volume fraction of ZnO and
CuO showed the optimum photocatalytic
activity which was attributed to the
formation of larger amount of p-n
interface.