Development of LaFeO3/CdS/rGO-nanosheet photocatalyst for

efficient visible light photocatalytic hydrogen production.

ADAMU ABDULLAHI MUSA

RESEARCH SUPERVISORS
DR. HAFEEZ YUSUF HAFEEZ
PROF. ABDUSSALAM BALARABE SULEIMAN

FEDERAL UNIVERSITY DUTSE

25/10/2023
 OUTLINE

INTRODUCTION

STATEMENT OF THE PROBLEM

AIM AND OBJECTIVES

LITERATURE REVIEW

Photocatalysis

Photocatalytic Water Splitting

Photocatalyst Requirement

Band Engineering

Heterojunction Requirement


METHODOLOGY
 Synthesis of ternary LaFeO /CdS/rGO nanocomposite
3
 Characterisation of LaFeO /CdS/rGO nanocomposite
3

EXPECTED RESULT

CONCLUSION

ACKNOWLEDGEMENT
 ABSTRACT

This research aims to develop a high-efficient photocatalyst for H 2 production using LaFeO3/CdS/rGO
nanocomposite. The proposed research will investigate the photocatalytic hydrogen production role of the material
using various techniques such as composition, functional groups, band gap, structure, and morphology of the
material to study the steps involved in the process, such as light absorption, charge separation, and charge transfer.
The expected outcomes of this research are development of a high-efficient photocatalyst for hydrogen production
and the identification of the key factors that affect the photocatalytic hydrogen production performance of the
developed photocatalyst material.
 Introduction
Global Energy Demand

Requirement For Carbon-Free Environment

Low-carbon or Zero-carbon Emissions

Scalability
Affordability
Energy Content

ENERGY CONSUMPTION
5.5 × 1020 J/y

Figure 1: Greenhouse
CO2 accounts 87% of the total global emission (world energy review, june 2023)
 INTRODUCTION CONT…

The only Viable Option

Renewable Energy Source
Clean
Abundant
Can Be Converted to Fuels
Sufficient

Figure 2: Conversion of Solar Energy to Chemical Fuels

Chemical Energy
H2O, CH3OH, CH4, NH3 SOLAR IRRADIATION
3.0 × 1024 J/y
INTRODUCTION CONT…..
Water Splitting Processes

Figure 3: Solar-water splitting

 INTRODUCTION CONT….

LaFeO3

LaFeO3/CdS/rGO
CdS

rGO
 SIGNIFICANCE OF THE STUDY

Achieve climate goal

Explore other impact of the

proposed photocatalyst. Develop new photocatalyst
 STATEMENT OF THE PROBLEM
WHY TERNARY LaFeO3/CDS/nanosheet- rGO
 Problem of the LaFeO3
• Weak Charge Separation
• Rapid recombination
• UnScalability

 Gap intends to fill

To this end, a ternary nanocomposite consisting of POs and metal sulfide semiconductors
(LaFeO3 and CdS) supported on reduced graphene oxide (rGO) nanosheets will be
hydrothermally synthesized. This ternary heterojunction is a novel material for SWS, and
no prior studies have been reported on its performance for this application.
 AIM AND OBJECTIVES

Aim: Development of LaFeO3/CdS/nanosheet-rGO based for efficient

visible light photocatalytic hydrogen production.

To characterize the structural,

To synthesize LaFeO3/CdS/rGO
morphological, and optical properties
ternary nanocomposites using of the LaFeO3/CdS/rGO ternary
hydrothermal method.
nanocomposites.

To evaluate the photocatalytic activity of the

LaFeO3/CdS/rGO ternary nanocomposite for
hydrogen production from water using visible light.
 LITERATURE REVIEW
Photocatalysis
A process that absorbs photons of light to activate a substance inorder to speed
up the rate of a reaction process without consuming it.

Photocatalytic Water Splitting

A process of using sunlight and a photocatalyst to split water molecules into
hydrogen and oxygen gas.
MECHANISM OF WATER
SPLITTING

hƲ −
+ ¿+4 𝑂𝐻 ¿
2 𝐻2 𝑂 ⇌ 4𝐻
𝑃h𝑜𝑡𝑜𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
 HETEROJUNCTION REQUIREMENT
Key requirements for effective type II Heterojunction

• Band gap alignment

• Surface area
• Chemical stability
• Cost-effectiveness
 Why Lanthanum ferrite (LaFeO3)?

1. Suitable Band Gap (2.1eV)

2. Charge Separation ability but weak

3. Chemical Stability

4. Abundance
 EMPIRICAL REVIEW
Reactant Band gap Activity
Main (eV)
S/N Co-catalyst Solution/Sacrific Incident Light Synthetic Route (µmol/g/ Ref
Photocatalyst
ial agent h)
2.07 (Tijare et al.,
1. LaFeO3 H2PtCl6 Ethanol 400W Visible region Sol-gel Method 3315
2012)
Sol-gel via nitrate 2.08 (Boulahouache et
2. LaFeO3 Thiosulfate S2O32- 13W Visible region 297
route al., 2023)
Aqueous solution 2.14
3. LaFeO3 MoS2 500 W Hg-Xe lamp Hydrothermal 179 (Das et al., 2021)
(no reagent)
250W 1.64 (Samajdar et al.,
4. LaFeO3 rGO Hydrothermal 82,000
Visible region 2023)
Two step 2.24-2.42
g-C3N4-
5. LaFeO3 Visible region Calcination 1,326.5 (Tian et al., 2022)
0.25Graphene
Method
Ru doped Solution 1.72
LaFeO3 (Iervolino et al.,
6. Ru3+ ions Visible region Combustion 532
2017)
Synthesis
(Manchala et al.,
7. LaFeO3 CdS/CQD Lactic acidic Sunlight Hydrothermal 25, 302
2021)
2.1 and 2.31
respectively (Manchala et al.,
8. LaFeO3 CdS Lactic acidic Sunlight Hydrothermal 22, 537
2021)

Methanol (Xu & Feng,

9. LaFeO3 g-C3N4 300W Xe Lamp Polycondensation 158
triethanol amine 2017)
 MOTIVATION FOR THE COUPLING OF
LaFeO3 AND CADMIUM SULFIDE (CdS)?

1. Complimentary band gap of LaFeO3 and CdS (2.1eV

and 2.34eV respectively)

2. CdS is a good absorber of visible light

3. Both can be produced inexpensively.

 ROLE OF REDUCED GRAPHENE
OXIDE

These factors can lead to a significant increase in the hydrogen

production rate of LaFeO3/CdS when rGO is added.

• Protecting LaFeO3/CdS from degeradation

• Enhancing charge separation

• Improving Light absorption

 MATERIALS
S/N Materials Models/Specifications Purchased Company Production Year
1 Glass wares (Beakers, Cylinders, 100-1000ml beakers Beijing Glass Group 2023
etc.) 50-200ml cylinders
2 Magnetic beads (Big, Medium and 100x24mm bead Dongguan Hawa Equipment Co. 2023
Small) 75x16mm bead Ltd
25x8mm bead

3 Magnetic heat stirrer 78HW-1 Dongguan Hawa Equipment Co. 2022

Ltd
4 Digital weighing balance 7RB153-A6ZH10A5 Chiwin Investment 2022
5 Hot plate/Oven DHG-9023A 22OV/50Hz, HINOTEK Group Ltd 2014
850W
6 Muffled Furnace TC-5-12 Wincomcompany limited 2019
7 Crucible with cover C-20/20ml Wincomcompany limited 2022
8 Mortar and pestle 400ml capacity Morgan advanced material 2022
company
9 Autoclave 100ml Tarrico Corporation 2023
10 High speed Centrifuge BKC-T1100 JINAN-BIOBASE Medical Co. 2023
Ltd
S/N Materials
CHEMICALS
Models/Specifications Prepared Company Prepared Production
Year
1. Lanthanum Nitrate (La(NO3)3) ·6H2O Analytical Reagent Acros Organics. 2023
(A.R)
2. Potassium Hydroxide (KOH) Analytical Reagent Merck 2023
(A.R)
3. Polyethylene glycol (PEG) Analytical Reagent Fisher Chemicals 2023
(A.R)
4. Fe(NO3)3·9H2O Analytical Reagent Merck 2023
(A.R)
5. Ethanol (C2H5OH) Analytical Reagent LobaChemie 2203
(A.R)
6. Cadmium Chloride (CdCl2) Analytical Reagent LobaChemie 2023
(A.R)
7. Thiourea (CH4N2S) Analytical Reagent LobaChemie 2023
(A.R)
8. Graphite powder Analytical Reagent LobaChemie 2023
(A.R)
9. Distilled water Laboratory Reagent Millipore System. 2023
(L.R)
10. Hydrogen peroxide (H2O2) Analytical Reagent LobaChemie 2020
(A.R)
11. Potassium permanganate (KMnO4) Analytical Reagent LobaChemie 2023
(A.R)
12. Sulfuric acid (H2SO4) Analytical Reagent RANKEM 2023
(A.R)
13. Phosphorus Pentoxide (P2O5) Analytical Reagent CDH 2023
(A.R)
14. Potassium Persulfate (K2S2O8) Analytical Reagent MOLYCHEM 2023
(A.R)
15. Hydrochloric acid (HCl) Analytical Reagent LobaChemie 2023
(A.R)
16. Lactic Acid Sacrificial agent LobaChemie 2023
(S.R)
 METHODOLOGY

B
A 0.004 M Fe(NO3)3·9H2O
30 mL of aqueous
&
0.002 M
PEG, ~1.6 g
La(NO3)3·6H2O
&
& Stir for 10 m 2 M KOH

Transfer to Autoclave and heat at 200 Add dropwise in to A solution under 1 h

°C for 72 h. vigorous stiring

Wash the resulting sampling and dry in

oven at 60 °C.
Label the Final Violet Powder of
LaFeO3 as LFO
 Synthesis of CdS
Dissolve 0.13 M of (CdCl2) in 40 ml of DI
Water

Add Thiourea (CH4N2S) and Stir for 1 h.

Heat at 180 °C For 24 Hours using Autoclave

Wash the resultant solution with DI Water

Dry in Oven at 80 °C
 SYNTHESIS of rGO
2 g of graphite powder & H2SO4

Stir and ice bath for 2 hours

Add slowly 8 g of KMnO4,

Stir and heat at 35 °C hot water bath for 3 hours

Add 160 mL of DI & raise the Temp. to 98 °C for 20 m

Add 10 mL of 30% hydrogen peroxide solution

Wash with HCl and DI Water Dry at 60 °C for 24 h.

Synthesis of LaFeO3/CdS/rGO nanocomposite

First, 30 wt% of Synthesized rGO will be dispersed in 40 ml of Deionized (DI) Water And Sonicated For
15 Minutes.

Second, 40 wt% and 30 wt% of Synthesized LafeO3 and CdS Will respectively be added to the mixture and
Stir For 30 Minutes.

Third, The resulting solution will then be transferred to a 50 ml Teflon-lined Stainless Steel Autoclave and
Hydrothermally treated at 180 °C For 6 Hours.

Quarto, The resultant solution will then be Centrifuged And Washed With DD Water.

Finally, The Precipitate Is Dried In An Oven At 80 °C Overnight.

CHARACTERIZATION OF TERNARY LAFEO3/CDS/rGO
EDS
FTI
TE R
M

LaFeO3/CdS/rGO

UV-
VIS
PL
NIR

XR
D
 EXPECTED RESULT

 Synthesized LaFeO3/CdS/rGO nanocomposite.

 Developed a photocatalyst with improved light absorption and

enhanced charge carrier separation.

 Developed a Photocatalyst that is able to produce Hydrogen on a

large scale at affordable price.
 PROPOSED MATERIALS

Material CBM (eV) VBM (eV) Eg (eV)

LaFeO3 - 0.1 + 2.0 2.1

CdS - 0.37 + 1.94 2.34

Cu2O - 0.46 +1.14 1.6

CsFeO3 - 0.83 + 2. 49 3.32

 BUDGET
S/N
Description of Item 1st Year 2nd Year Total (N)
1.
Registration Fess 120,000 200,000 320,000

2.
Equipment 70,000 60,000 130,000

3.
Supplies and Consumable (Reagents & Chemicals) 300,000 100,000 400,000

4.
Data Collections and Analysis (XRD, FESEM, XPS etc.) 110,000 90,000 200,000

5.
Travels (Conference & Workshops) 100,000 100,000 200,000

6.
Dissemination (Seminars & APC charges) 80,000 80,000 160,000

7.
Accommodation 100,000 100,000 200,000
8.
Others/Miscellaneous 100,000 120,000 220,000

9.
Grand Total 980,000 850,000 1,830,000
 GANT CHART
2023 2024

Task 12 Months Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

Registration and course

work.

Topic design

Literature review

Proposal writing

Review paper writing

Material synthesis

Characterization

Writing research papers

Thesis writing

Defense
 Conclusion

Small but Important adjustments to Solar Water Splitting (SWS)

Systems can Significantly increase Hydrogen Production by
Improving The Efficiency of the System, Reducing The Cost Of
Production, And Making The System More Durable And
Reliable.
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 Acknowledgement

This research was funded by Tertiary Education Trust Fund

(TETFUND) and Seed Grant for New African Principal
Investigation (SG-NAPI) (grant number 4500454078) under the
TWAS-BMBF-2021 program.
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