Introduction to Sustainable Energy Technologies

(SEE605A)

Experiment
on
Photocatalytic Degradation of Methylene Blue Dye
Under Visible Light

DEPARTMENT OF SUSTAINABLE ENERGY ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY KANPUR

 WATER REMEDIATION

Background
Nowadays, one of the major organic pollutants such as dyes (Methylene blue, Rhodamine, etc.)
are widely used in the textile industries, but it cannot be completely removed by wastewater
treatment methods. Their traces remained in the water discharged from the industry to the rivers
which are dangerous to the health of living organisms and lead to contamination of the drinking
water. Some techniques used to remove biological and chemical pollutants from wastewater
includes adsorption, filtration, ozonation, and sedimentation which results in high operating costs
and sludge production. However, photocatalysis is an efficient, cost-effective, andenvironmentally
friendly advance oxidation process (AOP) process that allows the complete degradation of various
organic pollutants into non-toxic substances. It is a sustainable method witha high oxidation and
reduction ability to degrade organic pollutants with lower energy consumption than other
processes.
Methylene blue is used not only to dye paper and office supplies but also to tone up silk colors. It
has largely been used in human and veterinary medicine for several therapeutic and diagnostic
procedures. It cannot be degraded through the conventional water treatment process due to its
complex aromatic structures, hydrophilic nature, and high stability against light, temperature,
water, chemicals, etc., and it may cause substantial environmental pollution.

Mechanism

Figure 1. Basic mechanism of Photocatalysis

The mechanism of photocatalysis is depicted in Figure 1 and it consists of the following steps:
1) Absorbance of energy greater than the band gap energy by the photocatalyst semiconductor
in the form of photons.
2) Excitation of electrons from the valance band to the conduction band and generation of holes
inthe valance band of the semiconductor.
3) Migration of electrons (e-) and holes (h+) towards the surface of the semiconductor. At the
same time recombination of the e- and h+ occurs.
4) These e- and h+ will reduce the adsorbed oxygen into the superoxide radical (O2• −) and oxidize
OH-/H2O into the hydroxyl radicals (OH•). These O2• − and OH• are the key reactive oxygen
species (ROS) that further degrade the organic pollutants into non-toxic products.

Excitation: Photocatalyst + hν (UV) → Photocatalyst (e−CB + h+VB)

Oxidation: Photocatalyst (h+VB) + H2O → Photocatalyst + H+ + OH•
Photocatalyst (h+VB) + OH− → Photocatalyst + OH•
Reduction: Photocatalyst (e−CB) + O2 → Photocatalyst + O2• −
O2• − + H+ → HOO•
Degradation: pollutant + OH• → Degraded products
pollutant + O2• − → Degraded products
Where, e−CB = Excited electrons in conduction band (CB)
h+VB = Generated holes in valance band (VB)
OH• = Hydroxyl radical
O2• − = Superoxide radical
HOO• = Hydroperoxyl radical
 WATER REMEDIATION

Overview of the Experimental Setup:

Figure 2. Photocatalysis experiment set-up.

In this experiment, we investigate the photocatalyst degradation efficiency towards the

degradation of organic pollutant (Methylene blue dye) under visible light illumination in
water system.
This setup is enclosed in a cardboard box (see Figure 2) which comprises of:
A. Visible Light Source (250 W)
B. Measuring Cylinder (100 mL)
C. Air Pump & Tubes

 UV-VIS-NIR Spectrophotometer
The Agilent Cary 5000 UV-Vis-NIR Spectrophotometer (depicted in Figure 3) is used to test
material absorbance, transmittance, and reflectance. This apparatus contains Deuterium and
Tungsten Halogen lamps to generate UV (200 ≤ λ ≤ 400 nm) and visible light (400 ≤ λ ≤ 800 nm).
The material absorption follows the Beer-Lambert law (A= εCL).

A= Absorbance, ε = Molar absorption coefficient, C= Molar concentration, L= Optical path length,

Transmittance to Absorbance: Transmittance and absorbance are closely related concepts.
Transmittance is defined as a ratio of the intensity of incident light (𝐼𝐼0 ) to the amount of intensity passes
through the object (I). The transmittance is denoted as T.
𝑇𝑇 = 𝐼𝐼/𝐼𝐼0 (1)
However, it is more commonly expressed as a percentage transmittance: 𝑇𝑇 (%) = 100 𝐼𝐼/𝐼𝐼0
The amount of radiation absorbed can be measured by the transmittance. The relation between
transmittance (T) and absorbance (A) is given by the Beer-Lambert law (Beer’s law).

𝐴𝐴 = 𝑙𝑙𝑙𝑙𝑙𝑙 10 𝐼𝐼0 /𝐼𝐼 (2)

𝐴𝐴 = 2 − 𝑙𝑙𝑙𝑙𝑙𝑙 10 (%𝑇𝑇) (3)

Figure 3: Agilent Cary 5000 UV-Vis-NIR Spectrophotometer

 Mini Centrifuge Machine: The centrifuge machine is used to remove the photocatalyst
particles from the dye solution so that the absorption of the dye can be measured accurately.

Figure 4: Mini centrifuge machine.

 EXPERIMENT

OBJECTIVE:
● Photocatalytic degradation of Methylene Blue (C16H18ClN3S) under visible light
illumination.

WHAT WILL YOU LEARN IN THIS EXPERIMENT?

a) Degradation efficiency of the photocatalyst towards Methylene Blue (MB) under visible
light illumination.
b) Effect of catalyst loading on the degradation of Methylene Blue.

SAFETY PROCEDURES FOR THIS EXPERIMENT:

a) Wear safety goggles, gloves, lab coats, and shoes during the whole experiment.
b) No shorts/sandals/slippers are allowed in the lab.
c) Do not touch, smell or taste any chemicals.
d) Do not work alone in the laboratory.
e) Do not open the lid of the spectrophotometer while measuring the absorbance.

PERSONAL PROTECTIVE EQUIPMENT (PPE) NEEDED:

● Gloves • Mask
● Safety goggles • Lab Coat

Abbreviations

MB Methylene Blue (C16H18ClN3S)

N Normality
V Volume of Solution (mL)
t Time (min)
C0 Initial Concentration of MB solution (ppm)
C Concentration of MB solution at time (t)
XA Percentage Degradation of MB with time (t)
k Rate Constant (min-1)
rA Reaction Rate (mol L-1min-1)
Calibration Curve measurement for Methylene Blue Dye:

NOTE: Due to time constraints, this part is already done by the TAs beforehand.

1. Calibration sample preparation for the Methylene blue

a) Prepare 1000 ppm (1 ppm = 1 mg/L) methylene blue stock solution by dissolving 20 mg of
MB powder in 20 ml of water (Millipore or Deionized Water).
b) Prepare 100 mL of 100 ppm MB stock solution using the normality equation (N*V=Const)
i.e.,
I. N1*V1=N2*V2
II. 1000 ppm*V1=100 ppm*100 mL; V1=10 mL of 1000 ppm solution
III. Hence, for preparing the 100 mL of 100 ppm MB solution, mix 10 mL of 1000 ppm MB
solution into the 90 mL of Millipore water and shake it well.

c) Repeat the steps (I to III) to prepare 3 mL of 6 ppm, 4 ppm, 2 ppm, 1 ppm MB solution for
the calibration of MB dye.

2. Absorption measurement by UV-Spectrophotometer

a) Load both the cuvette filled with Millipore water (2 mL) for baseline correction.
Note: Make sure that the transparent side of the cuvettes should be in the direction of the
beam sothat it can pass through the solution in the cuvettes.
b) Switch on the UV-VIS spectrophotometer and search for “Scan” in the taskbar. Now, open
the software and wait until the instrument stabilized itself (at the left top corner red color digit
will be highlighted).
c) Now, click on Setup option > Instrument setting > Cary option and set X mode from 200nm
to 800 nm and Y mode as absorbance.
d) Now, click on the Independent UV/VIS and NIR control > select independent control mode
and in measurement mode, click on the Fixed SBW.

e) Now click on Baseline > Baseline correction > OK.

f) Click on the Zero on the left side so that the measurement will start from zero. Now click
onthe Baseline and press Ok.

g) Now, wait for the spectrophotometer to measure the baseline of absorbance vs wavelength curve.
h) After completion, remove the water filled in the sample cuvette and fill it with 2 ml of 6 ppm
MB solution. Place the cuvette in the sample holder again and close the lid of the
spectrophotometer.
i) Now, click on the Zero option again and wait for the start button to turn green. Then, click on
the start button and create the folder Water_Remediation: Calibration curve of MB solution
for different concentrations and set the file name (ex: MB_Std_6ppm_date) and file type as
Batch(.*BSW) and then press save.

j) Similarly, create the sample name as specified above and press OK.
k) Now, wait for the spectrophotometer to measure the absorbance vs. wavelength curve for the
corresponding concentration of MB solution.
l) After completion of the measurement, wash the cuvettes thrice with Millipore water and
remove all the water in a beaker. Now, replace 2 mL of the 6 ppm solution in the sample
cuvettewith 4 ppm MB solution and repeat steps from h to i.
m) Similarly, perform the experiment for rest of the concentrations one by one.
n) After doing it for all the concentration, click on FILE tab > SAVE As > File format (.CSV).

o) Cross-check the saved file and then close the Cary WIN UV application, by clicking the cross
button on the top-right of the application window.

Equation (1):
y = 0.2316x + 0.0259
R² = 0.9997
where, y=absorbance
Abs

x=concentration

Calibration Curve
 EXPERIMENTAL PROCEDURE (To be Done by Students)
• Baseline Correction: UV-VIS Spectro-photometer

 First, do the baseline correction by using the same steps from (a-g) as mentioned above in the
“Absorption measurement by UV-Spectrophotometer” section for calibration data. Empty
the sample cuvette and proceed next to the adsorption and degradation study.

• Adsorption & Degradation Study: (To be Done by Students)

1. Using the Normality Equation, prepare 250 mL of 2 ppm MB solution using 100 ppm MB
solution as a stock solution to carry out the degradation experiments.
2. Take photocatalyst weighing 1.0 g/L & 2.0 g/L in two 100 mL of 2 ppm [C0] MB solutions in a
measuring cylinder (Label them) & switch on the air pump for mixing (immerse pipe to the
bottom of the flask) in dark (~30 min) until the adsorption-desorption equilibrium is achieved.
3. Take 2 ml from each sample using a 1 mL pipette in the two microcentrifuge tube (2 mL each) at
fixed intervals (~10 min) and centrifuge it for 3 minutes at 5000 rpm using the centrifuge
machine to remove the catalyst particles and take out the clear liquid sample carefully (do not
shake it while removing from centrifuge) in the clean dry cuvette for the absorbance
measurement using the spectrophotometer.

Reference
Cuvette

Sample
Cuvette

Spectrophotometer Cuvette Holder Cuvette

4. After placing the cuvette in the spectrophotometer close its lid. Now in the software, click on the
Zero option and wait for the start button to turn green. Then, click on start button and create the
folder Water_Remediation: Group_X_Date (X: Group No.) and set the file name & sample
name (ex: MB_2ppm_1g_L loading_10 min D_GX) or (ex: MB_2ppm_2g_L loading_10 min
D_GX) and file type as Batch (.*BSW) and then press save.

Note: You need to create the folder only once, in further experiments keep on saving the file in
the created folder only.
5. After the measurement, put the sample back in the microcentrifuge tube having the catalyst,
shake it, and put back the sample into the measuring cylinder to avoid the change in catalyst loading
and liquid volume.
6. Repeat steps 2 to 4 for three more sample measurements in Dark (D10, D20, D30).
7. After 30 min switch on the visible light (> 400 nm) and repeat the same steps 2 to 4 to measure
the sample absorbance for 0 to 60 minutes at an interval of 10 mins.
8. After doing it for all the samples, click on the FILE tab > SAVE As > File format (.CSV).
9. Cross-Check the saved file and then close the Cary WINUV application, by clicking the cross
button on the top-right of the application window.
Experimental Data Table:

Catalyst loading (g/L) 0.25 g/L, 1.0 g/L 2.0 g/L

Initial MB concentration (ppm) 2 ppm
Lamp power (W) 250 W

A. For Catalyst Loading = 0.25 g/L

Mode Time(t) Absorption Conc. C1/C0 XA1 k1 rA1 (mol L-
1
(min) (C1) (%) (min-1) min-1)
(ppm)
Dark 0 - -
DARK 15 - -
LIGHT 0 - -
LIGHT 15
LIGHT 30
LIGHT 45
LIGHT 60
LIGHT 75
LIGHT 90

B. For Catalyst Loading = 1.0 g/L

Mode Time(t) Absorption Conc. C2/C0 XA2 k2 rA2 (mol L-

1
(min) (C2) (%) (min-1) min-1)
(ppm)
DARK 0 - -
DARK 15 - -
LIGHT 0 - -
LIGHT 15
LIGHT 30
LIGHT 45
LIGHT 60
LIGHT 75
LIGHT 90
C. For Catalyst Loading = 2.0 g/L (Absorbance Data has been provided below)

Mode Time(t) Absorption Conc. C3/C0 XA3 K3 rA3 (mol L-

1
(min) (C3) (%) (min-1) min-1)
(ppm)
DARK 0 0.3906 - -
DARK 15 0.3675 - -
LIGHT 0 0.3675 - -
LIGHT 15 0.3643
LIGHT 30 0.3463
LIGHT 45 0.3399
LIGHT 60 0.3317
LIGHT 75 0.3178
LIGHT 90 0.3124

Note: Use Equation (1) to calculate C1, C2 & C3 for absorbance obtained at the fixed intervals.

CALCULATION:
1. Plot a calibration graph between concentration and absorption.
Note: At t = 0, Ci = C0 = 2 ppm. (Where i = 1, 2 or 3)
2. Plot Ci /C0 vs. time (t).
3. Calculate the % degradation of MB using the following formula:
XMB (%) = (1- Ci /C0) *100
4. Plot % degradation vs. time(t).
5. Plot (-ln Ci) vs. time (t) and calculate its slope (slope= k).
C0
Ci
ln = - kt
C0

6. Calculate rate constant by pseudo first order reaction equation

dCi
rA = - = k* Ci
dt

7. Plot rA vs. time (t).

 Equation (1): y = 0.2316x + 0.0259
QUESTIONS:

• What are the requirements for a good photocatalyst?

• What are homogeneous and heterogenous photocatalysis?
• What is the formula and structure of Methylene blue (MB)?
• How the change in catalyst loading (0.25 g/L, 1.0 g/L, 2.0 g/L) affects the degradation of
MB? Compare the %Degradation vs time for different loading and comment.
• State the equation of -ln(Ci/Co) vs time for different loading with its R2-Score. Explain the
observed differences.
• What are the advantage and disadvantages of the photocatalyst?
• Give few names of UV and visible light active photocatalysts.

****END****