Green Synthesis ZnO/TiO2 for High Recyclability Rapid Sunlight

Photodegradation Textile Dyes Applications

Erviani Rusman, Heryanto Heryanto, Ahmad Nurul Fahri, Inayatul Mutmainna, Dahlang Tahir*

Department of Physics, Hasanuddin University, Makassar 90245, Indonesia

Corresponding authors email:*dtahir@[Link]

Telp./Fax: +62-411-587634

Abstract. Composite ZnO/TiO2 have been successfully synthesized by green synthesis method

with various calcination temperature 500oC, 600oC, 700oC, and 800oC (TiO2 concentrations: 2.5

g and 5 g) for photocatalyst application. In this study, Calopogonium mucunoides leaf extract

was used as reducing and stabilizing agent. The synthesized composites were characterized by

using Fourier Transform Infra-Red (FTIR), X-Ray Diffraction (XRD), and UV-Visible

spectroscopy. The XRD spectra shows the hexagonal phase with wurtzite structure of ZnO and

anatase for TiO2. The best degradation performance is 98.26% (only 10 min) for ZnO/TiO2 (5 g)

with calcination temperature is 800oC. This is due to the highest distance between two optical

phonon mode (LO-TO) and lowest attenuating and propagating constant. The composite

ZnO/TiO2 shows high potentials photodegradation of organic dyes with the high stable

recyclability up to 5 cycles (>95%) only for every 15 minutes. High potentials for applicability

with the concept environmentally friendly principles and stability for circular chemistry, and

efficiency of use the energy and chemicals.

Keywords: green synthesis, composite ZnO/TiO2, photocatalytic degradation, high

recyclability, textile dye.

INTRODUCTION
 Hazardous contaminants in wastewater are affected by the textile industries,

cosmetics manufacturing, pharmaceutical, metals industries, paper making, and

agricultural industries [1-3]. Azo dye is a hazardous pollutant that contains (-N=N-)

bond and phenyl or naphthyl group [4-6]. They are producing aromatic amines during

the decomposition process and potentially cause carcinogenic and mutagenic. On the

other hand, the presence of azo dye in water causes severe effects on clean water

availability and the environment [5-8]. The type of azo dyes is a mono-azo dye

(methylene blue, methylene orange, AO7 (acid orange 7)), diazo dye (congo red, 6B

(direct lake blue)), and poly azo dyes (direct black BN) [6]. One of the most widely

used azo dye is Congo Red (CR). CR is used in processing textile, paper, cosmetic, and

pharmaceutical industries [9,10]. Those dye are difficult to degrade to be a severe issue

for environmental and human health. The increased contaminant compounds in

wastewater are interested researchers in finding the polluted water treatment method to

provide clean and healthy water [11].

Water purification methods were varied through a physical, biological, and

chemical process [12,13]. The photocatalyst is one of the most effective and simple

techniques used in water treatment because it removes organic contaminants easily [11,

14,15]. Green synthesis is used as an alternative method to produce nanoparticles for

photocatalyst applications. It has several advantages, such as eco-friendly, and it does

not produce second contaminants [3]. This method used extracts of various plants as

reducing or stabilizing agents. Plant extract contains phytochemicals that act as bio-

reduction materials for capping agents in particular nanoparticles' synthesis process [16].

The reported materials nanoparticles have been produced by using green synthesis are:

Au, Ag, Pt, Pd, α-Fe2O3, CeO2-, ZnO, TiO2, ZrO2, and SnO2 [19-22]. TiO2 and ZnO are
chemically stable semiconductors that can produce an active charge during irradiation

by light with suitable wavelengths [12,23,24]. Zinc oxide is n-type semiconductor with

high excitation binding energy, bandgap width (3,37eV for anatase phase),

biocompatibility, and it is more active when irradiation by visible light. Irradiation

process for ZnO will create electron-hole by gain energy of electron for exciting to the

conduction band [1]. The electron at the conduction band moves easily to the valence

band by the recombination processes. The heterostructure method is effective approach

to control and minimize the recombination rate in ZnO consequently increase the charge

carrier lifetime [25-28].

The TiO2 is an effective semiconductor that combines with ZnO nanoparticles

displays improvement in photocatalytic activities [29-35]. TiO2 has higher efficiency as

a photocatalytic because it is responsive to the visible spectrum with bandgap 3.2 eV

[36-41]. It is using as a photocatalytic due to its good optical properties, low cost, and

high chemical stability [40-42]. The catalyst was used for photodegradation of chemical

or organic pollutants in wastewater under visible irradiation [43,44]. Doping TiO2 with

metals or non-metal ions will increase the visible light absorbance capacity or reactivity

in the UV wavelength [45,46]. The previous reports for ZnO/TiO2 as a photocatalysis

with various synthesized methods are: ZnO/TiO2 nanohybrids by using a hydrothermal

method for MB, R6G, OTC degradation [1], ZnO/TiO2 by using solid-state for

quinoline degradation [29], ZnO/TiO2 by using sol-gel for dye degradation of

methylene blue [13,35], ZnO and TiO2 commercial for phenothiazine decolorization

[36], and ZnO/TiO2 thin film by using the hydrothermal method for orange G

degradation [10]. However, the green, appropriate, and efficient photocatalysts

materials that can be easily integrated into wastewater plants and reused for real
applications is crucial. The principles process of synthesized these photocatalysts

materials should be environmentally friendly, circular chemistry, and increasing the

efficiency of the use of energy and chemicals.

For environmentally friendly materials, we synthesize ZnO/TiO2 using

Calopogonium mucunoides leaf extract by green method. Calopogonium mucunoides is

a legume and easily grow were impacting agricultural if growth uncontrolled and semi-

natural ecosystems which becoming an environmental problem mainly in Indonesia. By

using this type of a legume for photocatalyst, means that contributes to the green

environment, low-cost fabrication, efficient, recyclable, and applicability in short time

to produce clean water from decontaminant. In this study, a facile, suitable for mass-

productive, green, and cost-effective method for the fabrication of nanohybrid

ZnO/TiO2 photocatalyst for enhanced visible-light was developed. The process of

photocatalyst materials potentials to be holistically integrates with environmentally

friendly principles, circular chemistry, and efficiency of use the energy and chemicals

[47-49].

The ZnO/TiO2 composites for concentration of TiO2 are 2.5 g and 5 g, and various

calcination temperatures (500oC, 600oC, 700oC, and 800oC) characterized by using

XRD, FTIR, and UV-Vis spectroscopy. The XRD spectra used for analysis the

structural properties and FTIR spectra for the optical properties in the form of the

refractive index (n) and extinction coefficient (k) by applying Kramers Kronig (KK)

relation. The longitudinal and transversal optical phonon mode, the complex dielectric

function (real part (1) and imaginary part (2)), energy loss function (Im (-1/ 𝜀)), and

the optical absorption coefficient were determined from the n and k. The photocatalyst

efficiency for degradation of CR were analysis using UV–Vis spectrometer spectra.

High recyclability of the ZnO/TiO2 composites as catalyst in photodegradation

processes are also reported in this study.

EXPERIMENTAL

Materials and Preparation Sample

Calopogonium mucunoides (CM) leaves were taken from the Enrekang district,

South Sulawesi, Indonesia. Zinc acetate dihydrate (Zn(CH 3COO)2 ∙ 2H2O) (Merck),

titanium dioxide (TiO2) (Merck), and natrium hydroxide (NaOH) (Merck), and congo

red (C32H22N6Na2O6S2) (Merck).

The CM leaves were washed several times by distilled water to remove debris and

dirt, then dry them at room temperature for one week. The leaves were powdered using

blender and sieved the powder with 100 Mesh for uniform size. The extract was

prepared by adding 5 g of CM leaves powder in 100 ml distilled water and stirred at

80oC for 20 minutes. It was filtered with Whatman No.1 filter paper. The filtrate was

used for synthesis ZnO/TiO2, for more detail illustration of synthesized processes see

Figure 1.

Synthesis of ZnO/TiO2

Sol gel method was used for green synthesis ZnO/TiO2. The solution prepared

with 20 ml CM leaf extracts, 80 ml distilled water, and 5 g Zn(CH3COO)2∙2H2O as a

precursor. It was stirred at constant temperature 95oC and speed 500 rpm. After 15

minutes heated, TiO2 was added to the zinc oxide solution. TiO2 solution was prepared

2.5 g and 5 g TiO2 powder by added 10 ml distilled water, then homogenized for 5

minutes by constant stirring at 200 rpm using magnetic stirrer. NaOH was added
dropwise to the solution till pH 7. The paste was formed after continuous heating and

stirring for overnight. The sample paste was evaporated at 80oC for 10 hours and

continue calcined for 2 hours at the temperature 500oC, 600oC, 700oC, and 800oC to

obtain ZnO /TiO2 powder, the illustration procedure as shown in Figure 2.

Figure 1. Schematic illustration for extraction of Calopogonium mucunoides leaves

 Figure 2. Illustration procedure of green synthesis ZnO/TiO2 using Calopogonium

mucunoides leaf extract

Characterization

The synthesized powder was characterized by XRD spectroscopy, FTIR

spectroscopy, and UV-Vis spectrophotometer. XRD spectroscopy (Shimadzu 700) with

CuKα radiation at wavelength (λ) 1.54 Å (25o ≤ 2θ ≤ 65o, 40kV, 30 mA, scan rate 2

min-1, step size 0.02o) was used to determine the structure and crystallite size of the

samples by using Debye Scherrer formula. Fourier Transform Infra-Red Spectroscopy

(FTIR Spectroscopy) (IRPrestige-21 (Shimadzu Corp.)) to analyze the functional

groups that present and optical properties of the samples. UV-Vis spectrophotometer

(Shimadzu UV-Vis Spectrophotometer UV-1800) was used to study the photocatalytic

activity of CR.

Photocatalytic Mechanism

The photocatalytic degradation procedure consisted of adding 0.02 g of ZnO/TiO2

powder into 100 ml of CR solution (40 mg/L). The solution was stirred and exposed to

light using 300W Osram Tungsten Halogen lamp as a light source. To analyze the CR

concentration after degradation process, the solution was carried out every 5 minutes

and filtered it. Concentration of the solution after the degradation process was

determined by using UV-Vis spectrophotometer and the percentage of degradation

determined by:

C0 -Ct
D (%)= ( ) ×100% (1)
C0
where D (%) is the percentage of degradation, C0 is the initial concentration (at t is 0

min), and Ct is the concentration after time irradiation t min.

The recyclability of composite in photodegradation was studied by using

ZnO/TiO2 (2.5 g) at temperature 500oC. The 0.04 g of ZnO/TiO2 was added into 100 ml

CR solution (40 mg/L). The solution was stirred at 150 rpm by using magnetic stirrer

and it was irradiated for 15 minutes. The solution was filtered, and the concentration

was analyzed by using UV-Vis spectrophotometer. The composite was washed with

distilled water and centrifuged at 1500 rpm within 5 minutes. These steps were applied

repeatedly for 5 times. The sediment was dried at 80 oC within 10 minutes. Dried

composite was added back into 100 ml CR solution. It was repeated for five cycles.

RESULTS AND DISCUSSION

XRD analysis

The XRD spectra were used to identify the crystalline phase of composites

ZnO/TiO2 extracted by green synthesis mediated by Calopogonium mucunoides leaf.

Figure 3 shows XRD diffraction patterns for composite ZnO/TiO2 (TiO2 is 2.5 g and

5.0 g) at various calcination temperature. For all samples shows several diffraction

peaks 2θ of ZnO at 31.84o, 34.48o, 36.36o, 47.68o, 56.74o, and 62.98o which correspond

to the crystal planes (100), (002), (101), (102), (110), and (103) based on JCPDS card

no: 36-1451 [50]. The presence of TiO2 in the composite ZnO/TiO2 was confirmed by

the peaks 2θ at 25.38o, 37.94o, 47.64o, and 62.96o which correspond to the crystal planes

(101), (004), (200), and (204) for structure anatase based on JCPDS card no: 21-1272

[51] as can be seen in Figure 3 (a) and for TiO2 is 5 g in Figure 3 (b).
 Figure 3 (c) and (d) shows enlarger XRD spectra for diffraction peak from 30 o to

37 o for various calcination temperature. It shows there are shifts toward the highest of

the diffraction angle for 2.5 gr TiO2 at 600oC and 700oC due to the lattice reduction and

for 800oC small shits backward to the lower of the diffraction angle due to the some of

the atoms are uniform arrangement and forming new cluster crystal [52-54]. For

composite with 5.0 g TiO2 shows shifts to the higher diffraction angle regularly due to

the number of atoms Ti filled the lattice of ZnO over than the capacity for the lattice

reduction or may due to the large ionic radius of Ti compared with that of Zn [55].

Figure 3. XRD analysis of ZnO/TiO2 synthesized from Calopogonium mucunoides

leaves extract for various calcination temperature (500 oC, 600oC, 700oC, 800oC) and

TiO2 concentration (2.5 g and 5 g)

 The intensity (101) crystal plane of TiO2 clearly can be seen in composite at the

temperature ≤ 600oC but for > 600oC the intensity peak reduces drastically or almost

disappears may due to the phase change from TiO2 to ZnTiO3. In addition, the (102) and

(103) planes of ZnO overlap with the (200) and (204) planes of TiO 2. It shows that there

is perfect interaction occurs between the lattice of ZnO and TiO 2 to produce ZnO/TiO2

composite [56]. At the lowest temperature, there are some small peaks that occur at 2θ:

30.14o, 42.96o, 50.78o, and 60.70o correspond to the crystal plane (220), (400), (422),

and (440), respectively, identified ZnTiO3 phase based on the JCPDS card No: 39-0190

[57]. For the temperature increases from 500 oC to 600oC, the diffraction peaks intensity

of ZnTiO3 were decrease and the phase transformation occurred at the temperature

800oC clearly can be seen the intensity of ZnTiO3 decreases and Zn2TiO4 increase. It

shows that some of the ZnTiO3 phase were decomposed to forming Zn2TiO4 phase as

can be seen at the diffraction peaks 32.24 o, 34.90 o, 36.82 o, and 56.96o based on the

JCPDS: 01-073-0578 [11,14,58]. The peak intensities decrease and the width of FWHM

increase by increasing the calcination temperature from 600oC to 700oC may due to the

crystallite size or the interatomic spacing decreased [14,59].

Table 1. The average crystallite size, dislocation density, and strain determined by the

quantitative analysis of XRD spectra in Figure 3.

Temperature Average crystallite Dislocation density Strain

Sample
(oC) size (nm) (nm-2) (S)
500 19.99 0.0025 0.0048
ZnO/TiO2 600 11.87 0.0071 0.0081
(2.5 g) 700 7.62 0.0172 0.0132
800 17.64 0.0032 0.0057
500 15.73 0.0040 0.0062
ZnO/TiO2 600 15.21 0.0043 0.0063
(5 g) 700 8.86 0.0127 0.0111
800 8.94 0.0125 0.0120

From the XRD spectra in Figure 3 clearly shows relationship between calcination

temperatures with the peak intensities. At low calcination temperature (500oC) the

intensity of diffraction peaks are sharp and decrease with increasing the calcination

temperature, consequently decrease the crystallite size as can be seen in Table 1

calculated from the Debye Scherrer’s equation [3,60,61]:

𝐾.𝜆
Γ= 𝛽.𝐶𝑜𝑠 𝜃 (2)

where Γ is the crystallite size, θ is the Bragg diffraction angle, K is the constant about

0.9, λ is the wavelength of X-ray (for Cu is 1.5406 Å), and  is full width at half-length

maximum (FWHM). The average of crystallite size, dislocation density, and strain were

shown in the Table 1.

FTIR analysis
 Figure 4. FTIR spectra of ZnO/TiO2 synthesized from Calopogonium mucunoides

leaves extract for various calcination temperature (500 oC, 600oC, 700oC, 800oC) and

TiO2 concentration (2.5 g and 5 g)

Figure 4 shows FTIR spectra at the wavenumber 350-4000 cm-1 for identified the

functional groups and vibrational bonds of composite ZnO/TiO2. The peak 446 cm-1

corresponding to the vibration bond of Zn-O [3,62]. The peak at 723 cm-1 correspond to

the O-Ti-O band [63]. The function group of C-H band at the wave number 1000-1100
cm-1 [14] and at the wavenumber 1447 cm-1 and 1665 cm-1, there are chemical bonds of

C=C-C and C=C tensile vibration, respectively [21,55]. O-H bond appears at the

wavenumber 2504 cm-1 and 3455 cm-1 corresponding to vibration band from suspension

of hydroxyl group in adsorbed water [3,64]. A weak infrared peak at 2338 cm-1

probably due to the CO2 vibration bond absorbed during calcination process. The peak

at 2968 cm-1 is mainly due to the stretching vibration of C-H bond from the absorption

of the alkane groups [14].

Optical properties

The optical properties (refractive index (n) and extinction coefficient (k)) were

determined from the quantitative analysis of FTIR spectra by applying K-K relation

[65-67]. For the analysis optical properties, we have used only wavenumber in the range

from 860 cm-1 to 1115 cm-1 due to the C=C-C bonding which probably come from the

green synthesis methods. The FTIR spectra form the equipment is in the form of

transmittance (T(ω)), where need to be converted to the reflectance (R(ω)) [68] by the

relations:

A(ω)=2-log[T(ω)%] (3)

R(ω)=100-[T(ω)+A(ω)] (4)

The reflectance R(ω) as a function of the wavenumber is substitute in the

following equations for determining the optical properties (refractive index for real part

n(ω) and extinction coefficient for imaginary part k(ω)) [68]:

1-R(ω)
n(ω)= (5)
1+R(ω)-2√R(ω)cos∅(ω)

2√R(ω)cos∅(ω)
k(ω)= (6)
1+R(ω)-2√R(ω)cos∅(ω)
(ω) is the phase change from the incident photon beam bombardment to the sample

and traveling at the surface down to few atoms at the sample and then reflected photon

beam out which calculated by the following equation:

ω ∞ lnR(ω' )-lnR(ω)
φ(ω)=- π ∫0 (7)
ω'2 -ω2

For easily computational of by (ω), the K-K (Kramers-Kronig) relation was used and

the new equation of phase change (ω):

4ωj ln(√R(ω))
φ(ω)=- ∆ω ∑i (8)
π ω2i -ω2j

where ∆𝜔 = 𝜔𝑖+1 − 𝜔𝑖 and j is series of wavenumber, if j is an odd number, so then i

parts is 2,4,6,8,…,j-1, j+1 and while wavenumber j is an even, i parts is 1,3,5,7,…,j-1,

j+1.
 Figure 5. The optical properties (refractive index (n) and extinction coefficient (k))

determined from the FTIR spectra in Figure 4, from the optical properties the dielectric

function, the energy loss function Im (−1/ε1(ω)) are determined for various calcination

temperature for (a) ZnO/TiO2 (2.5 g) and (b) ZnO/TiO2 (5 g).

 Figure 5 (a and b) shows the intersection at higher wavenumber indicated by LO

and intersection point at the lower wavenumber indicated by TO and the values are

presented in Table 2. Figure 5(a) depicts the transverse optical (TO) of ZnO/TiO2 (2.5

g) shifts to the lower wavenumber by increase the calcination temperature up to 700 oC,

but for 800oC the TO shifts to the higher wavenumber may due to the effect of the weak

strain in the crystal structure. Figure 5(b) shows TO was decreased with increasing the

temperature. In this study, the highest distance between the two optical phonon

vibration mode ((LO-TO)) for ZnO/TiO2 (5 g) at 800oC may due to some H2O loses in

the lattice consequently increase optical bandgap [64,69]. The (LO-TO) was increased

with the increasing the TiO2 concentration at the same calcination temperature but not

for 700oC may due to the number of defect (dislocation density) increase consequently

the atomic bonding unstable and rearrange to form new atomic cluster in the lattice

structure [70,71].
Table 2. Transverse optical (TO) phonon mode, longitudinal optical (LO) phonon

mode, and (LO-TO)

Sample Temperature (oC) TO (cm-1) LO (cm-1) (LO-TO) (cm-1)

500 1012 1109 97
600 956 1128 172
ZnO/TiO2 (2.5 g)
700 864 1112 248
800 866 1112 246
500 1010 1153 143
600 948 1124 176
ZnO/TiO2 (5 g)
700 916 1118 202
800 902 1184 282

The real part (ε1 ) and imaginary part (ε2 ) of dielectric function functions were

calculated from the relation between n and k as follows [66]:

ε1 (ω)=n2 (ω)-k2 (ω) (9)

ε2 (ω)=2n(ω)k(ω) (10)

The main peak position of the imaginary part (ε2 ) and the energy loss function Im

(-1/1(ω)) were used for confirmation of the TO and LO phonon vibration modes from

the intersection point between n and k, respectively. These finding shows consistency

result as can be seen in the Figure 5, indicated that the effectiveness of the FTIR spectra

for determining optical properties and for identification optical phonon modes. The

energy loss function also identified as a plasma frequency as reported in Ref. [65,66,72]

from the quantitative analysis of electron spectroscopy [66,73]. The (LO-TO) is

important parameters to identified stability of the covalent bond and the lattice match in

the ZnO/TiO2 composite [70].

 The next important parameters are attenuation constant α and propagation

constant β which determined from the following relations:

𝜇0 𝜀0 𝜀1(𝜔) 2
𝜀 (𝜔)
𝛼 = 𝜔√ [√1 + ( 2 ) − 1] (11)
2 𝜀 (𝜔)
1

𝜇0𝜀0 𝜀1(𝜔) 2
𝜀 (𝜔)
𝛽 = 𝜔√ [√1 + ( 2 ) + 1] (12)
2 𝜀 (𝜔)
1

where µ0 is a constant related to the permeability and ε0 is also constant for permittivity

in a free space.

Figure 6. Attenuation constant (α) (first and third rows) and propagation constant (β)

(second and fourth rows) as a function of the wavenumber for calcination temperature

from 500oC (left) to 800oC (right). First and second rows for 2.5 gr of TiO 2 in ZnO/TiO2

composite and the third and fourth rows for 5 gr of TiO 2 in ZnO/TiO2 composite.
For 2.5 gr of TiO2 in ZnO/TiO2 composite shows the attenuation and propagation

constant increase with increasing the calcination temperature from 500oC (left) to 800oC

(right) and opposite trend for 5 gr of TiO2 in ZnO/TiO2 composite as can be seen in

Figure 6. The best composite for photocatalyst is for low attenuating and propagating

constant, means that the structure will easily suppressing recombination of the charge

particle due to the higher strain between the atoms [52, 54]. In this study shows 5 gr of

TiO2 in ZnO/TiO2 composite high potentials compared than that of 2.5 gr TiO2 in

ZnO/TiO2 composite for the same calcination temperature [64].

Bandgap and Photocatalytic Degradation

Figure 7. Band gap of ZnO/TiO2 synthesized from Calopogonium mucunoides leaves

extract for various calcination temperature (500oC, 600oC, 700oC, 800oC) and TiO2

concentration (2.5 g and 5 g)

 Band gap of ZnO/TiO2 composites indicated by the arrows at the absorbance

spectra in Figure 7. Band gap values were obtained by using Touch Plot method and

the corresponding results are presented in Table 4, which determined by the relation as

follows:

(αh𝑣)1/𝑚 = C(h𝑣 − E𝑔 ) (13)

where α is absorption coefficient, h𝑣 refers to photon energy, C is band form parameter,

m=1/2 for the direct allowed transition, and E g is band gap energy.

The calcination temperature from 500oC to 700oC, the band gap of composite

ZnO/TiO2 for 5 g TiO2 is same but for composite with 2.5 g TiO2 is fluctuates due to the

effect of cohesion force between the atoms of Zn and Ti. For calcination temperature

from 700oC to 800oC, the sample for the different concentration of TiO2 shows

increases the band gap may due to the effect of particle size and crystal phase in the

composite is increase [14,74].

The ability of ZnO/TiO2 as photocatalytic materials for degradation of CR was

analyzed using UV-Vis spectrophotometer. Figure 8 shows the absorbance spectrum of

CR with ZnO/TiO2 during irradiation, for the solution can be identified visually or by

the absorbance spectra at the wavelength 400-600 nm. The time for every sample to

degrade CR was different, it influenced by the ability of charge particle to produce

hydroxyl and superoxide radical which play the important roles in photodegradation.

The relation between the percentages of degradation with irradiation times are

shown in Figure 9 and the corresponding results of percentage degradation for all

sample with various calcination temperature and various TiO2 concentration were

shown in Table 3. The efficiency of photocatalyst ZnO/TiO2 mediated by

Calopogonium mucunoides leaves extract is higher than 94%. The highest efficiency is
98,26% that obtained by ZnO/TiO2 (5 g) with calcination temperature is 800oC. It

indicates the synthesis composites ZnO/TiO2 have a great potential for photocatalytic

materials.

Photocatalytic activity was affected by some factors: type of photocatalyst

material, crystallite size, and agglomeration level. It means that, the photodegradation

process may related to the different competing factors [14]. Based on the previous

reported which published by Selvi [Link], a diminution of the crystallite size led to an

increase in the specific surface area that could enhance the active reaction of the

photocatalyst materials [75].

Figure 8. UV-visible absorption spectra of ZnO/TiO2 (2.5 g and 5 g) synthesized from

Calopogonium mucunoides leaves extract for various calcination temperature (500oC,

600oC, 700oC, and 800oC)

 Figure 9. Percentage degradation of CR with the different catalysts (a) 500 oC,

(b) 600oC, (c) 700oC, and (d) 800oC

Table 3. The degradation ability of samples ZnO/TiO2 to degrade CR with the different

catalysts

Percentage Degradation
Sample Temperature (oC)
degradation (%) time (min)
500 97.17 30
600 96.31 15
ZnO/TiO2 (2.5 g)
700 94.81 10
800 95.39 15
500 96.63 30
600 95.29 15
ZnO/TiO2 (5 g)
700 96.56 10
800 98.26 10
 Figure 9 shows the kinetic model photocatalytic degradation of composites

ZnO/TiO2 for CR solution under light irradiation. Based on the kinetic model,

ZnO/TiO2 (5 g) at 800oC shows the best material for photocatalyst with the highest

photocatalytic activity. Figure 9(c) records the photocatalytic performance of CR

degradation by using ZnO/TiO2 (5 g) at 800oC is faster than the other samples.

Figure 10. Photocatalytic performance and kinetic model of composites (a-b) ZnO/TiO2

(2,5 g) and (c-d) ZnO/TiO2 (5 g) for various calcination temperature in CR solution

Figure 10(b) and 10(d) shows the photodegradation rate kinetic curves of CR for

various calcination temperature of composite materials. The degradation rate constant

(kr) in the photocatalytic reaction was calculated by the following equation [60,64]:

C
ln C0 =kr .t (14)
t
where C0 is the initial concentration and Ct is the concentration at the time t and

corresponding results for kr and R2 for composite ZnO/TiO2 are shown in Table 4. The

kr and R2 were increased with increasing the calcination temperature for ZnO/TiO 2 (5 g)

compared to ZnO/TiO2 (2.5 g) and the highest rate constant is for composite ZnO/TiO2

(5 g) at 800oC which faster degradation only for 10 min irradiation.

Table 4. Rate constants (kr), correlation coefficient values (R2), and band gap of

ZnO/TiO2 composites synthesized from Calopogonium mucunoides leaves

Sample Temperature (oC) kr (min-1) R2 Band gap (eV)

500 0.11883 0.64629 3.08
600 0.21997 0.74324 3.11
ZnO/TiO2 (2.5 g)
700 0.28380 0.86531 2.89
800 0.20506 0.78970 3.02
500 0.11305 0.50827 3.05
600 0.20374 0.62944 3.05
ZnO/TiO2 (5 g)
700 0.33696 0.64080 3.05
800 0.40521 0.79886 3.07

Photocatalytic activity

The degradation of wastewater in the photocatalytic process by demineralization

of pollutant targets with final molecules are CO2, H2O, and N2 [29]. During irradiation

processes, there is interaction between photon with the charge particle in composite

ZnO/TiO2 at the valence band and produce electron which having energy for moving by

excitation to the conduction band and remaining hole in the valence band. The

heterojunction band offset link between ZnO and TiO2 used for transfer electrons from

conduction band of ZnO to conduction band of TiO2 and transfer holes from the valence
band of TiO2 to the valence band of ZnO [1]. By this process, the number of electrons in

the conduction band of TiO2 and the number of holes in the valence band of ZnO are

increased and suppressing the recombination process. The lifetime of carrier also

increases which consequently the degradation process is faster [1,29]. The schematic of

degradation process of CR from the incoming photon, transfer charge (electron and hole)

to the final product as shown in Figure 11 for composite ZnO/TiO2.

Figure 11. Schematic degradation process of CR from the incoming photon, transfer

charge (electron and hole), produce radicals to break the bond of CR, and the final

product of photocatalytic in the composite ZnO/TiO2

Enhancement of electron density in conduction band of TiO 2 interacts with the

surface of oxygen and it will increase superoxide radicals as products. Hole in valence

band reacted with H2O that absorbed in surface of semiconductor and the result of the

reaction were hydroxyl radicals (∙OH). Species of radical active such as ∙OH and ∙O2 -
were used to mineralize the organic and inorganic contaminants in wastewater [1,21].

Figure 12 shows the active radicals degraded CR dye start by the breaking the bond of

molecules CR and continue with intermediates reaction to mineralize into carbon

dioxide, hydrogen dioxide (water), ammonium, and nitrate ion [76].

 Figure 12. Demineralization mechanism of CR by the composite ZnO/TiO2 in the

photodegradation process

Recycle

In this work, five cycles successfully show the ability of composite ZnO/TiO2 as a

new and high potentials photocatalyst to be holistically integrates with environmentally

friendly principles and circular chemistry, minimizing wastewater and efficiency of use

the energy, water, and chemicals. Figure 13 shows the excellent performance > 95.02%

degradation of CR dye with high stability up to 5 times for every 15 min irradiation.

Figure 13. Stability degradation performance of composite ZnO/TiO2 for CR dye up to

five times

To show the novelty in this study, we have compared the performance of green

synthesized composite ZnO/TiO2 in this study with the previous reported references as

shown in Table 5. The treatment time and the degradation performance in this study
shows high potentially with faster and high stability. It’s indicated that the high

applicability for the concept holistically integrates with environmentally friendly

principles and stability for circular chemistry, minimizing wastewater and efficiency of

use the energy and chemicals.

Table 5. Comparison in this study with previous reported reference of composite ZnO/TiO 2 for various synthesized methods, dye type,

light sources, treatment time, and degradation performance. Clearly in this study shows faster (10 min up to30 min) with high stability (5

cycle).

Photocatalyst Syntesized Photocatalyst Dye type Light Treatment Degradation Kinetic Ref.
method dosage source time (min) (%) rate
(min-1)
ZnO–TiO2 Hydrothermal 0.5 g/L MB Solar light 6 (MB) 98.40 0.65172 [1]
nanohybrids MO (862 W) 8 (OTC) 90.30 0.27400
OTC 30 (R6G) 81.30 0.06116
(60 mg/L)
ZnO/TiO2 Sol gel 0.5 g/L Methylene UV light 360 82.00 0.2925 [14]
composite blue
(2 mmol/L)
2-D fern-like Green synthesis 0.12 g/L Methylene Tungsten 135 98.00 0.99429 [21]
ZnO/TiO2 blue lamp
(0.2 mg/L) (500W)
ZnO/TiO2 Solid state 2.5 g/L Quinoline UV light 240 92.00 0.00560 [29]
(100 mg/L)
TiO2/ZnO Solvothermal 0.2 g/L Rhodamine Xenon 80 Not available 0.01400 [32]
composite sphere B lamp
(20 µmol/L) (300 W)
ZnO/TiO2 Pulsed laser 0.5 g/L Methyl Xenon 60 98.00 0.11420 [56]
nanocomposite ablation orange lamp
(500 W)
ZnO/TiO2 Chemical 0.5 g/L Bentazon UV light 120 84.20 0.01540 [62]
nanocomposite method (20 mg/L)
ZnO/TiO2 thin DC reactive Thin film Methyl UV light 150 91.00 Not [77]
film magnetron orange available
sputtering (10 mg/L)
technique
ZnO/TiO2 Mechanical 0.5 g/L Rhodamine Mercury 30 ~45.00 Not [78]
heterojunction mixing B lamp available
(80 mg/L) (UV light)
ZnO/TiO2 Hydrothermal Not available MB Sun light 60 (MB) Not available 0.06100 [79]
composite MO 60 (MO) 0.04700
(0.02 mM)
ZnO/TiO2 Sol gel and 0.5 g/L Methyl UV light 360 99.5 0.01760 [80]
precipitation orange (40W)
(10−5 mol/L)
ZnO/TiO2 Sol gel Thin film Methylene LED 160 Not available 0.00700 [81]
core/shell deposition blue (140 mW,
(10 mM) monochro
matic light
of 400
nm)
ZnO/TiO2 Hydrothermal A piece of Methyl Xe lamp 210 ~100 Not [82]
nanocomposite composite on orange (300 W) available
Ti fabric (20 mg/L)
(1 cm×1 cm)/
100 mL
ZnO/TiO2 Electrostatically 0.6 g/L Methyl UV light 360 Not available 0.01270 [83]
modified orange
electrospinning (3 mg/L)
ZnO/TiO2 (2.5 g)
500oC Green synthesis 0.2 g/L Congo red Tungsten 30 97.17 0.11883 Present
(40 mg/L) lamp
(300W)
600 oC Green synthesis 0.2 g/L Congo red Tungsten 15 96.31 0.21997 Present
(40 mg/L) lamp
(300W)
700 oC Green synthesis 0.2 g/L Congo red Tungsten 10 94.81 0.28380 Present
(40 mg/L) lamp
(300W)
800 oC Green synthesis 0.2 g/L Congo red Tungsten 15 95.39 0.20506 Present
(40 mg/L) lamp
(300W)
ZnO/TiO2 (5 g)
500 oC Green synthesis 0.2 g/L Congo red Tungsten 30 96.63 0.50827 Present
(40 mg/L) lamp
(300W)
600 oC Green synthesis 0.2 g/L Congo red Tungsten 15 95.29 0.62944 Present
(40 mg/L) lamp
(300W)
700 oC Green synthesis 0.2 g/L Congo red Tungsten 10 96.56 0.64080 Present
(40 mg/L) lamp
(300W)
800 oC Green synthesis 0.2 g/L Congo red Tungsten 10 98.26 0.79886 Present
(40 mg/L) lamp
(300W)
Conclusion

The composite ZnO/TiO2 was synthesized from Calopogonium mucunoides leaf

extract by using green synthesis method. The composites were prepared for various

calcination temperature (500oC, 600oC, 700oC, and 800oC) and different concentration

of TiO2 (2.5 g and 5 g). From XRD analysis, the crystallite size of composites was

influenced by the concentration of TiO2 and calcination temperature during the

synthesis. FTIR spectra observed the Zn-O band at the peak 446 cm-1 and O-Ti-O band

at the peak 723 cm-1. The optical properties were analyzed by using K-K relation from

the infra-red spectra, it shows the highest energy loss function and distance between

optical phonon vibration modes (LO-TO) is in the ZnO/TiO2 (5 g) at temperature

800oC. It indicates the stable and strong bonding formation and the lattice match in the

composite which has effect to enhance photocatalytic activity. According to UV-Vis

study, the synthesis of ZnO/TiO2 shows high effectivity in photodegradation of CR dye.

The materials presented the excellent photocatalytic performance with highest

degradation efficiency for composite ZnO/TiO2 (5 g) at 800oC. In this study shows high

potentially with faster and high stability, indicated that high applicability concept for

holistically integrates with environmentally friendly principles and high stability for

circular chemistry, and efficiency of use the energy and chemicals.

Acknowledge

This work was supported by the PT (Penelitian Terapan) funded by the Indonesia

Government (Kemenristek/BRIN) grants 2021.

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