# Visible Light Photocatalytic Property of Ag/TiO2 Composite

A Padmanaban, T Dhanasekaran, S Praveen Kumar, G Gnanamoorthy, S

Munusamy, A Stephen, V Narayanan

► To cite this version:

A Padmanaban, T Dhanasekaran, S Praveen Kumar, G Gnanamoorthy, S Munusamy, et al.. Visible Light Photocatalytic Property of Ag/TiO2 Composite. Mechanics, Materials Science & Engineering Journal, 2017, 9 (1), 10.2412/mmse.97.67.748. hal-01498142

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Submitted on 29 Mar 2017

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Visible Light Photocatalytic Property of Ag/TiO₂ Composite

A. Padmanaban¹, T. Dhanasekaran¹, S. Praveen Kumar¹, G. Gnanamoorthy¹, S. Munusamy¹, A. Stephen², V. Narayanan¹,ᵃ

1 – Department of Inorganic Chemistry, University of Madras, Chennai, India

2 – Department of Nuclear Physics, University of Madras, Chennai, India

a – vnnara@yahoo.co.in

<figure><img src="image_2.png" /></figure>

DOI 10.2412/mmse.97.67.748 provided by [Seo4U.link](https://link.springer.com/10.2412/mmse.97.67.748)

**Keywords:** Ag/TiO₂, photo catalyst, methylene blue.

**ABSTRACT.** Ag/TiO₂ composite was synthesized by thermal decomposition method using tetraethyl orthotitanate, silver nitrate and hexamine as a surfactant. The synthesized materials were confirmed by X-ray diffraction. The morphology of the sample was investigated by field emission scanning electron microscope (FE-SEM). The morphology of the Ag/TiO₂ composite was found to be the cubic microstructure with complete decoration of Ag nanoparticles over the TiO₂ surface uniformly. The optical property of the photo catalyst was observed from UV-vis spectroscopy. The photocatalytic activity of the Ag/TiO₂ composite was investigated by the degradation of a methylene blue under visible light irradiation. The observed results showed that Ag incorporation enhance the visible-light adsorption and improved the photocatalytic efficiency of TiO₂ composite significantly under visible light.

**Introduction.** Recent years we are facing number of environmental issues related to the energy disaster, water pollutions, etc. To overcome this problem the semiconductor materials have been used as a photocatalyst for degradation of organic pollutants, hydrogen production from water splitting and dye sensitized solar cells. Among various semiconductor oxides titanium dioxide (TiO₂) is one of the well-known wide band gap n-type semiconductor materials. Since last decade, TiO₂ has been widely investigated for photocatalytic degradation of harmful organic pollutants from the waste water due to its nontoxicity, low cost and excellent chemical stability. Because of its limited visible-light absorption nature and low photocatalytic efficiency their practical application is limited and need to be improved. Consequently, the surface modification in TiO₂ lattice such as doping of various transition metals, noble metals and combine with narrow band gap semiconductor materials could make it as more sensitive to visible light and improve the photocatalytic efficiency. In general, the noble metals Pt, Pd, Rh, Au and Ag are having superior photocatalytic efficiency but their high cost limit their large scale applications. Recently, TiO₂ with noble metals combination have received more attention towards photodegradation. Among them the above noble metals Ag is the less expensive and can be used as visible sensitive material for photocatalytic activity. Since the surface loading of metallic Ag nanoparticles on different semiconductors would be an effective way to improve the photocatalytic activity [1, 2]. Hence, in this work the metallic Ag nanoparticle has been incorporated into TiO₂ matrix and used as visible photo catalyst material with improved degradation efficiency. Here, the Ag nanoparticles are readily available to accept photogenerated electrons from excited semiconductor which facilitates dioxygen reduction and thereby Ag/TiO₂ showed an enhanced UV-light photocatalytic activity for the decomposition of organic substances.

**Experimental.**

© 2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/
**Materials.** Analytical reagents of Tetraethyl orthotitanate, Silver nitrate and Hexamine were used as received without further purifications. Ethanol and double distilled water were used as the solvents.

Ag/TiO₂ was synthesized by simple thermal decomposition method. Typically, 2.4 ml (0.01 M) of Tetraethyl orthotitanate was dissolved in 30 ml of ethanol and 0.01 M of silver nitrate dissolved in 50 ml of double distilled water and it was slowly added to reaction mixture. 2.5g of hexamine was added to the above mixture and the solution was stirred for 3h in 70 °C. The final product was centrifuged and washed with several times by water and ethanol. The synthesized materials was dried in room temperature and calcined at 450 °C.

**Results and Discussion.** The crystalline phase of Ag/TiO₂ composite are confirmed by XRD pattern as shown in Fig.1. (a). The observed XRD pattern clearly evidences the formation of mixed phase of face centered cubic Ag and rutile TiO₂. Typical 2θ° values at 38.1°, 44.3°, 64.4° corresponds to the metallic Ag in the face centered lattice and it is well matched with JCPDS card (No.65-2871). Similarly, the observed 2θ° values are 27.3°, 36.0°, 41.1°, 54.2°, 56.5° and 68.8° corresponds to tetragonal phase and can be indexed to the JCPDS card (No. 77-0441). And no other secondary phase is observed in the XRD pattern which confirms that phase purity of the composite.

<figure><img src="image_3.png" /><figcaption>Fig. 1. (a) Shows the XRD pattern and (b) FTIR spectrum of Ag/TiO₂.</figcaption></figure>

The FTIR spectrum of the prepared Ag/TiO₂ was shown in Fig.1 (b). The strong absorption band at 400 cm⁻¹ to 700cm⁻¹ corresponds to the Ti-O stretching vibrations [3]. The band appearing at 1610 cm⁻¹ is attributed to the bending vibrations of O-H. The broad absorption at 3464 cm⁻¹ corresponds to the O-H stretching vibrations due to absorption of water molecules from the moisture.

The optical properties of prepared sample were measured using UV-Vis Diffuse reflectance spectroscopy. Fig.2 (a) displays the UV-Vis spectrum of Ag/TiO₂ composite. The broad absorption in visible light is attributed to the surface plasmon resonance (SPR) confirming the formation of Ag nanoparticles [4]. The band gap energy can be estimated by following equation.

$$ahv = A (hv - Eg)^{n/2}$$

where a represents the absorption coefficient, v is the light frequency, Eg is the band gap energy, A is a constant and n depends on the characteristics of the transition in a semiconductor.

The band gap plot of (ahv)² vs hv of Ag/TiO₂ shown in Fig. 2. (b), the calculated band gap value for Ag/TiO₂ is 2.8eV.
<figure><img src="image_4.png" /><figcaption>Fig.2 (a) shows the DRS UV-Vis spectrum, (b) band gap plot of $(ahv)^2$ vs $hv$ of Ag/TiO$_2$.</figcaption></figure>

The surface morphology of the Ag/TiO$_2$ composite is analyzed by field emission scanning electron microscope. As shown in (Fig. 3), the surface of theTiO$_2$ is found to be cube like morphology and size of the cube is ~100 to 200nm. The small Ag nanoparticles uniformly dispersed on the surface of the TiO$_2$ cubes. The size of the Ag nanoparticles is ~5nm to 10nm. The EDS spectrum confirms the presence of primary elements of Ti, Ag and O without any impurities.

<figure><img src="image_5.png" /><figcaption>Fig. 3. shows the FESEM images and Edax spectrum of Ag/TiO$_2$.</figcaption></figure>

**Photocatalytic activity.** The photocatalytic activity of the prepared materials was irradiated under visible light degradation of methylene blue. The photo chamber was designed with a 500 W xenon lamp. The photocatalytic degradation of methylene blue was examined by taking 100ml of reaction mixture containing 0.001M of methylene blue and 0.02g of Ag/TiO$_2$. The prepared solutions were irradiated under visible light for 2 h. The concentration of the solution taken out from reaction mixture at different time intervals. The photocatalytic degradation solution was analyzed by UV-Vis spectroscopy. Fig. 4 shows the UV-Vis absorption spectrum of methylene blue under visible light irradiation time in presence of Ag/TiO$_2$. As shown, the intensity of the methylene blue peak decreases with increasing the time, meantime the 85% of methylene blue degraded in 60 min under visible light degradation. Ag/TiO$_2$ material can absorb and degrade the methylene blue solution in visible light degradation.
Ag nanoparticles are photoexcited due to the plasmon resonance. Consequently, the photoexcited electrons are migrated from the surface of the Ag nanoparticles to the conduction band of TiO2. In meantime, due to crystallinity of the Ag nanoparticles, the electron migration is suppressed so as to reduce the recombination of e-/h+ pairs. The electrons which accumulate on the surface of TiO2 are then scavenged by dissolved oxygen molecules in water to yield highly oxidative species such as the superoxide radical anion (O2⁻) and hydroxyl radical (OH), which can degrade the organic dyes effectively[1, 5, 6]. These oxidative species can easily diffuse out of the composite to attack the MB dye.

<figure><img src="image_6.png" /><figcaption>Fig. 4 shows the UV-Vis absorption spectrum of methylene blue under visible light irradiation time in presence of Ag/TiO2.</figcaption></figure>

**Summary.** The Ag/TiO2 material was synthesized by simple thermal decomposition method and investigated for MB photodegradation. The Ag/TiO2 composite formation and microstructure was confirmed by XRD pattern and SEM analysis. It was observed that Ag decorated nano/micro cubes of TiO2 microstructure. The estimated band gap value for prepared composite materials is about 2.8eV. The enhanced photocatalytic activity was observed for Ag/TiO2 under visible light towards the degradation of methylene blue, which is mainly due to the surface plasmon resonance based recombination reaction between Ag and TiO2. From this investigation, it can be concluded that Ag/TiO2 composites could be better choice of photocatalyst material for MB degradation.

**References**

[1] Chunyan Su, Lei Liu, Mingyi Zhang, Yue Zhang and Changlu Shao "Fabrication of Ag/TiO2 nanoheterostructures with visible light photocatalytic function via a solvothermal approach" CrystEngComm, (2012), 14, 3989-3999. [DOI: 10.1039/c2ce25161b].

[2] Rui Liu, Ping Wang, Xuefei Wang, Huogen Yu and Jiaguo Yu. "UV and Visible Light Photocatalytic Activity of Simultaneously Deposited and Doped Ag/Ag (I)-TiO2 Photocatalyst" J. Phys.Chem.C, (2012), 116, 17721-17728. [DOI:10.1021/jp305774n].

[3] Yanfeng Chen, Weixin Huang, Donglin He, Yue Situ and Hong Huang "Construction of Heterostructured g-C3N4/Ag/TiO2 Microspheres with Enhanced Photocatalysis Performance under Visible-Light Irradiation" ACS Appl. Mater. Interfaces (2014), 6, 14405-14414. [DOI:10.1021/am503674e]
[4] Di Wang, Zhong-Hua Zhou, Huan Yang, Kai-Bo Shen, Yue Huang and Shirley Shen "Preparation of TiO2 loaded with crystalline nano Ag by a one-step low-temperature hydrothermal method" *J. Mater. Chem.*, (2012), 22, 16306–16311 [DOI: 10.1039/c2jm16217b]

[5] Thanh-Dong Pham, Byeong-Kyu Lee and De Pham-Cong, "Advanced removal of toluene in aerosol by adsorption and photocatalytic degradation of silver-doped TiO₂/PU under visible light irradiation" *RSC Adv.* (2016) 6, 25346–25358. [DOI: 10.1039/c5ra23786f]

[6] P.V.R.K. Ramacharyulu, J. Praveen kumar, G.K. Prasad and A. R. Srivastava, "Synthesis, Characterization and Photocatalytic activity of Ag-TiO₂ Nanoparticulate film" *RSC Adv.* [DOI: 10.1039/b000000x]

Cite the paper

A. Padmanaban, T. Dhanasekaran, S. Praveen Kumar, G. Gnanamoorthy, S. Munusamy, A. Stephen, V. Narayanan (2017). *Visible Light Photocatalytic Property of Ag/TiO₂ Composite*. *Mechanics, Materials Science & Engineering*, Vol 9. doi:[10.2412/mmse.97.67.748](https://doi.org/10.2412/mmse.97.67.748)