*2.4. Theoretical Review*

This specific review covers theories related to organizational culture change and organizational performance. The study is mostly based on Hofstede's theory, the Edgar Schein model, and the Denison dimension model. The study of theories of organizational culture has proven to be quite difficult due to a lack of sufficient tangible evidence on various cultures. A shared understanding of organizational culture is one of the many different theories within private and public sector organizations. Top management hires like-minded individuals to support a specific, well-defined purpose, and this results in the organization having a singular focus in terms of performance. These theories on organizational culture have different overall organizational mindsets, such as ethics, profits, or philanthropy. The shared characteristics only change over time when hiring managers replace older workers.

#### 2.4.1. Geert Hofstede's Theory

Hofstede's theory is a framework for cross-cultural communication and explains the effects of a society's culture on the values of its members and the ways in which these values relate to the behavior using a structure derived from factor analysis (Ebba 2020). Geert Hofstede's theory indicates that the differences in culture among nations are found specifically at the greatest level; that is, at the level of values. Through comparisons, these cultural differences between organizations are specifically identified based on practices. Compared to values, practices have proven to be more tangible. In Hofstede's theory (1980), he used the gathered data from IBM employees in over 50 countries to classify organizational culture into four dimensions: power distance: the extent to which management and employees have a certain relationship distance, i.e., how they relate both formally and informally; individualism: the degree to which various individuals can create a schism between the interests of the entire organization and their own self-interests; uncertainty avoidance: this is the level at which the people in the organization are willing to mitigate the uncertainty and tolerance of ambiguity; and the definition of success, normally filled with ambition, challenge, and insolence, instead of caring and promotion.

Hofstede and Bond (1988) later on carried out a joint study and came up with a fifth dimension recognized as short-term versus long-term orientation that was entirely based on a study conducted among students in 23 different countries using a questionnaire (Shahzad et al. 2012). Hofstede also proposed that regional and national factors contribute a lot to the culture of the organization and, finally, have a great influence on the behavior of the employees in the organization itself. He gave several reasons for the cultural differences that may exist in different regions and the importance of international awareness and multiculturalism for individual cultural introspection. This is revealed by the cultural differences and distinctions in thinking and social action. He correlates ethnicity to culture as well as groups in the regions; organizations, professions, and families; and community as well as subcultural groups, political systems, and legal guidelines.

#### 2.4.2. Denison Dimension Model

Denison describes organizational culture in four general dimensions of adaptability, mission, involvement, and consistency. Adaptability is the ability to cope with a changing environment. How fast the change is understood and how fast the competitive environment is reacted to will differentiate high-performing organizations from low-performing organizations. He described culture as a mission where employees do each task. The reason for each activity is the overall purpose of the way the organization exists: to have a clear mission and to let employees understand it helps an organization perform. Employees need to understand that each task and activity is related to the organization's vision. He also described it as an involvement in which an organization fosters a strong sense of responsibility and commitment, allowing employees to understand the types of decisions they are permitted to make. Employees are encouraged to work in teams and support each other to attain their work goals. In addition, culture was described in a consistency dimension as a set of procedures that help to govern the system. It is a procedure or acceptable standard of performing a given task in an acceptable way within a given time and standard. Each employee is aware of the fact that their work impacts others and how the work of others impacts them. Involvement is the creation of responsibility by empowering employees using different techniques to make them fit for job training and development. This way, employees will understand what their responsibility is, what kinds of things their decision is needed on, and what is beyond their responsibility.

#### **3. Research Methodology**

#### *3.1. Research Design*

The study adopted a descriptive survey research design in order to present a clear description of the aspects of the study. According to Osoro (2020), the descriptive research design refers to the scientific method that has no bias and includes observation and description of the subject. This method is able to facilitate comprehensive data collection by watching and portraying the conduct of a subject without affecting it in any way. This design was considered suitable for this study as it helped the researchers in collecting data describing the nature of the existing conditions in the organization. In line with this, several studies (Kimhi and Oliel 2019; Jumanne and Njoroge 2018; Onono 2018; Anyango and Chrispen 2018) adopted a descriptive research design and successfully addressed the research question. The study unit analysis entailed organization management and employees from various departments.

#### *3.2. Target Population*

Cooper and Schindler (2014) explain population as the total collection of elements about which a researcher wishes to make some inferences. For this study, the target population was composed of 100 employees working in the Corporate Secretary and Legal Services, Wildlife and Community Service, Wildlife and Security, Infrastructure Management, Partnership and Enterprise, Finance and Accounts, Service Training, Human and Administration departments at Kenya Wildlife Service Nairobi National Park. The list of the employees was obtained from the human resources office.

## *3.3. Sampling Frame*

Kabir (2016) defines a sampling frame to be consisting of items where a sample is drawn. From the sampling frame, we identify the elements of the population through explicit or implicit enumeration. In this study, the sampling frame is a list of employees of Kenya Wildlife Service Nairobi National Park obtained from the human resources department.

#### *3.4. Sampling Technique*

The sampling technique involves taking a subset from a selected sampling frame or an entire population (Taherdoost 2016). Sampling can be used to make inferences about a population or generalize an existing theory. In essence, this depends on the choice of sampling technique. For this study, a stratified sampling technique was used where every employee had an equal chance of being selected in relation to their proportion within the population. Matula et al. (2018) indicate that the population is divided into subgroups, in this case, various departments. Questionnaires were administered to the selected employees from different departments and accurate feedback was received. The stratified approach is accurate and obtains feedback from all the employees.

#### *3.5. Sample Size*

From the sampling frame, we were able to find the sample size as outlined by Mugenda and Mugenda (2003) where a sample of 10–50% of a population is sufficient. Based on this, the researchers decided to sample 10% of employees from each department to obtain a sample size of 100 employees working at Kenya Wildlife Service Nairobi National Park since the population is small and easily accessible.

#### *3.6. Description of Data Analysis Procedures*

Before analysis, the questionnaires were checked for completeness and were coded for analysis. The study used both inferential and descriptive statistics with the analysis of supporting research objectives. Descriptive statistics analyzed frequencies, percentages, means, and standard deviations while inferential statistics analyzed correlation to establish the relationship among study variables. Statistical Package for Social Studies (SPSS) software version 24 was employed in analyzing data gathered from the respondents. Findings gathered from the target respondents are presented using tables and figures.

## **4. Research Results**


Applications of Materials Based on Sol-Gel Synthesis

## **Chapter 5**

## Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency of Titanium Dioxide Nanomaterials in Aquatic Media – A Sol-Gel Approach

*Saptarshi Ghosh and Manoranjan Sahu*

## **Abstract**

Titanium dioxide (TiO2) nanoparticles enhance the intrinsic value of commercial products like various cosmetics, paints, self-cleaning products, etc. Several research on the fabrication of TiO2, stabilization of TiO2 to retain its nanometric scale and increasing the inherent property of the material (i.e., photocatalytic) is ongoing for the last few decades. Still, the synthesis of highly efficient, stable, reproducible and cost-effective TiO2 nanoparticles remains a grand challenge for the researchers and scientific community. Further research is needed to develop an in-depth understanding of synthesis, aggregation kinetics and efficiency to improve the performance of TiO2 nanomaterial for the degradation of persistent organic pollutants (POPs). In this book chapter, we have summarized the synthesis process using the sol-gel pathway followed by its stability behavior and photocatalytic activity in the aqueous solutions. This study also highlighted the effects of various process variables such as pH, catalyst concentration, inorganic species etc. in the photocatalytic performance of TiO2 nanoparticles. Finally, we have reviewed various strategies that have been performed for increasing the photocatalytic efficiency of TiO2 by overcoming its limitations.

**Keywords:** doping, DLVO theory, photocatalysis, sol-gel process, TiO2 nanoparticles

## **1. Introduction**

Titanium is a transition metals having electronic configuration 3d2 4S2 . In nature, it is mainly available in the form of ilmenite (FeTiO3) and binary metal oxides [1]. In a binary metal oxide form, Titania has three phases: anatase, brookite and rutile [2]. For the commercial purposes, anatase phase of titanium dioxide is largely used. It was found that, at high temperatures brookite and anatase phases transform to rutile,

which is the most stable form of TiO2. Now, as compared to bulk material, nanostructured TiO2 has showed unique optical [3], electronic [4] and catalytic properties [5]. Due to these special properties, the interest for nanostructured titanium dioxide has grown to use it in various applications such as photocatalysis, paint pigments [6], cosmetics, personal care products [7], sensors, water and air purification, etc.

## **1.1 Processes for synthesis of nanomaterials**

Nanomaterials synthesis processes can be broadly classified into top-down and bottom-up processes. In the bottom-up synthesis process, nanomaterials are synthesized from basic building units like, atoms or molecules. Whereas, in top-down approach, bulk materials are broken down into smaller counter parts. Top-down synthesis includes processes such as laser ablation, sputtering and grinding, ball milling, etc. In last few decades, use of nanomaterials have tremendously increased in several industries such as paint, cosmetics, catalyst, etc. In this regard, various synthesis process has been implemented and followed for fulfilling the industrial demand for nanomaterials. The commonly used nanomaterials synthesis processes are as follows:

## **1.2 Sol gel process for TiO2 synthesis**

At laboratory scale, sol-gel is the most commonly used process for nanomaterials synthesis. It is a bottom-up process in which a colloidal suspension is formed by dispersing solid particles in a liquid called a Sol and agglomerate together to form a continuous three-dimensional network extending throughout the liquid called a gel. Generally, a sol-gel process is based on following steps [8]:

*Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency… DOI: http://dx.doi.org/10.5772/intechopen.111377*

iv. Calcination: it is a thermal treatment in which very high temperature is employed to crystallize the nanomaterials by removing organics and volatile substances.

## **2. Stability of nanomaterials**

To retain the properties of nanomaterials, one of the biggest challenges is the agglomeration of nanoparticles. The stability of nanomaterials depends on two opposite forces; one being the electrostatic repulsive force and second is van der Waals forces of attraction. Deryaguin-Landau-Verwey-Overbeek (DLVO) theory first gave this concept of opposite forces in a suspension. According to DLVO theory, particle stability depends on particle to particle and surface to particle interactions but, it varies for nanomaterials of different structures and heterogeneity. The DLVO theory does not consider all these factors, which make the calculation of nanomaterials stability more challenging. The potential energy of interaction due to the Van Der Waals force is given by the expression

$$V\_a = \frac{-A}{6} \left[ \frac{2a^2}{\mathcal{S}(\mathcal{S} + 4a)} + \frac{2a^2}{\mathcal{S}(\mathcal{S} + 2a)^2} + \ln \frac{\mathcal{S}(\mathcal{S} + 4a)}{\mathcal{S}(\mathcal{S} + 2a)^2} \right]$$

where *A* is the Hamaker constant, *a* is the particle radius, and *s* is the separation distance between the particle surfaces [9]. The Hamaker constant indicates the strength of mutual attraction between two colloidal particles and depends on material properties, and was 4 � 10�20 J for TiO2 [10]. Similarly, potential energy between particles due to electrostatic repulsion is expressed as follow

$$V\_r = 2\pi e\_0 \varepsilon\_r a \zeta^2 \ln\left(1 + e^{-ks}\right)$$

where *ε*0*εr* is the dielectric permittivity of the medium, *ζ* is the potential at the surface of the particle, and k is the Debye length (reciprocal of double layer thickness). Now, the total potential energy is calculated as Vt = Vα + Vr. Another drawback of DLVO theory is that it did not considered hydration and Born forces in calculation [9].

Now, when nanoparticles are entered into the environment, due to influence of various physicochemical factors and environmental conditions, they got agglomerated and with time these agglomerates might transformed into strong aggregates or rather loose agglomerates. Various studies reported that mobility of TiO2 in porous media is affected by various factors such as pH of the medium, ionic strength, presence of Natural Organic matters (NOMs), etc. [11, 12]. It was observed that with rise in pH, the mobility of TiO2 nanoparticles increases whereas ionic strength promotes the retention of nanoparticles in porous media. The reason for the retention at higher ionic concentration is because of enhanced agglomeration resulting into greater retention.

Similarly, Brownian motion is another important factor of colloids or nanoparticles for collisions with each other. The reasons for such collisions might be due to attractive forces or repulsive forces. In the colloidal systems, the dominant attractive force is Van Der Waals forces and to maintain the stability, an adequately strong repulsive force is required to neutralize the van der Waals attractions. In general, in a colloidal systems stability was achieved by the addition of surfactants [13], polymers [14] and/ or electrostatically.

## **2.1 Stability of TiO2 suspensions**

One of the major limitations of TiO2 nanoparticles in the suspension was its agglomeration because it reduces the surface area of nanoparticles resulting into reduction in catalytic performance [15]. Thus, it is important to identify and study the role of different parameters which significantly contributes towards agglomeration of TiO2 nanoparticles. Various parameters influence the stability of nanoparticles such as, ionic strength, pH, concentration of NPs, sticking coefficient, etc. But, predominantly it is the surface charge which controls the stability of nanoparticles. In particular, if the particles have a zeta potential more than �30 mV, they are considered stable [16]. However, addition of salts in a solution increases the ionic strength and promotes the attraction with opposite charge particles hence, their sticking efficiency increases. Basically, salt ions will reduce the thickness of electrostatic double layer and allows particles to come closer to each other by attractive forces and forms agglomerates [17]. In addition, collisions between particles also promotes aggregation and the Brownian motion is the driving force to bring collisions among nanoparticles in the aqueous medium. Another parameter affecting the stability of nanoparticles is the pH of the medium. Now, depending on the pH value, surface ionization happens and it controls the surface charge of metal oxides present in water, including TiO2.

## **3. Titanium dioxide nanoparticles as photocatalyst**

TiO2 nanoparticles have been considered and studied widely as one of the most effective photocatalyst for the oxidation of organic pollutants [18]. It is because of its thermodynamic stability, nontoxicity, economically cheap and have higher photocatalytic performance comparing to other semiconductors [19]. The crystalline phases of TiO2 are anatase, rutile and brookite. Among these three, the most active form of TiO2 is anatase because of its high adsorptive rate (active sites), high hole trapping capacity and most thermally stable crystal phase of TiO2. TiO2 has an energy gap (Ebg) of 3.2 eV for anatase type and it performs both oxidation as well as reduction. However, TiO2 is active only under UV region (λ < 390 nm) and the earth's solar spectrum have around 5% of that. Thus, it performs limited photocatalysis in the visible regions.

#### **3.1 Mechanisms of photocatalysis**

The photocatalysis by TiO2 favors both oxidation (valence band) and reduction (conduction band) on its surface, typically in the band edges. In a TiO2 or in other semiconductor, the highest occupied molecular orbital is separated from the lowest unoccupied molecular orbital by an energy band gap (Ebg). When the photocatalyst comes under the light irradiation that have the energy greater than or equal to the band gap, the photoexcitation takes place as illustrated in **Figure 1**. It transfers the electron from the valence band of a semiconductor to the conduction band of a semiconductor, leaving behind a hole in the valence band [20]. This ultimately forms a positively charged hole and an electron i.e., electron-hole pairs or exciton. These photogenerated charged pairs have a strong tendency to recombine, it may be a surface recombination or volume recombination. Thus, if we can reduce the recombination of these electronhole pairs, it can create a chain of photochemical reactions as stated below [21]:

i. Photoexcitation: TiO2 + hν! e� + *h*+

*Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency… DOI: http://dx.doi.org/10.5772/intechopen.111377*

#### **Figure 1.**

*Mechanisms of reactive oxygen species (ROS) generation by TiO2 under illumination.*

#### **3.2 Factors influencing photocatalysis**

#### *3.2.1 Effect of pH*

For the metal oxide like TiO2 the surface charge may be positive or negative due to amphoteric behavior. Zero Point Charge (ZPC) represents the pH in which the catalyst does not have any charge on the surface. Various literature concluded that the ZPC of TiO2 comes around 6–8 [22]. If the system is acidic (pH < pH ZPC), the catalyst protonated to gain positive charge on the surface and consecutively attracts negatively charged pollutants, but for alkaline conditions (pH > pH ZPC), the catalyst deprotonated to gain negative charge on the surface and favors the attraction of positively charged contaminants. The chemical transformation of TiO2 with pH is as follows:

$$\text{pH} < \text{pH} \text{ ZPC}: \text{TiO} + \text{H}^+ \rightarrow \text{TiO}\_2^+ \text{ (protonation)}$$

$$\text{pH} > \text{pH} \text{ ZPC}: \text{TiO} + \text{OH}^- \rightarrow \text{TiO}^- + \text{H}\_2\text{O} \text{ (deprotonation)}$$

Hence, pH is one of the important factors that controls photocatalysis.

### *3.2.2 Effect of catalyst concentration*

The efficiency of photocatalysis was depends on the concentration of the photocatalyst used, but the performance rates was independent of the concentration above a certain limit because of the complete absorption of light energy by the photocatalyst [23]. Adding catalyst more than its optimum concentration causes excessive scattering of irradiating radiation. Similarly, if the photocatalyst concentration is less than its optimum level then the generation of charged species was inadequate due to lack of availability of active sites.

#### *3.2.3 Effect of inorganic species*

Presence of inorganic species can alter the photocatalytic process in various ways. Species like H2O2, S2O8 2�, etc. can improve the photocatalytic removal of pollutants by acting as electron trappers, thus enhancing the synthesis of OH. and other reactive oxygen species. But, the excessive loadings of inorganic species can reduce the photocatalytic process by taking up the OH. from the system. The photocatalytic efficiency of TiO2 decreases with the availability of inorganic species like, FeCl2, Fe2(SO4)3, Na2SO4 and Na2CO3 because they alter the pH of the solution and also the active sites of the catalyst blocked by adsorption of ionic species. Ions that represent color in a solution can prevent the entry of light into the solution and decreases the photocatalytic process. Hence, ionic strength of a solution plays a prominent role in controlling the photocatalytic activity and pre-treatment was needed to achieve optimum photocatalytic treatment.

### *3.2.4 Effect of morphology of photocatalyst*

Photocatalyst with various shape and size do not shows the exact photocatalytic behavior because of the dissimilarity in surface areas, charge transfer capacity and associated properties of the catalyst. It was reported that the photocatalytic performance is highly dependent on the morphologies and dimensions of the photocatalyst. The varied structure of the catalyst includes nanosphere, nanotubes, and nanosheets. All these structures show some peculiar properties that can enhance the photocatalysis. The zero-dimensional nanosphere have the high surface area where as the interconnected pore structure and shorter carrier-diffusion paths in three dimensional nanocubes and nanotubes helps in the movement of charged species. Hence, the morphology of the nanomaterial has a fascinating role in the photocatalytic processes and it is better to perform the experiment after modifying its shape. Future research work is needed to study the performance by changing the shape of the photocatalyst.

## **3.3 Modification of TiO2 nanoparticles**

TiO2 has certain limitations and to improve the photocatalytic performance of TiO2 various doping and nanocomposite strategies have been used. Recently, modifications of TiO2 with carbon-based materials such as activated carbon, carbon nanotubes (CNT), [60]-fullerene and Graphene have received much attention to overcome the limitations of limited surface area. The mechanisms and strategies behind different doping patterns and nanocarbon-TiO2 systems such as AC-TiO2, CNT-TiO2 and Graphene-TiO2 nanocomposites are discussed in the below sections.

### *3.3.1 Doping*

Doping means addition of impurities within the crystal lattice to extend its absorption to a longer wavelength. Doping may be cationic or anionic that can replace the atoms within the crystal lattice and creates structural defects. It also restricts the recombination of photo-induced charged carriers. Anionic dopants are considered to be useful for modification of TiO2 because the p-orbitals of oxygen will interact with the p-orbitals of other anions and ultimately narrows down the band gap. Similarly, metal doping can stop the recombination of electron and hole pairs because the photoexcited charged species tends to move to the metals (electron traps). For cationic doping transition metals are generally preferred because they have a range of oxidation states. Thus, doping of TiO2 by metal or non-metal brings reduction in the recombination rate of the excitons and promotes the absorption to longer wavelength. TiO2 can be made visible light-active either by introducing structural defects such as Ti3+ and oxygen vacancies or by incorporation of non-metals such as N, C, and S, and transition metal ions. The various strategies of band gap modification are represented as follows:

#### *3.3.2 Formation of localized energy states*

Doping with non-metal, such as N, C, F, S and B extends the light adsorption of TiO2 towards the visible light region and thus enhances the photocatalytic activity. Among all the non-metal doped TiO2, nitrogen doped TiO2 has been found to exhibit superior photocatalytic activity under visible light irradiation. As shown in **Figure 2**, the ionic size of nitrogen was quite similar with the size of oxygen so that the orbital interactions (O2p orbital and N2p orbital) happens smoothly. And as the energy level for nitrogen was less than the oxygen, it forms a localized dopant state above the valence band of TiO2 and helps in the shifting of the absorption range from UV to visible [24].

#### *3.3.3 Broadening of valence band*

The broadening of valence band mainly happens through the co-doping. TiO2 co-doped with different elements, has attracted tremendous attention in the field of photocatalysis. Some studies reported that TiO2 co-doped with appropriate elements could exhibit a much higher photocatalytic activity than any singly doped photocatalyst, because of the existence of synergistic effects between the doping elements. As soon as two different doping elements will be present in the TiO2 matrix, their respective 2p orbital energy levels will both contribute to the creation of new energy states within the TiO2 band gap in a synergetic manner. As compared to other non-metal elements, the co-doping of titanium dioxide with carbon and nitrogen (**Figure 3**) has been found to exhibit synergistic effect in a most pronounced manner resulting in a considerable visible light response of the respective co-doped materials [25].

#### **Figure 3.**

*Formation of new energy bands leading to thickening of VB in C*d*N co-doped TiO2 Photocatalysts. Modified and adapted from Ref. [25].*

*Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency… DOI: http://dx.doi.org/10.5772/intechopen.111377*

#### *3.3.4 Formation of color centres*

Color centres give rise to formation of intra band gap energy states due to partial reduction of TiO2. Color centres forms due to oxygen vacancy as well as electron vacancy in a metal oxide like TiO2. Due to the loss of an O atom in a metal oxide the electron pair that remains trapped in the cavity VO (reaction 1) left behind gives rise to an F centre (reaction 2), whereas a positively charged F+ centre is equivalent to a single electron associated with the O vacancy (reaction 3). The electron-pair deficient oxygen vacancy, also known as an anion vacancy VA, is referred to as a doubly charged F++ centre (reaction 4). Hence, the Color centres associated with oxygen vacancies are the F, F+ , and F++ centres in TiO2. The electrons left in the VO cavity can also interact with adjacent Ti4+ ions to give Ti3+ centres (reaction 5).

$$\text{O}^{2-} \rightarrow \text{O} + \text{V}\_{\text{o}} + 2^{\text{e}-} \tag{1}$$

$$\text{V}\_{\text{o}} + \text{2}^{\text{e}-} \rightarrow \text{F} \tag{2}$$

$$\text{V}\_{\text{o}} + \text{e}^{-} \rightarrow \text{F}^{+} \tag{3}$$

$$\mathbf{V\_o} \to \{\mathbf{V\_A} \text{ or } \mathbf{F^{++}}\} \tag{4}$$

$$\text{F (or } \mathbf{F}^+) + \text{Ti}^{\mathfrak{A}^+} \rightarrow \mathbf{F}^+ \text{ (or } \mathbf{F}^{++}) + \text{Ti}^{\mathfrak{A}^+} \tag{5}$$

And, this Ti3+ (d1 ) centres has a tendency to create a distortion within the crystal lattice called Jahn-Teller distortion that brings the electronic transition (2 T2 ! 2 E) in the crystal lattice as demonstrated in **Figure 4** and shifts the absorption into visible range [26].

**Figure 4.** *Formation of color centre in TiO2. Modified and adapted from Ref. [26].*

#### *3.3.5 Nanocomposite*

TiO2 based photocatalysis is one of the important catalytic process that can mineralizes the organic pollutant as well as the biological pollutant. But it suffers from low efficiency due to: (i) wide band gap (only activated under UV spectrum), (ii) very high recombination rate of photogenerated charged pairs, (iii) less surface area for the adsorption of pollutants. Now, the idea behind bringing composite of carbonaceous nanomaterials for improving the TiO2 photocatalysis was to solve the limitations of TiO2 and to promote forward reaction and adsorption of reactants through provision of adequate quality and quantity of active sites [27]. Various types of carbonaceous nanomaterials that are studied to make photocatalytic support (TiO2-nanocarbon composite) are activated carbon, carbon nanotubes (CNT), and most importantly graphene which are discussed below.

## *3.3.6 Activated carbon-TiO2 composites*

Activated carbon is highly used because it is cheap, inert and easy to manufacture. Activated carbon possesses a porous amorphous structure with porosity spanning macro (>25 nm), meso (1–25 nm) and micro (<1 nm) pore ranges. The fundamental benefit of activated carbon is to provide a high surface area (typically 900–1200 m2 g1 ) over which TiO2 particles may be distributed and immobilized. The activated carbon support on TiO2 particles increases the photocatalytic effect by synergistic effect. The synergistically enhanced photocatalytic activity was due to the adsorption of reactants on activated carbon followed by mass transfer to photoactive TiO2 through the common interface between two. Activated carbon does not chemically interact with TiO2, unless additional constituents are added to the system. So basically, activated carbon improves the photocatalytic process by adsorbing pollutants [28].

## *3.3.7 Carbon nanotubes (CNT)-TiO2 composites*

Carbon nanotubes may be single walled (SWCNTs) or multi walled (MWCNTs) having specific surface area of 400–900 m2 g1 and 200–400 m2 g1 respectively [28]. In addition to the high surface area, the surface chemistry of CNTs may be functionalized (incorporation of alcoholic group, ketonic group, carboxyl group, etc.) to promote specificity towards target pollutant. This represents an advantage over activated carbon, which are basically non-selective and therefore have a lower pollutant degradation rate due to breakdown of both target and neutral species. CNTs are widely reported to synergistically enhance the photocatalytic performance of TiO2 through the retardation of electron-hole recombination as follows:

I.CNTs are capable of forming Schottky barriers at the CNT-TiO2 interface, where there is a space charge region. And, TiO2 is a n-type semiconductor but in the presence of a CNT, the photogenerated electron may move freely towards CNT surface, which may have a lower Fermi level. Thus, CNTs act as an electron sink and the excess holes in the Valence band of TiO2 migrate to the surface and reacts. The TiO2 now behaving as a P-type semiconductor. The high electrical conductivity and electron storage capacity (one electron for every 32 carbon atoms) makes CNT as highly effective electron sinks [28].

*Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency… DOI: http://dx.doi.org/10.5772/intechopen.111377*

II.CNTs may enhance the TiO2 activity by acting as a photosensitizer, transferring electrons to the TiO2. This may be the reason behind the extending TiO2 photocatalytic activity to a longer wavelength. In this mechanism the photogenerated electrons in the CNTs is transferred into the conduction band of TiO2, promoting a reduction process (formation of superoxide anion by the adsorbed molecular oxygen). The positively charged CNTs then remove an electron from the valence band of TiO2, leaving a hole. The positively charged TiO2 then takes part in oxidation process with organic pollutants and water to form hydroxyl radicals.

## *3.3.8 Graphene-TiO2 composites*

Graphene is a single layered (one atom thick or thin) with a 2-D hexagonal structure arranged in a honeycomb lattice [29]. The sp2 hybridized carbon atoms have delocalized π-bonds that improves the structural stability and current conductivity. Graphene has high electron mobility, acts as an adsorbent and promotes ballistic transport, meaning that electrons can travel without scattering, making them electron sinks or ideal electron transfer bridges. These unique properties of the graphene plane are mainly due to its long polyaromatic π-electron systems and coordinative unsaturated terminal carbon atoms. It has an energy band gap of 0 eV because it's filled valence bands touches the empty conduction bands in a certain point called Dirac point, thus giving rise to a new band [30]. Most importantly, graphene is chemically inert and highly stable under conditions where maximum substances would undergo rapid phase transformation and chemical reactions [29, 31, 32].

It was reported that graphene and its derivatives have been successfully used in designing nanocomposite systems for their excellent performance in photocatalysis. These functional nanomaterials have been used in designing photocatalyst systems because of their excellent electron transfer properties, which help to prevent recombination of photoexcited charge carriers in metal oxides (TiO2). These also help in establishing good interaction of target molecules to the surface of the TiO2 nanomaterials due to their adsorption behavior [33]. In summary, adsorption, conductivity, tuning of band gaps and very large planar structure of graphene plays a critical role for photodegradation of various kinds of pollutants over graphene-TiO2 composites.

## **4. Conclusions**

This book chapter covered various nanomaterials synthesis processes specifically sol-gel process, stability of nanomaterials in suspension and the photocatalytic process. Various parameters affecting the photocatalytic efficiency of TiO2 in an aqueous medium is discussed. In addition, the chapter discusses various types of strategies that have been followed to improve the photocatalytic efficiency of TiO2 and also highlighted the current strategies that have been performed. The book chapter clearly indicates that due to distinctive properties like, optical, electronic and catalytic, nanostructured TiO2 becomes fascinating material for research. It is widely used in various environmental applications like disinfection, catalysis, sensing, etc. and for that extensively used in several industries. Thus, it is important to develop cost effective synthesis processes to support the industrial demands. Additionally, TiO2

suffers from certain limitations such as aggregation, wide bandgap, recombination of excitons, etc. which need to be addressed through research and development of technology to enhance its catalytic efficiency so that it can resolve emerging environmental problems.

## **Acknowledgements**

We are grateful to the University Grants Commission (UGC) and Indian Institute of Technology Bombay (IITB) for their support for this work.

## **Conflict of interest**

The authors declare no conflict of interest.

## **Author details**

Saptarshi Ghosh1 and Manoranjan Sahu1,2,3\*

1 Aerosol and Nanoparticle Technology Laboratory, Environmental Science and Engineering Department, Indian Institute of Technology Bombay, Mumbai, India

2 Inter-Disciplinary Program in Climate Studies, Indian Institute of Technology Bombay, Mumbai, India

3 Centre for Machine Intelligence and Data Science, Indian Institute of Technology Bombay, Mumbai, India

\*Address all correspondence to<EMAIL_ADDRESS>
© 2023 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Perspective Chapter: Mechanistic Understanding of Stability and Photocatalytic Efficiency… DOI: http://dx.doi.org/10.5772/intechopen.111377*

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## **Chapter 6**


**Acknowledgements**

We thank to the join Fund of the National Science and Technology Council (CONACyT) and the Morelos Government, Project FOMIX CONACyT 173996, as well as the Research and Postgraduate Studies Secretariat (SIP Instituto Politécnico Nacional SIP20121087).


**1. Introduction**

The cell wall is a protective layer that is located around the cell membrane, which is found in plant, fungi, bacteria, and archaea cells. The structure and functions of the cell wall were interconnected during the process of evolution in spite of the fact that its chemical structure, and to a lesser extent, its functions are diverse in different groups of organisms. In plants, its most fundamental function is to provide structural support and protection to the cell with some additional specific functions that may occur during plant development and cell differentiation [1].

The plant cell wall is a dynamic and highly specialised network that is formed by a heterogeneous mixture of cellulose, hemicelluloses, pectins and, to some extent, proteins and phenolic compounds. The cell wall that is formed during cell division is called the primary cell wall. In many plants, as/after

the cell completes its growth, additional layers of cellulose fibres are deposited on the inner surface of the primary cell wall, which produces a secondary cell wall. The cell wall composition in vascular plants is approximately 30% cellulose, 30% hemicellulose, and 35% pectins, and 1–5% structural proteins, on a dry weight basis [2,3]. However, the precise proportions of these compounds may differ significantly at different stages of plant development. For example, grass coleoptiles consist of 60–70% hemicelluloses, 20–25% celluloses, and 10% pectin substances and the grass endosperm cell wall may contain up to as much as 85% hemicelluloses. By contrast, the secondary cell walls are generally more cellulose-rich [4–7].

*Brachypodium distachyon* (Brachypodium) belongs to the Pooideae subfamily and is a wellestablished model species for the grasses. It has several features and advantages that make it useful for gaining a better understanding of the genetic, cellular and molecular biology of temperate climate zone cereals and forage crops [8]. There are many studies, which are often connected with the chemical composition of the Brachypodium cell wall [9–12]. A comparative study of the primary cell wall in the seedlings of Brachypodium, barley and wheat demonstrated similar relative levels and developmental changes of hemicelluloses [10]. Analyses of the Brachypodium proteome facilitate better understanding of the enzymes that are involved in cell wall remodelling during seed development; such research is of great importance for gaining better understanding of these processes in grasses and for finding the key components that are responsible for the size and weight of grass grains [9]. However, there is a dearth of information about the localisation of specific cell wall components at different stages of Brachypodium development.

Here, we characterise the chemical composition of the cell walls in Brachypodium embryos and describe the differences in the number of nucleoli that were observed in the cell nuclei in different parts of an embryo. We used light and transmission electron microscopy (TEM), histological and immunolocalisation techniques to analyse the distribution of selected pectins, arabinogalactan proteins (AGP), extensins, and hemicelluloses in the cell walls, internal cell compartments, and on the embryo surface.

#### **2. Results and Discussion**

#### *2.1. The Morphological and Histological Features of Brachypodium Embryos*

In their study, Wolny et al. [13] demonstrated that Brachypodium embryos are small in size, which makes their initial examination possible only by the use of a dissecting microscope. In this study, we distinguished the main parts of the embryo, such as scutellum, V scale, coleoptile, first and second leaf, shoot apex, mesocotyl, epiblast, radicula, root cap, and coleorhiza (Figure 1). The coleoptile and coleorhiza are two organs that are found exclusively in grass species [14]. A comparison of the cell nuclei in different parts of Brachypodium embryos demonstrated that the majority contained only one nucleolus (Figure 1). However, some cells of the shoot apex, mesocotyl, radicula and root cap were characterised by the presence of a round nuclei that contained two nucleoli (Figure 1; nucleoli indicated by red arrows). TEM analysis of the selected embryo parts confirmed these observations and demonstrated the presence of a centrally positioned nucleus with one or two large nucleoli as well as a high nucleus:cytoplasm ratio (Figure 2a,b). The cytoplasm of these cells was dense and contained lipid droplets and starch granules around the nucleus. Interestingly, we also found cells in the embryo with nuclei that were extended in their shape but that also contained two nucleoli (Figure 2c). The architecture of these cells is typical for the initial vascular tissue [15]. According to Verdeil et al. [16], pluripotent plant stem cells, which are located within the root and shoot meristems, are isodiametric, have a dense cytoplasm, a high nucleus:cytoplasm ratio, a fragmented vacuome, contain granules of starch, and have a spherically-shaped nucleus with one or two nucleoli. Both of the meristematic cells of the oil palm (*Elaeis guineensis*) [17], maize (*Zea mays*) [18], and onion (*Allium cepa*) [19] have similar characteristics to those described by Verdeil et al. [16], which appear to be universal for monocots.

**Figure 1.** Schematic representation of Brachypodium embryo. Asterisks in different colours represent nuclei from histological sections of specified parts of the embryo. Red arrows mark two nucleoli. Purple arrows show respective parts of the embryo: V scale, coleoptile, first leaf, second leaf, shoot apex, mesocotyl, epiblast, coleorhiza, radicula, and root cap. Bars: 5 μm.

**Figure 2.** TEM (transmission electron microscopy) of radicula nuclei (**a**–**c**). Abbreviations: *CW*—cell wall, *LD*—lipid droplets, *N*—nucleus, *Nu*—nucleolus, *Pl*—plastid. Bars: (**a**) 3 μm; (**b**) 1.5 μm; and (**c**) 2.5 μm.