**TURBULENCE MODELLING APPROACHES - CURRENT STATE, DEVELOPMENT PROSPECTS, APPLICATIONS**

Edited by **Konstantin Volkov**

#### **Turbulence Modelling Approaches - Current State, Development Prospects, Applications**

http://dx.doi.org/10.5772/65527 Edited by Konstantin Volkov

#### **Contributors**

Keith Walters, Galina Ilieva, Lei-Yong Jiang, Gervásio Degrazia, Charles R. P. Szinvelski, Lidiane Buligon, Michel Baptistella Stefanello, Silvana Maldaner, Débora Regina Roberti, Yuriy Nuzhnov, Jesús Manuel Fernández Oro, Andrés Meana-Fernández, Bruno Pereiras García, Hector E. Nistazakis, Lydia Gkoura, George D. Roumelas, Andreas Tsigopoulos, H.G. Sandalidis, Alexander Vavoulas, George S. Tombras, Tao Wang, Jingsong Bai, Nikolai A. Alexandrovich Magnitskii, N. M. Evstigneev

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Turbulence Modelling Approaches - Current State, Development Prospects, Applications Edited by Konstantin Volkov p. cm. Print ISBN 978-953-51-3349-0 Online ISBN 978-953-51-3350-6 eBook (PDF) ISBN 978-953-51-4719-0


**5. Electrodeposition of chiral films**

Electrodeposition is a versatile method for depositing metals, metal oxides, semiconductors, and biomaterials. [20, 21] It is a simple and a low cost process which uses electrically conductive aqueous, organic, or fused salt solutions. Electrodeposition also offers the ability to tune the characteristics of the film by varying factors such as the electrolyte composition, the additives, the pH and temperature of the electrolyte, and the applied overpotential or current density. [40]

The most familiar method to electrodeposit a film involves electrochemically oxidizing or reducing the cation in the electrolyte at the electrode surface. In this process, the electrochemically produced species reacts with water or hydroxide ions to form a metal oxide on the electrode. [41-57] A second method to produce thin films is to electrochemically change the pH of the electrolyte at the electrode surface. Because the solubility of any material is dependent on pH, the pH can be electrochemically changed at the electrode surface, thus lowering the solubility of the material and resulting in the precipitation of the material only on the electrode surface. The pH can be decreased by electrochemically oxidizing water, ascorbates, hydroquinone, and other organics to produce metal oxides. Likewise, the pH can be electrochemically increased by reducing water, molecular oxygen, nitrate, peroxide, or organic molecules such as quinones. [58]

178 Recent Advances in Crystallography

GaN on sapphire and MgO films grown on GaAs.

**5. Electrodeposition of chiral films**

nitrate, peroxide, or organic molecules such as quinones. [58]

current density. [40]

well as the film for comparison of mosaic spread. If the mosaic spread of the film is low and comparable to the substrate, the peaks in the pole figure become sharper and more intense. Rocking curves have been used to understand the in-plane misorientation of ZnO, AlN, and

**Figure 5.** X-ray diffraction pattern of an epitaxial magnetite (Fe3O4) film on Ni(111) single crystal.

Electrodeposition is a versatile method for depositing metals, metal oxides, semiconductors, and biomaterials. [20, 21] It is a simple and a low cost process which uses electrically conductive aqueous, organic, or fused salt solutions. Electrodeposition also offers the ability to tune the characteristics of the film by varying factors such as the electrolyte composition, the additives, the pH and temperature of the electrolyte, and the applied overpotential or

The most familiar method to electrodeposit a film involves electrochemically oxidizing or reducing the cation in the electrolyte at the electrode surface. In this process, the electrochemically produced species reacts with water or hydroxide ions to form a metal oxide on the electrode. [41-57] A second method to produce thin films is to electrochemically change the pH of the electrolyte at the electrode surface. Because the solubility of any material is dependent on pH, the pH can be electrochemically changed at the electrode surface, thus lowering the solubility of the material and resulting in the precipitation of the material only on the electrode surface. The pH can be decreased by electrochemically oxidizing water, ascorbates, hydroquinone, and other organics to produce metal oxides. Likewise, the pH can be electrochemically increased by reducing water, molecular oxygen,

**Figure 6.** An illustration of the method to produce a (311) magnetite pole figure of a (111) oriented magnetite film on a Ni(111) substrate. The azimuthal scan on the bottom right is obtained by running the ϕ scan at a fixed χ.

Electrodeposited films orientation and morphology are determined by the electrochemical/chemical reaction, potential, current, pH, temperature, and additives. [40] For example, Switzer group has previously shown that varying the applied potential and pH changes the orientation and size of the electrodeposited Cu2O films. [59, 60] Films follow the orientation of the substrate at low overpotentials and change to a kinetically controlled orientation at a critical thickness. As the overpotential increases, the critical thickness for the transition decreases. Similarly, Cu2O films from a pH 9 solution have a [001] preferred orientation while films from a pH 12 solution have a [111] preferred orientation. Siegfried and Choi have examined the stability of facets of Cu2O in the presence of additives where ammonium salts stabilize {111} planes, whereas sodium chloride stabilizes {100} planes. [61]

Thin films of metals and metal oxides can be electrodeposited on polycrystalline substrates or single crystalline substrates. Polycrystalline films grow on polycrystalline substrate and are usually used for identification and characterization. Different planes of atoms produce different diffraction peaks, which contain information about atomic arrangement within the crystal. Therefore, every crystalline material has a unique X-ray diffraction pattern. [62] This pattern can be used to determine the crystallinity and phase of the deposited polycrystalline material. The lattice parameters of a material can be calculated from the peaks by properly assigning Miller indices (hkl) and accurately measuring the d-spacing. However, if the films are grown on single crystals such as Au(001), Au(111), Si(111), Ni(110) and InP(110) we get epitaxial films. Single crystals eliminate the presence of grains of various orientations, which may have different film growth rates as discussed above. If a crystalline film grows with an out-of-plane and in-plane orientation that is dependent on the orientation of the substrate, the film is said to be epitaxial.

The properties of epitaxial films depend on the substrate. The film will have better crystalline quality and more uniform morphology when fewer defects are present on the substrate. Generally, an epitaxial film will deposit with an orientation providing the lowest lattice mismatch with the substrate. In some cases, the film will become strained or will rotate to obtain this low mismatch. Thus, different substrates will produce different orientations of the film. Since properties of a material can be dependent on the orientation, this control over selection of orientation permits optimization of the properties of a deposited material. Epitaxial films are useful in device applications, since the intrinsic properties of the material can be exploited rather than its grain boundaries. Epitaxial films can be characterized using X-ray diffraction, pole figures, azimuthal scans, and rocking curves. For example, the diffraction pattern of a polycrystalline film is different than that of an epitaxial film. Whereas a polycrystalline film has all possible planes, resulting in multiple peaks in the pattern, an epitaxial film will normally grow with one orientation and show family of planes in the pattern. The details of X-ray characterization for epitaxial films have been discussed in the above section. [40]

Enantiospecific epitaxial thin films of CuO can be electrodeposited onto Au(100), Cu(111), and Cu(110) single crystals from alkaline solutions. [18, 19, 33] The Chirality of the electrodeposited film in alkaline bath was determined by the enantiomer used to complex Cu(II). Chiral CuO films were deposited on Au(001), Cu(111) and Cu(110) single crystals from alkaline solutions of copper(II) complexed with tartaric acid, malic acid, and amino acids. The films were deposited either at constant current density or at constant potential. The CuO films deposited on Au(001) using tartaric acid as complexing agent in the deposition bath resulted in {1-1-1} set of peaks. [18, 19] Chirality of the film cannot be determined by the θ-2θ X-ray scan. The films grown from a solution of L-tartaric acid or Dtartaric acid can have either (1-1-1) or (-111) orientations. It is impossible to distinguish between the orientations based on the θ-2θ scans as they have identical d-spacing. The orientations can be assigned with the help of X-ray diffraction pole figure. The CuO(111) pole figures and stereographic projections indicated that the films grown from L-tartaric acid has (1-1-1) orientation whereas the film grown from D-tartaric acid has (-111) orientation.  The enantiomeric excess of one orientation over the other was determined from azimuthal scans probing the higher angle CuO (111)-type reflections. The percentage enantiomeric excess for the (1-1-1) orientation can be calculated quantitatively from the area under all the peaks obtained at higher angle using the formula.

$$\mathbf{ee} = \left( \mathbf{A}\_{(1\cdot 1\cdot 1)} - \mathbf{A}\_{(\cdot 111)} \mathbf{\hat{A}}\_{(1\cdot 1\cdot 1)} + \mathbf{A}\_{(\cdot 111)} \right) \mathbf{\hat{}}100 \mathbf{\hat{}}$$

180 Recent Advances in Crystallography

the film is said to be epitaxial.

been discussed in the above section. [40]

under all the peaks obtained at higher angle using the formula.

material. The lattice parameters of a material can be calculated from the peaks by properly assigning Miller indices (hkl) and accurately measuring the d-spacing. However, if the films are grown on single crystals such as Au(001), Au(111), Si(111), Ni(110) and InP(110) we get epitaxial films. Single crystals eliminate the presence of grains of various orientations, which may have different film growth rates as discussed above. If a crystalline film grows with an out-of-plane and in-plane orientation that is dependent on the orientation of the substrate,

The properties of epitaxial films depend on the substrate. The film will have better crystalline quality and more uniform morphology when fewer defects are present on the substrate. Generally, an epitaxial film will deposit with an orientation providing the lowest lattice mismatch with the substrate. In some cases, the film will become strained or will rotate to obtain this low mismatch. Thus, different substrates will produce different orientations of the film. Since properties of a material can be dependent on the orientation, this control over selection of orientation permits optimization of the properties of a deposited material. Epitaxial films are useful in device applications, since the intrinsic properties of the material can be exploited rather than its grain boundaries. Epitaxial films can be characterized using X-ray diffraction, pole figures, azimuthal scans, and rocking curves. For example, the diffraction pattern of a polycrystalline film is different than that of an epitaxial film. Whereas a polycrystalline film has all possible planes, resulting in multiple peaks in the pattern, an epitaxial film will normally grow with one orientation and show family of planes in the pattern. The details of X-ray characterization for epitaxial films have

Enantiospecific epitaxial thin films of CuO can be electrodeposited onto Au(100), Cu(111), and Cu(110) single crystals from alkaline solutions. [18, 19, 33] The Chirality of the electrodeposited film in alkaline bath was determined by the enantiomer used to complex Cu(II). Chiral CuO films were deposited on Au(001), Cu(111) and Cu(110) single crystals from alkaline solutions of copper(II) complexed with tartaric acid, malic acid, and amino acids. The films were deposited either at constant current density or at constant potential. The CuO films deposited on Au(001) using tartaric acid as complexing agent in the deposition bath resulted in {1-1-1} set of peaks. [18, 19] Chirality of the film cannot be determined by the θ-2θ X-ray scan. The films grown from a solution of L-tartaric acid or Dtartaric acid can have either (1-1-1) or (-111) orientations. It is impossible to distinguish between the orientations based on the θ-2θ scans as they have identical d-spacing. The orientations can be assigned with the help of X-ray diffraction pole figure. The CuO(111) pole figures and stereographic projections indicated that the films grown from L-tartaric acid has (1-1-1) orientation whereas the film grown from D-tartaric acid has (-111) orientation.  The enantiomeric excess of one orientation over the other was determined from azimuthal scans probing the higher angle CuO (111)-type reflections. The percentage enantiomeric excess for the (1-1-1) orientation can be calculated quantitatively from the area For a film deposited from L-tartaric acid has an enantiomeric excess of 95% while the films deposited from D-tartaric acid has an enantiomeric excess of 93%. The film from DL-tartaric acid has equal amounts of both the orientations and zero enantiomeric excess. For the CuO films grown from alkaline solutions using amino acids on Au(001) resulted in {1-1-1} and {- 111} orientations. The films were grown with the alkaline amino acids solutions of alanine, valine, and glycine. The films grown from Cu(II) complexes of amino acids have two chiral orientations with a smaller enantiomeric excess. The films grown from L-alanine and Lvaline solutions have a small excess of (-111) and (-1-1-1) orientations, while the films grown from D-alanine and D-valine have a small excess of the (1-1-1) and (111) orientations. The pole figures obtained from achiral glycine as a complexing agent have equal amounts of the chiral CuO(-111) and CuO(1-1-1) orientations.

For the films grown from Cu(II) complexes of malic acid on Cu(111) single crystals, two chiral orientations were obtained. The films produced from L-malate in the deposition bath have (-111) and (311) orientations and the ones produced from D-malate have (1-1-1) and (- 3-1-1) orientations. CuO films grown on Cu(110) from L-malate had (110) and (31-1) orientations while the one grown from D-malate deposition bath had (-1-10) and (-3-11) orientations. The films grown from racemic malate showed equal amounts of only (-111) and (1-1-1) orientations on Cu(111) and CuO(110) and CuO(-1-10) orientations on Cu(110) single crystal. It is still not clear as to why the CuO films grown from malic acid in the deposition bath show 2 chiral orientations where as the films grown from tartaric acid show only one dominant chiral orientation. One argument can be that in a strong alkaline solution that the crystal structure of chiral Cu(II) malate has a different packing than the racemix Cu(II) malate. It is difficult to grow crystals of Cu(II) malate or Cu(II) tartarate from highly alkaline solutions. To understand the phenomenon of chiral electrodeposition, the crystals of copper(II) malate were grown at pH=1.5. Both L- and D- chiral complexes polymerize in a similar fashion where each copper is coordinated to two malate ligands of the same chirality via one hydroxyl oxygen atom and one carboxyl oxygen atom. Both the chiral complexes crystallized in P21 monoclinic space group. Whereas the complxes grown from racemic Cu(II)-malate crystallized in a centrosymmetric space group P21/c with copper atoms at the inversion center. Similarly, other copper(II) complexes have structures which are determined by the handedness of the ligand. It is believed that the chiral complexes formed in the solution are initially adsorbed on the surface and imprint chirality on the surface. However, further study has to be done to understand this phenomenon better.

To get a better understanding for the chiral electrodeposition further studies were done by growing CuO films on Cu(111) single crystal with different amino acids in the solution bath. Table 2 shows different chiral reagents used for depositing CuO films. The table also indicates their handedness in different conventions.1 Usually, there are three different types of conventions which are followed for chiral molecules. Optical activity (+/-) is based on the direction in which the enantiomer rotates the plane polarized light. The (+) and (-) enantiomer are also identified as dextrorotatory (d) and levorotatory (l). This notation can be easily confused with D and L labeling. The D/L labeling is unrelated to +/- notation; it does indicate which enantiomer is dextrorotatory or levorotatory. Rather, it says that the compound's stereochemistry is related to the stereochemistry of the dextrorotatory and levorotatory enantiomer of glyceraldehydes. Another convention which is generally used is the R/S configuration. In this convention, each chiral center in the molecule is either named R or S according to a system by which its substituent's are each assigned a priority. The priorities are based on Cahn Ingold Prelog rules, based on atomic number. The R/S system has no fixed relation with +/- or D/L systems. An R isomer can be either dextrorotatory or levorotatory, depending on its exact substituents. [63]

**Table 2.** List of chiral precursors used for depositing CuO on Cu(111) single crystal. The table also lists different types of notations used for chiral molecules.

In this work, different chiral reagents were used to deposit CuO films on Cu(111) single crystals to understand the role of the precursor on chiral film formation. Figure 7 shows the (111) pole figures for CuO on Cu(111) deposited from different chiral reagents. The pole figures were obtained by setting 2θ equal to the angle of diffracted intensity for the (111) planes (2θ = 38.742o) and performing azimuthal scans at tilt angles, χ, from 0 to 90o. The pole figures in Figure 7 (A) - (E) show peaks at 57o and 63o. These peaks correspond to either (- 111) orientation or (1-1-1) orientation. On the other hand, the pole figures in Figures 7 (F) – (H) have extra peaks at tilt angle of 27o, which correspond to either (311) or (-3-1-1) orientation. To interpret pole figures, we use stereographic projections. Figures 8(A) and 8(B) shows the (-111) and (1-1-1) stereographic projections of monoclinic CuO. The radial direction is the tilt angle, χ, while the azimuthal angle, φ, is the rotation of the sample about the axis. The positions of CuO{111} and CuO{200} reflections are specified. Figure 8(A) shows that for the (-111) orientation, reflections from the (-11-1) plane at a χ of 57o, and the (111) planes at a χ of 63o, are separated azimuthally by 115o rotated counterclockwise (∆φ = - 115o). Figure 8(B) shows that for (1-1-1) orientation, reflections from the (1-11) plane at χ = 57o and the (-1-1-1) plane at χ = 63o are separated azimuthally by 115o rotated clockwise (∆φ

= 115o). The calculated interplanar angles obtained from stereographic projections correspond with the measured interplanar angles of the pole figures. Figure 7 (F)-(H) also show reflections at χ = 27o. These reflections can be explained by figures 8(C) and 8(D). Figure 8(C) shows that for the (311) orientation, reflections from the (111) plane at a χ of 27.19o, and the (1-11) plane at a χ of 68.14o, are separated azimuthally by 125.18o rotated counterclockwise. Figure 8(D) shows that for the (-3-1-1) orientation, reflections from the (-1- 1-1) plane at χ of 27.19o, and the (-11-1) plane at a χ of 68.14o, are separated azimuthally by 125.18o rotated clockwise. Figures 8(A) and 8(C) clearly explains the pole figure of Figure 7 (F)-(H) and confirms the presence of (-111) and (311) orientations for the film grown from different amino acid deposition bath. Similarly, Figures 8(A) and 8(B) explain the pole figure of Figure 7 (A)-(E) and confirm the presence of (1-1-1) and (-111) orientations.

182 Recent Advances in Crystallography

levorotatory, depending on its exact substituents. [63]

different types of notations used for chiral molecules.

indicate which enantiomer is dextrorotatory or levorotatory. Rather, it says that the compound's stereochemistry is related to the stereochemistry of the dextrorotatory and levorotatory enantiomer of glyceraldehydes. Another convention which is generally used is the R/S configuration. In this convention, each chiral center in the molecule is either named R or S according to a system by which its substituent's are each assigned a priority. The priorities are based on Cahn Ingold Prelog rules, based on atomic number. The R/S system has no fixed relation with +/- or D/L systems. An R isomer can be either dextrorotatory or

**Table 2.** List of chiral precursors used for depositing CuO on Cu(111) single crystal. The table also lists

In this work, different chiral reagents were used to deposit CuO films on Cu(111) single crystals to understand the role of the precursor on chiral film formation. Figure 7 shows the (111) pole figures for CuO on Cu(111) deposited from different chiral reagents. The pole figures were obtained by setting 2θ equal to the angle of diffracted intensity for the (111) planes (2θ = 38.742o) and performing azimuthal scans at tilt angles, χ, from 0 to 90o. The pole figures in Figure 7 (A) - (E) show peaks at 57o and 63o. These peaks correspond to either (- 111) orientation or (1-1-1) orientation. On the other hand, the pole figures in Figures 7 (F) – (H) have extra peaks at tilt angle of 27o, which correspond to either (311) or (-3-1-1) orientation. To interpret pole figures, we use stereographic projections. Figures 8(A) and 8(B) shows the (-111) and (1-1-1) stereographic projections of monoclinic CuO. The radial direction is the tilt angle, χ, while the azimuthal angle, φ, is the rotation of the sample about the axis. The positions of CuO{111} and CuO{200} reflections are specified. Figure 8(A) shows that for the (-111) orientation, reflections from the (-11-1) plane at a χ of 57o, and the (111) planes at a χ of 63o, are separated azimuthally by 115o rotated counterclockwise (∆φ = - 115o). Figure 8(B) shows that for (1-1-1) orientation, reflections from the (1-11) plane at χ = 57o and the (-1-1-1) plane at χ = 63o are separated azimuthally by 115o rotated clockwise (∆φ

Figure 9 shows the SEM images of the CuO films deposited on Cu(111) single crystal from different chiral reagents. The chiral reagents influence the morphology of the deposited films. Figure 9 (D) shows the SEM image of the CuO film deposited using L-asparatic acid precursor. The image shows that CuO grows like spears and are approximately 50 nm in diameter. On the other hand, films deposited using L- arginine has cross hatch morphology with individual crystallites made up of multiple platelets. The morphology of the films deposited from other amino acids and simple carboxylic acids like malic acid and tartaric acid have simple cross hatch morphology with different crystallite sizes.

**Figure 7.** (111) CuO pole figure for CuO films deposited from different amino acids on Cu(111)single crystals. (A) tartaric acid, (B) asparatic acid, (C) glutamic acid, (D) proline, (E) arginine, (F) alanine, (G) valine and (H) malic acid.

The scanning electron microscopy (SEM) does not correlate the handedness of the electrodeposited films with their microstructure. However, the SEM images of the electrodeposited biominerals show very clearly the effect of additives in the solution. Different additives in the solutions are known to cause face-selective crystallization of inorganic crystals in biosystems. It was recently shown that in presence of chiral precursors, calcite and other biominerals with chiral morphology can be electrodeposited. [29] A combination of geometric matching, electrostatic interactions and stereochemistry is believed to be the cause of bimonineralization. [64] Researchers have shown that in the presence of chiral amino acids, asymmetric crystals of gypsum can be crystallized. [28] In nature, gypsum crystallizes in symmetric space group but by changing the solution precursors systematically one can control the handedness of the crystallites. Other researchers have studied the affect of step-edge free energies for the formation of chiral etch pits. [26]

**Figure 8.** Stereographic projections for (A) (-1-11), (B) (11-1), (C) (311) and (D) (-3-1-1) orientations indicating the positions where the (111) type and (100) type reflections should be observed in the pole figures. For the (-1-11) orientation, reflections from the (1-11) plane at χ = 57o and the (-1-1-1) plane at χ = 63o are separated azimuthally by 115o rotated counterclockwise. For the (-3-1-1) orientation the (1-11) plane is at χ = 68.14o, the (-1-1-1) planes at χ = 27.41o and (100) planes at χ = 27.19o. For the (11- 1) orientation the (-11-1) plane is at χ = 57o and the (111) plane is at χ = 63o are separated azimuthally by 115o rotated clockwise. For the (311) orientation the (1-11) plane at χ = 68.14o, the (111) plane at χ = 27.41o are separated azimuthally by 125.8o.

Surface templating and imprinting can be the two main ways of obtaining chiral surfaces. Studies have shown that adsorption of chiral tartaric acid on low index surfaces of Cu and Ni can break the symmetry of the substrate causing chiral templates. On the other hand, adsorption of (R,R)-tartaric acid on Ni(110) surfaces results in chiral imprinting. [6] The difference between the two can be best described as following, in the case of chiral imprinting; the adsorbed molecule irreversibly reconstructs the substrate, whereas in the case of templating; the underlying substrate is not affected upon the removal of adsorbed molecule.

184 Recent Advances in Crystallography

pits. [26]

The scanning electron microscopy (SEM) does not correlate the handedness of the electrodeposited films with their microstructure. However, the SEM images of the electrodeposited biominerals show very clearly the effect of additives in the solution. Different additives in the solutions are known to cause face-selective crystallization of inorganic crystals in biosystems. It was recently shown that in presence of chiral precursors, calcite and other biominerals with chiral morphology can be electrodeposited. [29] A combination of geometric matching, electrostatic interactions and stereochemistry is believed to be the cause of bimonineralization. [64] Researchers have shown that in the presence of chiral amino acids, asymmetric crystals of gypsum can be crystallized. [28] In nature, gypsum crystallizes in symmetric space group but by changing the solution precursors systematically one can control the handedness of the crystallites. Other researchers have studied the affect of step-edge free energies for the formation of chiral etch

**Figure 8.** Stereographic projections for (A) (-1-11), (B) (11-1), (C) (311) and (D) (-3-1-1) orientations indicating the positions where the (111) type and (100) type reflections should be observed in the pole figures. For the (-1-11) orientation, reflections from the (1-11) plane at χ = 57o and the (-1-1-1) plane at χ = 63o are separated azimuthally by 115o rotated counterclockwise. For the (-3-1-1) orientation the (1-11) plane is at χ = 68.14o, the (-1-1-1) planes at χ = 27.41o and (100) planes at χ = 27.19o. For the (11- 1) orientation the (-11-1) plane is at χ = 57o and the (111) plane is at χ = 63o are separated azimuthally by 115o rotated clockwise. For the (311) orientation the (1-11) plane at χ = 68.14o, the (111) plane at χ =

27.41o are separated azimuthally by 125.8o.

**Figure 9.** SEM micrographs for CuO films deposited on Cu(111) single crystal from different chiral precursors. (A) L(+)-Alanine, (B) L(-)-Arginine, (C) L(+)-Valine, (D) L(-)-Aspartic acid, (E) L(+)-Glutamic acid

In the case of electrodeposited chiral CuO films, it would not be unreasonable to expect chiral Cu(II) complexes to adsorb on the single crystal surfaces and break its symmetry. As discussed earlier, complexes of copper(II) with different chiral reagents have a dimeric structure with a symmetry that is determined by the handedness of the ligands. Surface reconstruction of the underlying single crystal substrate from adsorbed molecules can be another cause for the asymmetry. The precise mechanism, however, is not known at this time. Studies have shown that presence of chiral modifiers is necessary for the nucleation of chiral CuO domains. Once the nucleation layer is produced, the film maintains the orientation regardless of the precursor. [47] Studies on adsorption of organic molecules on surfaces have shown that local chiral imprinting can be obtained without the need of extended surface Chirality. [6] Adsorption of amino acids on Au [66] and Ag [67] surfaces are reported to be physical in nature, while amino acids chemisorb on Cu single crystals. Based on this argument the films grown on Cu single crystals should have more order as compared to other crystals. We have shown in this study that this is indeed true. To get more insight into the mechanism of chiral electrodeposition, further investigation is required. In-situ AFM during the chiral electrodeposition can be helpful in understanding the initial nucleation and whether or not it is local chiral imprinting which results in chiral films.

#### 186 Recent Advances in Crystallography

An interesting aspect of the electrodeposited chiral films is that they show chiral selectivity. [18, 19] In this process, the chiral film selectively oxidizes the chiral molecules in the solution. This property of the chiral films can be utilized post enantiomeric separation to detect the amount of enantiomeric excess in the mixture.

### **6. Electrochemical selectivity**

Researchers have studied the electrochemical oxidation of sugars on chiral Pt surfaces. [15] In this study, enantiospecific electrochemical oxidation of glucose was demonstrated on Pt(643) and Pt(-6-4-3) surfaces. Recent studies show that chiral cyclodextrin based coatings applied to a three-transducer microsystem shows distinct chiral discrimination for different compounds. [68] CuO has been shown to be catalytic for the electrochemical oxidation of amino acids, carbohydrates and amines with very high sensitivities. [69-71] It has been reported that increased sensitivity for the electroxidation of amino acids with an increase in solution pH. [72] Electrodeposited chiral CuO films also show chiral selectivity in high pH chiral solutions. [18] It was shown that the film grown from L-tartaric acid selectively oxidizes L-tartaric acid over D-tartaric acid, whereas the films grown from D-tartaric acid does the opposite. For the films grown from a racemic tartaric acid, no selectivity was observed.

**Figure 10.** Cyclic voltammograms in unstirred solutions of alkaline solutions of L-, D-, and DL- tartaric acid by scanning from open circuit potentials to 0.75 V vs. SCE at a scan rate of 10 mV/sec for the films grown (A) L-malic acid, (B) D-malic and (C) DL-malic acid

The study was extended to understand the selectivity behavior of a chiral film deposited with malic acid precursor and oxidizing tartaric acid films. The cyclic voltammograms (CV) were obtained in unstirred solutions by scanning from open circuit potentials to 0.75 V vs. SCE at a scan rate of 10 mV/sec. Before switching solutions the electrode was cleaned by scanning in 0.1 M NaOH from the OCP to 0.75 vs. SCE to remove adsorbed remnants from the electrode. Figure 10(A) shows the film grown from L-malic acid selectively oxidizes for D-tartaric acid, whereas the Figure 10 (B) film grown from D-malic acid does the opposite. Figure 10 (C) shows for the film grown from racemic malate has a very slight selectivity for D-tartaric acid but it is insiginificant difference compared to the selectivity shown by the chiral films. This study is in agreement with the pole figures for the CuO films grown on Cu(111) single crystals from the solutions of malic and tartaric acid precursors. The CuO films grown from D-malic acid and L-tartaric acid have similar dominant orientations and hence the similar selectivity. Another study has shown that by selectively etching the chiral CuO films the selectivity can be enhanced considerably. However, a detail study on more complex molecules still needs to be studied to validate this model. The final goal should be to have a sensor grown from one chiral molecule which can selectively distinguish any chiral molecule with the same handedness.

In summary, enantiospecific epitaxial CuO films can be electrodeposited onto single crystal substrates from copper (II) complexes of chiral molecules. Chirality of a crystal is dependent on the symmetry operations in the structure. Chirality can be imparted to non chiral crystals by depositing the films in the presence of chiral precursors. The chiral orientation of the films can be determined by X-ray pole figures and stereographic projections. The chiral CuO films show selectivity in the alkaline chiral solutions. At this point, the mechanism of the chiral electrodeposition is not very well understood and needs further study.


**Abstract**

In this study, we reported the synthesis of hydroxyapatite modified with biopolymers as λ-carrageenan and sodium alginate, which could be used as effective adsorbents of cationic dyes. Evidence of chemical modification was proved through chemical analysis, Fourier Trans-form Infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and specific surface area. The adsorption process was studied using methylene blue as representative cationic dye. The adsorbed quantity reached, at equilibrium, 142.85 mg/g and 98.23 mg/g using hydroxyapatite-sodium alginate and hydroxyapatite-(λ-carrageenan), respectively. However, it does not exceed 58.8 mg/g in the case of the unmodified hydroxyapatite. The adsorption of methylene blue using hybrid materials complied well with the pseudo-second-order suggesting a chemi-sorption. Freundlich and Langmuir isotherm described well the adsorption mechanism of the hydroxyapatite-(λcarrageenan) and hydroxyapatite-sodium alginate, respectively. The high capacities of MB removal obtained in this study suggest the potential use of these materials in the treatment from wastewaters.

**Keywords:** hydroxyapatite, biopolymer alginate, dye, kinetic

### **1. Introduction**

Contaminated waters can be successfully treated using inexpensive adsorbents. In this sense, many biopolymers were proposed including cellulose [1–3], chitosan [4, 5], chitin [6, 7], etc. Hybrid materials have attracted a particular attention. The interaction between calcium hydroxyapatite and biopolymers has been the subject of many studies such as carboxymethyl cellulose [8], polygalacturonic acid [9], collagen [10], Agar-Agar [11], polycaprolactone [12], banana peel [13], chitosan [14], and gelatin [15]. Currently, the application of hydroxyapatite modified by biopolymers for immobilization of various pollutants has been considered as a promising pollution control technology [16–20]. For example, Huijuan and colleagues [21] have, recently, reported interesting results about the preparation of hydroxyapatite-Chitosan composite and its efficiency for the removal of Congo red dye from aqueous solution.

The results indicate that the kinetic and isotherm studies showed that pseudo-second-order model and Langmuir model could well describe the

adsorption behavior, while thermodynamic investigation of Congo red adsorption by hydroxyapatite-Chitosan composite confirmed a spontaneous adsorption. It has been demonstrated that this composite is an effective and low-cost adsorbent for the dye-polluted water purification [21].

In the same framework, the present work describes the synthesis of hybrid compounds CaHAp-Alginate and CaHAp-(Carrageenan) as an adsorbent using a facile method by varying the content of the bio-polymer. Evidence of interaction between hydroxyapatite and Alg or (λ-Carr) was confirmed using various techniques including FT-IR, SSA, DRX and SEM. The factors that influence the dye uptake by the prepared adsorbents were also investigated and discussed.

### **2. Experimental**

#### **2.1 Synthesis of hydroxyapatite (CaHAp1 and CaHAp2)**

Hydroxyapatite was synthesized via co-precipitation method [22, 23]. As starting reagents, analytical grade CaCl2, Na2HPO4, Ca(NO3)2.4H2O, (NH4)2HPO4 and NH4OH were used. The chemicals equations that describes the reactions is given as follow:

#### **CaHAp1**

$$\begin{aligned} \text{10Ca(NO}\_3\text{)}\_2\text{4H}\_2\text{O} &\star 6\text{(NH}\_4\text{)}\_2\text{HPO}\_4 \star 8\text{(NH}\_4\text{OH)} \rightarrow\\ \text{Ca}\_{10}\text{(PO}\_4\text{)}\_6\text{(OH)}\_2 &\star 20\text{(NH}\_4\text{)} + 20\text{(NO}\_3^-\text{)} \star 46\text{H}\_2\text{O} \end{aligned} \tag{1}$$

#### **CaHAp2**

$$\text{10\text{CaCl}\_2\text{+6Na}\_2\text{HPO}\_4\text{+2H}\_2\text{O} \rightarrow \text{Ca}\_{10}\text{(PO}\_4\text{)}\_6\text{(OH)}\_2\text{+12(Na\text{+},Cl\text{)}\_2\text{8(H}\_7,Cl}\text{)}\tag{2}$$

An aqueous solution of 250 mL of Ca(NO3)2.4H2O or CaCl2 (0.2 M) was added drop-wise to 150 mL of (NH4)2HPO4 or Na2HPO4 (0.2 M) solution under N2 bubbling with a stoichiometric ratio of Ca/P = 1.67.

The pH was adjusted to 10 by adding NH4OH solution gradually. After the complete addition, the suspension was matured for 72 h at room temperature under magnetic stirring, the resultant precipitate was filtered, washed with distilled water, and dried overnight at 80°C.

#### **2.2 Synthesis of hydroxyapatite modified by sodium alginate CaHAp1-Alg**

A similar procedure of CaHAp1 was adopted to synthesize the modified hydroxyapatite by sodium alginate CaHAp1-(Alg), except for the fact that the (NH4)2HPO4was prepared with x mass of sodium alginate (5%, 10% or 20% of the total mass of Ca(NO3)2.4H2O in the starting solution).

#### **2.3 Synthesis of hydroxyapatite modified by sodium alginate CaHAp1-(**λ**-Carr)**

**169**

taken as a pHZPC.

*Preparation of Functionalized Hydroxyapatite with Biopolymers as Efficient Adsorbents…*

In the text, Hydroxyapatite modified with (λ-Carr) is abbreviated as

MB (its structure is given in **Figure 1**) solution was prepared by dissolving the calculated powder dye in distilled water with different required concentrations. NaOH and acetic acid solutions were used for adjusting the p*H* of the dye solution. For the adsorption experiments, MB solution was mixed with modified hydroxyapatite. MB concentrations were measured before and after experiments using a double beam UV–vis spectrophotometer (UV-1601 Shimadzu, Japan) at 664 nm. The adsorbed amount of dye onto modified hydroxyapatite (q mg/g) was calculated

e Oe ( ) V q=C C x

Where Co and Ce are the initial and equilibrium dye concentration (mg/L), V is the solution volume (mL) and m is the weight of used modified hydroxyapatite

The FT-IR spectra were recorded on a Perkin Elmer model 597 using KBr pellet method in the 4000–400 cm−1 region. X-ray powder diffractograms were obtained at room temperature on a PANalytical X'Pert PRO MPD equipped with copper anticathode tube. The morphological observation of the synthesized samples was undertaken using a JEOL JSM-5400 scanning electron microscope. Specific surface area (SSA) measurements were performed by BET-method (adsorptive gas N2, carrier gas He, heating temperature 100°C) using an

Quantachrome Instruments, model: ASIM. LP2. The pH of the zero point charge (pHZPC) was determined by putting 0.15 g of adsorbent in a closed Erlenmeyer flask containing 50 mL of NaCl solutions (0.1 M). The initial pH of these solutions was adjusted by either adding NaOH (0.1 M) or HCl (0.1 M) and were then agitated for 48 h at 150 rpm at room temperature to reach equilibrium. The final pH of supernatant was, further, measured and the ΔpH = pH (final) − pH (initial) was plotted against the initial pH. The pH at which ΔpH was zero was

( ) 100.

*m Carr m calcium* ×

m − (3)

(CaHAp-(Carr) n), where n represents the mass ratio ( )

*DOI: http://dx.doi.org/10.5772/intechopen.95347*

**2.4 Adsorption experiments**

**Figure 1.**

*Structure of methylene blue.*

using the following equation [24]:

sample (g) for the adsorption.

**3. Characterization techniques**

CaHAp2-(Carr) was synthesized, following a similar procedure of CaHAp2, except for the calcium containing solutions that were prepared by mixing 0.05 moles of CaCl2 with x mol (x = 0.0025, 0.005 and 0.01) of (λ Carr).

*Preparation of Functionalized Hydroxyapatite with Biopolymers as Efficient Adsorbents… DOI: http://dx.doi.org/10.5772/intechopen.95347*

**Figure 1.** *Structure of methylene blue.*

*Dyes and Pigments - Novel Applications and Waste Treatment*

prepared adsorbents were also investigated and discussed.

**2.1 Synthesis of hydroxyapatite (CaHAp1 and CaHAp2)**

bling with a stoichiometric ratio of Ca/P = 1.67.

total mass of Ca(NO3)2.4H2O in the starting solution).

and dried overnight at 80°C.

the dye-polluted water purification [21].

**2. Experimental**

**CaHAp1**

**CaHAp2**

adsorption behavior, while thermodynamic investigation of Congo red adsorption by hydroxyapatite-Chitosan composite confirmed a spontaneous adsorption. It has been demonstrated that this composite is an effective and low-cost adsorbent for

In the same framework, the present work describes the synthesis of hybrid compounds CaHAp-Alginate and CaHAp-(Carrageenan) as an adsorbent using a facile method by varying the content of the bio-polymer. Evidence of interaction between hydroxyapatite and Alg or (λ-Carr) was confirmed using various techniques including FT-IR, SSA, DRX and SEM. The factors that influence the dye uptake by the

Hydroxyapatite was synthesized via co-precipitation method [22, 23]. As starting reagents, analytical grade CaCl2, Na2HPO4, Ca(NO3)2.4H2O, (NH4)2HPO4 and NH4OH were used. The chemicals equations that describes the reactions is given as follow:

> ( ) ( ) ( ) ( ) ( ) ( ) ( ) 32 4 4 4 2 2

10 4 6 2 4 3 2 10Ca NO .4H O+6 NH HPO +8 NH OH Ca PO OH +20 NH +20 NO +46 H O

2 2 42 10 4 6 2 10CaCl +6Na HPO +2H O Ca PO OH +12 Na+,Cl- +8 H+,Cl → (2)

An aqueous solution of 250 mL of Ca(NO3)2.4H2O or CaCl2 (0.2 M) was added drop-wise to 150 mL of (NH4)2HPO4 or Na2HPO4 (0.2 M) solution under N2 bub-

The pH was adjusted to 10 by adding NH4OH solution gradually. After the complete addition, the suspension was matured for 72 h at room temperature under magnetic stirring, the resultant precipitate was filtered, washed with distilled water,

**2.2 Synthesis of hydroxyapatite modified by sodium alginate CaHAp1-Alg**

A similar procedure of CaHAp1 was adopted to synthesize the modified hydroxyapatite by sodium alginate CaHAp1-(Alg), except for the fact that the (NH4)2HPO4was prepared with x mass of sodium alginate (5%, 10% or 20% of the

**2.3 Synthesis of hydroxyapatite modified by sodium alginate CaHAp1-(**λ**-Carr)**

CaHAp2-(Carr) was synthesized, following a similar procedure of CaHAp2, except for the calcium containing solutions that were prepared by mixing 0.05

moles of CaCl2 with x mol (x = 0.0025, 0.005 and 0.01) of (λ Carr).

+ -

→

( ) ( ) ( ) ( )-

(1)

**168**

In the text, Hydroxyapatite modified with (λ-Carr) is abbreviated as (CaHAp-(Carr) n), where n represents the mass ratio ( ) ( ) 100. *m Carr m calcium* ×

#### **2.4 Adsorption experiments**

MB (its structure is given in **Figure 1**) solution was prepared by dissolving the calculated powder dye in distilled water with different required concentrations. NaOH and acetic acid solutions were used for adjusting the p*H* of the dye solution. For the adsorption experiments, MB solution was mixed with modified hydroxyapatite. MB concentrations were measured before and after experiments using a double beam UV–vis spectrophotometer (UV-1601 Shimadzu, Japan) at 664 nm. The adsorbed amount of dye onto modified hydroxyapatite (q mg/g) was calculated using the following equation [24]:

$$\mathbf{q}\_e = \left(\mathbf{C}\_0 - \mathbf{C}\_e\right) \mathbf{x} \frac{\mathbf{V}}{\mathbf{m}} \tag{3}$$

Where Co and Ce are the initial and equilibrium dye concentration (mg/L), V is the solution volume (mL) and m is the weight of used modified hydroxyapatite sample (g) for the adsorption.

#### **3. Characterization techniques**

The FT-IR spectra were recorded on a Perkin Elmer model 597 using KBr pellet method in the 4000–400 cm−1 region. X-ray powder diffractograms were obtained at room temperature on a PANalytical X'Pert PRO MPD equipped with copper anticathode tube. The morphological observation of the synthesized samples was undertaken using a JEOL JSM-5400 scanning electron microscope. Specific surface area (SSA) measurements were performed by BET-method (adsorptive gas N2, carrier gas He, heating temperature 100°C) using an Quantachrome Instruments, model: ASIM. LP2. The pH of the zero point charge (pHZPC) was determined by putting 0.15 g of adsorbent in a closed Erlenmeyer flask containing 50 mL of NaCl solutions (0.1 M). The initial pH of these solutions was adjusted by either adding NaOH (0.1 M) or HCl (0.1 M) and were then agitated for 48 h at 150 rpm at room temperature to reach equilibrium. The final pH of supernatant was, further, measured and the ΔpH = pH (final) − pH (initial) was plotted against the initial pH. The pH at which ΔpH was zero was taken as a pHZPC.