Synthesized and Characterization TiO2-AlLiH4 Nanostructure for Photocatalytic Activity Application for Removal the Residue of Hydrocarbons in Environment

The novel approach includes The sol-gel technique was used to make titanium dioxide nanoparticles and then for photodegradation Benz[a]anthracene a crystalline, aromatic hydrocarbon, as a trial sample of the residue of hydrocarbons in environments close to oil refining facilities and oil fields, methods, the bandgap was modified by solid-state reaction with Lithium aluminium hydride (AlLiH4) reductive compounds. The optical properties were measured using a UV-visible spectrophotometer (Absorbance (A), energy bandgap (Eg), and absorption coefficient (α). TiO2 and TiO2solid-state reaction showed a clear blue shift of the absorption bandgap which were (2.8ev, 2.7ev, 2.25ev, 2.0ev) to) TiO2, calcination TiO2-AlLiH4 (500C°) then TiO2 -AlLiH4 (750 C°)) respectively. The structure of prepared TiO2 Nanopowders was identified using XRD, Distribution of particle size varied significantly compared to the Sheerer formulation predicted crystallite size (D). which was in a good accordant compared with ASTM results, the particle size and their distribution were characterized using (AFM). To the surface forms and compositions diameters of nanoparticles) SEM) was implemented. The microanalysis of energy scattering X-ray (EDX) was used to examine the chemical makeup of the entire samples. Using UV-Vis spectrophotometry, the photocatalytic response was examined. The photocatalyst impact on the benz[a]anthracene decomposition rate by using catalyst TiO2and solid-state (TiO2NaBH4 (550,750)) and (TiO2-AlLiH4 (500,750 C°). A photocatalytic effect is the This work is licensed under a Creative Commons Attribution 4.0 International License. Journal of Petroleum Research and Studies PISSN: 2220-5381 EISSN: 2710-1096 Open Access No. 34 part 1, March 2022, pp.267-283 268 catalyst's influence on the catalyst. Using the constant weight of the catalyst and benz[a]anthracene The most effective weight was found (1*10-4 M).

catalyst's influence on the catalyst. Using the constant weight of the catalyst and benz [a]anthracene The most effective weight was found (1*10-4 M).

Introduction
Anion doping in broad band gap photo catalysts active under UV irradiation is another way to improve the visible light response [1][2][3]. Development of visible light photo catalysts from oxide semiconductors by doping with anions as examples (C, N, F, P, and S). The sol-gel technique was used to make AlLiH4-doped TiO2, with different titania precursors and nitrogen sources. Utilizing titanium(IV) tetraisopropoxide with AlLiH4solution and calcined at 673 K, it was discovered that AlLiH4-doped TiO2 using titanium(IV) tetraisopropoxide with AlLiH4solution offered the most suitable characteristics for serving as the photo catalyst [5][6][7][8]. The TGA, Raman, and XRD findings showed that this AlLiH4-doped TiO2 catalyst had a high crystallinity since the titania precursor had been fully hydrolyzed, with no organic component to obstruct initial phase formation. The results of SEM and TEM showed that the surface shape was spherical, similar to fluffy powders [8][9][10][11]. Furthermore, the inserted metal or nonmetals that's slowed the anatase-to-rutile phase transition as the calcination temperature rose. The findings of the elemental analysis and UV-Vis/DR showed that ions, metals, and nonmetals may be latent in the TiO2 lattice with strong connections, producing an influence on the band gap structure by adding energy levels near the valence band of TiO2. Under visible light, all of these characteristics improved the photocatalytic activity of co-doped TiO2 [12][13][14][15]. In terms of photocatalytic activity, TiO2 -AlLiH4 calcined at 673 K with titanium(IV) tetraisopropoxide and ammonia solution degraded phenanthrene, benz [a]anthracene, and phenol with the best efficiency. When calcined at a higher temperature, however, its photocatalytic activity was substantially reduced. In the instance of photodegradation of phenanthrene, a plausible mechanism was postulated based on two GC/MS identified intermediates: bis(2-ethylhexyl) benzene-1,2-dicarboxylate and dimethyl-4-methyl-1,2-benzene dicarboxylate. [13][14][15][16][17][18][19][20][21][22] Incomplete combustion of organic matter produces benz [a]anthracene, a crystalline aromatic hydrocarbon with four fused benzene rings. Benz(a)anthracene can be found in gasoline and diesel exhaust, tobacco and cigarette smoke, coal tar and coal tar pitch, coal combustion emissions, charcoal-broiled foods, amino acids, fatty acids, and carbohydrate pyrolysis products, wood and soot smoke, and creosote, asphalt, and mineral oils, among other things. Only for research purposes is this chemical utilized.

NCI Thesaurus (NCIt)
Colorless leaflets or plates, as well as coarse gold powder with a greenish-yellow fluorescence, are found in benz [a]anthracene. It's possible that this substance is carcinogenic. [15,28]

CAMEO Chemicals
Tetraphene is a four-fused benzene ring polycyclic arene with an angular ortho-fused structure. It is a tetraphenes member and an ortho-fused polycyclic arene. First and foremost, phenanthrene is a PAH made up of three fused benzene rings (Table 1). It is a recognized irritant that photosensitizes skin to light and is present in cigarette smoke. Phenanthrene is a white powder that is soluble in most organic solvents but insoluble in water. Second, benz [a]anthracene is a PAH [28][29][30], that has a four-member ring structure, as illustrated in Table 1. It is a natural substance that is created when organic material is incompletely burned. The toxicity of benz [a]anthracene and other PAHs is largely focused at tissues with growing cells [31][32][33]. Some TiO 2 -AlLiH 4 will be used in the photocatalytic degradation of benz [a]anthracene. Also investigated were the photocatalytic activity and rate constants of each TiO 2 -AlLiH 4 and P25 TiO 2 . Table 1 The structures and general properties of phenanthrene and benz [a]anthracene. H2O dissolved to produce hydroxyl. The major photoproduct was identified as benz [a]anthracene-7,12-dione based on GC/MS findings [37].

Solid State Reaction of TiO 2
Different weights of powder TiO 2 were mixed with equal proportions of NaBH4 and repeated for AlLiH 4 . Then, calcination process at different temperatures in the furnace to produce in hydrogen gas by dissociation AlLiH4 and NaBH4 at varies temperatures 500 and 550 according to convert TiO 2 by reduction process from anatase to rutile at 600 and 800. The calcination continues for 2h, were the powder appear in black and white colors according to calcination temperature. Then, the ratio (1:1) products (TiO2:NaBH 4 ) and (TiO2:AlLiH 4 ) have been characterization by X-ray diffraction, SEM, EDX, AFM and solid state UV-VIS spectrometer.

Preparation of benz[a]anthracene solution
25.00 ml of 1000 ppm stock benz [a]anthracene solution in pure methanol solvent was prepared by dissolving 0.0250 g standard benz [a]anthracene with a certain volume in a 25 ml volumetric flask. 500.00 ml of 20 ppm benz [a]anthracene solution was prepared by diluting 10.00 ml of stock benz [a]anthracene solution with distilled water and methanol in the volumetric ratio of 1:3. Concurrently, benz [a]anthracene solution was also sonicated, [40][41]

2.4The calibration curve of benz[a]anthracene solution
Initially, the series of benz [a]

Photo degradation of benz[a]anthracene
Five hours consisting of one hour in dark reaction and four hours in photoreaction were set up for benz [a]anthracene degradation. Under the photoreaction, the sample was collected every 30 min until 90 min of degradation. After that, the sample was continually collected every hour. All of samples were taken by passing the general process as mentioned above. Then, only 1 ml of a sample was picked up using an autopipette from the centrifuged sample and made up the volume by distilled water in a 10 ml volumetric flask. Fluorescent measurement at λ em of 527 nm was applied to detect the concentration of each sample. All samples were also conducted in three replicates. [19,33,35,40]

Luminescence Spectrophotometry
The decreasing concentration of reactants namely benz [a]anthracene was followed by measuring the absorption on a Perkin Elmer Lambda 35 spectrophotometer. To get an obvious spectrum, emission slit width or excitation slit width should be also adjusted to find the appropriate condition. Eventually, for benz [a]anthracene, the optimized condition was λ ex at 287.0 nm, with a scan speed of 1000 nm/min, the excitation slit width is 10.0 nm and the emission slit width is 2.5 nm [5,13,33].

Photo degradation of benz[a]anthracene
This section made only use of AlLiH 4 -doped TiO 2 using titanium(IV) tetraisopropoxide mixed with AlLiH 4 and calcined at 673 K as a photocatalyst due to its most appropriate photocatalytic properties such as crystallinity, phase composition, surface morphology as well as AlLiH 4 quantity.

Fig. (1): Photo degradation of benz[a]anthracene by using; (a) AlLiH 4 doped TiO 2 calcined at 673 K (♦), (b) P25 TiO 2 (■) and (c) without catalysts (▲).
The result as shown in Figure (1 With the increasing temperature, AlLiH 4 -doped TiO 2 got the larger crystallite size, the higher crystallinity and Transformation of anatase-to-use phase. The lowest crystallite size, the greatest anatasis and the high number of firmly bound Nitrogen are optimal Titanium (IV) Tetraisopropoxide as a titanium precursor combined to NH3 as a nitrogen source is calcined to 674 K compared to all AlLiH 4 -doped-TiO 2 , and AlLiH4doped-TiO 2 seemed to be closely within the scope of the ideal photo catalyst. It provided high crystallinity and spherical surface morphology although its crystallite size is 16 nm. Its phase transformation was retarded by the effect of the stronglybonded nitrogen in TiO 2 lattice. Moreover, the structural determination did also support that the structure of Titanium (IV) tetraisopropoxide was easy to be hydrolyzed by ammonia or water molecules. With regard to photocatalytic activity, AlLiH 4 -doped TiO 2 using titanium(IV) tetraisopropoxide mixed with NH 3 and calcined at 673 K provided the highest %conversion among three substrates; 33% of 20 ppm phenanthrene, 52% of 20 ppm benz [a]anthracene and 4% of 20 ppm phenol. It also rendered the fastest rate of reactions, which was able to be observed from the rate constants; 0.058 h -1 for phenanthrene, 0.074 h -1 for benz [a]anthracene, and 0.036 h -1 for phenol. Interestingly, the elevating temperature had an adverse repercussion on photocatalytic activity.
which resulted from thermal decomposition. Meanwhile, P25 TiO2 has a good ability to degrade benz [a]anthracene up to 22% conversion with the rate constant of 0.058 h-1 because of synergistic effect between anatase and rutile, like photodegradation of phenanthrene.  [a]anthracene was calculated from a graph Figure (2 a,b) which is a linear plot between (In (Ct/C0 ) versus (t). From slope = -k which equals (-k) according to the equation above are listed and Table (2).
The results in Figure (2) show the increase in temperature (293-313) K will increases the discoloration rate of benz [a]anthracene, and also the rate constant increase explained by the fact adsorption is an endothermic process. It was found that the benz [a]anthracene decolorization was obeyed the first-order rate law. Because interactions depend only on the degradation of benz [a]anthracene to it that the highest concentration which is considered basic material interaction, which can be expressed by Kinetic of Degradation of benz [a]anthracene. 52% of 20 ppm benz [a]anthracene and 4% of 20 ppm phenol. It also rendered the fastest rate of reactions, which was able to be observed from the rate constants; 0.058 h-1 for phenanthrene, 0.074 h-1 for benz [a]anthracene, and 0.036 h-1 for phenol.
Interestingly, the elevating temperature had an adverse repercussion on photocatalytic activity. In addition, the probable mechanism of the photodegradation reaction of phenanthrene was proposed based on the two detectable intermediates.