1 | Page THE INTERNATIONAL JOURNAL OF GLOBAL SCIENCES (TIJOGS) ISSN Print: 2663-0141; ISSN Online: 2663-015X Vol. 3(1) Jan-March,01-13; 2020 http://www.rndjournals.com THE INTERNATIONAL JOURNAL OF GLOBAL SCIENCES (TIJOGS) ISSN Print: 2663-0141; ISSN Online: 2663-015X Vol. 3(1) Jan-March,01-13; 2020 http://www.rndjournals.com SYNTHESIS OF MANGANESE-TIN BIMETALLIC MATERIALS AND STUDY OF ITS CATALYTIC APPLICATIONS Muhammad Usman Tahir 1 , Faheem Abbas 1* , Maimoona Tahira 1 , Hafiz Mohsin Shahzad 1 , Shahzad Sharif 2 , Ali Raza Ayub 1 , Sania Rafique 2 , Habib Ullah 2 & Muhammad Ziad 1 1 Department of chemistry, University of Agriculture Faisalabad, Pakistan 2 Lahore Garrison University, Lahore, Pakistan * Corresponding author: [email protected]_________________________________________________________________________________________________ ABSTRACT Manganese-Tin bimetallic materials are synthesized by various methods: Hydrothermal, Co-precipitation and Solvothermal methods. Products obtained from these methods are analyzed by using x-ray power diffractometry (XRD). Structural composition, purity of synthesized product is analyzed by x-ray diffraction. The characteristics of Crystal-like unit cell dimension, space group density, miller Indices are obtained from X-ray diffraction. The synthesized product was used in three applications: as a fuel additive, cement additive, and catalyst activity. The efficiency of fuel is checked by studying different parameters: fire point, flash point, cloud point, pour point, kinematics viscosity, specific gravity and calorific value. Synthesized materials are used as catalyst for the degradation of dye in aqueous medium. Catalytic degradation of dye is monitored at different concentration of catalyst and hydrogen peroxide. The mechanical properties are analyzed by studying various parameters such as thermal conductivity, ageing porosity, specific heat and thermal diffusivity. _________________________________________________________________________________________________ Introduction In the present period of advancement, the use of nanotechnology and nano science is increasing day by day in different fields like drug delivery, medicine, cosmetic etc. Nano science is the study of influence of material at molecular and atomic scales wherever properties fluctuate expressively from that at a bulk range (Nowak, Mueller et al. 2008). Various approaches have been used for synthesis of nanoparticles. These methods can be categorized into two main approaches top-down approach and bottom up approach. The second approach is bottom-up approach in which nanoparticles are synthesized from molecular and atomic scale by using different routes. The chemical vapor deposition process (CVD) and the physical vapor deposition are two examples of bottom-up approach (Wang and Liu 2009). Bimetallic materials contain two unlike metals that attained more tension than that of single particles. Bimetallic nanoparticles have catalytic, electronic, and optical properties that are not present in monometallic materials (Kang and Murray 2010). Bimetallic materials can be categories into six different architectures such as core shell, hetro, hollow and alloyed structure (Liu, Liang et al. 2012). In crown –jewel bimetallic nanomaterials, one metal atom is deposited on to the surface of another metal (Tao 2012). Bimetallic core-shell nanoparticles are synthesized by using the co-reduction or seed growth metallic precursor (Renzas, Huang et al. 2011). The size and shape of bimetallic depends on preparation method and conditions. Bimetallic materials depend upon the preparation condition, kinetics of reduction of metals, and miscibility (Aromal and Philip 2012). The bimetallic materials can be oriented in arbitrary for example cluster in cluster or alloy and core-shell structure. Bimetallic hetro-structure are entirely different forms of alloy and intermetallic structures. Hetro-structure of bimetallic material can be synthesized by the growth process (Lee, Huh et al. 2007). In diversity of chemicals responses, the activity of oxygen reduced in fuel cell is one of the major bimetallic nano-catalyst used for application. Application of bio-fuel from biomass, that changing the nano catalysts. Bimetallic materials have many applications in optic materials, catalysis, electronic coatings and cosmetic (Alonso, Wettstein et al. 2012). Hydrothermal method is an important method for the formation of nano-crystals. In this technique solution of precursor mixed with each other by constant stirring keeping at desired temperature and PH then put in to the stainless Teflon- Research Article
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1 | P a g e THE INTERNATIONAL JOURNAL OF GLOBAL SCIENCES (TIJOGS) ISSN Print: 2663-0141; ISSN Online: 2663-015X Vol. 3(1) Jan-March,01-13; 2020 http://www.rndjournals.com
THE INTERNATIONAL JOURNAL OF GLOBAL SCIENCES (TIJOGS)
ISSN Print: 2663-0141; ISSN Online: 2663-015X
Vol. 3(1) Jan-March,01-13; 2020
http://www.rndjournals.com
SYNTHESIS OF MANGANESE-TIN BIMETALLIC MATERIALS AND STUDY OF ITS CATALYTIC APPLICATIONS
Muhammad Usman Tahir1, Faheem Abbas1*, Maimoona Tahira1, Hafiz Mohsin Shahzad1, Shahzad Sharif2, Ali Raza Ayub1, Sania Rafique2, Habib Ullah2 & Muhammad Ziad1
1Department of chemistry, University of Agriculture Faisalabad, Pakistan 2Lahore Garrison University, Lahore, Pakistan
ABSTRACT Manganese-Tin bimetallic materials are synthesized by various methods: Hydrothermal, Co-precipitation and Solvothermal methods. Products obtained from these methods are analyzed by using x-ray power diffractometry (XRD). Structural composition, purity of synthesized product is analyzed by x-ray diffraction. The characteristics of Crystal-like unit cell dimension, space group density, miller Indices are obtained from X-ray diffraction. The synthesized product was used in three applications: as a fuel additive, cement additive, and catalyst activity. The efficiency of fuel is checked by studying different parameters: fire point, flash point, cloud point, pour point, kinematics viscosity, specific gravity and calorific value. Synthesized materials are used as catalyst for the degradation of dye in aqueous medium. Catalytic degradation of dye is monitored at different concentration of catalyst and hydrogen peroxide. The mechanical properties are analyzed by studying various parameters such as thermal conductivity, ageing porosity, specific heat and thermal diffusivity. _________________________________________________________________________________________________ Introduction In the present period of advancement, the use of nanotechnology and nano science is increasing day by day in different fields like drug delivery, medicine, cosmetic etc. Nano science is the study of influence of material at molecular and atomic scales wherever properties fluctuate expressively from that at a bulk range (Nowak, Mueller et al. 2008). Various approaches have been used for synthesis of nanoparticles. These methods can be categorized into two main approaches top-down approach and bottom up approach. The second approach is bottom-up approach in which nanoparticles are synthesized from molecular and atomic scale by using different routes. The chemical vapor deposition process (CVD) and the physical vapor deposition are two examples of bottom-up approach (Wang and Liu 2009). Bimetallic materials contain two unlike metals that attained more tension than that of single particles. Bimetallic nanoparticles have catalytic, electronic, and optical properties that are not present in monometallic materials (Kang and Murray 2010). Bimetallic materials can be categories into six different architectures such as core shell, hetro, hollow and alloyed structure (Liu, Liang et al. 2012). In crown –jewel bimetallic nanomaterials, one metal atom is deposited on to the surface of another metal (Tao 2012). Bimetallic core-shell nanoparticles are synthesized by using the co-reduction or seed growth metallic precursor (Renzas, Huang et al. 2011). The size and shape of bimetallic depends on preparation method and conditions. Bimetallic materials depend upon the preparation condition, kinetics of reduction of metals, and miscibility (Aromal and Philip 2012). The bimetallic materials can be oriented in arbitrary for example cluster in cluster or alloy and core-shell structure. Bimetallic hetro-structure are entirely different forms of alloy and intermetallic structures. Hetro-structure of bimetallic material can be synthesized by the growth process (Lee, Huh et al. 2007). In diversity of chemicals responses, the activity of oxygen reduced in fuel cell is one of the major bimetallic nano-catalyst used for application. Application of bio-fuel from biomass, that changing the nano catalysts. Bimetallic materials have many applications in optic materials, catalysis, electronic coatings and cosmetic (Alonso, Wettstein et al. 2012). Hydrothermal method is an important method for the formation of nano-crystals. In this technique solution of precursor mixed with each other by constant stirring keeping at desired temperature and PH then put in to the stainless Teflon-
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lined chamber. The chamber is place into oven and heated to the required temperature AT high pressure. Then resulting product is centrifuged and dried in oven at low temperature. After calcination bimetallic materials are formed. Zhang and his co-scientist synthesize manganese-tin bimetallic Materials at 180c by using this technique (Zhang, Jin et al. 2011). Co-precipitation method is efficient method for the synthesis of bimetallic materials, because it is non-expensive and simple method. In this technique the solutions are mixed with each other by continuous stirring keeping PH of medium in basic range. To reduce the particle size and aggregation, different types of surfactants can also be used (Lamdhade, Raghuwanshi et al. 2015). Venkatesh and his coworkers used the co-precipitation method for synthesis of bimetallic materials (Vattikuti, Byon et al. 2015). Green approach is good method for the synthesis of bimetallic materials. In this technique the composition of solution is tuned by varying the concentration of precursors at different ratios of reagents. Shankar and his coworkers used green chemistry method for the preparation of bimetallic materials using Neem leaves (Shankar, Rai et al. 2004) .They synthesize the bimetallic materials with diameter 50nm. Dimension of synthesized product 15-30nm in range. Metal alkoxide acts as precursor in sol-gel technique in which metal undergoes the hydrolysis and condensation reaction. In second step hydrolysis of nanoparticles take place. Gao and his coworker used sol-gel method for synthesis of manganese-tin bimetallic materials (Gao, Cui et al. 2004). They use citric acid which acts as chelating agent. They synthesized particles with diameter 5-30nm after annealing at 400c temperature. Micro emulsions method is extremely efficient method for synthesis of bimetallic materials. In this method surfactant help to prepare water in oil micro emulsion. The non- polar hydrocarbon head group is attracted toward the no-aqueous phase and the polar head is attracted aqueous phase. The characterization of bimetallic materials was done by Scanning electron microscopy (SEM) and X-ray powder diffractometry (XRD). Size of the particles is found to be 20nm with spherical morphology (Wu, Zhang et al. 2010). Co-reduction method is used for the synthesis of bimetallic materials. In this technique difference in redox potential of two metals can be controlled the morphology of bimetallic materials. By co-reduction method bimetallic materials of definite morphology as well as composition are obtained. La and his coworkers successfully synthesized manganese-tin bimetallic nanoparticles with diameter 3.5nm using co-reduction method (Li, Kuai et al. 2013). Bimetallic material structure and variety of functional parameter can be analyzed by various technique like X-ray diffraction (XRD). Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), UV-visible spectrophotometry, Transmission electron spectroscopy (FTIR),UV-visible spectrophotometry, Transmission electron microscopy (TEM), X-rays photoelectron spectroscopy(XPS),Diffusion reflectance infrared Fourier transform (DRIFT), Field emission electron microscopy (FE-SEM), Raman spectroscopy, Energy dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM) AND High resolution transmission electronic microscopy(HRTEM). Scanning electron microscopy provide information on the nanoparticles surface morphology. Bimetallic materials have a numerous applications in various fields on including catalysis, optical materials ,cosmetics, Electronics ,reduction of dye, Fuel additive and drug delivery etc. (Nejati-Moghadam, Esmaeili Bafghi-Karimabad et al. 2015). Catalytic behavior of manganese-tin bimetallic materials will be use to study the degradation of dye, checking the efficiency of petrol by various parameters and Mechanical application. Bimetallic materials are used as fuel additive to acquire better physicochemical properties of fuel. Efficiency of petrol is checked by studying different parameters of fuels in presence of prepared manganese-tin bimetallic materials. Pour point , cloud point, flash point ,fire point and calorific value are measured to analyze combustion characteristics of fuel, specific gravity and calorific value are measured to analyze combustion characteristics of fuel, specific gravity and kinematic viscosity are measured to analyze combustion characteristics of fuel, specific gravity and kinematic viscosity are measured to analyze physical properties. Flash point and fire point are measured by flash point detector. Bomb calorimeter are used to measure the calorific value. Specific gravity analyzed by specific gravity meter. While kinematic viscosity are measured by using the viscometer (Tat and Van Gerpen 1999).Semiconductor materials used as photo catalyst for the removal of organic dye from the water sources. Synthesized bimetallic materials will be used as catalyst for the production of pollutant in aqueous medium because most of the dye absorbs in UV- visible range by using the spectrophotometer. Chen and his coworkers prepared synergistic effect of bimetallic materials in three dimensions (Chen, Gambhir et al. 2011). They used these synthesized bimetallic materials for the removal of rhodamine B (RhB). They monitored the first order reaction, degradation rate (RhB) within 130 min by using the manganese-tin bimetallic materials. Nano spheres show
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good catalytic activity toward the degradation. By modification the size of particles, using nano catalyst that enhance the catalytic activity. The surface area of the metal inversely proportional to square of width of nanoparticles as surface enhance with reducing size of the metal particles. The size of the particles linearly increase the catalytic activity (Fu, Dang et al. 2012). Liu and his coworkers investigated the influence of catalytic composition effect on the surface of bimetallic nano catalyst (Liu, Li et al. 2012). For changing composition of synthesize catalyst, it is possible that decrease the poisoning effect. The ligand and strain effects generated by the insertion of additional metal modification of the electronic configuration. So, catalyst activity increase, bimetallic nanoparticles produce synergistic effect that changes the electronic configuration. Metallic materials show better flexibility and selectivity of the nano catalyst as compared to mono metallic nano-catalyst structure. The core shell structure, cluster in cluster the product of two metals has different modes. Synthesized product of bimetallic catalyst interrelated to the bimetallic structure (Friebel, Miller et al. 2011). The catalytic reaction occurs on metal surface, the morphology of catalyst has important effect on catalytic activity. By using different catalyst morphology effect the Au-Pd bimetallic materials. In the presence of Au-Pd/Tio2 catalyst found cuboctahedra geometry mixed (111) and (100) plants ends where as in the presence of Au-Pd/C catalyst decahedral and icosahedral geometry which exposed, (111) plane (Sankar, Dimitratos et al. 2012). Materials and Methods Description of all instruments that are used in catalytic application such as flash point, cloud point, specific gravity, kinematics viscosity is also given in this chapter. All the glass wares and Chemicals of research grade were used in research work without any further purification. Magnesium acetate, Stannic chloride, Sodium borohydride, ethanol and sodium hydroxide and sodium citrate, ethylene glycol hydrogen peroxide distilled water Congo red dye and diesel were used, catalytic reactions and solution preparations. Sodium hydroxide and urea of research grade were used to maintain the pH of bimetallic nanoparticles solutions. Product A Manganese-tin bimetallic materials were synthesized by hydrothermal method. Hydrated magnesium acetate was dissolved in 30 ml of ethylene glycol at room temperature and stirred for 45 min, 4g (Sncl2.4H2O), was dissolved in 30 ml of ethylene glycol during stirring until they were completely dissolved. Urea solution was added in mixed solution and stirred for 1 hour at room temperature. Then this final solution was put into the stainless-steel autoclave 180 degree centigrade for 8 hours. Then cool the solution at room temperature and the precipitates were collected by using centrifugation process. The impurities removed after continuous washing with distilled water and ethanol. The final solution was dried at overnight 60 degree centigrade. Product B The manganese-tin bimetallic materials were also synthesized by solvothermal method. Manganese chloride and stannic chloride were separately dissolved by ultra-sonication in ethylene glycol. Then sodium hydroxide solution was added into the mixed solution. Sonicate the solution for 30 min then sodium borohydrate solution was drop wise added. Then the solution was put into stainless steel autoclave at 160 degree centigrade for 3 hrs. Autoclave was allowed to cool down at room temperature. Then the product was collected by centrifugation and washed with distilled water and ethanol. Product was dried in oven at 60 degree centigrade for 24 hrs. Product C The Manganese-tin bimetallic nanoparticles were also synthesizing by co-precipitation method. Manganese chloride and stannic chloride were mixed together under constant magnetic stirring by maintaining the pH of solution. After the addition of NaBH4 the reaction mixture was further stirring for 1hr to make it homogeneous. Then this solution was centrifuged to collect the precipitates. Ethanol and distilled water were used for Purification of product. So, obtained product was dried in oven at 60 degree centigrade. At the end of dried product was grounded with pestle mortar and calcined in 600 centigrade for 4 hrs. Synthesis of manganese-tin bimetallic materials Three application of manganese-tin bimetallic materials were studied as a fuel additive, as a catalysis and as a cement additive.
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Application of Manganese-tin bimetallic materials as a Fuel Additive To study the effect of bimetallic materials as fuel additive samples of different concentration were prepared. Solution having concentration 0, 10, 20, 30 E and 40 ppm of manganese-tin bimetallic materials were prepared in diesel. The flash point and fire point were monitored by APEX-JCX309 open cup tester. The cup tester was made of copper metal and flame to generate spark. Five different samples prepared for flash and fire point measurement. The 0, 10, 20, 30, and 40ppm solution was made by dissolving the 0.001, 0.002,0,003 and 0.004 g of manganese-tin metallic materials in 100mL of diesel fuel. The pour point and clod point are the low temperature of diesel fuel, pour point was measured by ASTM-D90 method. The re-fined base stocks low temperature flow characteristics were determined by this method. The cloud point was measured by ASTM 2500 method. In this methods sample of different concentration cooled at specific time also examined. The 0, 10, 20, 30, and 0.004 g of product A in diesel. Kinematic viscosity was determined by ASTM-D445 method. In this method the volume of liquid was taken in viscometer which flow through a capillary tube and time of different concentration of fuel sample measured. Specific gravity was measured by ASTM-D6752 method. In this method first of all measuring the weight of empty flask then 5mL of prepared diesel samples was poured in to the flask and weighted one by one for each concentration. Specific gravity meter DA-640 was used to measure the specific gravity of diesel and diesel contains bimetallic materials with different dosages up to 40ppm. ASTM-D240 standard method is used to calculate the calorific values of diesel sample. The 10, 20, 30, 40ppm concentration was dissolving the 0.001, 0, 002, 0.003 and 0.004g of manganese-tin bimetallic materials in a diesel fuel. Application of manganese-tin bimetallic material as a cement additive Manganese-tin bimetallic materials were used to improve the efficiency of cement. Different concentration of additive was added into the cement and different parameters of cement were tested. First of all, using concentration of additive different cement sample were prepared. The prepared by metallic materials were used to check the mechanical properties of cement by using different parameters weight, porosity aging, volume, density, specific heat, thermal conductivity, thermal diffusivity and compressive strength. Application of manganese-tin bimetallic material as a catalyst The synthesized manganese-tin bimetallic materials were used as catalyst for the degradation of Congo red (CR) dye and for the reduction of 4-nitrophenol in the absence of Sunlight. The stock solution of Congo red was prepared by dissolving the 0.01g of dye into 100mL of distilled water. Then 3ppm solution of dye was prepared 0.1 mL of hydrogen peroxide and different dosage of the catalyst were added to solution to degrade the CR dye. The solution of dye was placed into cuvette and then spectra was recorded at Hallo DB 20 spectrophotometer from 200 to 800nm wavelength range and photometry was done on the specific wavelength. Maximum absorption of CR was recorded at 495nm. The catalyst was added into the dye solution and then Stirrer for 20 min. After that spectra of Congo red dye solution to check the activity of catalyst. The catalyst reduction of dye was measured by changing the concentration of H2O2 and dosage of manganese-tin bimetallic nanoparticles. Results and Discussion XRD Pattern of Manganese-Tin Bimetallic Materials (Product A) XRD diffraction pattern of synthesized bimetallic materials is shown in figure. Sharp diffraction peaks are present at 2-theta values 18.29o, 28.67o, 31.63o, 33.28o, 36.16o, 46.18o, 49.84o, 56.73o, 64.92o and 76.03o which are associated with planes (111), (101), (121), (101), (222), (232), (131), (333), (242) and (314) respectively. The sharp peaks indicate the characteristics of bimetallic oxide nanoparticles (PDF No 96-154-1522). All the peaks are sharp which indicates the crystalline nature of products. The study of diffraction peak shows that synthesized bimetallic product possesses cubic lattice with space group Fd-3 m (227). The calculated volume and density are 90.4650 Ao3 and 5.63400 g/cm3 respectively and the values of lattice parameter are a= 8.7710Ao.
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10 20 30 40 50 60 70 80
0
50
100
150
200
250In
tensity
2-theta
Intensity
(111)
(101)
(121)
(101)
(222)(232)
(131)
(333)
(212)
(314)
Mn(O)3Sn
Figure. XRD Pattern of Manganese-Tin Bimetallic Materials This study was conducted to synthesize Manganese-Tin Bimetallic compounds by using different methods such as hydrothermal method, solvothermal method and co-precipitation method. The synthesized products were used in three applications such as a fuel additive, as a cement additive and as a catalyst. 1. Application of Manganese-Tin Bimetallic Materials as Fuel Additive Diesel fuel was used to check the efficiency of prepared bimetallic materials, because fuel is mainly used in heavy engine machine. The NOx and SOX exhaust from heavy engine motor that causes global warming. Efficiency of diesel fuel was checked by studying various parameters in the presence and absence of prepared bimetallic materials. Flash point, fire point, cloud point, pour point and calorific values was measured to analyze the ignition characteristics of fuel while specific gravity and kinematic viscosity was analyzed to study the physical characteristics of diesel. These different parameters were analyzed in the presence of 10, 20, 30, and 40 ppm dosage of bimetallic additive. The results obtained in the presence of additive was compared with the control sample.
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1.1 Flash point and Fire point The flash points were measured in the presence of manganese-tin bimetallic materials synthesized by hydrothermal method. The plot of flash and fire points as a function of concentration of additive is given in figure. The 10, 20, 30 and 40 ppm concentration of additive was used to measure the fire point and flash point of fuel and compared with control fuel sample (contain no additive). Flash and fire points on the sample was measured to be 68ۨ
C and 75ۨ
C respectively. It was
observed that flash and fire points of control samples are higher as compared to all samples of modified fuel. This linear plot shows that flash and fire points are linearly decreased by increasing the concentration of additive. Efficiency of diesel fuel was enhanced by adding different amounts of additive. The flash and fire points were observed to be decrease in additive dosage up to 10 ppm. This decrease is prominent as observed in figure. The fire points are greater than flash point in all prepared samples. 1.2 Cloud point and Pour point Pure diesel has high cloud point but cloud point starts to decrease with increasing the concentration of additive. The cloud point was observed to decrease additive concentration up to 10 ppm. When increase the concentration of additive up to 20 ppm, it decreases at 7ۨ
C and at the concentration
of additive to 30 ppm, it also decreases at 3ۨ C and at the 30-ppm concentration, it also decreases very fast at 2ۨ
C. This is
all effect of manganese-tin bimetallic nanomaterials on the cloud point of diesel fuel has shown in figure. It can be observed in figure that pour point of diesel fuel is high at 0 ppm which is about 0ۨ
C but it also decreases by increasing concentration of bimetallic
materials. At 10 ppm concentration it decreases from 0ۨ C to -1ۨ
C.
Pour point was observed to remain same increase in additive dosage up to 20 ppm. The pour point value of diesel fuel with different bimetallic materials was found to be in the range 0ۨ
C to
-3ۨ C. By increase in the concentration of additive at 40 ppm, it
decreases linearly at -3ۨ C which indicates that pour point values
are significantly affected by the concentration of additive dosage. The plot shown that both cloud point and pour point are higher for control sample then the value of modified samples. When the concentration of additive increases then cloud and pour point lower, so that freezing of diesel fuel in the engine can be avoided and efficiency of heavy engine in enhanced. 1.3 Specific Gravity The dependence of specific gravity on dosage of additive is shown in figure. Specific gravity of pure diesel in found to be lower among all the samples. When additive dosage was increased, specific gravity was also increased. The plot of specific gravity of diesel as a function of concentration of additive is shown in figure. At first 10 ppm of dosage, specific gravity increases very slowly but it increases abruptly at higher concentration of additives. When concentration of additives was increased from 20 ppm, the value of specific gravity decreases to 0.8337 Kg/m3. Then at 30 ppm, it increased to 0.8338 Kg/m3. At 40 ppm, it increases very fast to 0.8360 Kg/m3
The behavior of Manganese-Tin bimetallic nanomaterials makes them an excellent additive in diesel fuel. This may be due to high surface area of nano catalyst. The denser diesel fuel shows greater efficiency. Specific gravity of the fuel
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increase with increase in the concentration of additive. Higher specific gravity means denser fuel which makes it containing high concentration of energy contents 1.4 Kinematic Viscosity Kinematic viscosity of diesel was measured in the presence of 10, 20, 30 and 40 ppm of additive is shown in figure. Kinematic viscosity of diesel fuel is decreased by increasing the additive dosage. Kinematics viscosity of pure diesel was found to be 4.301 x 10-6 m2 s-1. It can be seen from the figure that the flow rate of diesel fuel is as compared to the presence of additive. By increasing the concentration of additive, flow rate of diesel fuel decreases linearly. Low viscosity means that bimetallic materials decrease the resistance between layers of diesel fuel. So, high viscosity of diesel fuel cause turbulent flow that decrease the efficiency of heavy engine. 1.5 Calorific Value Calorific value of diesel fuel in the presence of different concentration of additive 10, 20, 30 and 40 ppm were monitored by using the Bomb calorimeter. It was observed that pure diesel has low calorific values calorific values. The calorific values increase with increasing the concentration of additive. Plot of calorific value as a function of concentration of additive is given in figure. Calorific value was 1.892, 11.782, 23.53, 35.41 and 44.73 J/g at 0, 10, 20, 30 and 40 ppm concentration of additive. It is observed from this figure that calorific value of diesel was linearly increased with increase in concentration of additive. The calorific value of diesel fuel with 20 ppm is 1.9 times greater than the calorific value of diesel fuel with 10 ppm additive dosage. While calorific value of fuel with 30 ppm is 1.5 times greater than 20 ppm dosage of fuel. It means that by increasing the additive concentration, calorific value increases slow, which may be due to agglomeration of particles. The concentration of additives shows high surface areas due to which large amount of diesel molecule observed on the surface of additive. So, additive can efficiently catalyze the combustion of diesel fuel. 2. Application of Manganese-Tin Bimetallic Materials as Cement Additive Aging time was measured in the presence and absence of additive synthesized by hydrothermal method. The plot of aging time as a function of w/w % of nano additive is shown in figure. It was observed that initial setting time of control sample was higher as compared to all samples of modified cement mortar. The continuous decreasing trend of setting time increase the w/w % of additives. First of all 0.1 w/w % of nano additive was added into the cement then the time started to decrease as shown as shown in figure. By increase the w/w% of additive setting time of cement sample remains same. Decreasing trend of aging time was due to additive role for sample modification. Setting time decreases due to hydration of calcium silicate which start weakly in the line hydration. The hydration give strength to the cement mortar. Hydration of silicates was obviously increased in the presence of additives that decrease the setting time linearly. Final setting time was observed to be remain same with increase in the additive dosage up to 0.5 % as shown in figure. When increase the concentration of additive into the samples, setting time also increased
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Table: Effect of aging on different w/w% of nano additive
composition Replicates Initial time (ti) (min)
Final time (tf) (min)
Setting time (min) t=ti-tf
Average setting time (min)
1/3 (control) A 15 30 15 15
B 15 30 15
1/3(0.1% nanoparticles)
A 10 30 20 20
B 10 30 20
1/3(0.5% nanoparticles)
A 10 30 20 20
B 10 30 20
1/3(1% nanoparticles)
A 10 30 28 28
B 10 30 28
1/3(1.5% nanoparticles)
A 10 30 29 29
B 10 30 29
2.2 Porosity The prepared replicates samples were soaked in 150 ml water for 12 hours and after 12 hours remaining water was measured. The absorbed water shown the porosity of cement samples. The plot of porosity as a function of w/w% of additive is shown in figure. The nonlinear trend was observed in porosity of cement mortar with increase the additive dosage. The 0, 0.1, 0.5,1 and 1.5 w/w% composition of additive was used to measure the porosity of sample and compare with control sample (contains no additive). Porosity of control samples was measured to be 8 ml. But will increase the additive dosage, the porosity of sample started to increase linearly. It was observed that porosity of control sample was lower as compared to all samples. The plot shows that porosity of cement samples increased by increasing the nano additive. At 0.1 w/w% additive, the porosity was increased to 10 ml. Then at 0.5 w/w% of additive added into the sample, the value of porosity was 12 ml. By increasing the additive dosage 1 to 1.5 w/w% porosity also increase because it changes the surface boundary with cement aggregates that leads to increase the average porosity of cement.
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At high dosage of additive was much efficient for the increase of porosity because high dosage of additive act as nano strengthening, leads to dense microstructure, so, low porosity is favorable for better quality cement, required for construction of bridges buildings and houses and dams. Table: Effect of average porosity on composition of different Mn-Sn bimetallic materials
composition Replicates Water level before soaking (mL)
Water level after soaking (mL)
Porosity (absorbed water) (mL)
Average porosity (mL)
1/3 (control) A 150 142 8 8
B 150 142 8
1/3(0.1% nanoparticles)
A 150 140 10 10
B 150 140 10
1/3(0.5% nanoparticles)
A 150 138 12 12
B 150 138 12
1/3(1% nanoparticles)
A 150 135 15 15
B 150 135 15
1/3(1.5% nanoparticles)
A 150 134 16 16
B 150 134 16
2.3 Thermal Conductivity The instrument used TPS-500 for thermal conductivity, heating power is 100 MW and measuring time was 160 sec. Thermal conductivity is the ratio between concentration of current in that bimetallic materials through which the current applied (electrons are flowing through the material). Thermal conductivity was measured in the presence of additive dosage. The plot of thermal conductivity and function of additive is shown in figure. Thermal conductivity of controlled sample was measured to be 1.410 W/mK. When increase the w/w% of additive into the sample then thermal conductivity started to decrease. Plot show sharp decrease at 0.1, to 1% nanoparticles with 1.32, 1.16 and 1.07 W/mk respectively. And with increase in the more bimetallic materials, the value of thermal conductivity was 1.165 W/mK. It started to increase very fast with 1 w/w% of nano additive into the cement. The value of thermal conductivity was 1.66 W/mK, shown in figure, due to heat transfer through materials by conductive flow. Table: Effect of thermal conductivity by the composition of nano additive
Composition Thermal conductivity (W/mK)
1/3 (control) 1.410
1/3(0.1% nanoparticles) 1.320
1/3(0.1% nanoparticles) 1.165
1/3(1% nanoparticles) 1.075
1/3(1.5% nanoparticles) 1.66
2.4 Thermal Diffusivity The instrument used TPS-500, heating power was 100 MW and measuring time was 160 seconds. By increase the concentration of nano additive in cement, so the value of thermal diffusivity started to decrease very slowly. The plot of thermal diffusivity as a function of additive is shown in figure. The 0, 0.1, 0.5, 1 and 1.5 w/w% additive was used to
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measure thermal diffusivity and compared with the control sample. Thermal diffusivity of control sample was measured to be 0.6699 mm2/s. But with increase the additive dosage, it started to decrease linearly. It was observed that thermal diffusivity of control sample was higher. Thermal diffusivity is linearly decreased by increasing at 0.5 w/w% nano additive. When percentage of additive was increased from 1 % the value of thermal diffusivity increased to 0.4854 mm2/s. After that, when increase the additive at 1.5 %, it decreases rapidly at 0.2003 mm2/s shown in figure. Table: Effect of thermal diffusivity of different composition of additive
Composition Thermal Diffusivity (mm2/s)
1/3 (control) 0.6699
1/3(0.1% nanoparticles) 0.4854
1/3(0.1% nanoparticles) 0.2230
1/3(1% nanoparticles) 0.4854
1/3(1.5% nanoparticles) 0.2003
2.5 Specific Heat The instrument used TPS-500, heating power was 100 MW and measuring time was 160 seconds. The plot of specific heat as a function of additive is shown in figure. The different additives are used to measure specific heat of samples. Specific heat of control sample is measured to be 9.33 MJ/m3k. But with increase in w/w% of additive, specific heat is decreased very quickly. It was observed that specific heat of control sample is higher than all modified samples of cement. The plot show that specific heat decreases with increasing the additive dosage. The 0.1 w/w% additives added into the sample, the specific heat started to decrease 7.039 MJ/m3k. The value of specific heat at 0.5 % is 5.27 MJ/m3k. When additive was 1%, the value of specific heat starts to decrease quickly at 0.536 MJ/m3k. The value of specific heat is 2.205 MJ/m3k with 1.58 w/w% of additives shown in figure. The decreasing trend of specific heat is due to aggregation of cement sample and cement/water ratio. The role of nano additive modifies the property of specific heat due to high demand of temperature-controlled building construction. Table: Measurement of specific heat of cement samples on composition of bimetallic materials
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3. Catalytic Reduction of Congo Red (CR) Catalytic reduction of Congo red was chosen to study the catalytic activity of synthesized manganese-tin bimetallic materials. It is mostly used in color apparel industries and water-soluble dyes. Congo red is difficult to remove from water waste because of its aromatic rings which make it stable. The reaction was studied by UV-visible spectrophotometer because CR absorbs in visible range. The wavelength of maximum absorbance of Congo red was observed to be 495 nm. Degradation of dye was carried out in the presence of hydrogen peroxide. Effect of catalyst dosage manganese-tin bimetallic material and the effect of concentration in hydrogen peroxide on Kapp value was studied and spectra of dye taken after different time intervals. The catalytic reduction of Congo red was started absorbance at 495 nm, with the passage of time broadband peak reduced which indicates that congo red degrade in the absence of sunlight. The color of congo red (CR) dye changed from red to orange which indicates that dye degrade in the absence of sunlight. Structure of Congo red dye is shown in figure.
NH2
NNSO
O O-Na+N
N
S
H2N
OO
O-Na+
3.1 Effect of Catalyst Dosage on the Degradation of Congo Red (CR) Figure shows the plot of ln (At/A0) versus time for 0.2, 0.5 and 0.9 mg/ml dosage of catalyst. The value of ln (At/A0) with time initially was very small which shows that the degradation rate of Congo at very slow. This time of interval make them as induction period, after the interval of time if value of ln (At/A0) decrease rapidly for 0.9 mg/ml catalyst dosage but the value of ln (At/A0) change very slowly for 0.2 and 0.5 mg/ml. Catalytic dosage plot show that at low concentration of catalyst dosage, the reduction of CR was very slow. The plot between the different catalytic dosage and Kapp value shown in figure. This plot shows that Kapp values increase linearly, when the concentration of catalyst increase. This is due to great number of dye molecules absorb on the active site with increase in the catalyst dosage, so, the value of Kapp also increases.
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3.2 Effect of Catalyst Dosage on the Degradation of mixture of Congo Red and 4-Nitrophenol Figure shows that plot of ln (At/A0) verses time for 0.024, 0.048 and 0.073 mg/ml dosage of catalyst in a mixture of Congo red and 4-nitrophenol. Initially the values of ln (At/A0) does not change very much with the passage of time which show that the degradation rate of mixture was very slow. After the period of time, the value of ln (At/A0) abruptly rapidly for 0.024 and 0.048 mg/ml catalyst dosage but the value of ln (At/A0) change very slowly for 0.073 mg/ml dosage plot show that at high concentration of catalyst dosage, the degradation of mixture was very slow. The value of ln (At/A0) of all plots decrease with time which shows that degradation rate is in process. The plot between the catalytic dosage in a mixture and Kapp
value shown in figure. The value of Kapp increases by increasing the concentration of catalyst in a mixture from 0.048 to 0.073 mg/ml. Due to mixture of dye molecules can absorb on the substrate molecule with increase the catalyst dosage, so, the value of Kapp also increases.
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
0.00
0.01
0.02
0.03
0.04
0.05
0.06
Ka
pp (
min
-1)
Catalytic dosage (mg/ml)
Conclusion In this research work, Manganese-Tin bimetallic materials were synthesized by using hydrothermal method, solvothermal method and Co-precipitation method. Hydrothermal method gives better morphology of Manganese-Tin bimetallic materials than that of other methods. The synthesized products were used in three applications: as a fuel additive, as a cement additive and as a catalyst. Efficiency of fuel is analyzed by studying the different parameters: fire point, flash point, cloud point, pour point, kinematics viscosity, specific gravity and calorific value. Flash and fire point of the samples increase with increase the concentration of nanoparticles. The volatility of fuel decreases by addition of additives so, the flash and fire point increases. The chances of accident during transportation that decrease the vaporization of fuel. Calorific value increase when the concentration of Manganese-Tin bimetallic materials increases in diesel fuel. Good catalytic effect of synthesized product on the calorific value that related to the heat of combustion. Cloud point and pour point are low temperature characteristics. Synthesized materials are used as catalyst for the degradation of dye in aqueous medium. Congo red dye showed maximum absorbance at 495 nm. Catalytic degradation of dye is monitored at different concentration of catalyst and hydrogen peroxide. Manganese-Tin bimetallic materials were used to check the mechanical properties of cement by using different parameters such as thermal conductivity, thermal diffusivity, aging, porosity and specific heat.
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