Mesoporous Silica Nanoparticle (MNS) Properties

Mesoporous Silica Nanoparticle (MNS) PropertiesINTRODUCTION1.1 Background Study expectant amount of unfluctuating remnant from agriculture industries divisionn faecal matter create disposal worry to environment much(prenominal) as generation of odour and outhouse make pests that can endangered mankind health. Due to this problem the use of this waste is widely explored to control the disposal problem. accord to Norsuraya, Fazlena and Norshasyimi (2016), primary fuel witness and additive in construction industries utilise the application of solid resi due(p). The practice agricultural waste is corn cob, rice husk, popsiclecane leaf and bagasse. Studies collapse been conducted to enhance the use of this solid residue into profitable product. atomic procedure 53 of the exclusively- chief(prenominal)(a) element present in the waste is silicon oxide that has wide application.According to Norsuraya, Fazlena and Norshasyimi (2016), among the agriculture residue pops icle cane bagasse change (SCBA) consist the exaltedest of the silica means with the value of 96.93%. This studies comply with the studies conducted by Rahman et al. (2015), that stated the amount of silica sate in SCBA is much than 50%. Bagasse ash is the product of combustion of bagasse that be mutually use as a source energy to l comfort plant. Bagasse is unrivaled waste product in sugar application that incurs additional disposal speak to. Bagasse is cellular fiber remaining after extraction of the sugar-bearing succus from sugarcane. It consist of lignin (20-30 %), cellulose (40-45 %) and hemicelluloses (30-35 %) (Peng et al., 2009). The silica content varies depending on the environment, soil nature and the affect involves in harvesting it.In Malaysia the application of sugar cane Bagasse (SCB) is still not widely explored but studies already conducted to form silica jelly as chemosorptive, additive for concrete, cosmetic and another(prenominal)s because of its characteristic. SCB is more related to by-product in sugarcane mills intentness. After the juice retaining sucrose c totallyed as table sugar extracted from the sugarcane by pressing the sugarcane. The residue is the SCB which contains tall fibrous residue. The largest sugarcane plantation in Malaysia is at the northern region of Malaysia which can go more than 70 000 tonne of sugarcane. The sugarcane bagasse waste from the extraction accomplish contribute to huge disposal waste problem.SCBA can be the close valuable stock for production of mesoporous silica that be useful application such as surface assimilation and catalyst (Rahman et al., 2015). For that purposes, the size and surface surface argona of the mesoporous silica argon importance. Mesoporous silica is a silica that has pore with dia molar concentration range of 2 50 nm depending on the crop of synthesis of the mesoporous silica. The large surface atomic number 18a of the mesoporous silica functions as the active range that useful for the application such adsorption. blot is a natural or synthetic existents that can add a specific warp onto the material that are apply to. Every year more than 10 000 types of discolor are produced around the world and are use in distinct types of industries (Malakootian et al., 2015). The application of disgrace utilize widely from food industry to cloth industry with the biggest consumer of tint is fabric industry. This industry is cognise to be the one of the main contributor of industrial sewer water pollution and it is the most polluting of all the industrial sector. 10-50% of the tinge yield end up in the wastewater (Axelsson et al., 2006). Dye are significantly hepatotoxic and mutagenic that poses hazard to aquatic life and support beingness. One of example of dishonor is m ethyl radicalene inexorable (MB) that are an important aromatic compound with chemical substance formula of C16H18ClN3S. Large amount of this co lour are kick outd in the water sources and according to Malakootian et al. (2015) it is more importance removing blot from textile wastewater than get bying other twistless perfect and in constitutional because only a small amount of dye can affect the water quality and colour. Various intervention mode phase angle to extirpates dye from textile wastewater such as corporal, chemical and biological but it is not powerive due to interlocking chemical body expression that lead to foul to this type of sermon other than the treatment cost. Thus, it is important to find other alternative action of removal of dye.Currently, the most known regularity to treat textile wastewater is by use adsorption process method because of it has more advantages compared to traditional method especially in environmental aspects and its ease of operation, cost impellingness, biodegradability as well as greater efficiency. In ordinance to carry out the adsorption, the main important matter is the adsorbent. According to Malakootian et al. (2015) the most typical adsorbent used for adsorption treatment for the removal of dyes from slanted water or wastewater, but due to its noble production, regeneration and reactivation procedures cost research has been difficult on alternative adsorbents with richly adsorptive capacity and low cost such as mesoporous silica nanoparticle (MSN). These adsorbents have high efficiency due to their high surface battleground, high mechanical properties and good resistivity to thermal degradation, and they exist in some(prenominal) structures and amphoteric properties.1.2 Problem StatementThe wastewater from textile contain high concentration of dye. So it required for the sewer water from the industry to undergo treatment. effluent resulting from these industries is generally characterize by high COD, pH, dissolved solid temperature and dye and surfactant content. Dye to a fault can be toxic to environment because of its chemi cal properties.In order to treat effluent from textile industry that contain high percentage of dye, various method introduced and used. Examples of the methods are physical, chemical, biological, membrane separation, radiation, electrochemical, advanced oxidation, photolysis, electrochemical, sonolysis processes, etc. However, these methods are relatively ineffective because most dyes as azo reactive dyes are highly water soluble, have complex structures, and are stable to light, chemical and biological degradation, etc. Furthermore, these methods have certain(p) disadvantages such as high capital and operational costs, secondary liquid ecstasy disposal problems and the release of large volumes of toxic by-products (Malakootian et al., 2015).Among all these methods, adsorption is the dress hat method because of its advantages and the best adsorbents is by using nanotechnology method such as Mesoporous Silica Nanoparticle. It is because it has high adsorptive capacity and low cos t.1.3 Objectives of StudyThe objectives of the make can be outlined as followsTo prepare Mesoporous Silica Nanoparticle (MSN) from bagasse ashTo characterize the physicochemical properties of MSN.To study the potential of MSN as an environmental adsorbent in wastewater treatment1.4 Research ScopeThe research is to analyze the effluent of low cost adsorbent materials which is Mesoporous Silica Nanoparticle (MSN) from bagasse ash as the adsorbent to remove the Methylene drear. The MSN are prepared from Sol-Gel Method and then(prenominal) Hydrothermal Synthesis by using methanal, water and without methanal and water.The MSN entrusting be characterize and will be subjected toFourier Transform Infrared Spectroscopy (FTIR) to break the major operational chemical groups present in the silica transmittance Electron Microscopy (TEM) to determine the average particle size and the morphology of the materials.Brunauer-Emmett-Teller (BET) to try the specific surface area. examine Electr on Microscope (SEM) to evaluate the image of the MSNThe surgical procedure of MSN adsorbent in removing methylene blue from sedimentary closure will be carried out in various parameter which are piece of pH the sedimentary methylene blue in pH 3, 5, 7, 9, 11 exercise of MSN dosage (0.1 g, 0.2 g, 0.3 g, 0.4 g and 0.5 g)Effect of initial concentration of aqueous methylene blue (10 ppm, 20 ppm, 30 ppm, 40 ppm and 50 ppm)Effect of temperature of the aqueous methylene blue (30 C, 50 C and 70 C)The do by aqueous methylene blue dye will be characterized and subjected to UV-Visible spectrometer (UV-Vis) to evaluate the percentage of methylene blue dye remove from the aqueous solution from adsorbent by MSN.LITERATURE REVIEW2.1 IntroductionOne of the major problem in environment is water contamination. The bad effect of water contamination will affect everything in this world such as human, animals and plants. It is because water is the main elements to support all living things and earth . tight all of water contamination is caused by human activities. Apart from human activities, water contamination is excessively caused by natural waste. From long sentence ago, the water contamination is studied by researcher. There are many an(prenominal) technique and method to treat and remove contaminants in the waste water. It is for preserving twain human and the environment in this world.Among all contaminant in water, dye is one of the contaminant that exist in the water. The waster that contain dye is mainly from industry that related to textile industry, plastic and paper. It contain up to 10% of used dye. It is turn out that dye is dangerous to all living things due to its harmful behaviour of dye molecules and their metabolites is significant for the development of strategies to settle their desperate damaging impacts (Hebbar, Isloor, Zulhairun, Sohaimi Abdullah, Ismail, 2017). In addition to having harmful adverse effect, the front of colour in water is visua lly unpleasant and can unload the entire ecosystem.One of the most effective method to overcome the problem of effluent water containing dye is by using adsorption technique. It has been proven to be very effective by many researchers. This is because adsorption method offers more advantages compared to other method especially in environmental aspects and its ease of operation, cost effectiveness, biodegradability as well as greater efficiency.2.2 DyesDyes are produced all over the world with approximately 10 000 different type of dyes produced per year and it has been used extensively in so many industries. Most common industry that utilizing dye is textile industry and estimated to utilize around 7 - 105 1 - 106 tons (Malakootian et al., 2015). Dyes are used to dye a textile products, fur products, and others. Dye can be creationated mainly from vegetables and also animal sources. There also the existence of synthetic dye that replacing the natural sources. The main function o f dye are to add colour to a certain materials such as textile. Dye are also generally utilized as part of industry such as rubber, paper, cosmetic etc. Among these different industry, textile industry positions initiatory in utilization of dyes for colouring of fiber. The dye are constantly left as major waste in these industries. Because of their compound structure, dyes are impervious to weaken on presentation of light, water and numerous chemicals and this manner are unattackable to be decolorized once discharged into the nature or aquatic environment. Basically, dyes are ionising and aromatic compound. Inside the dyes, in that respect are chromophores present in them. base on their structures of the dyes, it has aryl rings that has delocalised negatron systems. These structures are said to be trusty for the adsorption of electromagnetic radiation that has varying wavelengths, based upon the energy of the electron clouds.Dye can set aquatics life, human wellbeing and env ironmental framework when dye wastewaters are greatly released wastewater into water sources due to complex compound in the dye. It has big complicated molecular structure and harmful properties. It in the end rolls out improvements of ecological system and other serious pollution issues. Dye wastewaters can contain harmful organic residue with the significant mixes of phenol derivatives, aniline derivatives, organic acid and benzol derivatives (Likhar Shivramwar, 2013)2.2.1 Classification of DyeDyes can be characterized into a few classes as per their utilization, for example, reactive, disperse, direct, vat, sulphur, cationic, acid and solvent dyes. The classification of dyes according their application is as shown in table 2.1.Table 2.1 General dyes classification and its application (Hunger, 2003)Class straits SubstrateApplicationChemical TypesAcid DyesNylon, woolen, Silk, Paper, Inks and LeatherUsually from neutral to acerbic dyebathsAzo (including premetallised), antraqui none, triphenylmethane, azine, xanthene, nitro and nitrosoCationic (Basic Dyes)Paper, Polyacrylonitrile, Modified Nylon, Polyester and InksAppliedApplied from acidic dyebathscyanine, hemicyanine, diazahemicyanine, diphenylmethane, triarylmethane, azo, azine, xanthene, acridine, oxanine and anthraquinonecotton,Direct DyesCotton, Rayon, Paper, Leather and NylonApplied from neutral or slightly basic baths containing additional electrolyteAzo, phthalocyanine, stilbeneand oxanineDispersed DyesPolyester, Polyamide, Acetate,Acrylic and PlasticsFine aqueousdispersions often applied by high temperature/ pressure or lowertemperature carrier methods dye may be padded on cloth and baked on or thermofixedAzo, anthraquinone, styryl, nitro and benzodifuranoneReactive DyesCotton, Wool, Silk and NylonReactive site on dye reacts with functional group on fiber to bind dye covalently under influence of heat and pH (alkaline)SolventAzo, anthraquinone, phthalocyanine, formazan, oxanineSolvent DyesPlasti cs, Gasoline, Varnishes Lacquers, Stains, Inks, Fats, Oils and WaxesDissolution in the substrateAzo, triphenylmethane, anthraquinone and phthalocyaninecottonSulphur DyesCotton and RayonAromatic substrate vatted with sodium sulfide and reoxidised to insoluble sulphur- containing products on fiberIndeterminate structureVat DyesCotton, Rayon and WoolWater-insoluble dyes Solubilised by reducing with Sodium hydrogensulphide, then exhausted on fiber and ReoxidisedAnthraquinone (including polycyclic quinines) and indigoidsSynthetic dye are being used extensively used in different dyeing industry with textile is leading industry that utilize it with 56% of world dye production annually. Its effluent contain critical level of organic contaminants, which are toxic as it will create odour, bad taste, unsightly colour, foaming, etc. These substances are often resistant to degradation by biological methods and are not removed in effect by conventional physico-chemical treatment methods. Remova l of these dyes from effluents in an economic shape remains a major problem for textile industries.2.2.2 Methylene BlueMethylene Blue (MB) or also known as Methylthioninium Chloride was first synthesized at 1876 by a German Chemist, Heinrich Caro. Paul Guttman and Paul Ehrlich used MB in the treatment of Malaria dieses in 1891. During that time also, the function of MB as a dye were discovered and were used in number 1 World War as a biological weapon and part staining the soldiers.MB has many uses in different field, For instance, chemists use it to disclose oxidizing agents and biologists use it to stain tissue samples and detect nucleic acids. In medicine, it is used as a treatment for various illnesses and disorders, including methemoglobinemia, schizophrenia, kidney stones, and herpes infections. In aquaculture, it is used to foresee freshwater fish eggs from being infected by bacterium and fungi (Methylene blue New World Encyclopedia, 2014)In term of dye application onl y, MB a basic blue dye used for dyeing silk, leather, plastics, paper, and cotton mordant with tannin as well as for the production of ink and copying paper in the office supplies industry. The release of this dye to earth is troubling for both toxicological and aesthetical reasons as dye hinder light infiltration, harm the nature of the accepting streams and are toxic to food chain organisms. The dye has a synthetic origin and complex aromatic molecular structures, it is an inactive and hard to biodegrade when released into waste streams. This military position has dependably been neglected in their discharge. The removal of synthetic dye is of astounding worry since a few dyes and their degradation products might be cancer-causing agents and condemnable and, thus, their treatment cannot rely on upon biodegradation alone.Table 2.2 Properties of Methylene Blue (MB) methylene radical BLUEIUPAC name7-(dimethylamino)phenothiazin-3-ylidene-dimethylazaniumchloridePropertiesMolecular f ormulaC16H18ClN3SMolar mass319.86 g/molDensity43 600 mg/L at 25 CMelting point100 CBoiling pull downDecomposesOdourOdourlessSolubility in waterSoluble in ethanol, chloroform slightly soluble in pyridine insoluble in ethyl etherAdapted from https//pubchem.ncbi.nlm.nih.gov/compound/methylene_bluesection=WIPO-IPC2.2.3 Technologies for Dye RemovalDye are used widely in all sector to colour their product. In order to colour the product large amount of dye is used. Apart to colour their product the dye also been used as paper, and plastic. This will result in large amount of effluent containing dye as contaminant into the nature. According to study conducted by Axelsson et al. (2006), 10 50 % of the dye used in industry will go to effluent because of the dye molecule might react with hydroxyl ions in the solution giving rise to even more water-soluble hydrolysed molecules. Because of the good solubility of dye in water it will endangered the nature. It is also describe by Sapawe et al . (2012) that 15 % of the total world production of dyes is released in textile industry. This proves that from out of 7-105 tons of effluent produce large number of dye is discharges as wastewater.Without further treatment to the effluent containing dye contaminant, it can cause extreme problems if not toughened legitimately because of dyes are harmful, toxic, mutagenic, carcinogenic to human life as well to another living organism (Sapawe et al., 2012). To treat the dye so many method had been introduced and the best method reported by Malakootian et al. (2015), is by using adsorption method and support by Marrakchi, Ahmed, Khanday, Asif, Hameed (2017) due to some advantages. From all types of treatment, it can be classified into three categories which are divided for the technologies which are physical, chemical and biological. However, it is hard to treat the dye because of their synthetic origin and mainly complex aromatic structure. both of these technologies possess pros and cons.2.2.3.1 Physical and Chemical TreatmentThere are numerous method falls under physical and chemical treatment such as anion exchange resins, cogulations, flotation, electroflotation, electrochemical destruction, irradiation, Ozonation,adsorption, and the use of actuate carbon. Physical and chemical treatment is far more effective than biological treatment in decolourizing dye but it will use more energy, chemicals, and biological process hence increasing the capital cost for the treatment (Miao, 1992). Apart from that, it will lead to secondary sludge disposal problems and the release of large volumes of toxic by-products (Malakootian et al., 2015).2.2.3.2 Biological TreatmentBiological have three stages or phases. It is because in the first place the effluent arriving to the biological phase, it will go through some physical and chemical treatment. For comparison to the physical and chemical method, physical and chemical treatment will treated physically or chemically wi thout going through another phases. It is reported by Malakootian et al. (2015) that biological treatment is in effective in decolorizing water because most dyes as azo reactive dyes are highly water soluble, have complex structures, and are stable to light, chemical and biological degradation. The example of biological treatment are fungal biodegradation, bacteria biodegradation, yeast biodegradation, and microbial biosorption, Biological treatment has lower capital cost compared to physical treatment and chemical treatment (Miao, 1992).2.3 Decolorizing of Dyes by Adsorption treatAbsorption has been proved as the best method for treatment wastewater containing dye. It offers noteworthy advantages over customary treatment techniques particularly from the environmental situation and its simplicity of operation and also more prominent efficiency. Some adsorbents, which are utilized for the expulsion of dye from aqueous solutions with differing achievement include activated carbon, m agnesium oxide grafted chitosan, modified bentonite, TiO2 powder, TiO2 nanotube and others. Among all these materials, activated carbon is a standout amongst the most much of the time adsorbents utilized for the removal of dye from coloured waters and wastewaters, yet because of its high generation, recovery and reactivation procedure cost, research has been concentrated on alternative adsorbents with high adsorptive capacity and low cost.Therefore, belatedly there has been a lot of attention toward using nanotechnology methods. Nowadays using nanomethods, especially by using Mesoporous Silica Nanoparticle, The large surface area allows for binding at a great number of active sites distributed inside the framework of the porous materials. The large pores can overcome the pore-diffusion limitation and provide high-speed pathways for gas molecules (Rahman et al., 2015). Apart from that, it is reported that, Mesoporous Silica Nanoparticle which is synthesized from natural sources clai med to riskless in handling, cheap and can be generated from cheap resources (Norsuraya et al., 2016) which is bagasse ash in this case. Due to this advantages, the usage and studies regarding Mesoporous Silica Nanoparticle increase exponentially as adsorbent.methodological analysis3.1 IntroductionThe aim of this study is to synthesis Mesoporous silica from bagasse ash by using green route and to study the performance of the Mesoporous silica in wastewater treatment by utilizing aqueous methylene blue as the wastewater. The mesoporous silica is prepared by carrying out combustion of bagasse to produce bagasse ash and then using Sol-Gel method to make gel from the bagasse ash. The product of Sol-Gel method will undergo hydrothermal synthesis by using formaldehyde, water and without formaldehyde and water to synthesis Mesoporous Silica Nanoparticle (MSN). The MSN produced will be characterize by using Fourier Transform Infrared Spectroscopy (FTIR), Transmission Electron Microscopy (T EM), Brunauer-Emmett-Teller (BET), Scanning Electron Microscope (SEM). The performance study for wastewater treatment to treat aqueous methylene blue by using MSN will be examine under four parameter which is the effect of pH, effect of MSN dosage, effect of initial concentration of the dye, and effect of temperature.The research methodology is summarized in the research extend chart in Figure 3.1 below.3.2 Material and MethodsIn this study there are six stages of preparations and experiment. Which are the preparation of bagasse ash, preparation of silica gel from bagasse ash, production of Mesoporous Silica Nanoparticle (MSN), characterization of the MSN, Performance study of MSN and characterization of treated wastewater.3.2.1 Preparation of Bagasse ashThe material, apparatus and glasswork needed for this stage as shown in table 3.1Table 3.1 listing of Materials, Glassware and instrumentMaterials toolSugarcane BagasseOvenFurnaceSugarcane Bagasse can be collected from sugarcan e juice hawker at Tampin, Negeri Sembilan. First step need to be interpreted is to cut the bagasse in small pieces and boil the bagasse to remove the remaining sugar in the bagasse, after that the bagasse need to be wash and rinse by using distilled water to remove impurities. After that, the bagasse will be subjected to oven ironicing process at 70C 80 C for 24 hours. To bear ash from the bagasse, combustion are to be carried out in furnace at 800 C for 3 hours at heating rate of 10 C/min. The ash need to be collected and labelled as Sugarcane Bagasse Ash (SBA).3.2.2 Preparation of Silica Gel from Bagasse Ash (Sol-Gel Method)The material, apparatus and glassware needed for this stage as shown in table 3.2Table 3.2 List of Materials, Glassware and Apparatus for Sol-Gel MethodMaterialsApparatusSBAErlenmeyer Flask1M Lye Solution (NaOH) (1 litre)stirrerDistilled WaterBeaker1M Sulphuric Acid (H2SO4)Pipette (25 ml capacity)pH meterBoil 30g of Bagasse Ash and 1 L of 1M Lye Solution (Na OH) in Erlenmeyer flask for 1 hour with a constant stirring to dissolves the silica and produce a sodium silicate solution. Filter the solution through whatman No. 41 ashless filter paper and wash the residue with boiled distilled water. Let the filtrate to cool to room temperature. Reduce the pH of the solution to pH 7 by using 1M Sulphuric Acid (H2SO4) by using titration method and constant stirring. When gel form from the solution from the solution, age it for approximately 18 hours. After the ageing, gently broke the gel and centrifuge at 2500 revolutions per minute for 10 minutes. Discard the supernatant and transfer the gel into a beaker and dry for 11-13 hours at 80C to produce xerogels. Wash with deionized water to remove minerals and impurities from the silica3.2.3 Production of Mesoporous Silica Nanoparticle (Hydrothermal Synthesis)The material, apparatus and glassware needed for this stage as shown in table 3.3Table 3.3 List of Materials, Glassware and Apparatus for Hy drothermal SynthesisMaterialsApparatusCetyltrimethylammonium Bromide (CTAB)Conical FlaskAmmonium hydroxide (NH4OH)StirrerDistilled WaterBeakerMicrowaveMix 0.64 g of cetyltrimethylammonium bromide (CTAB) and 30 ml formaldehyde solution (37 wt %) in 100 ml unlikable conical flask and stir at 27C for 5 minutes. Quickly add 2.8 ml NH4OH and stir for 30 minutes. Add 2.8 ml of silica prepared in Sol-Gel method and stir vigorously for 24 hours. Transfer the mixture to 100 ml beaker and place it in zap at 800 Watt for 30 minutes. Filter the product and wash with deionize water and dried it overnight at 60C. Calcinate the dried product in air at 540C for 3 hours to remove surfactants in order to obtain MSNs. Repeat all step by replacing formaldehyde with water and without formaldehyde. The product form is Mesoporous Silica Nanoparticle (MSN).3.2.4 Characteriza