Description:Field of the Invention

The present disclosure relates to systems for manufacturing nanocomposites, particularly for degrading dyes in water treatment applications.
Background
The background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
The field of environmental remediation has encountered several challenges specifically concerned with the treatment of water bodies contaminated with industrial dyes. Pollution of aquatic ecosystems through the discharge of toxic dye effluents is a significant environmental concern. Industries such as textile and leather processing release substantial volumes of coloured wastewater, which poses a persistent threat to the health of aquatic systems and consequently to human health. Traditional water treatment methods like adsorption, coagulation, and biological treatment, though widely implemented, often fall short in terms of efficacy, selectivity, and cost-effectiveness. Said conventional techniques are further challenged by their reliance on chemicals that may be hazardous or yield harmful byproducts, thus exacerbating ecological disturbances.
In response to said issues, prior art solutions were not sustainable for degrading dye pollutants. Prior art solutions failed to harness unique compositional advantages and catalytic properties that offer an enhanced alternative to conventional methods. Prior art solutions yielded detrimental effects on the environment. The usage of harmful chemicals and the generation of dangerous byproducts during the remediation process further exacerbated said concern. Said solutions were not able to address pollution, contributing further to environmental degradation.
Additionally, contemporary water treatment practices often depend on non-renewable or scarce resources, raising concerns about long-term sustainability and supply chain implications. None of the prior art utilized materials such as graphene oxide and polyaniline, which are abundant and renewable. None of the prior art solution realized the integration of said materials into the nanocomposites that aligns with sustainability goals by reducing reliance on finite resources and facilitating a shift towards more environmentally responsible manufacturing and remediation processes.
Furthermore, the prior art solutions are not scalable, which is important for addressing the global issue of water contamination. The effective and large-scale application of said prior art solutions in water treatment processes cannot be considered as a practical solution to the pervasive problem of dye pollution. In light of the aforementioned challenges associated with traditional water treatment methods, there exists a persistent need in the art for a system to effectively break down dyes in water without the associated drawbacks of prior techniques. Said system can stand as a testament to research in said field of sustainable and environmentally conscious water treatment.
Summary
The following presents a simplified summary of various aspects of this disclosure in order to provide a basic understanding of such aspects. This summary is not an extensive overview of all contemplated aspects, and is intended to neither identify key or critical elements nor delineate the scope of such aspects. Its purpose is to present some concepts of this disclosure in a simplified form as a prelude to the more detailed description that is presented later.
The following paragraphs provide additional support for the claims of the subject application.
The disclosure unveils a system to manufacture a water treatment nanocomposite material for the degradation of dyes. Said system encompassing various steps each designed to perform specific tasks in the synthesis process. The first synthesis step is equipped with a magnetic stirrer and an ice bath, preparing a first reaction mixture containing graphite powder, potassium nitrate, concentrated sulfuric acid, and potassium permanganate.
Temperature control is maintained by a temperature controller maintaining the first reaction mixture within a specific temperature range. An oxidant addition step, integrated with the first synthesis step, facilitates the addition of hydrogen peroxide and dilution with water, increasing the temperature to a preset range.
The washing and filtration step is responsible for purifying the crude graphene oxide product through washing until a neutral pH is achieved, ultrasonication for exfoliation, and drying of the exfoliated graphene oxide. A second synthesis module synthesizes doped polyaniline through oxidative polymerization, while a polymer synthesis step prepares undoped polyaniline through a process involving the addition of polyaniline emeraldine salt to an ammonia solution.
A composite synthesis process prepares a second reaction mixture containing exfoliated graphene oxide, ethylene glycol, and both undoped and doped polyaniline. The separation step includes a Buchner funnel connected to a vacuum source for filtration, an ethanol wash station for purification, and a drying station to remove solvent traces, yielding a dry, granulated doped/undoped polyaniline graphene oxide composite for water treatment.
Further disclosed is that the doped polyaniline comprises aniline monomer, dopant, and oxidant in a specific molar ratio. Modifications to the first synthesis module allow for controlled addition of potassium permanganate to mitigate exothermic reactions. The oxidant addition step includes a precision delivery unit for the dropwise addition of hydrogen peroxide. An integrated pH meter in the washing and filtration module provides real-time pH level monitoring and adjustment.
A cooling step in the second synthesis module maintains the reaction temperature during oxidative polymerization. The composite synthesis unit benefits from a secondary stirring unit for thorough mixing of the second reaction mixture. An automated control valve in the washing and filtration module and an ethanol recycling unit in the separation module enhance the efficiency and sustainability of the process.
A method for manufacturing a water treatment nanocomposite material designed for the degradation of dyes involves a series of steps executed in a coordinated manner. Initially, graphite powder and potassium nitrate are mixed with concentrated sulfuric acid in a first synthesis module equipped with a magnetic stirrer and an ice bath. The temperature of the first reaction mixture is controlled within a preset range using a temperature controller.
An oxidant addition step, integrated with the first synthesis module, is utilized to add hydrogen peroxide within a preset range to halt the reaction and dilute the mixture, permitting the temperature to rise within a predefined range. Subsequently, the crude graphene oxide product is transferred to a washing and filtration module where purification is conducted until the supernatant attains a neutral pH. Said step is followed by exfoliation through an ultrasonication unit and drying of the product within a preset temperature range.
Further steps include the synthesis of doped polyaniline (DP) in a second synthesis module through the oxidative polymerization of aniline monomer in an aqueous solution containing dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate at a controlled temperature range, with continuous stirring. Undoped polyaniline (UDP) is prepared in a polymer synthesis module by adding polyaniline emeraldine salt into an ammonia solution, followed by stirring, washing, and filtering to achieve a neutral pH of the filtrate.
A second reaction mixture is then formed in a composite synthesis unit by combining exfoliated graphene oxide with both undoped and doped polyaniline in ethylene glycol. The second reaction mixture is filtered using a Buchner funnel connected to a vacuum source in a separation module, followed by washing with ethanol to purify the nanocomposite material. The final step involves drying the washed nanocomposite material in a drying station to remove solvent traces, yielding a dry, granulated doped/undoped polyaniline graphene oxide composite suitable for water treatment.

Brief Description of the Drawings

The features and advantages of the present disclosure would be more clearly understood from the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 illustrates a system to manufacture a water treatment nanocomposite material for the degradation of dyes, in accordance with the embodiments of the present disclosure.
FIG. 2 illustrates a method for manufacturing a water treatment nanocomposite material for the degradation of dyes, in accordance with the embodiments of the present disclosure.
FIG. 3 illustrates a process flow for the synthesis of doped/undoped polyaniline-graphene oxide composite, in accordance with the embodiments of the present disclosure.
FIG. 4 illustrates the X-ray diffraction (XRD) patterns, indicative of the crystalline structure of the doped polyaniline-graphene oxide composite, in accordance with the embodiments of the present disclosure.
FIG. 5 illustrates the XRD patterns for the undoped polyaniline-graphene oxide composite, in accordance with the embodiments of the present disclosure.
FIG. 6 illustrates the SEM-EDX micrographs of doped (A) and undoped (B) polyaniline-graphene oxide composites, alongside the corresponding energy-dispersive X-ray (EDX) spectra, in accordance with the embodiments of the present disclosure.
FIG. 7 illustrates the TEM (Transmission Electron Microscopy) micrographs of a doped polyaniline-graphene oxide composite (A) and an undoped polyaniline-graphene oxide composite (B), in accordance with the embodiments of the present disclosure.
FIG. 8 illustrates the thermogravimetric analysis (TGA) of doped and undoped polyaniline-graphene oxide nanocomposites, in accordance with the embodiments of the present disclosure.
FIG. 9 illustrates the ultraviolet (UV)-visible absorbance spectra using the doped (DP) polyaniline graphene oxide nanocomposite measured over time during the degradation of Chromotrope 2R dye using nanocomposite materials, in accordance with the embodiments of the present disclosure.
FIG. 10 illustrates the ultraviolet (UV)-visible absorbance spectra using the undoped (UDP) polyaniline graphene oxide nanocomposite measured over time during the degradation of Chromotrope 2R dye using nanocomposite materials, in accordance with the embodiments of the present disclosure.
Detailed Description
In the following detailed description of the invention, reference is made to the accompanying drawings that form a part hereof, and in which is shown, by way of illustration, specific embodiments in which the invention may be practiced. In the drawings, like numerals describe substantially similar components throughout the several views. These embodiments are described in sufficient detail to claim those skilled in the art to practice the invention. Other embodiments may be utilized and structural, logical, and electrical changes may be made without departing from the scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is defined only by the appended claims and equivalents thereof.
The use of the terms “a” and “an” and “the” and “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
Pursuant to the "Detailed Description" section herein, whenever an element is explicitly associated with a specific numeral for the first time, such association shall be deemed consistent and applicable throughout the entirety of the "Detailed Description" section, unless otherwise expressly stated or contradicted by the context.
The present disclosure pertains to a system 100 to manufacture a water treatment nanocomposite material for the degradation of dyes. The system 100 comprises several modules each equipped with specific functions and apparatus to facilitate the synthesis of the nanocomposite material.
According to a pictorial illustration of FIG. 1, showcasing an architectural paradigm of the system 100 that can comprise functional elements, yet not limited to a first synthesis module 102, a temperature controller 104 an oxidant addition module 106, a washing and filtration module 108, a second synthesis module 110, a polymer synthesis module 112, a composite synthesis unit 114, a separation module 116, and a drying station 118. A person ordinarily skilled in art would prefer those elements or components of the system 100, to be functionally or operationally coupled to/ with each other, in accordance with the embodiments of present disclosure.
In an embodiment, the first synthesis module 102 forms an integral part of the system 100, equipped with a magnetic stirrer and an ice bath. The primary function of the first synthesis module 102 involves the preparation of a first reaction mixture. Said reaction mixture includes graphite powder in a quantity ranging from about 1.5 g to about 3.5 g, potassium nitrate within the range of about 1.5g to about 3.5 g, concentrated sulfuric acid from about 80 ml to about 120 ml, and potassium permanganate from about 10g to about 14g. The technical effect of utilizing specific ranges of said reactants facilitates optimal conditions for the synthesis process, contributing to the efficient production of graphene oxide (GO), a component of the nanocomposite material.
In an embodiment, adjacent to the first synthesis module 102, the temperature controller 104 is positioned to regulate the temperature of the first reaction mixture. The temperature controller 104 maintains the temperature within a precise range from about 308 K to about 313 K. Such regulation of temperature is important for maintaining the reaction proceeds under controlled conditions, thus enhancing the quality and yield of the GO product.
In an embodiment, the oxidant addition module 106 is integrated with the first synthesis module 102. The function of said oxidant addition module 106 extends to adding hydrogen peroxide in a volume range from 10ml to 14ml and diluting with water ranging from 300ml to 500ml. Following the addition of said components, the temperature of the mixture is elevated to a range from about 360 K to about 365K. Said elevation of temperature is instrumental in the oxidation process, which further refines the graphene oxide (GO), preparing said GO for subsequent synthesis steps.
In an embodiment, the washing and filtration module 108 is dedicated to purifying the crude GO product. Said filtration module 108 comprises a water supply for washing until the supernatant achieves a neutral pH, an ultrasonication unit for the exfoliation of the GO product, and a drying unit for drying the exfoliated GO at a temperature range of 310 K to 313 K. The exfoliation process is vital for separating graphene oxide layers, enhancing the surface area and reactivity, which are significant characteristics for the target application in water treatment.
In an embodiment, following the GO preparation, the second synthesis module 110 is employed to synthesize doped (DP) polyaniline through oxidative polymerization of aniline monomer in an aqueous solution containing dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate. The polymerization process is conducted in a temperature range of 0°C to 5°C, with continuous stirring, optimizing the polymerization conditions to obtain DP polyaniline with the predetermined properties for the composite material.
In an embodiment, the polymer synthesis module 112 is then utilized to prepare undoped polyaniline (UDP). In said polymer synthesis module 112, 8g to 12g of polyaniline emeraldine salt is added into 90 ml to 100ml of 0.5 M ammonia solution. Following the addition, the solution is stirred, washed, and filtered to achieve a neutral pH of the filtrate. Said step is crucial for producing UDP that, when combined with DP and the GO, contributes to the overall effectiveness of said nanocomposite in the dye degradation.
In an embodiment, the composite synthesis unit 114 plays a pivotal role in the system 100, preparing a second reaction mixture comprising the exfoliated GO in a range from about 0.3g to about 0.6 g, 30 ml to 50 ml of ethylene glycol, and 0.4g to 0.6g of each of said UDP and DP. The preparation of said mixture is fundamental to the formation of the nanocomposite material, with each component contributing to the structural and functional properties of said nanocomposite material ideal for water treatment applications.
In an embodiment, the system 100 incorporates a separation module 116, which includes a Buchner funnel connected to a vacuum source for filtration of the second reaction mixture. An ethanol wash process is also part of the separation module 116, purifying the filtered second reaction mixture to acquire the nanocomposite material. A drying station 118 is then employed to remove solvent traces from the nanocomposite material, yielding a dry, granulated doped/undoped polyaniline GO composite. Said final product is tailored for the effective degradation of dyes in water treatment processes, demonstrating the capacity of said system 100 to produce materials that address environmental concerns associated with dye pollution.
In an embodiment, the DP comprises aniline monomer, said dopant, and said oxidant in a molar ratio of 1:1:1. Said specific stoichiometric ratio facilitates the effective synthesis of DP by optimizing the reaction conditions for oxidative polymerization. The uniform molar ratio facilitates the formation of a homogenous polymer, which is vital for achieving consistent electrical and chemical properties within the DP polyaniline. Such properties are important for the enhanced performance of the nanocomposite material in water treatment applications, particularly in the degradation of dyes. The precise control over the molar ratio of reactants contributes to the reproducibility of the DP synthesis, so that the nanocomposite material maintains the quality and efficacy across different batches.
In another embodiment, said first synthesis module (102) is further configured to control the rate of potassium permanganate addition to said first reaction mixture for the mitigation of the exothermic reaction between said potassium permanganate and said concentrated sulfuric acid. The controlled addition of potassium permanganate is significant for preventing rapid temperature increases that could compromise the integrity of the reaction mixture and negatively affect the quality of the graphene oxide produced. By modulating the rate of addition, the system 100 effectively minimizes the risk of undesirable side reactions, maintaining a safer and more controlled synthesis environment. Said approach enhances the safety of the manufacturing process and also contributes to the production of graphene oxide with optimal properties for inclusion in the nanocomposite material.
In an embodiment, said oxidant addition module (106) comprises a precision delivery unit to add said hydrogen peroxide dropwise to said first reaction mixture. The inclusion of a precision delivery unit enables the controlled addition of hydrogen peroxide, facilitating a gradual oxidation process. Said controlled addition is crucial for maintaining the stability of the reaction mixture and maintaining the effective incorporation of oxygen groups onto the graphene oxide. Such a meticulous approach to hydrogen peroxide addition enhances the quality of the graphene oxide, thereby improving the overall performance of the nanocomposite material in dye degradation.
In an embodiment, said washing and filtration module (108) includes a pH meter integrated with said water supply to provide real-time monitoring and adjustment of the pH level of the supernatant to reach neutrality. The integration of a pH meter allows for precise control over the washing process, so that the graphene oxide is thoroughly purified without compromising the structural integrity. Achieving a neutral pH is vital for the stability of the graphene oxide and the subsequent functionalization with polyaniline. Said real-time monitoring system 100 facilitates that the final product is of the highest quality, with properties tailored for efficient water treatment.
In an embodiment, said second synthesis module (110) includes a cooling unit to circulate a coolant around said reaction vessel to maintain the reaction temperature between 0°C to 5°C. Maintaining a low and constant temperature during the oxidative polymerization of aniline is crucial for the formation of high-quality DP polyaniline. The cooling unit facilitates that the reaction conditions are optimal for the polymerization process, leading to the synthesis of DP with desirable conductivity and structural properties. Said properties are instrumental in enhancing the effectiveness of the nanocomposite material in dye degradation applications.
In an embodiment, the composite synthesis unit (114) is equipped with a secondary stirring unit to stir said second reaction mixture of said graphene oxide, ethylene glycol, and both UDP and DP for 24 hours at room temperature. The extended stirring period facilitates uniform distribution of components within the mixture, facilitating the effective integration of graphene oxide with polyaniline. Said uniform distribution is key to achieving a nanocomposite material with enhanced surface area and reactive sites for dye degradation. The secondary stirring unit thus plays a key role in optimizing the structural and functional properties of the nanocomposite material.
In an embodiment, the washing and filtration module (108) further includes an automated control valve to regulate the flow of water for washing the graphene oxide until the neutral pH is reached. The automated control valve enables precise control over the washing process, so that the graphene oxide is thoroughly cleaned without excessive water usage. Said control is important for maintaining the structural integrity of the graphene oxide and maintaining the optimal performance within the nanocomposite material. The automation of the water flow contributes to the efficiency and sustainability of the manufacturing process.
In an embodiment, the separation module (116) comprises an ethanol recycling step for recovering and reusing ethanol after the washing process. The inclusion of an ethanol recycling unit enhances the sustainability of the manufacturing process by reducing waste and minimizing the consumption of ethanol. The recycling of ethanol contributes to the environmental friendliness of the process and also reduces the overall cost of manufacturing the nanocomposite material. Said recycling feature can facilitate that the system 100 is both economically and environmentally efficient, aligning with the principles of green chemistry.
The disclosed method 200 involves a series of steps for manufacturing a water treatment nanocomposite material specifically for the degradation of dyes. Each step in the method 200 is important for maintaining the optimal synthesis and functionality of the nanocomposite material. Referring to a diagrammatic depiction put forth in FIG. 2, representing a flow diagram of the method 200 that can comprise steps of, yet not restricted to, (at step 202) mixing graphite powder and potassium nitrate with concentrated sulfuric acid, (at step 204) controlling the temperature of the resulting first reaction mixture, (at step 206) adding hydrogen peroxide in a preset range to stop the reaction and dilute the mixture with water, (at step 208) transferring the crude graphene oxide product, and (at step 210) synthesizing doped polyaniline.
Referring to the preceding embodiment, further said method 200 comprises (at step 212) preparing undoped polyaniline (at step 214) forming a second reaction mixture, (at step 216) filtering the second reaction mixture and (at step 218) drying the washed nanocomposite material. Said steps of the method 200 can be performed or executed, collectively or selectively, randomly, or sequentially or in a combination thereof, in accordance with the embodiments of current disclosure.
In an embodiment, at step 202, graphite powder and potassium nitrate are mixed with concentrated sulfuric acid in the first synthesis module (102) equipped with a magnetic stirrer and an ice bath. Said initial mixing step is fundamental in starting the synthesis process of graphene oxide, a core component of the nanocomposite material. The use of concentrated sulfuric acid as an oxidizing agent in the presence of graphite powder and potassium nitrate under controlled cooling conditions facilitates the efficient oxidation of graphite. Said step is important for producing graphene oxide with desirable properties, such as a high degree of oxidation and suitable structural integrity, which are significant for the subsequent functionalization and integration into the nanocomposite material.
In an embodiment, following the initial mixing, at step 204, the temperature of the resulting first reaction mixture is controlled within a range of about 308 K to about 313 K using the temperature controller (104). Said temperature control is imperative for the reaction to proceed under optimal conditions, minimizing the risk of undesirable side reactions. Maintaining the reaction mixture within said temperature range maintains the stability and quality of the graphene oxide produced, contributing to the effectiveness of the nanocomposite material in water treatment applications.
In an embodiment, at step 206, an oxidant addition module (106) integrated with the first synthesis module (102) is employed to add hydrogen peroxide in a preset range to stop the reaction and dilute the mixture with water, allowing the temperature to rise to a range from about 360 K to about 365 K. The addition of hydrogen peroxide serves as a termination step for the oxidation process and initiates the exfoliation of the graphene layers. Said controlled increase in temperature aids in the complete exfoliation and dispersion of graphene oxide, enhancing the surface area and reactivity, which are crucial for the performance in the nanocomposite material.
In an embodiment, at step 208, the crude graphene oxide product is transferred to the washing and filtration module (108) and purified until the supernatant reaches a neutral pH. Subsequently, the graphene oxide undergoes exfoliation via an ultrasonication unit and is dried at a temperature range of 310 K to 313 K. Said purification and exfoliation processes are significant for removing impurities and achieving a high-quality graphene oxide with enhanced physical and chemical properties. The drying step facilitates that the graphene oxide is in an appropriate form for subsequent synthesis steps, maintaining the structural integrity and functionality.
In an embodiment, at step 210, doped polyaniline is synthesized in the second synthesis module (110) through the oxidative polymerization of aniline monomer in an aqueous solution containing dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate, at a temperature range of 0°C to 5°C, with continuous stirring. Said step 210 is important for producing doped polyaniline with specific electrical and chemical properties, which significantly contribute to the ability of said nanocomposite material to degrade dyes in water treatment processes. The controlled temperature and continuous stirring maintain a homogeneous polymerization reaction, leading to the formation of high-quality doped polyaniline.
In an embodiment, at step 212, undoped polyaniline is prepared in the polymer synthesis module (112) by adding polyaniline emeraldine salt into an ammonia solution, followed by stirring, washing, and filtering to achieve a neutral pH of the filtrate. Said step 212 results in the synthesis of undoped polyaniline, which, when combined with doped polyaniline and graphene oxide, enhances the overall efficiency and effectiveness of the nanocomposite material in degrading dyes. The neutral pH of the filtrate indicates the removal of excess reactants and by-products, maintaining the purity and quality of the undoped polyaniline produced.
In an embodiment, at step 214, a second reaction mixture is formed in the composite synthesis (114) by combining exfoliated graphene oxide with both UDP and DP in ethylene glycol. Said step 214 is fundamental in integrating the synthesized components into a cohesive nanocomposite material. The use of ethylene glycol as a solvent facilitates the uniform dispersion of the components, maintaining the formation of a homogenous nanocomposite material with enhanced properties for water treatment applications.
In an embodiment, at step 216, the second reaction mixture is filtered using a Buchner funnel connected to a vacuum source in the separation module (116), followed by washing with ethanol to purify the nanocomposite material. Said purification step 216 is important for removing any residual reactants, by-products, or solvent from the nanocomposite material, maintaining the purity and enhancing the performance in degrading dyes.
In an embodiment, at step 218, the washed nanocomposite material is dried in a drying station (118) to remove solvent traces and yield a dry, granulated doped/undoped polyaniline GO composite for water treatment. The drying step is important for preparing the nanocomposite material in a form suitable for practical application in water treatment processes. The removal of solvent traces maintains the stability and storage longevity of the nanocomposite material, facilitating the effective use in degrading dyes and improving water quality.
FIG. 3 illustrates the process flow for the synthesis of doped/undoped polyaniline-graphene oxide composite. The process begins with graphene oxide (GO) and ethylene glycol, which are combined and left to stir at room temperature for 24 hours. Subsequently, doped/undoped polyaniline is added to the mixture, and said combination is stirred with ethylene glycol again at room temperature for another 24 hours using a magnetic stirrer, resulting in a dark black paste. Said paste is then transferred to a Buchner funnel connected to a vacuum source for filtration. During filtration, the material is washed with ethanol and water to purify the material. The final product obtained is a doped/undoped polyaniline graphene oxide composite, which is then dried and converted into a granular form. The flow indicates a multi-step synthetic procedure to obtain a nanocomposite material suitable for water treatment applications, particularly for the degradation of dyes.
FIG. 4, labelled as (A), illustrates the X-ray diffraction (XRD) pattern exhibits significant peaks, indicative of the crystalline structure of the doped polyaniline-graphene oxide composite. The most pronounced peak is observed at a 2-theta value of approximately 10 degrees, which corresponds to a d001 basal spacing of 8.80 Å. Said prominent peak suggests the presence of oxygen-containing functional groups, which are typically introduced during the oxidation of graphite. Additional smaller peaks are present at 2 theta values of 15.0, 25.2, and 42.7 degrees, which correspond to interlayer spacings of 4.001, 2.128, and 3.536 Å, respectively. Said peaks are indicative of the semi-crystalline and amorphous nature of the doped polyaniline component within the composite.
FIG. 5, labelled as (B), illustrates the XRD pattern for the undoped polyaniline-graphene oxide composite shows peaks at similar 2 theta values, suggesting the retention of the crystalline structure in the absence of a doping agent. The pattern features peaks that represent the characteristic interlayer spacing and suggest the presence of oxygen functional groups, which imply successful oxidation of graphite. Thus, FIG. 4 and FIG. 5 collectively demonstrate both the doped and undoped polyaniline-graphene oxide composites maintain a semi-crystalline and amorphous structure with identifiable interlayer spacings, indicating the successful incorporation of polyaniline with the graphene oxide framework. Said structural composition is important for the intended function of said nanocomposite material in the degradation of dyes in water treatment.
FIG. 6 illustrates the SEM-EDX micrographs of doped (A) and undoped (B) polyaniline-graphene oxide composites, alongside the corresponding energy-dispersive X-ray (EDX) spectra. The SEM images show the morphology of the composites. In both doped and undoped samples, observed the agglomeration of graphene oxide (GO) within the composites. GO is identified as a two-dimensional polyelectrolyte due to imperfections on the basal planes and the presence of negative charges at the edges. In the doped sample, the polyaniline (PANI) appears to nucleate on the edges of the negatively charged GO sheets, due to its positive charge from the emeraldine salt form. The interaction between the opposing charges of GO and PANI suggests an electrostatic attraction facilitating their binding.
Referring to the preceding embodiment, however, despite said interaction, there is an indication that PANI does not adhere strongly to the extensive conjugated basal planes of the GO sheets. Said indication could be attributed to the aggregation of GO or weak π–π interactions, which may not provide a strong enough force for PANI to uniformly coat the GO sheets.
Referring to the preceding embodiment, the EDX spectra corroborate the presence of the constituent elements of the composites, likely confirming the successful synthesis of the doped and undoped polyaniline-graphene oxide composites. The elemental analysis provided by EDX highlights the characteristic peaks corresponding to the elements within the composites, which may include carbon, nitrogen, oxygen, and other dopant elements specific to the doped composite.
FIG. 7 illustrates the TEM (Transmission Electron Microscopy) micrographs of a doped polyaniline-graphene oxide composite (A) and an undoped polyaniline-graphene oxide composite (B). Said FIG. 7 reveal the nanoscale cubic particles, confirming the successful formation of the respective graphene oxide nanocomposites. The dark areas represent the polyaniline coating on the lighter graphene oxide sheets, indicating a change in surface morphology due to the interaction between polyaniline and graphene oxide.
The TEM micrographs demonstrate that both doped and undoped versions of polyaniline result in a discernible alteration of the surface of said graphene oxide (GO), which is characterized by the deposition of cubic polyaniline particles. Said transformation is important for the intended application of said nanocomposite material in dye degradation, as the nanocomposite structure is important for the effective catalytic performance of the material.
FIG. 8 illustrates the thermogravimetric analysis (TGA) of doped and undoped polyaniline-graphene oxide nanocomposites. TGA is a technique used to determine the thermal stability and composition of materials by measuring the weight loss as a function of temperature. The TGA curves show that upon heating to 600 degrees Celsius, the doped polyaniline-graphene oxide nanocomposite exhibits a weight loss of approximately 65%, whereas the undoped polyaniline-graphene oxide nanocomposite shows a significantly higher weight loss of around 90%. Said differential in thermal degradation between the two materials indicates that doping with polyaniline substantially improves the thermal stability of the graphene oxide composite.
Additionally, the TGA data reveals a shift in the decomposition temperature of about 50 degrees Celsius, which further suggests that the doped composite has enhanced thermal properties compared to the undoped version. The improvement in thermal stability is likely due to the interaction between graphene oxide and the doped polyaniline, which could confer added structural integrity to the composite, making more resistant to thermal decomposition. The TGA results imply that even a modest amount of graphene oxide can significantly enhance the thermal stability of polyaniline-based composites, which is a desirable property for materials used in high-temperature applications or environments.
FIG. 9 illustrates the ultraviolet (UV)-visible absorbance spectra using the doped polyaniline graphene oxide nanocomposite measured over time during the degradation of Chromotrope 2R dye using nanocomposite materials. The graph shows the decrease in absorbance at various wavelengths as the degradation reaction progresses over time, marked from 0 to 55 minutes. From the data observed that the intensity of the absorbance peak, which is indicative of the concentration of the Chromotrope 2R dye, decreases significantly over time, suggesting the breakdown of the dye molecules. The decrease is more pronounced when using the doped polyaniline-graphene oxide composite, with the dye decomposing to 96% in 55 minutes.
FIG. 10 illustrates the ultraviolet (UV)-visible absorbance spectra using the undoped polyaniline graphene oxide nanocomposite measured over time during the degradation of Chromotrope 2R dye using nanocomposite materials. The undoped polyaniline-graphene oxide composite shows a 65% degradation rate over a longer period of 180 minutes. The breakdown of the Chromotrope-2R dye involves the fragmentation of the aromatic structure, including azo groups, -OH, and -SO3H. The degradation byproducts, identified by GC-MS, include oxalacetic acid, malonic acid, oxalic acid, and oxamic acid, which can eventually mineralize to carbon dioxide (CO2). The experimental results demonstrate that the doped polyaniline-graphene oxide composite is a highly effective catalyst for the rapid degradation of Chromotrope 2R dye, offering a straightforward, reusable, and quick solution for dye decomposition in water treatment applications.
Sustainable doped and undoped polyaniline-graphene oxide nanocomposites represent a significant advancement in the field of environmental remediation, particularly for water treatment to tackle water pollution effectively. Said nanocomposites, formulated by integrating graphene oxide (a graphene derivative with oxygen-containing groups) with polyaniline (a conductive polymer), demonstrate improved dye degradation capabilities. The synergy of unique attributes of said materials enhances performance, making the process eco-friendly and sustainable. The availability and renewability graphene oxide (GO), derived from graphite, add to the sustainability quotient of said composites.
Said nanocomposites exhibit excellent catalytic activity in breaking down dyes, reducing them into harmless byproducts, which is especially beneficial for industries facing dye pollution such as textiles. The nanocomposites offer advantages over traditional water treatment methods due to their high conductivity and large surface area, promoting efficient electron transfer and degradation kinetics. The robustness of said nanocomposites facilitates longevity, maintaining performance without significant degradation over time.

The composites are effective in degrading dyes and also are cost-effective and scalable, supporting their use in widespread wa

I/We claims:

A system 100 to manufacture a water treatment nanocomposite material for the degradation of dyes, said system 100 comprising:
a first synthesis module 102 equipped with a magnetic stirrer and an ice bath, wherein said first synthesis module 102 is configured to prepare a first reaction mixture comprising:
graphite powder in a range from about 1.5g to about 3.5 g;
potassium nitrate in a range from about 1.5g to about 3.5 g;
concentrated sulfuric acid in a range from about 80ml to about 120ml; and
potassium permanganate in a range from about 10g to about 14g;
a temperature controller 104 is arranged to maintain the temperature of said first reaction mixture in a range from about 308 K to about 313 K;
an oxidant addition module 106 is integrated with said first synthesis module 102 to:
add hydrogen peroxide in a range from 10ml to 14ml; and
dilute with water in a range from 300ml to 500ml, wherein said maintained temperature increases to a range from about 360 K to about 365K;
a washing and filtration module 108 to purify the crude graphene oxide product, wherein said washing and filtration module 108 comprises:
a water supply to wash until the supernatant reaches a neutral pH;
an ultrasonication unit for the exfoliation of the graphene oxide product; and
a drying unit for drying the exfoliated graphene oxide at a temperature range of 310 K to 313 K;
a second synthesis step 110 is arranged to:
synthesize doped (DP) polyaniline by oxidative polymerization of aniline monomer in an aqueous solution of dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate, wherein said oxidative polymerization is performed in a temperature range of 0°C to 5°C, with continuous stirring;
a polymer synthesis step 112 is arranged to prepare undoped (UDP) polyaniline, wherein said undoped polyaniline comprises:
8g to 12 g of polyaniline emeraldine salt is added into 90 ml to 100ml of 0.5 M ammonia solution, wherein said ammonia solution is stirred, washed, and filtered, post the addition of said polyaniline emeraldine salt, to achieve a neutral pH of the filtrate;
a composite synthesis unit 114 is arranged to prepare a second reaction mixture comprising:
said exfoliated graphene oxide in a range from about 0.3g to about 0.6 g;
30 ml to 50 ml of ethylene glycol; and
0.4g to 0.6g of each of said UDP polyaniline and DP polyaniline;
a separation step 116 comprising:
a Buchner funnel connected to a vacuum source for filtration of the second reaction mixture;
an ethanol wash station purifies the filtered second reaction mixture to acquire the nanocomposite material; and
a drying step 118 to remove solvent traces from the nanocomposite material for yielding a dry, granulated doped/undoped polyaniline graphene oxide composite for the water treatment.
The system 100 of claim 1, wherein the DP polyaniline comprises aniline monomer, said dopant and said oxidant in a molar ratio of 1:1:1.
The system of claim 1, wherein said first synthesis step (102) is further configured to control the rate of potassium permanganate addition to said first reaction mixture for mitigation of the exothermic reaction between said potassium permanganate and said concentrated sulfuric acid.
The system of claim 1, wherein said oxidant addition step (106) further comprises a precision delivery unit to add said hydrogen peroxide dropwise to said first reaction mixture.
The system of claim 1, wherein said washing and filtration module (108) further comprises a pH meter integrated with said water supply to provide real-time monitoring and adjustment of the pH level of the supernatant to reach neutrality.
The system of claim 1, wherein said second synthesis module (110) includes a cooling unit to circulate a coolant around said reaction vessel to maintain the reaction temperature between 0°C to 5°C.
The system of claim 1, wherein said composite synthesis step (114) is equipped with a secondary stirring unit to stir said second reaction mixture of said graphene oxide, ethylene glycol, and both UDP and DP polyaniline for 24 hours at room temperature.
The system of claim 1, wherein said washing and filtration module (108) further includes an automated control valve to regulate the flow of water for washing the graphene oxide until the neutral pH is reached.
The system of claim 1, wherein said separation step (116) further comprises an ethanol recycling unit for recovering and reusing ethanol after the washing process.
A method 200 for manufacturing a water treatment nanocomposite material for the degradation of dyes, the method 200 comprising:
(at step 202) mixing graphite powder and potassium nitrate with concentrated sulfuric acid in a first synthesis module (102) equipped with a magnetic stirrer and an ice bath;
(at step 204) controlling the temperature of the resulting first reaction mixture within a range of about 308 K to about 313 K using a temperature controller (104);
(at step 206) integrating an oxidant addition module (106) with the first synthesis module (102) to add hydrogen peroxide in a preset range to stop the reaction and dilute the mixture with water, wherein the temperature is allowed to rise to a range from about 360 K to about 365 K;
(at step 208) transferring the crude graphene oxide product to a washing and filtration module (108) and purifying until the supernatant reaches a neutral pH, followed by exfoliation via an ultrasonication unit and drying the product at a temperature range of 310 K to 313 K;
(at step 210) synthesizing doped polyaniline in a second synthesis module (110) by oxidative polymerization of aniline monomer in an aqueous solution containing dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate at a temperature range of 0°C to 5°C, with continuous stirring;
(at step 212) preparing undoped polyaniline in a polymer synthesis step (112) by adding polyaniline emeraldine salt into an ammonia solution, stirring, washing, and filtering to achieve a neutral pH of the filtrate;
(at step 214) forming a second reaction mixture in a composite synthesis step (114) by combining exfoliated graphene oxide with both UDP and DP polyaniline in ethylene glycol;
(at step 216) filtering the second reaction mixture using a Buchner funnel connected to a vacuum source in a separation module (116), followed by washing with ethanol to purify the nanocomposite material; and
(at step 218) drying the washed nanocomposite material in a drying station (118) to remove solvent traces and yield a dry, granulated doped/undoped polyaniline graphene oxide composite for the water treatment.
The system of claim 1, wherein degradation of dye under optimum conditions using nanocomposite for waste water treatment.

SUSTAINABLE POLYANILINE-GRAPHENE OXIDE NANOCOMPOSITE FOR DYE DEGRADATION IN WATER TREATMENT

Disclosed is a system to manufacture a nanocomposite material for the efficient degradation of dyes in water treatment. The system encompasses a first synthesis module for preparing graphene oxide from graphite powder, potassium nitrate, concentrated sulfuric acid, and potassium permanganate, with precise temperature control. An integrated oxidant addition module adds hydrogen peroxide to the mix, initiating a temperature rise conducive to the reaction. Subsequent purification involves a washing and filtration module with ultrasonication for exfoliation, achieving a neutral pH, and a drying unit for the graphene oxide product. A second module synthesizes doped polyaniline via oxidative polymerization, while a separate polymer synthesis module prepares undoped polyaniline. Both polymers are then combined with graphene oxide in a composite synthesis unit. The resulting mixture undergoes separation and ethanol washing, with a drying station finalizing the production of a granulated, dual-form polyaniline graphene oxide composite, tailored for dye degradation in large-scale water treatment processes.

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, Claims:I/We claims:

A system 100 to manufacture a water treatment nanocomposite material for the degradation of dyes, said system 100 comprising:
a first synthesis module 102 equipped with a magnetic stirrer and an ice bath, wherein said first synthesis module 102 is configured to prepare a first reaction mixture comprising:
graphite powder in a range from about 1.5g to about 3.5 g;
potassium nitrate in a range from about 1.5g to about 3.5 g;
concentrated sulfuric acid in a range from about 80ml to about 120ml; and
potassium permanganate in a range from about 10g to about 14g;
a temperature controller 104 is arranged to maintain the temperature of said first reaction mixture in a range from about 308 K to about 313 K;
an oxidant addition module 106 is integrated with said first synthesis module 102 to:
add hydrogen peroxide in a range from 10ml to 14ml; and
dilute with water in a range from 300ml to 500ml, wherein said maintained temperature increases to a range from about 360 K to about 365K;
a washing and filtration module 108 to purify the crude graphene oxide product, wherein said washing and filtration module 108 comprises:
a water supply to wash until the supernatant reaches a neutral pH;
an ultrasonication unit for the exfoliation of the graphene oxide product; and
a drying unit for drying the exfoliated graphene oxide at a temperature range of 310 K to 313 K;
a second synthesis step 110 is arranged to:
synthesize doped (DP) polyaniline by oxidative polymerization of aniline monomer in an aqueous solution of dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate, wherein said oxidative polymerization is performed in a temperature range of 0°C to 5°C, with continuous stirring;
a polymer synthesis step 112 is arranged to prepare undoped (UDP) polyaniline, wherein said undoped polyaniline comprises:
8g to 12 g of polyaniline emeraldine salt is added into 90 ml to 100ml of 0.5 M ammonia solution, wherein said ammonia solution is stirred, washed, and filtered, post the addition of said polyaniline emeraldine salt, to achieve a neutral pH of the filtrate;
a composite synthesis unit 114 is arranged to prepare a second reaction mixture comprising:
said exfoliated graphene oxide in a range from about 0.3g to about 0.6 g;
30 ml to 50 ml of ethylene glycol; and
0.4g to 0.6g of each of said UDP polyaniline and DP polyaniline;
a separation step 116 comprising:
a Buchner funnel connected to a vacuum source for filtration of the second reaction mixture;
an ethanol wash station purifies the filtered second reaction mixture to acquire the nanocomposite material; and
a drying step 118 to remove solvent traces from the nanocomposite material for yielding a dry, granulated doped/undoped polyaniline graphene oxide composite for the water treatment.
The system 100 of claim 1, wherein the DP polyaniline comprises aniline monomer, said dopant and said oxidant in a molar ratio of 1:1:1.
The system of claim 1, wherein said first synthesis step (102) is further configured to control the rate of potassium permanganate addition to said first reaction mixture for mitigation of the exothermic reaction between said potassium permanganate and said concentrated sulfuric acid.
The system of claim 1, wherein said oxidant addition step (106) further comprises a precision delivery unit to add said hydrogen peroxide dropwise to said first reaction mixture.
The system of claim 1, wherein said washing and filtration module (108) further comprises a pH meter integrated with said water supply to provide real-time monitoring and adjustment of the pH level of the supernatant to reach neutrality.
The system of claim 1, wherein said second synthesis module (110) includes a cooling unit to circulate a coolant around said reaction vessel to maintain the reaction temperature between 0°C to 5°C.
The system of claim 1, wherein said composite synthesis step (114) is equipped with a secondary stirring unit to stir said second reaction mixture of said graphene oxide, ethylene glycol, and both UDP and DP polyaniline for 24 hours at room temperature.
The system of claim 1, wherein said washing and filtration module (108) further includes an automated control valve to regulate the flow of water for washing the graphene oxide until the neutral pH is reached.
The system of claim 1, wherein said separation step (116) further comprises an ethanol recycling unit for recovering and reusing ethanol after the washing process.
A method 200 for manufacturing a water treatment nanocomposite material for the degradation of dyes, the method 200 comprising:
(at step 202) mixing graphite powder and potassium nitrate with concentrated sulfuric acid in a first synthesis module (102) equipped with a magnetic stirrer and an ice bath;
(at step 204) controlling the temperature of the resulting first reaction mixture within a range of about 308 K to about 313 K using a temperature controller (104);
(at step 206) integrating an oxidant addition module (106) with the first synthesis module (102) to add hydrogen peroxide in a preset range to stop the reaction and dilute the mixture with water, wherein the temperature is allowed to rise to a range from about 360 K to about 365 K;
(at step 208) transferring the crude graphene oxide product to a washing and filtration module (108) and purifying until the supernatant reaches a neutral pH, followed by exfoliation via an ultrasonication unit and drying the product at a temperature range of 310 K to 313 K;
(at step 210) synthesizing doped polyaniline in a second synthesis module (110) by oxidative polymerization of aniline monomer in an aqueous solution containing dopant amino Tris methylene phosphonic acid and ammonium peroxydisulfate at a temperature range of 0°C to 5°C, with continuous stirring;
(at step 212) preparing undoped polyaniline in a polymer synthesis step (112) by adding polyaniline emeraldine salt into an ammonia solution, stirring, washing, and filtering to achieve a neutral pH of the filtrate;
(at step 214) forming a second reaction mixture in a composite synthesis step (114) by combining exfoliated graphene oxide with both UDP and DP polyaniline in ethylene glycol;
(at step 216) filtering the second reaction mixture using a Buchner funnel connected to a vacuum source in a separation module (116), followed by washing with ethanol to purify the nanocomposite material; and
(at step 218) drying the washed nanocomposite material in a drying station (118) to remove solvent traces and yield a dry, granulated doped/undoped polyaniline graphene oxide composite for the water treatment.
The system of claim 1, wherein degradation of dye under optimum conditions using nanocomposite for waste water treatment.

SUSTAINABLE POLYANILINE-GRAPHENE OXIDE NANOCOMPOSITE FOR DYE DEGRADATION IN WATER TREATMENT