MACROCYCLIC AMINES INTERCALATED TWO DIMENSIONAL ANODIC MATERIALS AND THEREOF FOR ENERGY STORAGE MATERIALS AND BIOSENSOR APPLICATIONS

Abstract

TITLE: MACROCYCLIC AMINES INTERCALATED TWO DIMENSIONAL ANODIC MATERIALS AND THEREOF FOR ENERGY STORAGE MATERIALS AND BIOSENSOR APPLICATIONS APPLICANT: KARUNYA INSTITUTE OF TECHNOLOGY AND SCIENCES ABSTRACT The present invention discloses a process of preparation of macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and biosensor applications comprising of dissolving Graphene Oxide in double distilled water and adding tetrahydrofuran to Macrocyclic amines slowly under ice cold condition followed by mixing the GO solution and macrocylce solution under ice cold condition and centrifuging the mixture multiple times by adding ethanol and acetone. It is then followed by adding few drops of diethyl ether to the obtained pellet and allowing to dry under room temperature and grinding to form macrocyclic amines intercalated two dimensional anodic materials.

Specification

Description:Form 2


THE PATENT ACT, 1970
(39 of 1970)
&
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)






"MACROCYCLIC AMINES INTERCALATED TWO DIMENSIONAL ANODIC MATERIALS AND THEREOF FOR ENERGY STORAGE MATERIALS AND BIOSENSOR APPLICATIONS"






in the name of KARUNYA INSTITUTE OF TECHNOLOGY AND SCIENCES an Indian national having address at KARUNYA INSTITUTE OF TECHNOLOGY AND SCIENCES, KARUNYA NAGAR, COIMBATORE, COIMBATORE - 641114, TAMIL NADU, INDIA.


The following specification particularly describes the invention and the manner in which it is to be performed.
FIELD OF THE INVENTION:

The present invention generally relates to a process of preparation of anodic material. More particularly, the present invention relates to a process of preparation of macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and biosensor applications and product thereof.

BACKGROUND OF THE INVENTION:

The rapid consumption of traditional fossil energy not only results in an energy crisis but also leads to serious environmental pollution. Therefore, environmentally friendly energy sources such as solar energy, wind energy, geothermal energy, and tidal energy have recently gained enormousre search interest. However, those energy sources are unreliable because of their unstable and discontinuous natures. Thus, there is an urgent demand for the development of energy storage systems with high-energy densities, high efficiencies, and long cycling lives to modulate the discontinuous supplies of the clean energy sources.

Among the materials investigated, two-dimensional(2D) nanomaterials and their composites as electrode materials for contemporary energy storage devices such as supercapacitors and rechargeable batteries offer opportunities for clean and sustainable energy demands. The compositions and structures of these electrode materials play significant roles in determining the performance of energy storage devices.

Further, biosensors based on two-dimensional(2D) nanomaterials could make analytical results available within a few minutes at the patient bedside or physician office, at low cost and with a very low limit of detection. The nano-sized nature of nanomaterials and their unique chemical and electrical properties can improve patient care by making the sensors minimally invasive and extremely sensitive.

There are reports available in the state of art revealing the existence of electrode materials.

US20230411610A1 discloses a method for forming a pre-lithiated layered anode material. The method includes removing cations from a precursor material including a layered ionic compound to form creates a two-dimensional structure that defines a layered anode material. The method further includes inserting lithium ions using an anion insertion wet-chemical process into the layered anode materials to form the pre-lithiated layered anode material. The anion insertion wet-chemical process can be the same as or different form the cation extraction wet-chemical process. In each instance, the precursor material is be represented by MX2, where M is one of calcium (Ca) and magnesium (Mg) and X is one of silicon (Si), germanium (Ge), and boron (B) and the precursor material has alternating layers of M and X.

NL2023642B1 discloses asilicon composite material for use as a rechargeable battery anode, comprising (i) an electrically conductive substrate comprising a foil of copper or titanium, (ii) an adhesion layer attached to the foil comprising at least one or more metals and/or metal compounds and (iii) an electrode layer comprising silicon attached to the adhesion layer.

Shahzadi Noreen, Muhammad Bilal Tahir, Abid Hussain, T. Nawaz, Jalil Ur Rehman, A. Dahshan, MeshalAlzaid, Hussein Alrobei, reported on Emerging 2D-Nanostructured materials for electrochemical and sensing Application-A review. The study discloses a brief survey on preparation methods of 2D-nanostructured materials Borophene and Bismuthene. Also, an overview of the applications' status of Borophene in electrochemical area, batteries, sensors, and catalysis and gas storage devices along with an assessment on 2D-nanostructured Bismuthene being an extremely efficient electrocatalyst.

However, the above disclosed materials display nominal or less energy density or are unable to produce the expected performances. Further, the reported 2D materials show variations in their energy storage capacity along with its stability. Furthermore, the process for preparing 2D material is complex and cumbersome.

Thus, there exists a need in the state of art for an alternative anodic material that addresses the aforementioned limitations.

Hence, an attempt has been made to develop a simple and cost-effective process for preparation of macrocyclic amines intercalated two-dimensional anodic material overcoming the above said limitations.

OBJECT OF THE INVENTION:

The main object of the present invention is to develop a cost-effective process for preparation of electrode materials for energy storage materials and biosensor applications.

Another object of the present invention is to develop a process of preparation of macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and biosensor applications.

Yet another object of the present invention is to develop a highly efficient reduced graphene oxide(rGO) for intercalation of macrocycles on graphene oxide surface.
Yet another object of the present invention is to develop a process to enhance interlayer spacing between graphene oxide basal planes by covalent conjugation of macrocyclic polyamines.

Yet another object of the present invention is to fabricate a functionalized, intercalated 2D materials exhibiting higher energy storage capacity along with higher stability.

Yet another object of the present invention is tocharacterize the prepared macrocyclic amines intercalated two-dimensional anodic material to identify its physical, electrochemical and optical properties.

Further object of the present invention is to utilize the prepared macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and in biosensor applications

SUMMARY OF THE INVENTION:

The present invention discloses a process of preparation of macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and biosensor applications. The process of the present invention comprises of following steps;
a. dissolving Graphene Oxide in double distilled water and stirring to form GO solution;
b. adding tetrahydrofuran to (6-, 9-, 12-, 14- membered) Macrocyclic amines slowly under ice cold condition and stirring for 1 hr to form macrocylce solution;
c. mixing the GO solution and macrocylce solution under ice cold condition and stirring for 4 days to form a mixture;
d. centrifuging the mixture at 6000rpm for 30min to form pellet I and supernatant I in which the supernatant I is discarded;
e. dissolving the pellet I with ethanol and centrifuging at 6000rpm for 30min to form pellet II and supernatant II in which the supernatant II is discarded;
f. dissolving the pellet II with acetone and centrifuging at 6000rpm for 30min to form pellet III and supernatant III in which the supernatant III is discarded;
g. repeating the step (f) for two more times and adding few drops of diethyl ether to the obtained pellet and allowing to dry under room temperature and grinding to form macrocyclic amines intercalated two dimensional anodic materials.
The present invention also discloses Macrocyclic Amines Intercalated Two Dimensional Anodic materials for Energy Storage materials and Biosensor Applications prepared by the process as described above.

BRIEF DESCRIPTION OF THE DRAWINGS:

Figure 1 depicts flow chart representation of process of the present invention.
Figure 2 depicts pictorial representation of the intercalated 2D anodic materials.
Figure 3 depicts structure of intercalants (6-,9-,12-,14-membered macrocyclic amines).
Figure 4 depicts Powder XRD of Intercalated GO.
Figure 5 depicts 13C-MAS NMR Spectrum of Intercalated GO.
Figure 6 depicts XPS Survey Spectrum of Intercalated GO.
Figure 7 depicts FT-IR Spectrum of Intercalated GO.
Figure 8 depicts SEM Images of Intercalated GO.
Figure 9 depicts CV Curve of Intercalated GO.
Figure 10 depicts Energy Density Vs Power Density Curve of Intercalated GO.
Figure 11 depicts Nyquist plot of Intercalated GO.

DETAILED DESCRIPTION OF THE INVENTION:

The present invention discloses a process of preparation of macrocyclic amines intercalated two dimensional anodic materials for energy storage materials and biosensor applications and product thereof.

Graphene oxide has oxygen-containing functional groups, such as hydroxyl, epoxy, and carboxyl groups, on its surface. The macrocyclic amines as intercalants undergo nucleophilic attack on the epoxide present in the surface for the formation of amino alcohol moieties on the basal planes. In the case of graphene oxide (GO), the functionalized GO materials create room for the formation of reduced Graphene Oxide (rGO) which has improved electrical conductivity and increased surface area.By incorporating functional groups onto the surface of the 2D nanostructures, a specific binding sites for biomarkers were created, enabling their detection with high sensitivity and selectivity. Functionalization with specific molecules or polymers provide selective binding sites for biomarkers, allowing for their capture and detection.

Upon the intercalation of macrocyclic amine on the basal planes of 2D materials, the interlayer d-spacing is enhanced to 1.0 to 1.7nm with the corresponding 2D value of 9.3 to 6.9 degree through the functionalization of Polyazamacrocycles for the formation of amino alcohol moieties with increased one more co-ordination site confirmed by PXRD, 13C-MAS NMR, XPS studies.


The process of the present invention comprises of preparation of graphene oxide (GO) solution by dissolving GO in double distilled water. The GO was then kept for stirring. The macrocycles in tetrahydrofuran (THF) were then added slowly in drop wise to Cyclenunder cold conditions with continuous stirring for 1hr to obtain macrocyle solution. The GO solution and macrocycle solution were then mixed andsubjected to stirring for 3-4 days. The Graphene Oxide and (6-, 9-, 12-, 14- membered) Macrocyclic amines were in 1:1 weight ratio. After this, the solution was centrifugedat 6000rpm for 30min to obtain pellet I and supernatant I in which supernatant I is discarded. The pellet I is then dissolved with ethanoland centrifugedat 6000rpm for 30min to obtain pellet II and supernatant II in which supernatant II is discarded. The obtained pellet II is then dissolved with acetone and centrifugedat 6000rpm for 30min to obtain pellet III and supernatant III in which supernatant III is discardedand it is repeated for 3 times. To the pellet III, a few drops of Diethyl ether is added to obtain pellet and kept in room temperature for drying. The dried powder is then finely ground using a mortar and pestleto form macrocyclic amines intercalated two dimensional anodic materials.

Then, the synthesized nanostructured material is then subjected for the characterization and to electrochemical studies.

The macrocyclic amine intercalated 2Dnanosheets were characterized by both spectroscopic and microscopic techniques such as Powder XRD, FT-IR, 13C MAS-NMR, RAMAN, XPS, SEM, TEM, and AFM techniques, to ensure the covalent functionalization and surface morphology analysis. (Refer FIG 04-08)

The macrocyclic amine intercalated 2Dnanosheets were then employed in energy storage materials and biosensor and found to exhibit higher energy storage capacity along with higher stability. (Refer FIG 09-11)
Advantages of the present invention:

• Upon the intercalation of macrocyclic amine on the basal planes of 2D materials, the interlayer d-spacing enhanced in the range of above 1.0 nm to 1.8 nm through the functionalization of amino-, hydroxyl-, acids conjugations.
• Due to the interaction of the intercalants on the surface of basal planes of 2D materials, in the case of GO, the new amino ethanol moieties have been formed due to the nucleophilic ring opening epoxide moieties and it was proven by the PXRD studies.
• The existing functionalized 2D materials frameworks exhibit FIVE-membered room for metal coordination through the M-O, or M-N, or M-S ionic bonds. The heteroatom conjugations eventually enhance the wettability of the materials.
• The incoming metals like alkali, alkali earth, and transition metals for metal-heteroatom coordination with the intercalants in between the two layers facilitate higher energy density due to the higher loading and display enhanced performances.
• The functionalized, intercalated 2D materials show limited interactions on the surface as it is coordinated with the intercalant. And it is a covalent bond formation followed by metal-heteroatom ionic interaction exhibit higher energy storage capacity along with higher stability.


In one of the preferred embodiments, the present invention shall disclose a process of preparation of Macrocyclic Amines Intercalated Two Dimensional Anodic materials for Energy Storage materials and Biosensor Applications. The process of the present invention comprises of following steps;

a. dissolving Graphene Oxide in double distilled water and stirring to form GO solution;
b. adding tetrahydrofuran to (6-, 9-, 12-, 14- membered) Macrocyclic amines slowly added to the ice-cold condition and stirring for 1 hr to form macrocyclic solution;
c. mixing the said GO solution and macrocyclic solution under ice cold condition and stirring for 4 days to form a mixture;
d. centrifuging the said mixture at 6000rpm for 30min to form pellet I and supernatant I wherein the said supernatant I is discarded;
e. dissolving the said pellet I with ethanol and centrifuging at 6000rpm for 30min to form pellet II and supernatant II wherein the said supernatant II is discarded;
f. dissolving the said pellet II with acetone and centrifuging at 6000rpm for 30min to form pellet III and supernatant III wherein the said supernatant III is discarded;
g. repeating the step (f) for two more times and adding few drops of diethyl ether to the obtained pellet and allowing to dry under room temperature and grinding to form macrocyclic amines intercalated two dimensional anodic materials.

As per the invention, in the process of the present invention, the Macrocyclic amines is selected from group consisting of Polyaza compounds, Piperazine (1,4-Diazacyclohexane), TACN (1,4,7-Triazacycloanonane), Cyclen (1,4,7,10-Tetraazacyclododecane), Cyclam (1,4,7,10-Tetraazacyclotetradecane).

In accordance with the invention, in the process of the present invention, the Graphene Oxide and (6-, 9-, 12-, 14- membered) Macrocyclic amines are in 1:1 weight ratio.

In further preferred embodiment, the present invention shall disclose a Macrocyclic Amines Intercalated Two Dimensional Anodic materials for Energy Storage materials and Biosensor Applications prepared by the process as described above.

Working example:

Process of preparation of Macrocyclic Amines Intercalated Two Dimensional Anodic materials.

100 mg of graphene oxide (GO)was dispersed in thedouble distilled water and stirred to form GO solution. 150 mL of tetrahydrofuran to 67 mg/mL of (6-, 9-, 12-, 14- membered) Macrocyclic amines(Polyaza compounds, Piperazine (1,4-Diazacyclohexane), TACN (1,4,7-Triazacycloanonane), Cyclen (1,4,7,10-Tetraazacyclododecane), Cyclam (1,4,7,10-Tetraazacyclotetradecane))was slowly added in dropwise under ice cold condition and stirred for 1 hr to form macrocycle solution. The GO solution and macrocycle solution were then mixed under ice cold condition and stirred for 4 days to form a mixture. The mixture was then centrifuged at 6000rpm for 30min to form pellet I and supernatant I in which the supernatant I was discarded. The pellet I was then dissolved with ethanol and centrifuged at 6000rpm for 30min to form pellet II and supernatant II in which the supernatant II was discarded. The pellet II was then dissolved with acetone and centrifuged at 6000rpm for 30min to form pellet III and supernatant III in which the supernatant III is discarded. It was then repeated for 2 more times and few drops of diethyl ether was then added and allowed to dry under room temperature.It was then finely ground to form macrocyclic amines intercalated two dimensional anodic materials.

Although the invention has now been described in terms of certain preferred embodiments and exemplified with respect thereto, one skilled in the art can readily appreciate that various modifications, changes, omissions, and substitutions may be made without departing from the scope of the following claims.
, Claims:WE CLAIM:

1. A process of preparation of Macrocyclic Amines Intercalated Two Dimensional Anodic materials for Energy Storage materials and Biosensor Applications, comprises of following steps;

a. dissolving Graphene Oxide in double distilled water and stirring to form GO solution;

b. adding tetrahydrofuran to (6-, 9-, 12-, 14- membered) Macrocyclic amines slowly under ice cold condition and stirring for 1 hr to form macrocylce solution;

c. mixing the said GO solution and macrocylce solution under ice cold condition and stirring for 4 days to form a mixture;

d. centrifuging the said mixture at 6000rpm for 30min to form pellet I and supernatant I wherein the said supernatant I is discarded;

e. dissolving the said pellet I with ethanol and centrifuging at 6000rpm for 30min to form pellet II and supernatant II wherein the said supernatant II is discarded;

f. dissolving the said pellet II with acetone and centrifuging at 6000rpm for 30min to form pellet III and supernatant III wherein the said supernatant III is discarded;

g. repeating the step (f) for two more times and adding few drops of diethyl ether to the obtained pellet and allowing to dry under room temperature and grinding to form macrocyclic amines intercalated two dimensional anodic materials.

2. The process as claimed in claim 1 wherein the said (6-, 9-, 12-, 14- membered) Macrocyclic amines is selected from group consisting of Polyaza compounds, Piperazine (1,4-Diazacyclohexane), TACN (1,4,7-Triazacycloanonane), Cyclen (1,4,7,10-Tetraazacyclododecane), Cyclam (1,4,7,10-Tetraazacyclotetradecane).

3. The process as claimed in claim 1 wherein the said Graphene Oxide and (6-, 9-, 12-, 14- membered) Macrocyclic amines are in 1:1 weight ratio.

4. A Macrocyclic Amines Intercalated Two Dimensional Anodic materials for Energy Storage materials and Biosensor Applications prepared by the process asclaimed in claim 1.

Dated this 21st day of NOV 2024



For KARUNYA INSTITUTE OF TECHNOLOGY AND SCIENCES
By its Patent Agent

Dr.B.Deepa
IN/PA 1477

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