Electrocatalytic reactor with one or more stainless steel electrodes for electrocatalytic reduction of co 2

Abstract

The present disclosure provides an electrocatalytic reactor and method of electrochemical conversion of carbon dioxide (CO2) into value-added products (VAPs) The electrocatalytic reactor includes Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu-alloy) electrodes, wherein one or more anode is an SS electrode, wherein the electrodes act as electrocatalyst, and acidified deionised water (H3O+) is used as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator that includes 80% by weight of metal carbonates or bicarbonates of Mg or Na with 20% by weight of MgO is used to facilitate the reaction of the short-lived cation radical intermediates formed by C- C coupling reactions on the cathode surface leading to hydrolysis and VAPs formation with high specificity and selectivity.

Description

[0001] TITLE

[0002] ELECTROCATALYTIC REACTOR WITH ONE OR MORE STAINLESS STEEL ELECTRODES FOR ELECTROCATALYTIC REDUCTION OF CO2

[0003] FIELD

[0004] The present disclosure relates to methods of electrochemical conversion of carbon dioxide into value-added products by using one or more stainless steel electrodes.

[0005] CROSS REFERENCE TO RELATED APPLICATIONS

[0006] The present application is based upon and claims priority to India complete patent application number 202441027250 filed on April 02, 2024, the entire contents of which are herein incorporated by reference.

[0007] BACKGROUND

[0008] Global warming has been a major concern, which poses a serious threat to life on the earth in the forms of widespread flooding and extreme weather conditions. While, scientists continue to study global warming and its impact on the earth, and several strategies are being attempted to reduce carbon dioxide emission, the electrochemical reactions of CO2 are of specific interest for the synthesis of chemicals and for approaches to decrease global warming. Work has been done looking at synthesizing specialty chemicals such as formate and urea from carbon dioxide. However, a far greater impact on decreasing atmospheric CO2 levels might be obtained by converting CO2 into fuels, or in other words synthesising fuels from CO2.

[0009] In such carbon-based energy cycles, energy from renewable power would be used to synthesize fuels from captured CO2, which, when used, would not release additional CO2 to the atmosphere (i.e., “CO2 neutral fuels”). As such, these processes represent the storage of these energy sources as chemical energy, which allows them to be more widely used, particularly for transportation applications.

[0010] The main advantages of such carbon-based fuels, vs. storing electricity in batteries or as hydrogen, are the ease of use within existing infrastructures and the higher energy density. Because this involves converting electrical energy to chemical energy, here electrochemistry is an important enabling technology.

[0011] In one carbon-based energy cycle concept, electrolytic hydrogen would be reacted with CO2 to form methanol and water, which, following distillation, yields liquid methanol.

[0012] Another concept would react electrolytic hydrogen and CO2 to form methane (with condensation of water to shift the equilibrium and achieve good yields).

[0013] Electro-reduction of CO2 to VAPs such as ethanol, acetates that can be used as fuels is practically promising and utilization of the same as renewable electricity and mitigation of CO2 emissions, leads to carbon neutrality.

[0014] The electrochemical reduction of CO2 is a process in which electrical energy is converted to organic chemicals of importance from CO2. Although different organic molecules may be obtained from electrochemical CO2 reduction such as formic acid, hydrocarbons (methane, ethane), alcohols (methanol, ethanol, propanol), production of ethanol specifically becomes an important and inevitable process due to the utility of ethanol as alternate fuel to fossil fuel and also as an important organic commodity chemical. Ethanol possesses high energy density and compatibility with present day IC engines and thus can be blended with fossil fuel and used as fuel for automobiles. Ethanol is also a key precursor in the synthesis of various chemical compounds that cater to the medical and food industries. The extensively followed procedure for production of ethanol worldwide is via fermentation of starch rich biomass such as sugarcane, corn, paddy etc. Recently, electrochemical reduction of CO2 to ethanol had become a potentially more effective and sustainable alternative.

[0015] IN202341047481 discloses a method of electrochemical conversion of carbon dioxide into value-added products, wherein the method utilises an electrochemical reactor having metallic Copper (Cu) or Cu-alloy symmetric electrodes (cathode and anode).

[0016] WO2020176575A1 discloses method of electrochemical reduction of CO2 includes the use of a catalyst of Cu / CmO particles including Cu / Cu20 interfaces, which is included in an electrochemical cell for the conversion of CO2 to value- added products. The electrochemical cell may include an anode, a cathode including the CU / CU2O particles including CU / CU2O interfaces, and an aqueous medium containing CO2 or CO3(-2The CO2 or CO3(-2)is reduced by contacting the Cu / Cu20 particles with the aqueous medium while supplying electricity to the cell.

[0017] Journal article, “Oxide Derived Copper for Electrochemical Reduction of CO2 to C2+Products”, Nanomaterials, 2022, 12(8):1380; doi:10.3390 / nanol2081380, discloses a study directed to electrochemical reduction of CO2 on copper electrode derived from cupric oxide (CuO), named oxide derived copper (ODCu), in the potential range of -1.0 V to -1.5 V versus RHE. The CuO nanoparticles were prepared by the hydrothermal method. The ODCu electrode was used for carbon dioxide reduction and the results revealed that this electrode is highly selective for C2+products with enhanced current density at significantly less overpotential.

[0018] Journal article “Electroreduction of carbon dioxide to hydrocarbons using bimetallic Cu-Pd catalysts with different mixing patterns”, J. Am. Chem. Soc. 2017, vol. 139, issue.l, pages: 47-50; doi:10.1021 / jacs.6bl0740, discloses bimetallic Cu-Pd catalysts for reduction of carbon dioxide to Ci or C2 chemicals.

[0019] CN 104321293 A discloses a process for the preparation of methanol having the process a carbon oxides per-pass conversion equal to or higher than 65%, and a selectivity to methanol formation equal to or higher than 75% by submitting carbon dioxide, carbon monoxide or a mixture of carbon monoxide and carbon dioxide to a hydrogenation reaction using a specific metal compound and specific reaction conditions of temperature, pressure, space velocity and a specific range of molar ratio of hydrogen to carbon dioxide, of hydrogen to carbon monoxide, or of hydrogen to the mixture of carbon monoxide and carbon dioxide. It further relates to a process for converting the methanol obtained into dimethyl ether or into a mixture of (C2-C8) alkene and (C1-C8) alkane.

[0020] Journal article “Chong Wang et al. Silver-modified copper foam electrodes for enhanced reduction of CO2 to C2+ products, Mater. Adv., 2022, 3, 4964-4972, DOI: 10.1039 / D2MA00188H” discloses an Ag-modified Cu / CuO-Ag catalyst with a porous structure via a galvanic replacement reaction method, which reduced CO2 to C2+ products with the faradic efficiency (FE) of 52.5% at 1.1 V (vs. RHE). DI states that the experimental results and density functional theory (DFT) calculations show that the addition of Ag in Cu is beneficial to increasing the coverage of *CO on the Cu surface, which can decrease the potential barrier energy of the C-C coupling reaction and favour the generation of C2+ products.

[0021] Journal article “Mun, Yeongdong et. al (2019). Cu-Pd Alloy Nanoparticles as Highly Selective Catalysts for Efficient Electrochemical Reduction of CO2 to CO. Applied Catalysis B: Environmental, (), S0926337319300219. doi: 10.1016 / j.apcatb.2019.01.021” discloses alloying of Cu with Cu-Pd in 1:1 ratio achieves CO2 to CO electrochemical reduction of 87% CO faradic efficiency (FE). D2 discloses that this increase in the FE of CO2 to CO conversion suppresses the formation of hydrocarbons from CO2.

[0022] Journal article “M. Watanabe, M. Shibata, A. Kato, M. Azuma, T. Sakata, J. Electrochem. Soc. 1991, 138, 3382-3389” discloses Cu based alloys such as Cu- Zn, Cu-Cd, Cu-Ag, Cu-Sn and Cu-Pb as electrocatalyst for CO2 electrochemical reduction into CH3OH, HCOOH, and CO in highly selective approach via low overpotentials on Cu-alloy catalysts.

[0023] US2022119966A1 discloses a method of electrochemical reduction of CO2 involving the use of a catalyst of CU / CU2O nanoparticles including CU / CU2O interfaces wherein the catalyst may be included in an electrochemical cell for the conversion of CO2 to value-added products. The electrochemical cell may include an anode, a cathode including the Cu / Cu20 nanoparticles including Cu / Cu20 interfaces.

[0024] GB202202262D0 discloses a catalyst for the electrochemical conversion of carbon dioxide or carbon monoxide to a C2+ product wherein the catalyst comprises copper and a metal (M) selected from the group consisting of: yttrium (Y), zinc (Zn), lanthanum (La) and gadolinium (Gd); wherein the molar ratio of Cu: M is from 100: 1 to 100: 10.

[0025] Thus, to overcome the above-mentioned bottle necks, it becomes clear that there is a need for designing of more efficient electrocatalysts and clear understanding of the mechanism of electro-reduction of CO2 to enhance the VAP production under commercial current densities and viability.

[0026] SUMMARY

[0027] The present disclosure provides an electrocatalytic reactor and method of electrochemical conversion of carbon dioxide (CO2) into value-added products (VAPs). The electrocatalytic reactor is equipped with symmetric or asymmetric electrodes, wherein the electrodes include Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu-alloy), wherein at least one anode is an SS electrode, wherein the electrodes act as electrocatalyst, and acidified deionised water (H3O+) is used as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator is included in the deionised water.

[0028] The catalyst initiator for of the present disclosure is a mixture of 80% by weight of metal carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 20% by weight of MgO to facilitate the reaction of the short-lived cation radical intermediates formed by C-C coupling reactions on the cathode surface leading to hydrolysis and VAPs formation with high specificity and selectivity.

[0029] The method of electrocatalytic reduction operation occurs at ambient temperature. The application of the current and voltage from an external power source is continued for 3 to 5 hours. An external current of 5 to 10 A was applied to the electrodes in a voltage range of 3 to 10 V, which initiates C-C coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the shortlived cation radical intermediates react with the in-situ produced H2 gas, or both, leading to the formation of the VAPs.

[0030] In an embodiment, the electrocatalytic reactor uses two SS electrodes (one SS anode, and one SS cathode).

[0031] In another embodiment, the electrocatalytic reactor uses four SS electrodes (two SS anodes, and two SS cathodes).

[0032] In yet another embodiment, the electrocatalytic reactor uses six SS electrodes (three SS anodes, and three SS cathodes).

[0033] In yet another embodiment, the electrocatalytic reactor uses three SS anodes and three Cu-alloy cathodes.

[0034] In still another embodiment, the electrocatalytic reactor uses one SS anode and one Cu cathode.

[0035] BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS

[0036] Fig. 1 illustrates the electrocatalytic reactor including two electrodes to convert CO2 to value-added products (VAPs).

[0037] Fig. 2 illustrates the electrocatalytic reactor including four electrodes to convert CO2 to value-added products (VAPs).

[0038] Fig. 3 illustrates the electrocatalytic reactor including six electrodes to convert CO2 to value-added products (VAPs).

[0039] Fig. 4A-4E illustrate UV-Vis analysis of the VAPs formed after the electrocatalytic conversion of CO2 employing two SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 1). (Fig. 4A) Blank (Deionised Water), (Fig. 4B) as distilled VAP from reactor output, (Fig. 4C) dilution of 75ml of the distilled VAP in 100ml deionized water, (Fig. 4D) dilution of 50ml of the distilled VAP in 100ml deionized water and (Fig. 4E) dilution of 10 ml of the distilled VAP in 100 ml deionized water.

[0040] Fig. 4F illustrates absorbance versus percentage concentration of VAP in the sample obtained through two SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 1) before and after distillation and dilution (as said above), where absolute alcohol is used as reference, deionized water is the blank.

[0041] Fig. 4G-4H illustrates Gas Chromatography-Mass Spectroscopy (GC-MS) spectra of the VAPs formed after the electrocatalytic conversion of CO2 employing two SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 1).

[0042] Fig. 5A-5E illustrates UV-Vis analysis of the VAPs formed after the electrocatalytic conversion of CO2 employing four SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 2). (Fig. 5A) Blank (Deionised Water), (Fig. 5B) as distilled VAP from reactor output, (Fig. 5C) dilution of 75ml of the distilled VAP in 100ml deionized water, (Fig. 5D) dilution of 50ml of the distilled VAP in 100ml deionized water and (Fig. 5E) dilution of 10 ml of the distilled VAP in 100 ml deionized water.

[0043] Fig. 5F illustrates absorbance versus percentage concentration of VAP in the sample obtained through four SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 2) before and after distillation and dilution (as said above), where absolute alcohol is used as reference, deionized water is the blank.

[0044] Fig. 5G-5H illustrates Gas Chromatography-Mass Spectroscopy (GC-MS) spectra of the VAPs formed after the electrocatalytic conversion of CO2 employing four SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 2).

[0045] Fig. 6A and Fig. 6B depicts the GC-MS analysis of the VAPs formed after the electrocatalytic conversion of CO2 employing Six SS 316 electrodes as electrocatalyst in Cone. HC1 medium (Example 3), (Fig. 6A) Raw sample after the completion of the electrocatalytic reduction, and (Fig. 6B) Distilled sample from the distillation storage tank.

[0046] Fig. 6C depicts the m / z peaks from the GC-MS spectra of the Double Distilled sample of the VAPs formed after the electrocatalytic conversion of CO2 employing Six SS 316 electrodes as electrocatalyst in Cone. HC1 medium (Example 3).

[0047] Fig. 7A and Fig. 7B depicts the GC-MS analysis of the VAPs formed after the electrocatalytic conversion of CO2 employing three SS 316 electrodes and three Cu-alloy electrodes as electrocatalyst in Cone. HC1 medium (Example 4), (Fig. 7 A) Raw sample after the completion of the electrocatalytic reduction, and (Fig. 7B) Distilled sample from the distillation storage tank.

[0048] Fig. 7C and Fig. 7D depicts the m / z peaks from the GC-MS spectra of the VAPs formed after the electrocatalytic conversion of CO2 employing three SS 316 electrodes and three Cu-alloy electrodes as electrocatalyst in Cone. HC1 medium (Example 4) (Fig. 7C) Raw sample after the completion of the electrocatalytic reduction, (Fig. 7D) Distilled sample from the distillation storage tank.

[0049] Fig. 8A depicts the GC-MS analysis of the Distilled sample for the VAPs formed after the electrocatalytic conversion of CO2 employing one SS 316 electrode and one Cu electrode as electrocatalyst in Cone. HC1 medium (Example 5).

[0050] Fig. 8B depicts the m / z peaks from the GC-MS spectra of the Distilled sample for the VAPs formed after the electrocatalytic conversion of CO2 employing one SS 316 electrode and one Cu electrode as electrocatalyst in Cone. HC1 medium (Example 5).

[0051] DETAILED DESCRIPTION

[0052] The subject matter of the present disclosure is described in detail with reference to the accompanying drawings. Unless otherwise specified, all the technical and scientific terms used herein have the same meaning as is generally understood by a person skilled in the art pertaining to the present disclosure. Headings are used solely for organizational purposes, and are not intended to limit the disclosure in any way.

[0053] The use of the singular includes the plural unless specifically stated otherwise. As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well. The use of “or” means “and / or” unless stated otherwise. Unless otherwise indicated, all numbers used herein to express quantities, dimensions, and so forth used should be understood as being modified in all instances by the term "about." It is to be understood that wherein a numerical range is recited, it includes all values within that range, and all narrower ranges within that range, whether specifically recited or not. As used herein, "including," "containing" and like terms are understood to be synonymous with "comprising" and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, phases or method steps.

[0054] In addition, it should be appreciated that any figures are provided herewith, are for explanation purposes to persons ordinarily skilled in the art and that the drawings of them are not necessarily drawn to scale.

[0055] Any method / process steps and / or operations and / or instructions used in this disclosure, are for illustrative purposes in a particular order and / or grouping. Other orders and / or grouping of the process steps or its portions and / or operations or its portions and / or instructions or its portions are possible and, one or more of the process steps and / or operations and / or instructions can be combined and / or deleted.

[0056] The present disclosure provides a method of electrochemical conversion of carbon dioxide (CO2) into value-added products (VAPs) such as ethanol, acetic acid, ethyl acetate, metal ethanoates and acetaldehyde, ethylene dichloride (EDC), trimethyl pentane, ethylene etc.

[0057] The present disclosure provides an electrocatalytic reactor and method of electrochemical conversion of carbon dioxide (CO2) into value-added products (VAPs). The electrocatalytic reactor is equipped with symmetric or asymmetric electrodes, wherein the electrodes include Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu-alloy), wherein at least one anode is an SS electrode, wherein the electrodes act as electrocatalyst, and acidified deionised water (H3O+) is used as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator is included in the deionised water.

[0058] The method of electrocatalytic reduction operation occurs at ambient conditions. The application of the current and voltage from an external power source is continued for 3 to 5 hours. An external current of 5 to 10 A was applied to the electrodes in a voltage range of 3 to 10 V, which initiates C-C coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the shortlived cation radical intermediates react with the in-situ produced H2 gas, or both, leading to the formation of the VAPs.

[0059] In an embodiment, the electrocatalytic reactor uses two SS electrodes (one SS anode, and one SS cathode).

[0060] In another embodiment, the electrocatalytic reactor uses four SS electrodes (two SS anodes, and two SS cathodes).

[0061] In yet another embodiment, the electrocatalytic reactor uses six SS electrodes (three SS anodes, and three SS cathodes).

[0062] In yet another embodiment, the electrocatalytic reactor uses three SS anodes and three Cu-alloy cathodes.

[0063] In still another embodiment, the electrocatalytic reactor uses one SS anode and one Cu cathode.

[0064] The method of electrochemical conversion of carbon dioxide (CO2) into value- added products (VAPs) includes:

[0065] - adding deionised water to an electrocatalytic reactor vessel and dipping electrodes in the deionised water, wherein the electrodes include Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu-alloy), wherein at least one anode is an SS electrode;

[0066] - adding a catalyst initiator to the deionised water in the reactor vessel forming an initiator solution;

[0067] - purging CO2 into the initiator solution from an external CO2 source;

[0068] - applying external current of 5 to 10 A to the electrodes in a voltage range of 3 to 10 V; and

[0069] - adding a concentrated acid to the initiator solution in the reactor vessel with constant stirring to form an acidified solution, which produces H2 gas in-situ from the acidified deionised water on the cathode surface, and produces CO2 gas in-situ through the reaction of initiator and the acid; wherein the applied current density initiates the reaction of asymmetric C-C coupling of CO2 molecules on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides; wherein, on the anode, the organic acid anions and alkoxides undergo hydrolysis to form acid or alcohol, esters or ethers; wherein, the acids or alcohols or esters or ethers or hydrocarbons or salts formed are distilled at appropriate temperature to form the value-added products (VAPs) in its purest form.

[0070] An external current of 5 to 10 A was applied to the electrodes in a voltage range of 3 to 10 V, which facilitates the formation of organic cation radical intermediates, which lead to the formation of the VAPs.

[0071] In an aspect, the application of current and voltage from an external power source to the electrodes is continued for 3 to 5 hours, preferably with high current density to accelerate the reaction and also to achieve specificity and selectivity of the products formed especially ethanol. The concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HNO3, H3PO4.

[0072] The Cu-alloy for the electrodes can be selected from Cu / CuO, Cu / Ag, Cu / Ti, Cu / Pt, and Cu / Pd, wherein the dopant i.e., CuO, Ag, Ti, Pt, and Pd is present in an amount of less than or equal to 2.5% by weight of the alloy.

[0073] Catalyst initiator:

[0074] The catalyst initiator of the present disclosure is a mixture of 80% by weight of metal carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 20% by weight of MgO to facilitate the reaction of the short-lived cation radical intermediates formed by C-C coupling reactions on the cathode surface leading to hydrolysis and VAPs formation with high specificity and selectivity.

[0075] Examples:

[0076] The present disclosure will now be explained in further detail by the following examples. These examples are illustrative of certain embodiments of the disclosure without limiting the scope of the present disclosure.

[0077] The materials employed for the experiments of the present disclosure are procured from SRL chemicals and are of analytical grade. The chemicals are used without further purification.

[0078] As shown in Fig. 1, 2 and 3, the electrodes are designed in the form of a slab with rectangular handle. The handle of the electrodes acts as the current collector that is connected to the power source (PS). Inlets provided on the lid of the reactor are the provisions to pass CO2 (along with in-situ prepared through initiator-based reaction) and its conversion on the electrode surface. The rate of flow of CO2 is between 30 Litres / hour (30 LPH) to 50 Liters / hour (50 LPH).

[0079] The power source (from Won-a-Tech, Korea) with 12 V and 10 A capacity of voltage and current is applied, which is the required voltage and current to the reaction solution via the electrodes. The power source is provided with software interface to acquire the dynamic data of the voltage (V) and Current (I) during the reaction.

[0080] Example 1:

[0081] Electrocatalytic conversion of 99.9% pure CO2 - Two electrodes of SS 316 at an exhibition in Nagpur, India.

[0082] - Feed source: 99.9% pure CO2 supplied from cylinders.

[0083] - Electrocatalytic reactor capacity: 120 litres.

[0084] - Cathode: One SS 316 plate of dimension 50cm*40cm*3cm

[0085] (length*breadth*thickness).

[0086] - Anode: One SS 316 plate of dimension 50cm*40cm*3cm

[0087] (length*breadth*thickness).

[0088] - Catalyst initiator: 40% MgCOs + 20% Na2COi + 20% NaHCOa with 20% MgO in distilled water.

[0089] - Flow rate of GHG: 500 ml / min (30LPH).

[0090] An electrocatalytic reactor was prepared according to the above specifications to carry out electrocatalytic conversion of CO2 to Value Added Products (VAPs), with CO2 inlet at the top. The experiment was carried out at pilot scale in an exhibition at Nagpur at ambient temperature of 28°C. 75 litres of deionised water was taken in the electrocatalytic reactor vessel, and the electrodes were dipped into the deionised water through the reactor lid. 75 gm of the catalyst initiator was added to the deionised water to form the initiator solution. CO2 was purged into the initiator solution in the reactor vessel at a flow rate of 500ml / min at 50 bar pressure. Current and voltage was applied to the cathode and anode from an external DC source at an applied potential of 3 V and current 5 A for 3 hours, and the initiator solution was acidified with 1000 ml of cone. H2SO4. The acidified solution generated in-situ hydrogen gas by bulk electrocatalysis of acidified deionised water to facilitate the reduction of CO2 into VAPs. A colourless solution is formed after the reaction. After the completion of the reaction, the solution is distilled by steam heating at 79.8°C and the distilled sample is tested by UV-Vis spectroscopy, GC-MS to understand the products formed. In this example, it was identified that the solution consists of ethanol as the major product leaving behind sulphates of sodium, potassium, and Magnesium.

[0091] The plot of absorbance vs wavelength of different samples of Example 1 has been shown in Fig. 4A-4E.

[0092] (Fig. 4A) Blank (Deionised Water),

[0093] (Fig. 4B) as distilled VAP from reactor output,

[0094] (Fig. 4C) dilution of 75ml of the distilled VAP in 100ml deionized water, (Fig. 4D) dilution of 50ml of the distilled VAP in 100ml deionized water, and (Fig. 4E) dilution of 10 ml of the distilled VAP in 100 ml deionized water.

[0095] The absorbance of the Raw output VAPs from the reactor was noted using Shimadzu UV-Vis equipment.

[0096] The absorbances and the respective wavelengths have been provided in Table 1, which indicates that ethanol is the major product, wherein ethanol was separated by fractional distillation.

[0097] Table 1

[0098] A plot of absorbance vs percentage alcohol (concentration in percentage) is made as shown in Fig. 4F.

[0099] As seen in Fig. 4F, a linear line passing through origin is noticed. According to the Beer-Lambert’s law

[0100] Absorbance = £cl

[0101] The slope of the linear line becomes £c. As seen in Fig. 4F, the slope is 2.8.

[0102] The absorbance of the raw output of the electrocatalytic reactor (VAP) is measured to be 0.851 (@ 193.12 nm).

[0103] Upon inputting the absorbance value in the graph, the unknown % concentration of ethanol in the raw output of the electrocatalytic reactor after reduction of CO2 is 32.5%. After fractional distillation of the raw sample obtained from electrocatalytic reactor, the distilled ethanol is measured for its absorbance and the value is found to be 2.174 (@ 193.389 nm). When this value is fit in the graph, the corresponding ethanol concentration percentage in the distilled sample is obtained as 76.5%. Thus, to achieve, 99.9% purity, multiple fractional distillation is required to remove the water miscible in the ethanol obtained from CO2.

[0104] Fig. 4G-4H illustrates Gas Chromatography-Mass Spectroscopy (GC-MS) spectra of the VAPs formed after the electrocatalytic conversion of CO2 employing two SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 1). The m / e peak at 45 demonstrates the presence of ethanol with area under the peak as 62.42% and the peaks yield as 83%.

[0105] Example 2:

[0106] Electrocatalytic conversion of 99.9% pure CO2 - Four electrodes of SS 316 at an exhibition in Nagpur, India.

[0107] - Feed source: 99.9% pure CO2 supplied from cylinders.

[0108] - Electrocatalytic reactor capacity: 120 litres.

[0109] - Cathode: Two SS 316 plates of dimension 50cm*40cm*3cm

[0110] (length*breadth*thickness).

[0111] - Anode: Two SS 316 plates of dimension 50cm*40cm*3cm

[0112] (length*breadth*thickness).

[0113] - Catalyst initiator: 40% MgCOs + 20% Na2COa + 20% NaHCCh with 20% MgO in distilled water.

[0114] - Flow rate of GHG: 500 ml / min (30LPH).

[0115] An electrocatalytic reactor was prepared according to the above specifications to carry out electrocatalytic conversion of CO2 to Value Added Products (VAPs), with CO2 inlet at the top. The experiment was carried out at pilot scale in an exhibition at Nagpur at ambient temperature of 28°C. 75 litres of deionised water was taken in the electrocatalytic reactor vessel, and the electrodes were dipped into the deionised water through the reactor lid. 75 gms of the catalyst initiator was added to the deionised water to form the initiator solution. CO2 was purged into the initiator solution in the reactor vessel at a flow rate of 500ml / min at 1 atm pressure. Current and voltage was applied to the cathode and anode from an external DC source at an applied potential of 3 V and current 5 A for 5 hours, and the initiator solution was acidified with 1000 ml of cone. H2SO4. The acidified solution generated in-situ hydrogen gas by bulk electrocatalysis of acidified deionised water to facilitate the reduction of CO2 into VAPs. A colourless solution is formed after the reaction. After the completion of the reaction, the solution is distilled by steam heating at 79.8°C and the distilled sampleis tested by Fourier Transform Infrared Spectroscopy (FTIR), UV-Vis spectroscopy, GC-MS to understand the products formed. In this example, it was identified that the solution consists of ethanol as the major product leaving behind sulphates of sodium, potassium, and Magnesium.

[0116] The plot of absorbance vs wavelength of different samples of Example 2 has been shown in Fig. 5A-5E.

[0117] (Fig. 5A) Blank (Deionised Water),

[0118] (Fig. SB) as distilled VAP from reactor output,

[0119] (Fig. SC) dilution of 75ml of the distilled VAP in 100ml deionized water, (Fig. 5D) dilution of 50ml of the distilled VAP in 100ml deionized water, and (Fig. 5E) dilution of 10 ml of the distilled VAP in 100 ml deionized water.

[0120] The absorbance of the Raw output VAPs from the reactor was noted using Shimadzu UV-Vis equipment.

[0121] The absorbances and the respective wavelengths have been provided in Table 2, which indicates that ethanol is the major product, wherein ethanol was separated by fractional distillation.

[0122] Table 2

[0123] A plot of absorbance vs percentage alcohol (concentration in percentage) is made as shown in Fig. 5F.

[0124] As seen in Fig. 5F, a linear line passing through origin is noticed. According to the Beer-Lambert’s law

[0125] Absorbance = £cl

[0126] The slope of the linear line becomes £c. As seen in Fig. 5F, the slope is 2.5.

[0127] The absorbance of the raw output of the electrocatalytic reactor (VAP) is measured to be 1.518 (@ 196.72 nm).

[0128] Upon inputting the absorbance value in the graph, the unknown % concentration of ethanol in the raw output of the electrocatalytic reactor after reduction of CO2 is 58%. After fractional distillation of the raw sample obtained from electrocatalytic reactor, the distilled ethanol is measured for its absorbance and the value is found to be 2.814 (@ 193.389 nm). When this value is fit in the graph, the corresponding ethanol concentration percentage in the distilled sample is obtained as 93.5%. Thus, to achieve, 99.9% purity, multiple fractional distillation is required to remove the water miscible in the ethanol obtained from CO2.

[0129] Fig. 5G-5H illustrates Gas Chromatography-Mass Spectroscopy (GC-MS) spectra of the VAPs formed after the electrocatalytic conversion of CO2 employing four SS 316 electrodes as electrocatalyst in Cone. H2SO4 medium (Example 2).

[0130] The m / e peak at 45 demonstrates the presence of ethanol with area under the peak as 100% and the peaks yield as 92%.

[0131] Example 3: Electrocatalytic conversion of 99.9% pure CO2 - Six electrodes of SS 316 at a demonstration in a facility Faridabad, India.

[0132] - Feed source: 99.9% pure CO2 supplied from cylinders (20 TPD throughput).

[0133] - Electrocatalytic reactor capacity: 1000 litres.

[0134] - Cathode: Three SS 316 plates of dimension 60cm*30cm*lcm

[0135] (length*breadth*thickness).

[0136] - Anode: Three SS 316 plates of dimension 60cm* 30cm* 1cm

[0137] (length*breadth*thickness).

[0138] - Catalyst initiator: 40% MgCOs + 20% Na2COa + 20% NaHCCh with 20% MgO in distilled water.

[0139] - Flow rate of GHG: 50 LPH

[0140] An electrocatalytic reactor was prepared according to the above specifications to carry out electrocatalytic conversion of CO2 to Value Added Products (VAPs), with CO2 inlet at the top. The experiment was carried out at pilot scale in a lab facility at Faridabad at ambient temperature of 28°C. 350 litres of deionised water was taken in the electrocatalytic reactor vessel (double walled reactor vessel to regulate temperature of the reaction), and the electrodes were dipped into the deionised water through the reactor lid. 350 gms of the catalyst initiator was added to the deionised water to form the initiator solution. CO2 was purged into the initiator solution in the reactor vessel at a flow rate of 50 EPH at 50 bar pressure. Current and voltage was applied to the cathode and anode from an external DC source at an applied potential of 10V and current 8 A for 3 hours, and the initiator solution was acidified with 1000 ml of cone. HC1. The acidified solution generated in-situ hydrogen gas by bulk electrocatalysis of acidified deionised water to facilitate the reduction of CO2 into VAPs. A colourless solution is formed after the reaction. The electrocatalytic reactor was connected to a flush tank and the reacted solution was flushed to the flush tank using pump (HP = 5). The flush tank is steam heated at 83.7°C for distillation of the solution (the temperature can be achieved up to 90°C, which is monitored through a digital temperature display). The distilled vapours were passed through a condenser and stored in storage tank. From the storage tank an aliquot of the distilled solution was taken for GC-MS analysis. After the completion of the reaction, the solution is tested by GC-MS to understand the products formed.

[0141] Fig. 6A and Fig. 6B depicts the GC-MS analysis of Example 3. (Fig. 6A) Raw sample after the completion of the electrocatalytic reduction, and (Fig. 6B) Distilled sample from the distillation storage tank.

[0142] It can be clearly demonstrated from the Fig. 6A that peaks at lower residential time such as 1.13, 1.19 with very low intensity, 1.27, 1.30 & 1.32 minutes with very high intensity sharp peaks. These peaks account for formation of 1, 3 dichlorobenzene (due to ring closure happening during the reaction via free radical *CH2 formation). With a long flat line from 1.32 to 9 minutes, the GC-MS showed a sinusoidal increase to high intensity at 9.25 minutes and reaching 90% intensity at 10.31 minutes and showing sharp peaks from 10.31 to 14.48 minutes. This broad band from 10.31 to 14.48 minutes account for the formation of 1,2 Dichloro ethylene hydrogen bonded to 1,2, dichlorobenzene and water molecules.

[0143] Fig. 6B depicts peaks at lower residential time such as 4.60 minutes with very high intensity sharp peak. This peak accounts for formation of ethanol. With a long flat line from 5.00 to 11.00 minutes, the GC-MS showed a high intensity at 11.596 minutes and reaching 80% intensity and sharp peak 13.47 minutes. This accounts for the formation of 1,2 Dichloro ethylene (EDC).

[0144] The clear difference between the intensity of the peaks in the raw and the distilled samples are due to double distillation of the raw sample.

[0145] Fig. 6C depicts the m / z peaks from the GC-MS spectra of the Double Distilled sample of the VAPs formed of Example 3. m / z = 51, 33% intensity peak accounts for the presence of the fragment CH2CI. m / z=77 , 100% intensity peak accounts for the presence of the fragment which is a negative ion ®O-C=C-C1. This is a short-lived intermediate that takes up a proton from the acidified water and leads to formation of water and acetylene chloride. This further reduces to ethylene dichloride. m / z = 100.1, 27% intensity peak accounts for the presence of CIH2C-CH2CI; ethylene dichloride, the major product in the electrocatalytic reduction of CO2. m / z = 141; 32% intensity peak denote the presence of ChHC-C=C-CH=O (1- dichlorobutyne-aldehyde) dehydrolysis and reduces to form ethylene dichloride and CH3CHO leading to ethanol or acetic acid via reduction / oxidation process. m / z = 170; 27% intensity peaks denote the ring closure reactions initiated in the process leading to formation of p-Nitro-o-hydroxy-Benzyl alcohol ((NO2) (OH)CeH3-CH2OH). This undergoes dehydration and protonation leading to benzene derivatives and ethylene dichloride m / z = 206.9; involves formation of l-chloro-4-Nitro-6-hydroxy-Benzyl alcohol ((C1)(NO2) (OH)C6H3-CH2OH). m / z = 252.9; 35% intensity peak denoting 1,2 diphenyl, dichloro ethylene formation due to ethylene substituted by ring closure phenyl moieties. m / z = 280.8; 15% intensity peak denoting 1,2, dibenzyl, dichloro ethylene formation due to ethylene disubstituted by ring closure benzyl moieties.

[0146] The rest of the m / z peaks such as 129 to 542 are negligible and are of very low yield aromatic compounds as by-products. Thus, from above points, it is understood that the major product formed in the pilot scale demonstration of CO2 to VAPs at the 20 TPD through put of the gas leads to phenyl or benzyl substituted ethylene dichloride (EDC) as major product.

[0147] Example 4:

[0148] Electrocatalytic conversion of 99.9% pure CO2 - Three SS electrodes of SS 316 and Three Cu-alloy electrodes at a demonstration in a facility in Faridabad, India.

[0149] - Feed source: 99.9% pure CO2 supplied from cylinders (20 TPD throughput).

[0150] - Electrocatalytic reactor capacity: 1000 litres.

[0151] - Cathode: Three Cu-alloy (97.5% Cu + 2.5% Ag) plates of dimension 60cm*30cm* 1cm (length*breadth*thickness).

[0152] - Anode: Three SS 316 plates of dimension 60cm* 30cm* 1cm

[0153] (length*breadth*thickness).

[0154] - Catalyst initiator: 40% MgCCh + 20% Na2CC>3 + 20% NaHCCh with 20% MgO in distilled water.

[0155] - Flow rate of GHG: 50 LPH

[0156] An electrocatalytic reactor was prepared according to the above specifications to carry out electrocatalytic conversion of CO2 to Value Added Products (VAPs), with CO2 inlet at the top. The experiment was carried out at pilot scale in a lab facility at Faridabad at ambient temperature of 28°C. 350 litres of deionised water was taken in the electrocatalytic reactor vessel (double walled reactor vessel to regulate temperature of the reaction), and the electrodes were dipped into the deionised water through the reactor lid. 350 gms of the catalyst initiator was added to the deionised water to form the initiator solution. CO2 was purged into the initiator solution in the reactor vessel at a flow rate of 50 E / h at 50 bar pressure. Current and voltage was applied to the cathode and anode from an external DC source at an applied potential of 10V and current 8 A for 3 hours, and the initiator solution was acidified with 1000 ml of cone. HC1. The acidified solution generated in-situ hydrogen gas by bulk electrocatalysis of acidified deionised water to facilitate the reduction of CO2 into VAPs. A colourless solution is formed after the reaction. The electrocatalytic reactor was connected to a flush tank and the reacted solution was flushed to the flush tank using pump (HP = 5). The flush tank is steam heated at 83.7°C for distillation of the solution (the temperature can be achieved up to 90°C, which is monitored through a digital temperature display). The distilled vapours were passed through a condenser and stored in storage tank. From the storage tank an aliquot of the distilled solution was taken for GC-MS analysis. After the completion of the reaction, the solution is tested by GC-MS to understand the products formed.

[0157] Fig. 7A and Fig. 7B depicts the GC-MS analysis of Example 4. (Fig. 7A) Raw sample from the reactor, and (Fig. 7B) Distilled sample.

[0158] Fig. 7A depicts peaks at lower residential time such as 0.35, with very low intensity, 1.25, 1.29 & 1.30 minutes with very high intensity sharp peaks. These peaks account for formation of 1, 3 dichlorobenzene (due to ring closure happening during the reaction via free radical *CH2 formation). With a long flat line from 1.32 to 9.2 minutes, the GC-MS showed a sinusoidal increase to high intensity at 9.25 minutes and reaching 80% intensity at 9.93 minutes and showing sharp peaks from 9.93 to 14.47 minutes. This broad band from 9.93 to 14.47 minutes account for the formation of 1,2 Dichloro ethylene hydrogen bonded to 1,2, dichlorobenzene and water molecules.

[0159] It can be clearly demonstrated from the Fig. 7B that peaks at lower residential time such as 1.13, 1.19 with very low intensity, 1.27, 1.30 & 1.32 minutes with very high intensity sharp peaks. These peaks account for formation of 1, 3 dichlorobenzene (due to ring closure happening during the reaction via free radical *CH2 formation). With a long flat line from 1.32 to 9 minutes, the GC-MS showed a sinusoidal increase to high intensity at 9.25 minutes and reaching 90% intensity at 10.31 minutes and showing sharp peaks from 10.31 to 14.48 minutes. This broad band from 10.31 to 14.48 minutes account for the formation of 1,2 Dichloro ethylene hydrogen bonded to 1,2, dichlorobenzene and water molecules.

[0160] The clear difference between the intensity of the peaks in the raw and the distilled samples are due to single distillation. To achieve >99.9% pure 1,2, dichloro ethylene, multiple distillation with appropriate temperature regulation at 83.7°C need to be carried out.

[0161] After achieving > 99.9% pure 1,3, dichloro ethylene, thermal treatment of the same in fluidized bed reactor would result in dehydrochlorination of the 1,2 dichloroethylene resulting in pure ethylene gas and HC1 which can be recirculated in the reactor.

[0162] Fig. 7C and Fig. 7D depicts the m / z peaks from the GC-MS spectra of the electrocatalytically reduced CO2 into Value Added Products of Example 4 (Fig. 7C) Raw sample after the completion of the electrocatalytic reduction, (Fig. 7D) distilled sample from the distillation storage tank. m / z = 51, 100% intensity peak accounts for the presence of the fragment CH2CI. m / z = 55, 40% intensity peak corresponds to the presence of the fragment HC=C=CHOH; this is an intermediate formed due to the presence of dissolved oxygen and highly reactive intermediate radical formed. This is linear chain propagation leading to propyne- l-ol radical. m / z = 56, 28% intensity peak represents the presence of the fragment HC=C- CH2OH; this product is the dehydration of acetylene formed with methanol. This product is also formed due to the participation of oxygen dissolved in the electrolyte as well as those generated during in-house hydrogen evolution. m / z = 69, 50% intensity peak denoting the presence of the fragment which is a positive ion H2O®-CH2-C1. This is a short-lived positive ion, as oxygen being a highly electronegative species, will take up the bonding pair of electrons from adjacent carbon covalent bond leading to water and ®CH2C1 carbocation and a reactive intermediate in the formation of ethylene dichloride m / 7=11 , 55% intensity peak accounts for the presence of the fragment which is a negative ion ®O-C=C-C1. This is a short-lived intermediate that takes up a proton from the acidified water and leads to formation of water and acetylene chloride. This further reduces to ethylene dichloride. m / z = 78, 57% intensity peak denoting the presence of 1 -hydroxy-2 -chloro acetylene (HO-C=C-C1) which on further protonation and reduction leads to formation of water and ethylene dichloride. m / z = 91, 72% intensity peak represents the presence of a resonance stabilized species such as

[0163] O

[0164] C1-HC=C=CH2. This species is a reactive intermediate which loses a water molecule and leads to formation of ethylene dichloride. m / z = 101, 77% intensity peak accounts for the presence of CIH2C-CH2CI; ethylene dichloride, the major product in the electrocatalytic reduction of CO2. m / z = 105; 15% intensity peak denote the presence of C1H2C-CH2-CH2-O®H2 this cation is unstable and dehydrates and further fragments to form ethylene dichloride and CH2CI radical (which is the initial radical for major product formation). m / z = 119; 12% intensity peaks denote the ring closure reactions initiated in the process leading to formation of l-hydroxy-2-phenyl acetylene (CeH5-C=C-®OH2). This undergoes dehydration and protonation leading to benzene derivatives and ethylene dichloride,

[0165] The rest of the m / z peaks such as 129 to 542 are negligible and are of very low yield aromatic compounds as by-products.

[0166] Thus, from the above m / z peaks, it is understood that the major product formed in the pilot scale demonstration of CO2 to VAPs at the 20 TPD throughput of the gas leads to ethylene dichloride (EDC) as major product and aromatic compounds via ring closure and propyne -l-ol as minor by-products.

[0167] Example 5:

[0168] Electrocatalytic conversion of 99.9% pure CO2 - One SS electrode of SS 316 and One Cu electrode at the inventors’ lab in Chennai, India.

[0169] - Feed source: 99.9% pure CO2 supplied from cylinders (20 TPD throughput).

[0170] - Electrocatalytic reactor capacity: 1000 litres.

[0171] - Cathode: One Cu plate of dimension 60cm*30cm*lcm (length*breadth*thickness).

[0172] - Anode: One SS 316 plate of dimension 60cm*30cm*lcm (length*breadth*thickness).

[0173] - Catalyst initiator: 40% MgCOs + 20% Na2COa + 20% NaHCOa with 20% MgO in distilled water.

[0174] - Flow rate of GHG: 50 LPH

[0175] An electrocatalytic reactor was prepared according to the above specifications to carry out electrocatalytic conversion of CO2 to Value Added Products (VAPs), with CO2 inlet at the top. The experiment was carried out at pilot scale in a lab facility at Faridabad at ambient temperature of 28°C. 350 litres of deionised water was taken in the electrocatalytic reactor vessel (double walled reactor vessel to regulate temperature of the reaction), and the electrodes were dipped into the deionised water through the reactor lid. 350 gms of the catalyst initiator was added to the deionised water to form the initiator solution. CO2 was purged into the initiator solution in the reactor vessel at a flow rate of 50 LPH at 50 bar pressure. Current and voltage was applied to the cathode and anode from an external DC source at an applied potential of 10V and current 8 A for 3 hours, and the initiator solution was acidified with 1000 ml of cone. HC1. The acidified solution generated in-situ hydrogen gas by bulk electrocatalysis of acidified deionised water to facilitate the reduction of CO2 into VAPs. A colourless solution is formed after the reaction. The electrocatalytic reactor was connected to a flush tank and the reacted solution was flushed to the flush tank using pump (HP = 5). The flush tank is steam heated at 83.7°C for distillation of the solution (the temperature can be achieved up to 90°C, which is monitored through a digital temperature display). The distilled vapours were passed through a condenser and stored in storage tank. From the storage tank an aliquot of the distilled solution was taken for GC-MS analysis. After the completion of the reaction, the solution is tested by GC-MS to understand the products formed.

[0176] Fig. 8A depicts the GC-MS analysis of the Distilled sample for the VAPs formed after the electrocatalytic conversion of CO2 employing one SS 316 electrode and one Cu electrode as electrocatalyst in Cone. HC1 medium (Example 5).

[0177] Fig. 8B depicts the m / z peaks from the GC-MS spectra of the Double Distilled sample for the VAPs formed after the electrocatalytic conversion of CO2 employing one SS 316 electrode and one Cu electrode as electrocatalyst in Cone. HC1 medium (Example 5).

[0178] It can be understood from the Fig. 8A that peaks at lower residential time such as 2.0975, 2.17, 2.263, 2.486 with very high intensity. These peaks account for formation of 2,3,4, trimethyl pentane as seen from the m / z graph with m / z of 43.1 as shown in Fig. 8B.

[0179] Advantages: The method of conversion of CO2 to VAPs of the present disclosure has the following non-limiting advantages.

[0180] - The source of carbon (from CO2) is free of cost or negligible cost

[0181] - Cu electrodes or Cu alloy electrodes as electrocatalyst employed is an earth abundant material and hence highly cost effective

[0182] - Recycling of the electrode and electrocatalyst is highly feasible and facile making the process highly closed loop

[0183] - Completely renewables driven - zero waste concept with 5R compliance

[0184] - Flow type electrocatalytic reactor design leads to high selectivity and yield of production of VAPs

[0185] - Carbon credits due to CO2 reduction

[0186] - Mitigation of CO2 content in the atmosphere at lower cost and involving production of useful fuels.

[0187] - To process tonnes of CO2 per day, continuous flow electrocatalytic reactor can be designed with ease and hence scaling up and mass production is highly feasible

[0188] - Less chemical intensive process, easy design and operation

[0189] - Use within existing infrastructures and the higher energy density,

[0190] - Cu and Cu-alloy electrodes possess high hydrogen overvoltage and negligible CO adsorption.

[0191] - Even when the CO2 from the external CO2 source has impurities such as NOx, or SOx gases (such as when flue gas is the external CO2 source), the VAP yield remains unaffected.

[0192] - Consistent batch yield, with minimum or negligible batch variation.

[0193] Applications:

[0194] The method of conversion of CO2 to VAPs of the present disclosure has the following non-limiting industrial applications.

[0195] - Production of VAPs such as ethylene dichloride (EDC), trimethyl pentane, ethanol, acetaldehyde, isoamyl alcohol, isopropanol, methanol, secondary alcohols, esters, ethers, metal-ethanoates, metal-ethoxides, metallorganic complexes.

[0196] Although the present disclosure is described in terms of certain preferred embodiments, it is to be understood that they have been presented by way of example, and not limitation. Thus, the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

Claims

CLAIMS1. An electrocatalytic reactor for conversion of CO2 into value-added products (VAPs) comprising: Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu- alloy) electrodes, wherein one or more anode is an SS electrode, wherein the electrodes act as electrocatalyst, and acidified deionised water (H3O+) as electrolyte for generation of H2 gas through bulk electrocatalysis, wherein a catalyst initiator is included in the deionised water, wherein an external current of 5 to 10 A is applied to the electrodes in a voltage range of 3 to 10 V, which initiates C-C coupling reactions on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the shortlived cation radical intermediates react with the in-situ produced H2 gas, or both, leading to the formation of the VAPs.

2. The electrocatalytic reactor as claimed in claim 1, wherein the concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HNO3, H3PO4.

3. The electrocatalytic reactor as claimed in claim 1, wherein the initiator mixture includes a mixture of 80% by weight of carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 20% by weight of MgO.

4. The electrocatalytic reactor as claimed in claim 1, wherein the major VAPs include ethanol, alkoxides, pentane, esters, acids, ethers, ethylene dichloride.

5. The electrocatalytic reactor as claimed in claim 1 includes one or more SS anodes, and one or more SS cathodes.

6. The electrocatalytic reactor as claimed in claim 1 includes one or more SS anodes, and one or more Cu or Cu-alloy cathodes.

7. A method of electrochemical conversion of carbon dioxide (CO2) into value- added products (VAPs) comprising:- adding deionised water to an electrocatalytic reactor vessel and dipping electrodes in the deionised water, wherein the electrodes include Stainless Steel (SS), or Copper (Cu) or Copper alloy (Cu-alloy), wherein one or more anode is an SS electrode;- adding a catalyst initiator to the deionised water in the reactor vessel forming an initiator solution;- purging CO2 into the initiator solution from an external CO2 source;- applying external current of 5 to 10 A to the electrodes in a voltage range of 3 to 10 V; and- adding a concentrated acid to the initiator solution in the reactor vessel with constant stirring to form an acidified solution, which produces H2 gas in-situ from the acidified deionised water on the cathode surface, and produces CO2 gas in-situ through the reaction of initiator and the acid; wherein the applied current density initiates the reaction of asymmetric C-C coupling of CO2 molecules on the cathode surface forming short-lived cation radical intermediates, wherein the short-lived cation radical intermediates react among themselves, or the short-lived cation radical intermediates react with the in-situ produced H2 gas, or both, forming organic acid anions and alkoxides, wherein, on the anode, the organic acid anions and alkoxides undergo hydrolysis to form acid or alcohol, esters or ethers, wherein, the acids or alcohols or esters or ethers or hydrocarbons or salts formed are distilled at appropriate temperature to form the value-added products (VAPs) in its purest form.

8. The method of electrochemical conversion as claimed in claim 7, wherein the concentrated acid added to the initiator solution in the reactor vessel is selected from HC1, H2SO4, HN03, H3PO4.

9. The method of electrochemical conversion as claimed in claim 7, wherein the initiator mixture includes a mixture of 80% by weight of carbonates or bicarbonates of Mg or Na or a combination of carbonates and bicarbonates of Mg and Na with 20% by weight of MgO.

10. The method of electrochemical conversion as claimed in claim 7, wherein the rate of flow of CO2 purging is between 150 ml / min to 500 ml / min.

11. The method of electrochemical conversion as claimed in claim 7, wherein the application of the current density is continued for 3 to 5 hours.

12. The method of electrochemical conversion as claimed in claim 7, wherein the major VAPs produced include ethanol, alkoxides, pentane, esters, acids, ethers, ethylene dichloride.

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