A method for electrochemical oxidation of glycerol to produce formic acid coupled with hydrogen production

Abstract

This invention belongs to the field of hydrogen production technology, specifically relating to a method for the electrochemical oxidation of glycerol to produce formic acid coupled with hydrogen production. The invention includes the following steps: Step 1: Preparing an electrolyte comprising: 0.1 mol / L to 2.0 mol / L soluble perchlorate; 1.5 mol / L to 2.5 mol / L soluble strong base; and 0.05 mol / L to 0.15 mol / L glycerol; Step 2: Assembling an electrolytic cell; Step 3: Connecting the assembled electrolytic cell to an electrochemical workstation; Step 4: Placing the electrolyte prepared in Step 1 into the assembled electrolytic cell in Step 2, and setting the hydrogen evolution parameters through the electrochemical workstation to perform the electrocatalytic hydrogen production reaction. By precisely controlling the intermediates of the glycerol electrocatalytic oxidation reaction using perchlorate ions, the generation of byproducts such as oxalic acid and glycolic acid is effectively suppressed, avoiding the drawbacks of complex products in traditional systems. This highly directs the glycerol reaction pathway towards formic acid production, thereby obtaining high-purity, high-Faraday-efficiency formic acid at the anode; while maintaining efficient hydrogen production at the cathode.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen production technology, specifically relating to a method for producing hydrogen by electrochemical oxidation of glycerol to produce formic acid coupled with hydrogen production. Background Technology

[0002] Currently, the main method for producing green hydrogen is water electrolysis using renewable energy. However, this method is limited by the relatively high energy input and low efficiency of the oxygen evolution reaction (OER) at the anode. Furthermore, the produced oxygen has limited industrial value, leading to a certain degree of energy waste. To overcome these limitations, researchers have proposed replacing the OER at the anode with the oxidation reaction of biomass. Biomass is mostly composed of polyols or sugars, which require less energy and can convert biomass molecules into high-value-added chemicals, thus achieving resource utilization of the anode products. Simultaneously, hydrogen can still be produced at the cathode, improving the overall energy and economic benefits of the system.

[0003] Glycerol, a typical triol, has a higher hydrogen content per molecule than water, giving it greater hydrogen production potential and making it an ideal feedstock for anodic replacement reactions. In particular, crude glycerol is a byproduct of biodiesel production; approximately one ton of crude glycerol is generated for every 10 tons of biodiesel produced, with a global annual output exceeding 4 million tons. Due to high purification costs and low quality, crude glycerol is mainly used for combustion, animal feed, or as waste, resulting in low utilization rates. Therefore, using crude glycerol in the electrolytic hydrogen production process can optimize hydrogen production efficiency and provide a feasible path for the high-value conversion of crude glycerol.

[0004] Among the various products generated by glycerol oxidation, formic acid has attracted much attention due to its wide range of industrial applications and potential energy value. Formic acid is not only an important chemical raw material for industries such as leather, textiles, and rubber, but also a key precursor for the synthesis of formate, oxalic acid, and pharmaceutical intermediates. Simultaneously, as an ideal liquid hydrogen carrier, formic acid can achieve reversible hydrogen storage and release at ambient temperature and pressure, demonstrating significant strategic prospects in fuel cells and clean energy systems. However, the glycerol electro-oxidation reaction (GOR) pathway is complex, potentially generating multiple oxidation products including formic acid, oxalic acid, glycolic acid, and dihydroxyacetone. The selectivity of these products is significantly influenced by multiple factors, including catalyst composition, electrolyte type, and electrolysis conditions. Therefore, developing an efficient and targeted electrolysis system for formic acid production, and achieving highly selective control of the glycerol oxidation process, is of great significance for improving the Faraday efficiency of formic acid, promoting the resource utilization of glycerol, and the co-production of green hydrogen. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies, such as complex glycerol electro-oxidation reaction pathways, poor formic acid selectivity, low Faraday efficiency, and difficulty in directly utilizing crude glycerol for high-value conversion. This invention provides a method for electrochemical oxidation of glycerol to produce formic acid coupled with hydrogen production by introducing perchlorate ions into the electrolyte to directionally regulate the glycerol reaction pathway.

[0006] The technical solution adopted by this invention to solve its technical problem is:

[0007] A method for producing formic acid from glycerol via electrochemical oxidation coupled with hydrogen production includes the following steps:

[0008] Step 1: Prepare the electrolyte, wherein the electrolyte comprises:

[0009] Soluble perchlorate at concentrations of 0.1 mol / L to 2.0 mol / L;

[0010] Soluble strong bases ranging from 1.5 mol / L to 2.5 mol / L;

[0011] And, glycerol at concentrations of 0.05 mol / L to 0.15 mol / L;

[0012] Step 2: Assemble the electrolytic cell, using the conductive substrate with the anode catalyst as the anode and the conductive substrate with the cathode catalyst as the cathode.

[0013] Step 3: Connect the assembled electrolytic cell to the electrochemical workstation for data transfer;

[0014] Step 4: Place the electrolyte prepared in Step 1 into the electrolytic cell assembled in Step 2, and set the hydrogen evolution parameters through the electrochemical workstation to carry out the electrocatalytic hydrogen production reaction; during hydrogen production, perchlorate ions at the anode react with glycerol in an electrochemical catalytic oxidation to produce formic acid, and hydrogen is obtained at the cathode.

[0015] Specifically, the electrocatalytic hydrogen production reaction at the anode in the electrolyzer in step four includes the following:

[0016] Glycerol undergoes electrocatalytic oxidation to produce C2 and C3 aldehyde intermediates;

[0017] The perchlorate ions in the electrolyte weaken the hydrogen bonds attached to the C2 and C3 aldehyde intermediates;

[0018] The carbon chains in C2 and C3 aldehyde intermediates are broken to generate formic acid solution, which is collected at the anode.

[0019] Specifically, the formic acid solution collected at the anode has a Faraday efficiency of 65% to 95%.

[0020] Specifically, the soluble perchlorate is one or a mixture of two of lithium perchlorate and sodium perchlorate.

[0021] Specifically, the soluble strong base is one or a mixture of two of potassium hydroxide and sodium hydroxide.

[0022] Specifically, both the soluble perchlorate and the soluble strong base meet the analytical purity standard, wherein the purity of the soluble perchlorate is greater than or equal to AR.99%.

[0023] Specifically, the anode catalyst is nickel hydroxide; the cathode catalyst is platinum.

[0024] Specifically, the hydrogen evolution parameters include mode parameters, electrocatalytic potential, current density, and electrolysis time;

[0025] The mode parameters include constant potential mode and constant current mode.

[0026] Specifically, the mode parameters adopt a constant potential mode, the electrocatalytic potential is 1.40V to 1.52V, the current density is controlled at 30mA·cm² to 120mA·cm², and the electrolysis time is set to 1h to 6h according to the glycerol conversion rate.

[0027] Specifically, the electrolytic cell is an H-type electrolytic cell, which includes an anode cell, a cathode cell, and an ion exchange membrane disposed between the anode cell and the cathode cell.

[0028] The beneficial effects of the electrochemical oxidation of glycerol to formic acid coupled with hydrogen production according to the present invention are:

[0029] In this invention, the electrolyte contains 0.1 mol / L to 2.0 mol / L of soluble perchlorate, 1.5 mol / L to 2.5 mol / L of soluble strong base, and 0.05 mol / L to 0.15 mol / L of glycerol. By flexibly adjusting the ratio of perchlorate, strong base, and glycerol in the electrolyte, and combining it with specific electrocatalytic oxidation conditions, the electrolyte exhibits excellent formic acid selectivity in the electrocatalytic reaction, significantly improving the Faraday efficiency and avoiding current waste on non-target side reactions, thereby greatly reducing the unit energy consumption for formic acid and hydrogen production. By adding soluble perchlorate to the electrolyte, the unique polarization effect of perchlorate ions effectively weakens the hydrogen bond constraints on C2 and C3 aldehyde intermediates generated during the electrooxidation of glycerol, promoting the selective breaking of their carbon-carbon bonds. This method utilizes perchlorate ions to precisely control the intermediates in the electrocatalytic oxidation of glycerol, effectively suppressing the formation of byproducts such as oxalic acid and glycolic acid. This not only avoids the drawbacks of complex products in traditional systems but also highly directs the reaction pathway towards the formation of formic acid, thereby obtaining a high-purity, high-faradaic-efficiency formic acid solution at the anode. Simultaneously, it maintains efficient hydrogen production at the cathode, achieving the simultaneous production of formic acid and hydrogen energy. Attached Figure Description

[0030] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0031] Figure 1 This is a flowchart of the electrochemical oxidation of glycerol to produce formic acid coupled with hydrogen production method of the present invention;

[0032] Figure 2 This is a comparison diagram of the decomposition process of glycerol in the prior art and in this invention.

[0033] Figure 3 This is a comparison diagram of the reaction pathway for the conversion of glycerol to formic acid in the prior art and the reaction pathway of this application.

[0034] Figure 4 This is a schematic diagram showing the Faraday efficiency and concentration of formic acid prepared using the method of this invention over six hours.

[0035] Figure 5 These are schematic diagrams illustrating the formic acid Faraday efficiency generated in Embodiments 1 to 4 of the present invention and in Comparative Example 1.

[0036] Figure 6 This is a schematic diagram comparing the overpotentials of glycerol-free, 0.1 mol / L crude glycerol, and 0.1 mol / L refined glycerol under a current density of 10 mA / cm² in Example 5 of the present invention.

[0037] Figure 7 A schematic diagram comparing the Faraday efficiency of crude glycerol and refined glycerol in the production of formic acid within 48 hours in Example 6 of this invention.

[0038] Figure 8 This is a comparison of the Raman spectra of the electrolyte of this invention and the electrolyte without added perchlorate.

[0039] Figure 9 This is a comparison of in-situ infrared spectra of the electrolyte using the present invention and the electrolyte without added perchlorate. Detailed Implementation

[0040] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0041] like Figures 1-9 A specific embodiment of the method for producing formic acid from glycerol coupled with hydrogen production according to the present invention is shown, comprising the following steps:

[0042] Step 1: Prepare the electrolyte, wherein the electrolyte comprises:

[0043] Soluble perchlorate at concentrations of 0.1 mol / L to 2.0 mol / L;

[0044] Soluble strong bases ranging from 1.5 mol / L to 2.5 mol / L;

[0045] And, glycerol at concentrations of 0.05 mol / L to 0.15 mol / L;

[0046] Step 2: Assemble the electrolytic cell, using the conductive substrate with the anode catalyst as the anode and the conductive substrate with the cathode catalyst as the cathode.

[0047] Step 3: Connect the assembled electrolytic cell to the electrochemical workstation for data transfer;

[0048] Step 4: Place the electrolyte prepared in Step 1 into the electrolytic cell assembled in Step 2, and set the hydrogen evolution parameters using an electrochemical workstation to carry out the electrocatalytic hydrogen production reaction. During hydrogen production, perchlorate ions at the anode react with glycerol in an electrochemical catalytic oxidation process to produce formic acid, and hydrogen gas is obtained at the cathode. After preparation, the formic acid solution at the anode is extracted, and the hydrogen gas obtained at the cathode is collected and stored.

[0049] It should be understood that the electrolyte in step one requires the following steps during preparation:

[0050] S101. Prepare the raw materials, ensuring that all raw materials except glycerol meet analytical purity or higher, and store and protect the prepared raw materials. It should be emphasized that the purity of the soluble perchlorate in this embodiment is greater than or equal to AR.99%. By ensuring the high purity of the raw materials, the efficiency of preparing high-quality sensors can be improved. Storage and protection measures prevent contamination and deterioration of materials during the preparation process, ensuring the smooth progress of subsequent steps.

[0051] S102. Accurately calculate and weigh the required materials as needed, and prepare deionized water. Using deionized water as a solvent is beneficial for the dissolution of raw materials and the progress of the reaction.

[0052] S103. Add the weighed solid material to deionized water, mix and stir to form a stable and uniform electrolyte. Thorough stirring ensures the raw materials are uniformly dispersed in the solvent, avoiding uneven reaction caused by excessively high or low local concentrations, and providing favorable conditions for subsequent electrocatalysis.

[0053] It should be further noted that the soluble perchlorate in this embodiment is one or a mixture of two of potassium perchlorate and sodium perchlorate, and the soluble strong alkali is one or a mixture of two of potassium hydroxide and sodium hydroxide. Those skilled in the art can make the selection based on usage requirements and available materials.

[0054] The electrolytic cell in step two is an H-type electrolytic cell, which includes an anode cell, a cathode cell, and an ion exchange membrane disposed between the anode cell and the cathode cell. In order to balance the charge accumulation caused by the continuous consumption of electrons at the cathode and the continuous generation of electrons at the anode cell, cations migrate from the anode cell to the cathode cell through the ion exchange membrane, thereby closing the circuit and allowing the reaction to proceed continuously and stably.

[0055] In step three, the electrolytic cell is connected to the electrochemical workstation. Specifically, the anode is connected to the working electrode clamp of the electrochemical workstation, the cathode to the counter electrode clamp, and the reference electrode to the reference electrode clamp. The anode of the electrolytic cell is connected to the working electrode clamp. The electrochemical workstation can precisely control the anode potential, ensuring that the reaction proceeds under optimal thermodynamic and kinetic conditions. This avoids excessively high potentials that could trigger oxygen evolution side reactions, or excessively low potentials that could cause reaction stagnation, thus guaranteeing high selectivity and Faraday efficiency for formic acid. Connecting the cathode to the counter electrode clamp ensures that hydrogen can be smoothly evolved at the cathode without affecting the accurate measurement of the anode potential. After connecting the reference electrode clamp, the electrochemical workstation can monitor and provide feedback on the working electrode potential in real time. This connection method between the electrolytic cell and the electrochemical workstation achieves efficient conversion of glycerol to formic acid and stable hydrogen production at the cathode.

[0056] In one embodiment, the anode catalyst in this example is nickel hydroxide, and the cathode catalyst is platinum.

[0057] The electrocatalytic hydrogen production reaction at the anode in the electrolyzer in step four includes the following:

[0058] S401. Glycerol undergoes electrocatalytic oxidation to produce C2 and C3 aldehyde intermediates;

[0059] S402. The perchlorate ions in the electrolyte weaken the hydrogen bonds attached to the C2 and C3 aldehyde intermediates;

[0060] S403. The carbon chains in C2 and C3 aldehyde intermediates are broken to generate formic acid solution, which is collected at the anode.

[0061] Specifically, such as Figure 2 As shown in the reaction diagrams with and without perchlorate ions, it can be seen that without perchlorate ions, glycerol is oxidized on the catalyst surface, passing through aldehyde intermediates, and ultimately tends to undergo deep oxidation to produce products such as CO2. However, with the addition of perchlorate ions, under the applied potential, glycerol molecules first undergo dehydrogenation on the anode catalyst surface, generating C2 and C3 aldehyde intermediates. Perchlorate ions in the electrolyte are structurally disruptive ions, capable of entering the hydrogen bond network formed by water molecules, weakening the hydrogen bond interactions between the C2 and C3 aldehyde intermediates and water or surrounding molecules. Specifically, as shown... Figure 2 As shown, this causes the ordered water structure to become disordered.

[0062] The weakening of the hydrogen bond network alters the stability and reaction microenvironment of C2 and C3 aldehyde intermediates, promoting the selective breaking of carbon-carbon bonds. The reaction pathway follows... Figure 3 The process proceeds along the rightmost path, efficiently converting the C3 intermediate into the C1 product, formic acid, while inhibiting the formation of other C2 or C3 byproducts, such as oxalic acid and glycolic acid. The generated formic acid collects in the anode tank, achieving high Faradaic efficiency resource utilization. It is important to emphasize that the Faradaic efficiency of the generated formic acid solution is 65%–95%, depending on the potential.

[0063] It should be understood that the hydrogen evolution parameters include mode parameters, electrocatalytic potential, current density, and electrolysis time; among which, the mode parameters include constant potential mode and constant current mode. In this embodiment, the mode parameters adopt constant potential mode, the electrocatalytic potential is 1.40V to 1.52V, the current density is controlled at 30mA·cm² to 120mA·cm², and the electrolysis time is set to 1h to 6h according to the glycerol conversion rate.

[0064] Since the selectivity of formic acid is strongly dependent on the anodic potential, the constant potential mode can lock the energy state at the reaction interface in the range most favorable for carbon-carbon bond breaking to form formic acid, avoiding the reaction path deviation caused by potential fluctuations. The electrocatalytic potential is 1.40V to 1.52V, which exceeds the thermodynamic barrier of glycerol oxidation, but is significantly lower than the traditional oxygen evolution reaction potential. This makes electrons more inclined to flow to glycerol molecules rather than water molecules. After extensive data verification, below 1.40V, the reaction kinetics are slow and the glycerol conversion rate is low. Above 1.52V, it is easy to trigger a serious oxygen evolution side reaction, reducing the formic acid Faraday efficiency.

[0065] like Figure 4 The diagram illustrates the Faradaic efficiency and concentration of formic acid production over 6 hours using an electrolyte containing 0.1 mol / L sodium perchlorate and 2 mol / L sodium hydroxide under crude glycerol conditions. The Faradaic efficiency of formic acid production remains above 80% throughout the six hours, with the final formic acid concentration reaching 65 mol / L. It should be understood that the concentration of sodium hydroxide in this embodiment can also be any value from 1.5 mol / L to 2.5 mol / L, such as 1.5 mol / L, 1.6 mol / L, 1.7 mol / L, or 2.5 mol / L. These values ​​will not be listed here; only a 2 mol / L sodium hydroxide concentration is used as an example.

[0066] This embodiment, by flexibly adjusting the ratio of perchlorate, strong base, and glycerol in the electrolyte, and combining it with specific electrocatalytic oxidation conditions, enables the electrolyte to exhibit excellent formic acid selectivity in the electrocatalytic reaction, significantly improving the Faradaic efficiency and avoiding current waste on non-target side reactions, thereby greatly reducing the unit energy consumption for formic acid and hydrogen production. By adding soluble perchlorate to the electrolyte, the unique polarization effect of perchlorate ions effectively weakens the hydrogen bond constraints on C2 and C3 aldehyde intermediates generated during glycerol electrooxidation, promoting the selective breaking of their carbon-carbon bonds. In other words, by precisely controlling the intermediates of the glycerol electrocatalytic oxidation reaction using perchlorate ions, the formation of byproducts such as oxalic acid and glycolic acid is effectively suppressed. This not only avoids the drawbacks of complex products in traditional systems, but also highly directs the reaction pathway towards formic acid production, thus obtaining a high-purity, high-Faradaic-efficiency formic acid solution at the anode; simultaneously, it maintains efficient hydrogen production at the cathode, achieving simultaneous formic acid production and hydrogen energy generation.

[0067] Example 1

[0068] 0.5 mol sodium perchlorate, 2.0 mol sodium hydroxide, and 0.1 mol refined glycerol were weighed and added one by one to 1 L of deionized water, and stirred thoroughly for 30 minutes. After stirring, nickel hydroxide was used as the anode, platinum electrode as the cathode, and silver / silver chloride (saturated potassium chloride) electrode as the reference electrode. Electrocatalysis was performed at 1.52 V. Formic acid with a Faraday efficiency of 81% was obtained at the anode, and hydrogen was obtained at the cathode.

[0069] Example 2

[0070] Weigh 1.0 mol sodium perchlorate, 2.0 mol sodium hydroxide, and 0.1 mol refined glycerol and add them one by one to 1 L of deionized water. Stir thoroughly for 30 minutes. After stirring, use nickel hydroxide as the anode, platinum electrode as the cathode, and silver / silver chloride (saturated potassium chloride) electrode as the reference electrode. Electrocatalysis is performed at 1.52 V. Formic acid with a Faraday efficiency of 95% is obtained at the anode, and hydrogen is obtained at the cathode.

[0071] Example 3

[0072] 1.5 mol sodium perchlorate, 2.0 mol sodium hydroxide, and 0.1 mol refined glycerol were weighed and added one by one to 1 L of deionized water, and stirred thoroughly for 30 minutes. After stirring, nickel hydroxide was used as the anode, platinum electrode as the cathode, and silver / silver chloride (saturated potassium chloride) electrode as the reference electrode. Electrocatalysis was performed at 1.52 V. Formic acid with a Faraday efficiency of 79% was obtained at the anode, and hydrogen was obtained at the cathode.

[0073] Example 4

[0074] Weigh 2 mol sodium perchlorate, 2.0 mol sodium hydroxide, and 0.1 mol refined glycerol and add them one by one to 1 L of deionized water. Stir thoroughly for 30 minutes. After stirring, use nickel hydroxide as the anode, platinum electrode as the cathode, and silver / silver chloride (saturated potassium chloride) electrode as the reference electrode. Electrocatalyze at 1.52 V to obtain formic acid with a Faraday efficiency of 65% at the anode and hydrogen gas at the cathode.

[0075] Comparative Example 1

[0076] Weigh 2.0 mol sodium hydroxide and 0.1 mol refined glycerol and add them one by one to 1 L of deionized water. Do not add sodium perchlorate. Stir thoroughly for 30 minutes. After stirring, use nickel hydroxide as the anode, platinum electrode as the cathode, and silver / silver chloride (saturated potassium chloride) electrode as the reference electrode. Electrocatalyze at 1.52 V to obtain formic acid with a Faraday efficiency of 52% at the anode and hydrogen gas at the cathode.

[0077] See details Figure 2 The diagrams show a comparison of the formation of oxalic acid and formic acid in Examples 1 to 4 and Comparative Example 1. It can be clearly seen that when the soluble perchlorate specified in this invention is added to the electrolyte, the Faradaic efficiency at the anode is significantly improved, while the Faradaic efficiency of oxalic acid is significantly reduced. The Faradaic efficiency of oxalic acid at the anode is highest when the added soluble sodium perchlorate is 1.0 mol / L, and the Faradaic efficiency of oxalic acid is lowest at this point.

[0078] Example 5

[0079] When the prepared electrolyte has a sodium perchlorate concentration of 2 mol / L and a sodium hydroxide concentration of 1.0 mol / L, current density-voltage curves are tested under different conditions to evaluate the catalytic performance of the glycerol oxidation reaction. Figure 3 As shown, the blue curve represents the current density curve without glycerol, indicating the lowest overall current density. This suggests that the current density is mainly due to the oxidation of the electrolyte itself or the capacitive current. The red curve shows that the current density increases significantly after adding crude glycerol, and the voltage required at the same current density is lower, indicating that crude glycerol can effectively undergo oxidation. The purple curve shows that the current density increases even more significantly after adding pure glycerol, and the voltage required at the same current density is lower than that of crude glycerol, indicating that the oxidation reaction of pure glycerol is easier to occur and that it has better catalytic performance.

[0080] Example 6

[0081] The following comparison shows the Faradaic efficiency of formic acid formation when pure glycerol and crude glycerol are used as reactants. See details below. Figure 7 The graph shows a comparison of the continuous reaction process over 48 hours. It can be seen that although the purer the glycerol, the higher the efficiency of the formic acid produced, but the difference is not significant. Crude glycerol can be directly used in this electrolyte.

[0082] like Figure 8 The Raman spectra comparison with and without NaClO4 show that, under the condition of 0.15 mol / L glycerol without NaClO4, no obvious characteristic peaks of the reaction intermediate were observed. This indicates that in the absence of NaClO4, the concentration of the intermediate in the glycerol oxidation process is low or unstable. (See [link to relevant documentation]). Figure 8 The figure shows the addition of potassium perchlorate, using the method of this invention, under the conditions of 0.15 mol glycerol and the addition of NaClO4, with... Figure 8 Compared to the graph without potassium perchlorate, the Ni³⁺ peak shows a similar trend, but the presence of ClO⁻ alters the chemical environment on the catalyst surface, thereby regulating the reaction pathway.

[0083] See Figure 9 The comparison of in-situ infrared spectra with and without NaClO4 shows that, without NaClO4 and under conditions of 1.52V, the reaction generates a variety of oxygen-containing intermediates, resulting in poor selectivity. Using the method of this invention, under conditions of NaClO4 and 1.52V, compared with the absence of potassium perchlorate, the characteristic peaks related to formate (HCOO⁻) show significant changes. The newly appearing peaks and changes in peak intensity indicate that the addition of ClO4⁻ significantly alters the distribution of reaction intermediates, promotes the formation of formate, and improves the selectivity of the reaction.

[0084] It should be understood that the specific embodiments described above are for illustrative purposes only and are not intended to limit the scope of the invention. Obvious variations or modifications derived from the spirit of the invention are still within the protection scope of the invention.

Claims

1. A method for producing formic acid through electrochemical oxidation of glycerol coupled with hydrogen production, characterized in that, Includes the following steps: Step 1: Prepare the electrolyte, wherein the electrolyte comprises: Soluble perchlorate at concentrations of 0.1 mol / L to 2.0 mol / L; Soluble strong bases ranging from 1.5 mol / L to 2.5 mol / L; And, glycerol at concentrations of 0.05 mol / L to 0.15 mol / L; Step 2: Assemble the electrolytic cell, using the conductive substrate with the anode catalyst as the anode and the conductive substrate with the cathode catalyst as the cathode. Step 3: Connect the assembled electrolytic cell to the electrochemical workstation for data transfer; Step 4: Place the electrolyte prepared in Step 1 into the electrolytic cell assembled in Step 2, and set the hydrogen evolution parameters through the electrochemical workstation to carry out the electrocatalytic hydrogen production reaction; during hydrogen production, perchlorate ions at the anode react with glycerol in an electrochemical catalytic oxidation to produce formic acid, and hydrogen is obtained at the cathode.

2. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that, The electrocatalytic hydrogen production reaction at the anode in the electrolyzer in step four includes the following: Glycerol undergoes electrocatalytic oxidation to produce C2 and C3 aldehyde intermediates; The perchlorate ions in the electrolyte weaken the hydrogen bonds attached to the C2 and C3 aldehyde intermediates; The carbon chains in C2 and C3 aldehyde intermediates are broken to generate formic acid solution, which is collected at the anode.

3. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 2, characterized in that, The formic acid solution collected at the anode has a Faraday efficiency of 65% to 95%.

4. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that: The soluble perchlorate is one or a mixture of two of potassium perchlorate and sodium perchlorate.

5. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that: The soluble strong base is one or a mixture of two of potassium hydroxide and sodium hydroxide.

6. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that: Both the soluble perchlorate and the soluble strong base meet the analytical purity standard, wherein the purity of the soluble perchlorate is greater than or equal to AR.99%.

7. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that, The anode catalyst is nickel hydroxide; the cathode catalyst is platinum.

8. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 1, characterized in that: The hydrogen evolution parameters include mode parameters, electrocatalytic potential, current density, and electrolysis time; The mode parameters include constant potential mode and constant current mode.

9. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 6, characterized in that: The mode parameters adopt a constant potential mode, the electrocatalytic potential is 1.40V to 1.52V, the current density is controlled at 30mA·cm² to 120mA·cm², and the electrolysis time is set to 1h to 6h according to the glycerol conversion rate.

10. The method for producing formic acid by electrochemical oxidation of glycerol coupled with hydrogen production according to claim 6, characterized in that: The electrolytic cell is an H-type electrolytic cell, which includes an anode cell, a cathode cell, and an ion exchange membrane disposed between the anode cell and the cathode cell.

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