A spontaneous working battery based on glucose oxidation coupled with hydrogen production and application thereof

Abstract

The application belongs to the technical field of water electrolysis and glucose electrooxidation, and discloses a spontaneous working battery based on glucose oxidation coupled hydrogen production and application thereof. The spontaneous working battery comprises an anode electrolyte and a cathode electrolyte. The anode chamber electrolyte is an alkaline glucose solution, and the cathode chamber electrolyte is an acid solution. The battery adopts an asymmetric pH design, so that the energy difference caused by the different chemical potentials of the anode chamber and the cathode chamber and the chemical energy of glucose oxidation can provide power for anode glucose oxidation and cathode HER, so that hydrogen is spontaneously produced in the cathode, glucose is spontaneously electrooxidized in the anode, and an external voltage is output.

Description

Technical Field

[0001] This invention belongs to the technical fields of water electrolysis and glucose electrooxidation, and more specifically, relates to a self-generating battery based on glucose oxidation coupled with hydrogen production and its application. Background Technology

[0002] With the energy crisis and environmental problems becoming increasingly severe, the search for new renewable and clean energy sources is urgently needed. Hydrogen energy, as one of the simplest and most abundant energy sources on Earth, has attracted considerable attention. Hydrogen gas has high energy density and is pollution-free, making it considered one of the most promising renewable and clean energy sources. Currently, the biggest challenge limiting the large-scale application of hydrogen energy lies in the cost and energy consumption of the hydrogen production process. The water electrolysis reaction consists of the oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode. However, due to the high theoretical potential of the anode OER (1.23V), conventional water electrolysis devices typically operate at 100mA / cm². 2 At current densities, hydrogen production requires voltages above 1.8V, making it difficult to generate effective profits.

[0003] In addition, current organic oxidation coupling hydrogen production schemes all require an input voltage of 0.4V or higher, which still results in a large amount of energy consumption. Summary of the Invention

[0004] To address the aforementioned deficiencies or improvement needs of existing technologies, this invention provides a self-generating battery based on glucose oxidation coupled with hydrogen production and its application. The battery employs an asymmetric pH design, which utilizes the energy difference caused by the difference in chemical potential between the anode and cathode chambers, as well as the chemical energy of glucose oxidation, to power the glucose oxidation at the anode and the hydrogen generation at the cathode. This results in spontaneous hydrogen production at the cathode and the anode spontaneously and selectively converting glucose into high-value-added gluconic acid while simultaneously outputting electrical energy.

[0005] This invention provides a self-generating battery for hydrogen production based on glucose oxidation coupling. The self-generating battery includes an anode electrolyte and a cathode electrolyte. The anode electrolyte is an alkaline glucose solution, and the cathode electrolyte is an acidic solution.

[0006] Furthermore, the electrolyte in the anode chamber is obtained by dissolving 0.1 mol / L to 0.5 mol / L glucose in a NaOH solution with a concentration of 0.5 mol / L to 4 mol / L.

[0007] Furthermore, the electrolyte in the anode chamber is obtained by dissolving 0.1 mol / L glucose in a 1 mol / L NaOH solution.

[0008] Furthermore, the electrolyte in the cathode chamber is an H2SO4 solution with a concentration of 0.2 mol / L to 2 mol / L.

[0009] Furthermore, the electrolyte in the cathode chamber is a 0.5 mol / L H2SO4 solution.

[0010] Furthermore, the self-generating battery includes an electrolytic cell, a proton exchange membrane, an anode electrode plate, and a cathode electrode plate. The proton exchange membrane is disposed within the electrolytic cell, dividing the electrolytic cell into an anode chamber and a cathode chamber. The electrolyte in the anode chamber and the electrolyte in the cathode chamber are respectively disposed within the anode chamber and the cathode chamber. The anode electrode plate and the cathode electrode plate are respectively disposed within the anode chamber and the cathode chamber.

[0011] Furthermore, the anode electrode sheet includes an anode catalyst, the cathode electrode sheet includes a cathode catalyst, and both the anode catalyst and the cathode catalyst are noble metal catalysts supported on carbon.

[0012] Furthermore, both the anode catalyst and the cathode catalyst are Au, Pt, or AuPt alloy catalysts supported on carbon, wherein the atomic content of Au in the AuPt alloy catalyst is 20% to 80%, and the atomic content of Pt is 20% to 80%.

[0013] This invention also provides a method for preparing a spontaneously operating cell based on glucose oxidation coupling for hydrogen production as described above, wherein the proton exchange membrane of the spontaneously operating cell needs to undergo the following treatment:

[0014] (1) Place the proton exchange membrane in 3-5% vol H2O2 and treat it at 70℃~80℃ for 2-3 hours, then remove and wash it;

[0015] (2) The proton exchange membrane washed in step (1) is placed in an H2SO4 solution with a concentration of 0.1 mol / L to 1 mol / L and treated at a temperature of 70℃ to 80℃ for 2h to 3h. After removal, it is washed to obtain the proton exchange membrane.

[0016] The present invention also provides an application of the self-operating cell based on glucose oxidation coupled to hydrogen production as described above in water electrolysis for hydrogen production and glucose electrooxidation.

[0017] In summary, compared with the prior art, the spontaneously operating battery based on glucose oxidation coupling for hydrogen production and its application provided by this invention mainly have the following advantages:

[0018] Beneficial effects:

[0019] 1. The self-generating working cell for glucose oxidation coupled with hydrogen production provided by this invention adopts an asymmetric pH design. The working principle is to use the energy difference (0.814V) caused by the difference in chemical potential between the anode and cathode, as well as the chemical energy of glucose oxidation, to power the glucose oxidation at the anode and the hydrogen generation at the cathode. Thus, hydrogen is spontaneously produced at the cathode, glucose is spontaneously electro-oxidized at the anode, and voltage is output to the outside.

[0020] 2. This invention exhibits high selectivity for the electro-oxidation of glucose due to the use of an AuPt alloy catalyst supported on carbon at the anode, which can catalyze the oxidation of glucose to the high-value product gluconic acid at low voltage. Therefore, the Faraday efficiency of this battery for producing gluconic acid is 60%–95%.

[0021] 3. Compared to traditional glucose oxidation coupled hydrogen production electrolyzers, which require input voltage and thus consume a lot of energy, the self-operating battery for glucose oxidation coupled hydrogen production provided by this invention utilizes the chemical potential difference between the asymmetric pH electrolytes of the cathode and anode to control the system's function, thereby achieving spontaneous hydrogen production at the cathode and spontaneous oxidation of glucose to gluconic acid at the anode, while simultaneously outputting voltage.

[0022] 4. Compared to traditional glucose fuel cells, whose cathode is an oxygen reduction reaction, the self-generating cell for glucose oxidation coupled with hydrogen production provided by this invention has a hydrogen evolution reaction at the cathode, which can produce hydrogen gas with usable value.

[0023] 5. The self-generating cell based on glucose oxidation coupled with hydrogen production provided by this invention can be applied to hydrogen production through water electrolysis and glucose electrooxidation, with a corresponding operating current density range of 0–70 mA / cm². 2 The output voltage range is 0–0.65V, and the power density range is 0–10mW / cm². 2 .

[0024] 6. The preparation method of the AuPt alloy catalyst supported on carbon in the spontaneous working cell based on glucose oxidation coupling hydrogen production in this invention is simple and suitable for industrial promotion. Attached Figure Description

[0025] Figure 1 This is an X-ray diffraction pattern of the AuPt alloy catalyst supported on carbon in Example 1 of the present invention;

[0026] Figure 2 This is a transmission electron microscope image of the AuPt alloy catalyst supported on carbon in Example 1 of the present invention;

[0027] Figure 3 This is a cyclic voltammetry curve of the AuPt alloy catalyst supported on carbon in the alkaline medium during the glucose oxidation reaction in Example 1 of the catalytic performance test of this invention.

[0028] Figure 4 This is a polarization curve of the hydrogen evolution reaction of the AuPt alloy catalyst supported on carbon in acidic medium in Example 1 of the catalytic performance test of the present invention.

[0029] Figure 5 This is a schematic diagram of the operation of the battery electrolysis hydrogen production and glucose oxidation of the present invention;

[0030] Figure 6 This is a battery discharge voltage-time graph from Embodiment 1 of the present invention, wherein the discharge current density is 5 mA·cm⁻¹. -2 The test temperature was 25℃.

[0031] Figure 7 This is a battery discharge voltage-time diagram of Embodiment 1 of the present invention, wherein the discharge current density is 10 mA·cm. -2 The test temperature was 25℃.

[0032] Figure 8 The power density curve of the battery in Example 1 of the present invention was obtained at a test temperature of 25°C.

[0033] Figure 9 This is the battery anode gluconate Faraday efficiency test curve of Example 1 of the present invention;

[0034] Figure 10 This is the electrolytic cell potential-time diagram for Comparative Example 1 of the present invention, where the test current is 10 mA·cm. -2 The test temperature was 25℃. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. Furthermore, the technical features involved in the various embodiments of this invention described below can be combined with each other as long as they do not conflict with each other.

[0036] This invention provides a self-generating cell for hydrogen production based on glucose oxidation coupled with hydrogen production. The self-generating cell couples an alkaline glucose electro-oxidation reaction catalyzed by an AuPt alloy catalyst with an acidic hydrogen evolution reaction (HER). The energy required for the reaction is provided by the potential difference created by the pH asymmetry between the anode and cathode, thereby achieving high-value gluconic acid output at the anode and spontaneous hydrogen production at the cathode, while simultaneously outputting voltage. Specifically, replacing the oxygen evolution reaction (OER) with the glucose reaction (0.05V) at the anode, which has a low theoretical reaction potential, can significantly reduce the energy consumption for hydrogen production. Glucose is derived from biomass and costs approximately 1800-2000 RMB / ton. The electrochemical oxidation of glucose to produce gluconic acid is a raw material for the production of biopolymers and pharmaceuticals, costing approximately 7700-8000 RMB / ton, demonstrating good economic benefits. Therefore, using the glucose electro-oxidation reaction to replace the oxygen evolution reaction coupled with HER has significant application prospects.

[0037] Please see Figure 5 The self-generating battery includes an electrolytic cell, a proton exchange membrane, an anode electrode, a cathode electrode, an anode electrolyte, and a cathode electrolyte. The proton exchange membrane is disposed within the electrolytic cell, dividing the electrolytic cell into an anode chamber and a cathode chamber. The anode electrolyte and the cathode electrolyte are respectively disposed within the anode chamber and the cathode electrolyte, respectively. The anode electrode and the cathode electrode are respectively disposed within the anode chamber and the cathode chamber, respectively.

[0038] The anode electrode includes an anode catalyst, and the cathode electrode includes a cathode catalyst. Both the anode and cathode catalysts are noble metal catalysts supported on carbon. Preferably, both the anode and cathode catalysts are AuPt alloy catalysts supported on carbon, wherein the Au atomic content and Pt atomic content of the AuPt alloy catalyst are 20%–80%. The loading amount of the noble metal alloy on carbon is 10–30 wt%.

[0039] The electrolyte in the anode chamber is an alkaline glucose solution, and the electrolyte in the cathode chamber is an acidic solution. In this embodiment, the electrolyte in the anode chamber is obtained by dissolving 0.1–0.5 mol of glucose in a NaOH solution with a concentration of 0.5–4 mol / L. Preferably, the electrolyte in the anode chamber is obtained by dissolving 0.1 mol / L of glucose in a NaOH solution with a concentration of 1 mol / L. The electrolyte in the cathode chamber is an H₂SO₄ solution with a concentration of 0.2–2 mol / L. Preferably, the electrolyte in the cathode chamber is an H₂SO₄ solution with a concentration of 0.5 mol / L.

[0040] This invention also provides a method for preparing a spontaneously working battery based on glucose oxidation coupling for hydrogen production as described above. The AuPt alloy catalyst supported on carbon is prepared by an aqueous phase reduction method, specifically: HAuCl4·3H2O (10–15 mg / mL) and H2PtCl6·6H2O (12.5–20 mg / mL) are dissolved in 120–150 mL of deionized water and stirred until homogeneous. Then, polyvinyl alcohol (90–120 mg) is added to the solution and stirred until homogeneous. Immediately afterwards, 10–20 mL of a 0.1–0.2 mol / L NaBH4 solution is added for reduction, with a reduction time of 20–40 min. Finally, 0.4–0.6 g of carbon support is added to the solution and stirred thoroughly for 20–40 min. The resulting mixture is filtered with deionized water and dried at 90–110 °C for 20–40 min.

[0041] The proton exchange membrane is treated by the following method:

[0042] (1) Place the proton exchange membrane in 3-5% vol H2O2 and treat it at 70-80℃ for 2-3 hours, then remove and wash it;

[0043] (2) The proton exchange membrane washed in step (1) is placed in an H2SO4 solution with a concentration of 0.1-1 mol / L and treated at 70-80℃ for 2-3 hours. After washing, the membrane is obtained.

[0044] This invention also provides an application of the self-generating battery based on glucose oxidation coupled to hydrogen production, as described above, in water electrolysis for hydrogen production and glucose electrooxidation. The battery can simultaneously produce hydrogen at the cathode and gluconic acid at the anode while outputting voltage, and its operating current density ranges from 0 to 70 mA / cm². 2 The output voltage range is 0–0.65V, and the power density range is 0–10mW / cm². 2 The Faraday efficiency for the production of gluconic acid at the anode is 60–95%.

[0045] The present invention will be further described in detail below with reference to embodiments.

[0046] Example 1

[0047] In the embodiments of this invention, all raw materials were purchased commercially and used directly without processing; the testing conditions of the instruments all adopted the parameters recommended by the manufacturer.

[0048] In this embodiment, the proton exchange membrane was purchased from DuPont, USA.

[0049] In this example, glucose was purchased from Inocare.

[0050] In the examples, the samples were characterized using X-ray diffraction (XRD) analysis with a DMAX-2400X.

[0051] In the examples, the transmission electron microscope (TEM) images of the samples were characterized using a FEI Tecani G2 20.

[0052] In the examples, the polarization curves and cyclic voltammetry curves of the samples were obtained by an electrochemical workstation (CHI760E) from Shanghai Chenhua Co., Ltd.

[0053] This embodiment 1 provides a self-generating cell based on glucose oxidation coupling for hydrogen production, and its preparation method includes the following steps:

[0054] (1) The preparation of AuPt alloy catalyst supported on carbon includes the following sub-steps:

[0055] Dissolve HAuCl4·3H2O (10 mg / mL) and H2PtCl6·6H2O (12.5 mg / mL) in 120 mL of deionized water and stir until homogeneous. Then, add polyvinyl alcohol (90 mg) to the solution and stir until homogeneous. Immediately afterwards, add 10 mL of 0.15 mol / L NaBH4 solution for reduction, which takes 30 min. Finally, add 0.5 g of carbon support to the solution and stir thoroughly for 30 min. Filter and wash the resulting mixture with deionized water and dry at 90 °C for 30 min.

[0056] (2) The proton exchange membrane is treated by the following methods:

[0057] First, the proton exchange membrane was placed in 3% vol H2O2 and treated at 70°C for 2 hours, then removed and washed.

[0058] Then, the washed membrane was placed in a 0.5 mol / L H2SO4 solution and treated at 70°C for 2 h. After removal, it was washed to obtain the proton exchange membrane.

[0059] (3) According to Figure 5 As shown, a glucose oxidation-coupled hydrogen production battery is assembled.

[0060] AuPt alloy catalysts supported on carbon were used as anode and cathode catalysts, respectively, for glucose electro-oxidation and hydrogen evolution reactions.

[0061] The diaphragm is a proton exchange membrane. The anode and cathode chambers are separated by the proton exchange membrane, which contains the anolyte and the catholyte, respectively. The anode chamber electrolyte is a mixture of 1 mol / L NaOH solution and 0.1 mol / L glucose. The cathode chamber electrolyte is a 0.5 mol / L H₂SO₄ solution.

[0062] After assembling into an electrolytic cell, the anolyte and catholyte are injected into the anode chamber and cathode chamber respectively through a peristaltic pump to obtain a glucose oxidation-coupled hydrogen production self-generating battery.

[0063] Comparative Example 1

[0064] This comparative example provides a conventional glucose oxidation-coupled hydrogen production electrolyzer.

[0065] Commercial Pt / C catalysts were used as anode and cathode catalysts, respectively.

[0066] Electrolyte in the anode chamber: 1 mol / L NaOH solution + 0.1 mol / L glucose.

[0067] Electrolyte in the cathode chamber: 1 mol / L NaOH solution.

[0068] Results and Analysis:

[0069] The AuPt alloy catalyst supported on carbon in Example 1 was characterized.

[0070] X-ray diffraction analysis was performed on the AuPt alloy catalyst supported on carbon. Figure 1 The XRD pattern shows that the diffraction peaks of the AuPt alloy catalyst on carbon prepared in Example 1 are shifted to a certain extent compared with the standard PDF cards of Au and Pt, indicating the formation of AuPt alloy.

[0071] The catalyst of the AuPt alloy supported on carbon prepared in Example 1 was analyzed by transmission electron microscopy. Figure 2 The catalyst of the prepared AuPt alloy supported on carbon consists of particles with a particle size of about 3-4 nm, which are uniformly dispersed on carbon.

[0072] The AuPt alloy catalyst supported on carbon prepared in Example 1 was tested for its glucose electro-oxidation performance in a 1 mol / L NaOH solution + 0.1 mol / L glucose solution. Comparative samples were commercial Pt / C and Au / C. The results are as follows: Figure 3 As shown, AuPt alloy catalysts have significant advantages over commercial Pt / C and Au / C catalysts in terms of current density and onset potential.

[0073] The HER performance of the AuPt alloy catalyst supported on carbon prepared in Example 1 was tested in a 0.5 mol / L H2SO4 solution. The results are as follows: Figure 4 As shown, the AuPt alloy catalyst exhibits certain advantages over commercial Pt / C in HER performance in a 0.5 mol / L H2SO4 solution.

[0074] The glucose oxidation-coupled hydrogen production battery of Example 1 of this invention was subjected to a discharge test, wherein the discharge current density was 5 mA / cm². 2 The test temperature was 25℃, and the results were as follows: Figure 6 As shown. The current density is 5 mA / cm². 2 At that time, the battery's initial discharge voltage is 0.52V, and it can discharge for up to 8 hours, achieving hydrogen production at the cathode and high-value gluconic acid production at the anode.

[0075] The glucose oxidation-coupled hydrogen production battery of Example 1 of this invention was subjected to a discharge test, wherein the discharge current density was 10 mA / cm². 2 The test temperature was 25℃, and the results were as follows: Figure 7 As shown. The current density is 10 mA / cm². 2 At that time, the battery's initial discharge voltage is 0.45V, and it can discharge for up to 4.5 hours, achieving hydrogen production at the cathode and high-value gluconic acid production at the anode.

[0076] The power density of the glucose oxidation coupled hydrogen production battery of Example 1 of this invention was tested at a temperature of 25°C, and the results are as follows. Figure 8 As shown. The battery's operating current density range is 0–70 mA / cm². 2 The output voltage range is 0–0.65V, and the power density range is 0–10mW / cm². 2 .

[0077] The Faraday efficiency of the glucose oxidation to gluconic acid anode in the glucose oxidation coupled hydrogen production battery of Example 1 of this invention was tested at a test current of 10 mA / cm. 2 The result is as follows Figure 9 As shown, the Faraday efficiency for the production of gluconic acid at the anode is around 80%.

[0078] The conventional glucose oxidation-coupled hydrogen production electrolyzer of Comparative Example 1 was tested at a test current of 10 mA / cm. 2 The test temperature was 25℃, and the results were as follows: Figure 10 As shown. This electrolytic cell requires an input voltage of 0.6V or higher to drive it at 10mA / cm. 2 Compared to other batteries that operate at higher current densities, the self-generating battery of this invention has a significant advantage in terms of energy consumption.

[0079] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A self-generating battery based on glucose oxidation coupling for hydrogen production, characterized in that: The self-contained working battery includes an anode electrolyte and a cathode electrolyte. The anode electrolyte is an alkaline glucose solution, and the cathode electrolyte is an acidic solution. The anode electrolyte is obtained by dissolving 0.1 mol / L to 0.5 mol / L glucose in a 0.5 mol / L to 4 mol / L NaOH solution. The cathode electrolyte is a 0.2 mol / L to 2 mol / L H2SO4 solution. The self-generating battery includes an electrolytic cell, a proton exchange membrane, an anode electrode, and a cathode electrode. The proton exchange membrane is disposed within the electrolytic cell, dividing the electrolytic cell into an anode chamber and a cathode chamber. The electrolyte in the anode chamber and the electrolyte in the cathode chamber are respectively disposed within the anode chamber and the cathode chamber. The anode electrode and the cathode electrode are respectively disposed within the anode chamber and the cathode chamber. The anode electrode includes an anode catalyst, and the cathode electrode includes a cathode catalyst. Both the anode catalyst and the cathode catalyst are AuPt alloy catalysts supported on carbon.

2. The self-generating battery based on glucose oxidation coupling for hydrogen production as described in claim 1, characterized in that: The electrolyte in the anode chamber is obtained by dissolving 0.1 mol / L glucose in a 1 mol / L NaOH solution.

3. The self-generating battery based on glucose oxidation coupling for hydrogen production as described in claim 2, characterized in that: The electrolyte in the cathode chamber is a 0.5 mol / L H2SO4 solution.

4. The self-generating battery based on glucose oxidation coupling for hydrogen production as described in claim 1, characterized in that: The atomic content of Au in AuPt alloy catalysts is 20%~80%, and the atomic content of Pt is 20%~80%.

5. A method for preparing a spontaneously operating cell based on glucose oxidation coupling for hydrogen production as described in any one of claims 1-4, characterized in that: The proton exchange membrane of the self-operating cell needs to undergo the following treatment: (1) Place the proton exchange membrane in 3-5% vol H2O2 and treat it at 70℃~80℃ for 2-3 h, then remove and wash it; (2) The proton exchange membrane washed in step (1) is placed in an H2SO4 solution with a concentration of 0.1mol / L to 1mol / L and treated at a temperature of 70℃ to 80℃ for 2 h to 3 h. After removal, it is washed to obtain the proton exchange membrane.

6. The application of the spontaneously operating cell based on glucose oxidation coupled to hydrogen production as described in any one of claims 1-4 in water electrolysis for hydrogen production and glucose electrooxidation.

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