A 3D printed electrode for electrosynthesis of hydrogen peroxide and its preparation method and application

Abstract

The present invention provides a 3D printed electrode for electrosynthesis of hydrogen peroxide, and its preparation method and application, belonging to the field of electrode material technology. The present invention first designs an electrode with an ordered porous structure, and then adopts a method combining 3D printing and carbonization to prepare the ordered porous electrode. The ordered porous electrode prepared by 3D printing has a large number of hierarchical porous structures, which makes the electrode have a higher specific surface area and porosity, can provide more active sites, and can also improve the mass transfer capacity; at the same time, the electrode is carbonized to improve the catalytic activity, so that it can further improve the catalytic performance. The 3D printing method of the present invention can easily print structures with complex geometries, adjustable porosity and size, providing a way for sustainable and cost-effective H2O2 synthesis, and has broad application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of electrode materials, and in particular to a 3D-printed electrode for electrosynthesis of hydrogen peroxide, and a preparation method and application thereof. Background Art

[0002] Hydrogen peroxide (H2O2) is a key chemical across various industries, widely used in pulp and paper bleaching, chemical synthesis, and wastewater treatment. However, current H2O2 production methods, primarily through anthraquinone oxidation, are expensive, energy-intensive, and generate significant waste. In situ generation of H2O2 through electrochemical catalytic two-electron oxygen reduction offers the advantages of a fully green, decentralized, and safe process, making it the most promising method for H2O2 synthesis.

[0003] In terms of electrode material systems, carbon-based materials are widely used as cathode materials for the 2e-ORR due to their intrinsic catalytic activity and chemical stability. Existing technologies limit the use of two-dimensional carbon materials (such as carbon paper, carbon cloth, and graphite sheets) due to their insufficient density of surface active sites. Traditional three-dimensional carbon materials (such as carbon felt), while offering high specific surface areas, suffer from low mass transfer efficiency due to their disordered pore structures. Furthermore, these materials present numerous challenges, such as complex preparation processes and poor structural consistency. Summary of the Invention

[0004] The present invention aims to provide a 3D-printed electrode for electrosynthesis of hydrogen peroxide, and its preparation method and application. The 3D-printed electrode has an ordered pore structure and good structural consistency, and has excellent electrosynthesis hydrogen peroxide activity and is easy to prepare.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a 3D printed electrode for electrosynthesis of hydrogen peroxide, comprising the following steps:

[0007] The electrode pores are designed using three-dimensional periodic channels, and M×N×H unit channels are orderly constructed through an array to form an electrode model; where M is the number of arrays in the horizontal direction, N is the number of arrays in the vertical direction, and H is the number of arrays in the vertical direction.

[0008] Performing 3D printing according to the structure of the electrode model to obtain an electrode substrate;

[0009] After the electrode substrate is solidified, carbonization is performed to obtain a 3D printed electrode.

[0010] Preferably, the shape of the three-dimensional periodic pores includes cubic, body-centered cubic or octagonal lattice; the porosity of the electrode pores is 90~95%, and the length of each unit pore is independently 0.5~1mm, the width is independently 0.5~1mm, and the height is independently 0.5~1mm.

[0011] Preferably, the material used for 3D printing is a high temperature resistant resin; the high temperature resistant resin is composed of one or more of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate; the mass ratio of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate in the high temperature resistant resin is (0~0.5):(0~0.3):(0~0.3):(0~0.3) and not 0 at the same time.

[0012] Preferably, the curing conditions include: a wavelength of 280-400 nm, a curing temperature of 30-60° C., and a curing time of 5-30 min.

[0013] Preferably, the carbonization procedure includes: heating to 350-375°C at 2°C / min in a nitrogen atmosphere, keeping warm for 1-1.5 hours, heating to 400-425°C at 1°C / min, keeping warm for 1-1.5 hours, heating to 700-800°C at 3°C / min, keeping warm for 0.5-1 hour.

[0014] Preferably, after carbonization, the obtained carbonized electrode is etched with an alkali solution, and then surface modified with a modifier to obtain a 3D printed electrode; the alkali solution includes an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution; the concentration of the alkali solution is 1~3 mol / L; the etching temperature is 25~40°C, and the time is 0.5~1h.

[0015] Preferably, the modifier includes polytetrafluoroethylene emulsion or polydimethylsiloxane; the mass fraction of the polytetrafluoroethylene emulsion is 10-60%; and the modifier is used in the form of spraying.

[0016] Preferably, the spraying conditions include: spraying pressure 0.25~0.6bar, atomization pressure 1~3bar, spray width pressure 1~3bar, platform temperature 60~80℃, number of spray layers 1~5 layers, spacing distance 10~30mm, spraying speed 50~100mm / s, and interval time between spraying each layer 30~50s.

[0017] The present invention provides a 3D printed electrode for electrosynthesis of hydrogen peroxide, which is prepared by the preparation method described in the above technical solution.

[0018] The present invention provides the use of the 3D printed electrode described in the above technical solution in the electrocatalytic synthesis of hydrogen peroxide.

[0019] The present invention provides a method for preparing a 3D-printed electrode for electrosynthesis of hydrogen peroxide. The present invention designs a topological model of an ordered porous structure based on three-dimensional periodic channels, and then adopts a method combining 3D printing technology and high-temperature carbonization to prepare the ordered electrode structure. The three-dimensional electrode prepared by 3D printing has a large number of hierarchical porous structures, which makes the electrode have a higher specific surface area and porosity, can provide more active sites, and can also improve the mass transfer capacity. At the same time, the electrode is carbonized and surface modified to increase the catalytic activity, thereby improving the catalytic performance.

[0020] The three-dimensional electrode constructed using 3D printing technology in this invention achieves precise control of porosity, pore connectivity, and surface topology through digital modeling. Its hierarchical porous properties simultaneously optimize the reaction interface area and material transfer dynamics, addressing the structural disorder problem of traditional three-dimensional electrode materials. By synergistically coupling 3D printing technology with a carbonization process, the topological ordering of the three-dimensional electrode pore structure is achieved, optimizing the reactant transport pathways and active site distribution within the three-dimensional electrode structure, offering significant advantages in the field of electrocatalytic hydrogen peroxide synthesis.

[0021] Compared with traditional methods, the 3D printing method provided by the present invention can easily print structures with complex geometries, adjustable porosity and size. The method of the present invention has the characteristics of controllable structure and simple preparation, and does not require catalyst loading, making it more economical. Moreover, the electrode exhibits excellent repeatability and a short production cycle, and can be well used for large-scale applications, providing a way for sustainable and cost-effective H2O2 synthesis and having broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a flow chart for preparing the 3D printed electrode of the present invention;

[0023] Figure 2 The electrode structure diagram designed for Example 1 of the present invention;

[0024] Figure 3 A diagram of the pore structure of the electrode unit designed for Example 1 of the present invention;

[0025] Figure 4 This is a scanning electron microscope image of the 3D printed electrode prepared in Example 1 of the present invention;

[0026] Figure 5 This is a water contact angle diagram of the 3D printed electrode prepared in Example 1 of the present invention;

[0027] Figure 6This is a water contact angle diagram of the 3D printed electrode prepared in Example 2 of the present invention;

[0028] Figure 7 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 1 under neutral conditions;

[0029] Figure 8 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 1 under alkaline conditions;

[0030] Figure 9 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 2 under neutral conditions;

[0031] Figure 10 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 2 under alkaline conditions;

[0032] Figure 11 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 3 under neutral conditions;

[0033] Figure 12 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 3 under alkaline conditions;

[0034] Figure 13 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 4 under neutral conditions;

[0035] Figure 14 This is a data graph showing the generation of hydrogen peroxide by the 3D printed electrode prepared in Example 4 under alkaline conditions;

[0036] Figure 15 This is a data graph of the production of hydrogen peroxide under neutral conditions in Comparative Example 1;

[0037] Figure 16 This is a data graph of the production of hydrogen peroxide in Comparative Example 1 under alkaline conditions. DETAILED DESCRIPTION

[0038] In the present invention, unless otherwise specified, the required raw materials or reagents are commercially available products well known to those skilled in the art.

[0039] like Figure 1 As shown, the present invention provides a method for preparing a 3D printed electrode for electrosynthesis of hydrogen peroxide, comprising the following steps:

[0040] The electrode pores are designed using three-dimensional periodic channels, and M×N×H unit channels are orderly constructed through an array to form an electrode model; where M is the number of arrays in the horizontal direction, N is the number of arrays in the vertical direction, and H is the number of arrays in the vertical direction.

[0041] Performing 3D printing according to the structure of the electrode model to obtain an electrode substrate;

[0042] After the electrode substrate is solidified, carbonization is performed to obtain a 3D printed electrode.

[0043] The present invention adopts three-dimensional periodic channels to design electrode pores, and constructs M×N×H unit channels in an orderly array to form an electrode model; wherein M is the horizontal number of the array, N is the vertical number of the array, and H is the vertical number of the array (i.e., perpendicular to the plane direction).

[0044] The present invention preferably uses 3D modeling software to design the electrode structure; the present invention has no special limitation on the 3D modeling software, and conventional 3D modeling software can be used.

[0045] In the present invention, the shape of the three-dimensional periodic channel preferably includes a cubic, body-centered cubic or octagonal lattice; the porosity of the electrode pores is preferably 90~95% (porosity formed by orderly arrangement), more preferably 93%, the length of each unit channel is independently preferably 0.5~1mm, more preferably 1mm, the width is independently preferably 0.5~1mm, more preferably 1mm, and the height is independently preferably 0.5~1mm, more preferably 1mm.

[0046] The present invention has no special limitation on the specific numbers of M, N and H, which can be adjusted according to actual needs. In an embodiment of the present invention, M is preferably 10, N is preferably 10, and H is preferably 3, 2 or 1.

[0047] The present invention designs electrode pores based on a three-dimensional periodic pore structure, thereby obtaining an orderly arranged electrode model.

[0048] After obtaining the electrode model, the present invention performs 3D printing according to the structure of the electrode model to obtain the electrode substrate.

[0049] The present invention preferably uses a 3D printing slicer to slice the designed electrode model structure in layers, and then imports it into a stereolithography 3D printer, projects the layers onto the surface of the printing material, solidifies the layers and accumulates them layer by layer to obtain a printed electrode with a macroporous structure.

[0050] In the present invention, in the step of layered slicing, the thickness of each slice is preferably 20 to 50 μm, more preferably 50 μm.

[0051] In the present invention, the material used for 3D printing is preferably a high-temperature resistant resin; the high-temperature resistant resin is composed of one or more of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate; the mass ratio of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate in the high-temperature resistant resin is preferably (0~0.5):(0~0.3):(0~0.3):(0~0.3) and not 0 at the same time, more preferably 0.4:0.3:0.15:0.15.

[0052] The present invention has no special limitation on the specific parameters and operations of the 3D printing, and the desired structure can be obtained according to the printing method well known in the art.

[0053] After completing the 3D printing, the present invention preferably removes the electrode substrate and cleans it with a solvent; the solvent is preferably isopropyl alcohol or ethanol, and the cleaning time is preferably 5 to 30 minutes, more preferably 5 to 10 minutes.

[0054] After obtaining the electrode base, the present invention solidifies the electrode base and then carbonizes it to obtain a carbonized electrode.

[0055] In the present invention, the printed electrodes are preferably cured using a UV curing box.

[0056] In the present invention, the curing conditions preferably include: a wavelength of 280-400 nm, more preferably 395 nm, a curing temperature of 30-60° C., more preferably 60° C., and a curing time of 5-30 min, more preferably 10-20 min.

[0057] In the present invention, the carbonization procedure preferably includes: heating to 350~375℃ at 2℃ / min in a nitrogen atmosphere, keeping warm for 1~1.5h, heating to 400~425℃ at 1℃ / min, keeping warm for 1~1.5h, heating to 700~800℃ at 3℃ / min, keeping warm for 0.5~1h, more preferably first heating to 375℃ at 2℃ / min, keeping warm for 1.5h, then heating to 425℃ at 1℃ / min, keeping warm for 1.5h, and finally heating to 800℃ at 3℃ / min, keeping warm for 1h.

[0058] After the carbonization is completed, the obtained carbonized electrode is washed with anhydrous ethanol, then washed with deionized water and dried to remove impurities on the electrode surface; the washing time of the anhydrous ethanol and deionized water is preferably 5~30min, more preferably 10~20min, the drying temperature is preferably 50~80℃, more preferably 60℃, and the drying time is preferably 3~6h, more preferably 3h.

[0059] After obtaining the carbonized electrode, the present invention preferably further comprises etching the obtained carbonized electrode with an alkaline solution and then performing surface modification with a modifier to obtain a 3D printed electrode.

[0060] In the present invention, the alkaline solution preferably includes an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution, more preferably an aqueous potassium hydroxide solution; the concentration of the alkaline solution is 1 to 3 mol / L, more preferably 1 mol / L; the etching temperature is preferably 25 to 40°C, more preferably 25 to 30°C, and the etching time is preferably 0.5 to 1 hour, more preferably 1 hour. In the present invention, micropores and mesopores are generated on the surface and inside the electrode through etching.

[0061] After completing the etching, the present invention preferably dries the electrode and then modifies it with a modifier; the drying temperature is preferably 60-80°C, more preferably 60-70°C, and the drying time is preferably 3-6 hours, more preferably 5 hours.

[0062] In the present invention, the modifier preferably comprises polytetrafluoroethylene emulsion or polydimethylsiloxane; the mass fraction of the polytetrafluoroethylene emulsion is preferably 10-60%, more preferably 10-30%. The modifier is preferably applied by spraying, and the present invention limits the amount of the modifier based on the spraying conditions. The present invention reduces the hydrophilicity of the electrode surface through modification, reducing water coverage on the electrode surface, thereby promoting the diffusion and adsorption of gaseous reactants, preventing active sites from being blocked by a water film, and thus improving electrode activity.

[0063] In the present invention, the spraying conditions preferably include: spraying pressure 0.25~0.6bar, atomization pressure 1~3bar, spray width pressure 1~3bar, platform temperature 60~80℃, number of spray layers 1~5 layers, spacing distance 10~30mm, spraying speed 50~100mm / s, and interval time between spraying each layer 30~50s; the spraying pressure is more preferably 0.3~0.6bar, the atomization pressure is more preferably 1~2bar, the spray width pressure is more preferably 1~2bar, the platform temperature is more preferably 60~70℃, the number of spray layers is more preferably 3 layers, the spacing distance is more preferably 10mm, the spraying speed is more preferably 80mm / s, and the interval time between spraying each layer is more preferably 30s.

[0064] After the spraying is completed, the obtained electrode is dried in an oven. The drying temperature is preferably 60-80° C., more preferably 80° C., and the drying time is preferably 6-12 hours, more preferably 12 hours.

[0065] The present invention provides a 3D printed electrode for electrosynthesis of hydrogen peroxide, which is prepared by the preparation method described in the above technical solution.

[0066] The present invention provides the use of the 3D printed electrode described in the above technical solution in the electrocatalytic synthesis of hydrogen peroxide. The present invention does not specifically limit the method of the application, and the application can be carried out according to methods well known in the art.

[0067] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited by the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. The experimental methods described in the embodiments of the present invention are all conventional methods unless otherwise specified.

[0068] The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the following reagents and raw materials, unless otherwise specified, are commercially available.

[0069] Example 1

[0070] (1) If Figures 2 and 3 As shown in the three-dimensional figure, the electrode was designed using 3D modeling software (Cinema 4D). The electrode pores were constructed with an octagonal lattice. M×N×H unit channels were arranged in an orderly array, where M is 10, N is 10, and H is 3. The length, width, and height of the unit channel were 1 mm, 1 mm, and the porosity was 93%, forming an electrode model.

[0071] (2) Using polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine, and tri(2-acryloyloxyethyl)isocyanurate in a mass ratio of 0.4:0.3:0.15:0.15 as printing materials, the electrode model structure designed in step (1) was sliced ​​by a 3D printing slicer, and 3D printing was performed with a thickness of 50 μm per layer. After slicing, the STL file was imported into a stereolithography 3D printer, and the layers were projected onto the surface of the printing material. The layers were solidified and accumulated layer by layer. After the 3D printing was completed, the printed structure was taken out and cleaned with isopropyl alcohol for 5 minutes to obtain a printed electrode;

[0072] (3) curing the printed electrode in a UV curing box at a wavelength of 395 nm and 60° C. for 10 min to obtain a cured printed electrode;

[0073] (4) The cured electrode was heated and carbonized in a tube furnace. In a nitrogen atmosphere, it was first heated to 375°C at 2°C / min and maintained for 1.5 h, then heated to 425°C at 1°C / min and maintained for 1.5 h, and finally heated to 800°C at 3°C / min and maintained for 1 h. The obtained electrode was first washed with anhydrous ethanol for 10 min, then washed with deionized water for 10 min, and dried in an oven at 60°C for 3 h to obtain a carbonized electrode.

[0074] (5) The carbonized electrode was chemically etched with a 1 mol / L potassium hydroxide aqueous solution at 25 °C for 1 h and then dried in an oven at 60 °C for 5 h. It was then surface-modified by spraying with a 10% mass fraction polytetrafluoroethylene emulsion (spraying pressure of 0.3 bar, atomization pressure of 1 bar, spray width pressure of 1 bar, platform temperature of 60 °C, number of spray layers of 3, spacing of 10 mm, spraying speed of 80 mm / s, and layer interval time of 30 s). The electrode was then dried in an oven at 80 °C for 12 h to obtain a carbonized and surface-modified 3D printed electrode.

[0075] Example 2

[0076] The only difference from Example 1 is that the chemical etching and surface modification in step (5) are not performed, and a carbonized 3D printed electrode without surface modification is obtained.

[0077] Example 3

[0078] The only difference from Example 1 is that H is 2 in step (1).

[0079] Example 4

[0080] The only difference from Example 1 is that H is 1 in step (1).

[0081] Figure 4 This is a scanning electron microscope image of the 3D printed electrode prepared in Example 1 of the present invention; Figure 4 It can be seen that after carbonization and modification treatment, the electrode surface is relatively complete, and the electrode pore structure remains stable without collapse.

[0082] Figure 5 、 Figure 6 The water contact angle diagrams of the 3D printed electrodes in Example 1 and Example 2 of the present invention are shown in order. By comparison, it can be seen that the electrode surface is more hydrophobic after modification, and the water contact angle is increased by about 16° relative to the unmodified electrode surface.

[0083] Application Example 1

[0084] In an H-type electrolytic cell, 0.1 M sodium sulfate aqueous solution was used as the electrolyte, the 3D printed electrode in Example 1 was used as the working electrode, Ag / AgCl was used as the reference electrode, and the platinum sheet was used as the counter electrode. The test was carried out at 20 mA / cm 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 7 .

[0085] Figure 7This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 1 at different times in a 0.1M sodium sulfate electrolyte; Figure 7 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 230 mg / L at 360 min.

[0086] Application Example 2

[0087] In an H-type electrolytic cell, 0.1 M sodium hydroxide aqueous solution was used as the electrolyte, the 3D printed electrode in Example 1 was used as the working electrode, Hg / HgO was used as the reference electrode, and a platinum sheet was used as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 8 .

[0088] Figure 8 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 1 at different times in a 0.1M sodium hydroxide electrolyte; Figure 8 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 563 mg / L at 360 min.

[0089] Application Example 3

[0090] In an H-type electrolytic cell, 0.1 M sodium sulfate aqueous solution was used as the electrolyte, the 3D printed electrode in Example 2 was used as the working electrode, Ag / AgCl was used as the reference electrode, and the platinum sheet was used as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 9 .

[0091] Figure 9 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 2 at different times in a 0.1M sodium sulfate electrolyte; Figure 9 It can be seen that the hydrogen peroxide concentration increases with time and can reach 105 mg / L at 360 min.

[0092] Application Example 4

[0093] In an H-type electrolytic cell, 0.1 M sodium hydroxide aqueous solution was used as the electrolyte, the 3D printed electrode in Example 2 was used as the working electrode, Hg / HgO was used as the reference electrode, and the platinum sheet was used as the counter electrode. 2Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 10 .

[0094] Figure 10 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 2 at different times in a 0.1M sodium hydroxide electrolyte; Figure 10 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 281 mg / L at 360 min.

[0095] Application Example 5

[0096] In an H-type electrolytic cell, 0.1 M sodium sulfate aqueous solution was used as the electrolyte, the 3D printed electrode in Example 3 was used as the working electrode, Ag / AgCl was used as the reference electrode, and the platinum sheet was used as the counter electrode. The test was carried out at 20 mA / cm 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 11 .

[0097] Figure 11 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 3 at different times in a 0.1M sodium sulfate electrolyte; Figure 11 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 193 mg / L at 360 min.

[0098] Application Example 6

[0099] In an H-type electrolytic cell, 0.1 M sodium hydroxide aqueous solution was used as the electrolyte, the 3D printed electrode in Example 3 was used as the working electrode, Hg / HgO was used as the reference electrode, and the platinum sheet was used as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 12 .

[0100] Figure 12 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 3 at different times in a 0.1M sodium hydroxide electrolyte; Figure 12 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 515 mg / L at 360 min.

[0101] Application Example 7

[0102] In an H-type electrolytic cell, 0.1 M sodium sulfate aqueous solution was used as the electrolyte, the 3D printed electrode in Example 4 was used as the working electrode, Ag / AgCl was used as the reference electrode, and the platinum sheet was used as the counter electrode. The test was carried out at 20 mA / cm 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 13 .

[0103] Figure 13 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 4 at different times in a 0.1M sodium sulfate electrolyte; Figure 13 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 176 mg / L at 360 min.

[0104] Application Example 8

[0105] In an H-type electrolytic cell, 0.1 M sodium hydroxide aqueous solution was used as the electrolyte, the 3D printed electrode in Example 4 was used as the working electrode, Hg / HgO was used as the reference electrode, and a platinum sheet was used as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; 10 mL of the reaction solution was taken out from the electrolytic cell every 60 min using a pipette, and the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. The results are shown in Figure 14 .

[0106] Figure 14 This is a data graph showing the concentration of hydrogen peroxide generated by the 3D printed electrode prepared in Example 4 at different times in a 0.1M sodium hydroxide electrolyte; Figure 14 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 482 mg / L at 360 min.

[0107] Comparative Example 1

[0108] The test was carried out in an H-type electrolytic cell with 0.1 M sodium sulfate aqueous solution as the electrolyte, using carbon felt as the working electrode, Ag / AgCl as the reference electrode, and platinum sheet as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. Figure 15 .Depend on Figure 15 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 52 mg / L at 360 min.

[0109] Comparative Example 2

[0110] The test was carried out in an H-type electrolytic cell with 0.1M sodium hydroxide aqueous solution as the electrolyte, using carbon felt as the working electrode, Hg / HgO as the reference electrode, and platinum sheet as the counter electrode. 2 Hydrogen peroxide was prepared by constant current; the H2O2 yield was measured by UV-visible spectrophotometry at 405 nm. Figure 16 .Depend on Figure 16 It can be seen that the hydrogen peroxide concentration increases with time, and the hydrogen peroxide concentration can reach 86 mg / L at 360 min.

[0111] From the above comparison, it can be seen that Example 1, Example 2, Example 3, and Example 4 all have better performance than the comparative example, and Example 1 also has better performance than Example 2, Example 3, and Example 4. This is because the ordered pore design enables the electrolyte to better contact the electrode, thereby improving the mass transfer capacity, and the porous structure increases the specific surface area and provides more active sites, thereby giving it higher catalytic performance.

[0112] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a 3D printed electrode for electrosynthesis of hydrogen peroxide, characterized in that: The following steps are involved: The electrode pores are designed using three-dimensional periodic channels, and M×N×H unit channels are orderly constructed through an array to form an electrode model; where M is the number of arrays in the transverse direction, N is the number of arrays in the longitudinal direction, and H is the number of arrays in the vertical direction; the shape of the three-dimensional periodic channels includes body-centered cubic or octagonal lattices; the porosity of the electrode pores is 90-95%; the length of each unit channel is independently 0.5-1 mm, the width is independently 0.5-1 mm, and the height is independently 0.5-1 mm; Performing 3D printing according to the structure of the electrode model to obtain an electrode substrate; After curing the electrode substrate, carbonizing it to obtain a 3D printed electrode; The material used for 3D printing is a high-temperature resistant resin; the high-temperature resistant resin is composed of one or more of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate; the mass ratio of polyurethane acrylate, diethylene glycol dimethacrylate, acryloylmorpholine and tris(2-acryloyloxyethyl)isocyanurate in the high-temperature resistant resin is (0~0.5):(0~0.3):(0~0.3):(0~0.3) and not 0 at the same time.

2. The preparation method according to claim 1, characterized in that The curing conditions include: a wavelength of 280-400 nm, a curing temperature of 30-60° C., and a curing time of 5-30 min.

3. The preparation method according to claim 1, characterized in that The carbonization procedure includes: heating to 350-375°C at 2°C / min in a nitrogen atmosphere, keeping warm for 1-1.5 hours, heating to 400-425°C at 1°C / min, keeping warm for 1-1.5 hours, heating to 700-800°C at 3°C / min, and keeping warm for 0.5-1 hour.

4. The preparation method according to claim 1, characterized in that After carbonization, the obtained carbonized electrode is etched with an alkaline solution, and then surface modified with a modifier to obtain a 3D printed electrode; the alkaline solution includes an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution; the concentration of the alkaline solution is 1-3 mol / L; the etching temperature is 25-40°C, and the time is 0.5-1h.

5. The preparation method according to claim 4, characterized in that The modifier includes polytetrafluoroethylene emulsion or polydimethylsiloxane; the mass fraction of the polytetrafluoroethylene emulsion is 10-60%; and the modifier is used in the form of spraying.

6. The preparation method according to claim 5, characterized in that The spraying conditions include: spraying pressure 0.25~0.6bar, atomization pressure 1~3bar, spray width pressure 1~3bar, platform temperature 60~80℃, number of spray layers 1~5 layers, spacing distance 10~30mm, spraying speed 50~100mm / s, and interval time between spraying each layer 30~50s.

7. A 3D printed electrode for electrosynthesis of hydrogen peroxide prepared by the preparation method according to any one of claims 1 to 6.

8. Use of the 3D printed electrode according to claim 7 in the electrocatalytic synthesis of hydrogen peroxide.

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