WO2023245868A1 - 一种宏观阵列电极及其制备方法和应用 - Google Patents

一种宏观阵列电极及其制备方法和应用 Download PDF

Info

Publication number
WO2023245868A1
WO2023245868A1 PCT/CN2022/116536 CN2022116536W WO2023245868A1 WO 2023245868 A1 WO2023245868 A1 WO 2023245868A1 CN 2022116536 W CN2022116536 W CN 2022116536W WO 2023245868 A1 WO2023245868 A1 WO 2023245868A1
Authority
WO
WIPO (PCT)
Prior art keywords
array electrode
cone
array
electrode
present
Prior art date
Application number
PCT/CN2022/116536
Other languages
English (en)
French (fr)
Inventor
孙晓明
罗亮
杨瑛泽
Original Assignee
北京化工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京化工大学 filed Critical 北京化工大学
Publication of WO2023245868A1 publication Critical patent/WO2023245868A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the fields of electrocatalysis, electrode design and manufacturing, and specifically relates to a macro array electrode and its preparation method and application.
  • gas evolution reaction is a large and important branch.
  • hydrogen evolution reaction, oxygen evolution reaction and chlorine evolution reaction are important components in the chemical industry.
  • the electrodes in the gas evolution reaction system directly affect the gas evolution efficiency.
  • the traditional electrode for gas evolution reaction is an electrode with a super-aerophilic surface. Using this kind of electrode for gas evolution reaction will easily cause the bubbles generated by the gas evolution reaction to adhere to the electrode surface, thus preventing direct contact between the active parts of the electrode surface and the electrolyte. , reducing the gas production efficiency of the gas evolution reaction.
  • researchers have developed electrodes with superaerophobic surfaces for use in gas evolution reaction systems.
  • the electrode with a supergas-repellent surface has minimal adhesion to the bubbles generated by the gas evolution reaction and can quickly release the bubbles generated by the gas evolution reaction, thereby improving the gas production efficiency of the gas evolution reaction.
  • the present invention provides an array electrode and its preparation method and application.
  • the array electrode provided by the present invention has an adherent gas-repellent surface.
  • Using the array electrode provided by the present invention as a gas evolution reaction electrode can make the gas evolution reaction electrode
  • the bubbles produced by the gas reaction are transported in a directional manner.
  • the present invention provides a macro array electrode, which includes a conductive substrate and a wettability control layer deposited on the surface of the conductive substrate;
  • the conductive substrate includes a base and a cone array on the surface of the base.
  • the cone array is composed of cones; the angle between the cones and the vertical direction of the base is 0 to 85°;
  • the wettability control layer is composed of nanoparticle aggregates.
  • the length of the busbar of the cone is 100-5000 ⁇ m
  • the diameter of the contact part between the cone and the base is 10-5000 ⁇ m
  • the distance between a single cone and adjacent cones in the cone array is It is 10 ⁇ 5000 ⁇ m.
  • the nanoparticle aggregates include catalytically active substances or non-catalytically active substances; when the nanoparticle aggregates are non-catalytically active substances, the cone array further includes a catalyst distributed on the surface of the wettability control layer.
  • the nanoparticle aggregates include several columns of nano branches distributed along the periphery of the main trunk, and a single nano branch in each column of nano branches includes secondary nano metal particle aggregates distributed all around.
  • the catalytically active material includes Cu, Ni, Co-Ni alloy, and Pt.
  • the non-catalytically active material includes carbon nanotubes.
  • the catalyst includes electrochemical catalyst metal, metal sulfide, metal nitride, metal carbide, metal oxide, metal hydroxide, and metal phosphide.
  • the conductive matrix includes an intrinsic matrix;
  • the intrinsic matrix includes a conductive substance or a non-conductive substance;
  • the surface of the intrinsic matrix further includes a conductive layer.
  • the conductive matrix includes a nickel-phosphorus conductive matrix, a copper conductive matrix or a zinc conductive matrix.
  • the contact angle between the wettability control layer and the bubbles generated by the gas evolution reaction is 120 to 150°.
  • the present invention also provides a method for preparing macroscopic array electrodes according to the above technical solution, which includes the following steps:
  • the conductive substrate includes a substrate and a cone array on the surface of the substrate, the cone array is composed of cones; the angle between the cones and the vertical direction of the substrate is 0 to 85°;
  • a wettability control layer is deposited on the surface of the conductive substrate to obtain the macroscopic array electrode; the wettability control layer is composed of nanoparticle aggregates.
  • the nanoparticle aggregates include catalytically active substances or non-catalytically active substances; when the nanoparticle aggregates are catalytically active substances, the preparation method of the wettability control layer includes the following steps:
  • the catalytic active material is first deposited on the surface of the conductive substrate to obtain the macro array electrode.
  • the nanoparticle aggregates include catalytically active substances or non-catalytically active substances; when the nanoparticle aggregates are non-catalytically active substances, the preparation method of the wettability control layer includes the following steps:
  • a third catalyst is deposited on the surface of the primary macro array electrode to obtain the macro array electrode.
  • the present invention also provides the application of the macro array electrode described in the above technical solution or the macro array electrode prepared by the preparation method described in the above technical solution as a gas evolution reaction electrode.
  • the invention provides a macro array electrode, which includes a conductive substrate and a wettability control layer deposited on the surface of the conductive substrate; the conductive substrate includes a base and a cone array on the surface of the base, and the cone array is composed of cones.
  • the angle between the cone and the vertical direction of the base is 0 to 85°; the wettability control layer is composed of nanoparticle aggregates.
  • the cone in the array electrode has a certain angle with the vertical direction of the substrate, which can provide good bubble traction force under the joint action of Laplace force and buoyancy component, and the wettability control layer makes the surface of the array electrode Having an adherent gas-repellent surface, using the array electrode provided by the present invention for gas evolution reaction electrodes can enable directional transport of bubbles generated by the gas evolution reaction.
  • Figure 1 is a physical diagram of the resin matrix, nickel-phosphorus conductive matrix, primary array electrode and array electrode prepared in Example 1;
  • Figure 2 is an SEM image of the surface of the primary array electrode prepared in Example 1;
  • Figure 3 is an XRD spectrum of copper on the surface of the primary array electrode prepared in Example 1;
  • Figure 4 is an SEM image of the surface of the array electrode prepared in Example 2.
  • Figure 5 is a diagram showing the bubble transport behavior at different tilt angles (10°, 35° and 50°) by performing HER reaction on the array electrodes prepared in Examples 1 to 3;
  • Figure 6 is a comparison chart of bubble slip rate and initial slip size at different tilt angles
  • Figure 7 is a statistical chart of the desorption time of bubbles of various sizes detaching from the surface of a single cone at different tilt angles
  • Figure 8 is a statistical chart of the proportion of bubble desorption size at different tilt angles
  • Figure 9 is a statistical diagram of the proportion of bubble desorption size for the flat electrode prepared in Comparative Example 3.
  • Figure 10 is a current density diagram corresponding to the HER reaction of the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • Figure 11 is a current density polarization curve (LSV) diagram corresponding to the HER reaction of the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • Figure 12 is a Tafel slope diagram corresponding to the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • Figure 13 is the AC impedance diagram corresponding to the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • Figure 14 is a diagram of the electric double layer capacitance and electrochemical active area (ECSA) corresponding to the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • ECSA electric double layer capacitance and electrochemical active area
  • Figure 15 is a normalized electrochemical active area (ECSA) diagram corresponding to the electrodes prepared in Examples 1 to 3 and Comparative Example 3;
  • ECSA electrochemical active area
  • Figure 16 shows the SEM images, adhesion force images and corresponding bubble behavior images of the electrodes prepared in Example 2 and Comparative Examples 1 and 2;
  • Figure 17 is a digital camera image of the single-cell electrolytic cell device used in the reactions of Example 4 and Comparative Example 4;
  • Figure 18 is a high-speed camera real shot of the corresponding bubble state in the reaction of Example 4 and Comparative Example 4;
  • Figure 19 is the corresponding gas chromatogram of Comparative Example 4 after 1 hour of reaction.
  • Figure 20 is the corresponding gas chromatogram after 1 hour of reaction in Example 4.
  • Figure 21 is an SEM image of the surface of the primary array electrode prepared in Example 5.
  • Figure 22 is an SEM image of the surface of the primary array electrode prepared in Example 6.
  • the invention provides an array electrode, which includes a conductive substrate and a wettability control layer deposited on the surface of the conductive substrate;
  • the conductive substrate includes a base and a cone array on the surface of the base.
  • the cone array is composed of cones; the angle between the cones and the vertical direction of the base is 0 to 85°;
  • the wettability control layer is composed of nanoparticle aggregates.
  • the angle between the cone and the vertical direction of the base is 0 to 85°, preferably 10 to 50°; the generatrix length of the cone is preferably 100 to 5000 ⁇ m, more preferably 300 to 1500 ⁇ m;
  • the diameter of the contact portion between the cone and the base is preferably 200-400 ⁇ m, more preferably 250-350 ⁇ m;
  • the spacing between a single cone and adjacent cones in the cone array is preferably 150-300 ⁇ m, more preferably 200 ⁇ 250 ⁇ m.
  • the present invention has no special limitation on the size of the base of the conductive substrate, and it can be designed according to the needs of the array electrode.
  • the wettability control layer is composed of nanoparticle aggregates; the nanoparticle aggregates preferably include several columns of nano-branches distributed along the periphery of the main trunk, and a single nano-branch in each column of nano-branches includes secondary nano-branches distributed all around. nanometer metal particle aggregates.
  • the nanoparticle aggregate is preferably in the shape of a wheat ear; the particle size of the nanoparticle aggregate is preferably 2 to 15 ⁇ m, and more preferably 8 ⁇ m.
  • the nanoparticle aggregates preferably include catalytically active substances or non-catalytically active substances; the catalytically active substances preferably include Cu, Ni, Co-Ni alloy or Pt, more preferably Cu, Ni or Co-Ni Alloy; the non-catalytically active material preferably includes carbon nanotubes.
  • the wettability control layer has two functions.
  • the first function is to ensure that the contact angle between the bubble and the cone is 120-150° to ensure that The movement of generating bubbles is adhesion and rolling; the second function is to act as a catalyst to catalyze the gas evolution reaction.
  • the cone array when the nanoparticle aggregate is a non-catalytically active substance, the cone array preferably further includes a catalyst distributed on the surface of the wettability control layer.
  • the catalyst preferably includes electrochemical catalyst metal, metal sulfide, metal nitride, metal carbide, metal oxide, metal hydroxide, metal phosphide, and is more preferably an electrochemical catalyst metal.
  • the electrochemical catalyst metal preferably includes Pt, Pd, Ru, Au, Ag, Ir or Rh, and is more preferably Pt.
  • the metal sulfide preferably includes MoS x , FeS 2 , NiS 2 or CoS 2 ;
  • the metal nitride preferably includes Ni-SN@C, Ni 3 N or Ni 3 FeN;
  • the metal carbide preferably Including Mo 2 C, CaC 2 , Cr 3 C 2 ;
  • the metal oxide preferably includes CuO or ZnO;
  • the metal hydroxide preferably includes Cu(OH) 2 or two-dimensional layered double hydroxides (LDHs);
  • the metal phosphide preferably includes FeP, CoP, NiP, FeCoP, FeNiP or CoNiP.
  • the conductive matrix preferably includes an intrinsic matrix; the intrinsic matrix preferably includes a conductive substance or a non-conductive substance.
  • the wettability control layer is directly deposited on the surface of the intrinsic matrix.
  • the conductive substance preferably includes graphitic carbon or metal material, and is more preferably graphitic carbon.
  • the metal material preferably includes copper, nickel or iron, and is more preferably copper.
  • the method for preparing the graphitic carbon matrix of the present invention preferably includes mechanical micro-cutting, chemical vapor deposition or redox, and more preferably mechanical micro-cutting.
  • the method for preparing the metal matrix in the present invention is preferably electrochemical etching.
  • the surface of the intrinsic matrix further includes a conductive layer.
  • the non-conductive substance preferably includes resin or polymethylmethacrylate (PMMA), more preferably resin.
  • the conductive layer preferably includes a nickel-phosphorus conductive layer, a copper conductive layer, and a zinc conductive layer.
  • the method for preparing the resin matrix of the present invention preferably includes photocuring, thermal curing or 3D printing, more preferably 3D printing. In the present invention, it is preferred to chemically deposit a conductive layer on the surface of the resin matrix.
  • the conductive matrix preferably includes a nickel-phosphorus conductive matrix, a copper conductive matrix, a zinc conductive matrix, and more preferably a nickel-phosphorus conductive matrix.
  • the nickel-phosphorus conductive matrix uses a resin matrix as an intrinsic matrix, and a nickel-phosphorus layer deposited on the surface of the resin matrix as a conductive layer.
  • the preparation method of the nickel-phosphorus conductive matrix preferably includes the following steps:
  • a nickel-phosphorus metal layer is chemically deposited on the surface of the resin matrix to obtain the nickel-phosphorus conductive matrix.
  • the present invention prepares a resin matrix through 3D printing. Before 3D printing, the present invention preferably also includes: using computer-aided design software to design a model of the resin matrix; importing the model into the customization software in the 3D printer. In the present invention, the size and shape of the model are consistent with the size and shape of the conductive substrate.
  • the 3D printing is preferably light-curing 3D printing
  • the raw material for light-curing 3D printing is preferably a photosensitive resin
  • the photosensitive resin is preferably a UV photosensitive resin.
  • the wavelength of the light for photocuring 3D printing is preferably 350 to 450 nm, and more preferably 405 nm.
  • the 3D printing equipment is preferably a UV stereolithography 3D printer, and the model of the UV stereolithography 3D printer is preferably BMF nanoArch P140.
  • the 3D printing process preferably further includes: ultrasonic treatment of the 3D printed product.
  • the solvent for ultrasonic treatment is preferably ethanol; the power of the ultrasonic treatment is preferably 200-300W, more preferably 290W; the temperature of the ultrasonic treatment is preferably 10-25°C, more preferably 19°C ; The time of the ultrasonic treatment is preferably 1 to 10 min, more preferably 5 min; the number of ultrasonic treatments is preferably 1 to 5 times, more preferably 3 times.
  • the ultrasonic treatment can remove uncured photosensitive resin on the surface of the 3D printed product.
  • the present invention chemically deposits a nickel-phosphorus metal layer on the surface of the resin matrix to obtain the nickel-phosphorus conductive matrix.
  • the chemical deposition preferably further includes: soaking the resin matrix in a sensitizing liquid and an activation liquid in sequence.
  • the sensitizing liquid preferably includes a mixed solution of soluble tin salt, acid solution and water.
  • the soluble tin salt preferably includes one or more of tin chloride, tin sulfate, tin acetate, tin tetrachloride, tin dichloride and tin bromide, and is more preferably tin chloride.
  • the present invention when the soluble tin salt is two or more of the above-mentioned specific substances, the present invention has no special restrictions on the proportion of the specific substances, and any proportion can be used.
  • the mass concentration of tin ions in the sensitizing solution in the soluble tin salt is preferably 9 to 11 g/L, and more preferably 10 g/L.
  • the acid solution preferably includes hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or hypochlorous acid, more preferably hydrochloric acid;
  • the molar concentration of hydrogen ions in the sensitizing solution in the acid solution is preferably 0.11 to 0.13 mol/L, more preferably 0.12 mol/L.
  • the soaking time in the sensitizing liquid is preferably 5 to 450 min, more preferably 13 to 100 min, and most preferably 15 to 30 min;
  • the soaking temperature in the sensitizing liquid is preferably 10 to 400°C, more preferably The temperature range is 40 to 100°C, and the most preferred temperature range is 50 to 80°C.
  • the activation solution preferably includes a mixed solution of soluble palladium salt, acid solution and water.
  • the soaked sample is preferably washed after soaking in the sensitizing solution.
  • the washing solvent is preferably deionized water.
  • the number of washings is preferably 2 to 4 times, and more preferably 3 times.
  • the soluble palladium salt preferably includes one or more of palladium nitrate, palladium sulfate, palladium acetate, palladium chloride and palladium dibromide, more preferably palladium chloride or palladium acetate.
  • the mass concentration of palladium ions in the activation solution in the soluble palladium salt is preferably 30 to 150 mg/L, and more preferably 100 mg/L.
  • the acid solution preferably includes hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid or hypochlorous acid, more preferably hydrochloric acid;
  • the molar concentration of hydrogen ions in the acid solution in the activation solution is preferably 0.01 to 0.1 mol. /L, more preferably 0.02mol/L.
  • the soaking time in the activation liquid is preferably 5 to 450 min, more preferably 20 to 100 min, and most preferably 25 to 50 min;
  • the soaking temperature in the activation liquid is preferably 10 to 400°C, more preferably 40 ⁇ 100°C, most preferably 50 ⁇ 80°C.
  • the soaked sample is preferably washed after soaking in the activation solution.
  • the washing solvent is preferably deionized water.
  • the number of washings is preferably 2 to 4 times, and more preferably 3 times.
  • the resin matrix is soaked in the sensitizing solution and the activation solution to increase the hydrophilicity of the surface of the resin matrix, which is beneficial to better combination of the subsequent nickel-phosphorus metal layer and the resin matrix.
  • the chemical deposition preferably involves soaking the resin matrix in a chemical deposition solution.
  • the pH value of the chemical deposition solution is preferably 9 to 11, and more preferably 10.
  • the chemical deposition solution is preferably an aqueous solution of NiSO 4 ⁇ 6H 2 O, C 6 H 8 O 7 ⁇ H 2 O and NaH 2 PO 2 ⁇ H 2 O.
  • the mass concentration of NiSO 4 in the chemical deposition solution is preferably 2 to 20 g/L, more preferably 10 to 15 g/L; the mass concentration of C 6 H 8 O 7 in the chemical deposition solution is preferably The mass of NaH 2 PO 2 in the chemical deposition solution is preferably 5 to 25 g/L, and more preferably 8 to 15 g/L.
  • the soaking step preferably further includes: mixing the chemical deposition solution and the complexing agent solution.
  • the complexing agent in the complexing agent solution preferably includes sodium citrate, sodium tartrate, malic acid, glycine, heptonate, sodium gluconate, sodium alginate or ammonia water; the complexing agent
  • the mass concentration of the complexing agent in the agent solution is preferably 5 to 30%, and more preferably 25%.
  • the volume ratio of the chemical deposition solution and the complexing agent solution is preferably 3 to 6:1, and more preferably 4:1.
  • the complexing agent can control the concentration of free nickel ions available for reaction, inhibit the precipitation of nickel phosphite, improve the stability of the nickel liquid, and extend the service life of the nickel liquid; it serves as a buffer and accelerator function to increase the deposition rate of nickel liquid.
  • the soaking temperature in the chemical immersion solution is preferably 10-400°C, more preferably 80-300°C, and most preferably 100-200°C; the soaking time in the chemical immersion solution is preferably 5-450 min, more preferably 28-300min, most preferably 50-150min.
  • the chemical deposition includes a reduction reaction and an oxidation reaction; the ionic reaction equation of the reduction reaction is as follows Equation 1 shows:
  • the nickel-phosphorus metal chemically deposited on the surface of the resin matrix has an amorphous flake structure.
  • the chemical deposition process preferably further includes: washing the chemical deposition product.
  • the washing solvent is preferably deionized water, and the number of washings is preferably 2 to 4 times, and more preferably 3 times.
  • the macro array electrode provided by the present invention has a viscous gas-aerophobic surface; the cone array can provide sufficient Laplace pressure and buoyancy components so that the bubbles generated on the array electrode surface are not easily detached directly from the surface under the action of buoyancy. Movement in solution irregularly.
  • the adhesion force of small-sized bubbles generated on the surface of the array electrode can overcome part of the buoyancy, causing the bubbles at the lower end of the cone to flip to the upper end of the cone without detaching. As the bubbles increase, the Laplace force And the buoyancy force also gradually increases. Under the combined action of the aggregates composed of nanoparticles and the cone array, large-sized bubbles are desorbed and directionally transported along the direction of the cone tilt.
  • the bubbles can expose more active sites (catalysts) during the flipping process and after desorption, thereby improving the gas production efficiency.
  • Using the array electrode provided by the present invention as an electrode for the gas evolution reaction can not only increase the gas yield but also improve the gas production efficiency.
  • the present invention also provides a method for preparing the array electrode described in the above technical solution, which includes the following steps:
  • the conductive substrate includes a substrate and a cone array on the surface of the substrate, the cone array is composed of cones; the angle between the cones and the vertical direction of the substrate is 0 to 85°;
  • a wettability control layer is deposited on the surface of the conductive substrate to obtain the macroscopic array electrode; the wettability control layer is composed of nanoparticle aggregates.
  • the present invention prepares a conductive substrate.
  • the conductive substrate includes a substrate and a cone array on the surface of the substrate.
  • the cone array is composed of cones; the angle between the cones and the vertical direction of the substrate is 0 to 85°.
  • the present invention has no special requirements on the method for preparing the conductive substrate, as long as the angle between the cone and the vertical direction of the base can meet the above requirements.
  • the nanoparticle aggregates include catalytically active substances or non-catalytically active substances; when the nanoparticle aggregates are catalytically active substances, the preparation method of the wettability control layer includes the following steps:
  • the catalytic active material is first deposited on the surface of the conductive substrate to obtain the macro array electrode.
  • the first deposition is preferably electrodeposition; the time of the electrodeposition is preferably 100-950s, more preferably 200-900s, and most preferably 300-800s; the voltage of the electrodeposition is preferably - 0.08 to 10.60V, more preferably -0.58 to 8.60V, most preferably -0.7 to 2.60V.
  • the electrolyte for electrodeposition is an aqueous solution of metal sulfate and H 2 SO 4 ; the concentration of metal sulfate in the electrolyte is preferably 6 to 90 g ⁇ L -1 , more preferably 16 to 70 g ⁇ L - 1 , most preferably 20 to 40 g ⁇ L -1 ; the pH value of the electrolyte is preferably 0.8 to 6, more preferably 1.5 to 4.
  • the electrolyte solution is preferably obtained by dissolving a metal sulfate in a sulfuric acid aqueous solution.
  • the electrolyte solution is preferably obtained by dissolving copper sulfate in a sulfuric acid aqueous solution.
  • the voltage of the electrodeposited metal is -0.1 ⁇ 1.6V, preferably -0.6V ⁇ 1.6V; the time of the electrodeposited metal is preferably 200 ⁇ 950s, more preferably 300 ⁇ 860s.
  • the electrolyte for electrodeposition is an aqueous solution of CuSO 4 and H 2 SO 4 ; the concentration of copper sulfate in the electrolyte is preferably 0.05 to 0.9 mol ⁇ L -1 , more preferably 0.1 to 0.6 mol ⁇ L -1 ; the pH value of the electrolyte is preferably 0.5 ⁇ 5.2, more preferably 1 ⁇ 4; the voltage of the electrodeposited copper is preferably -0.05 ⁇ -0.95V, more preferably -0.3 ⁇ - 0.8V; the time for electrodeposition of copper is preferably 200-850s, more preferably 240-700s.
  • the electrodeposited metal preferably uses platinum wire as the counter electrode and Ag/AgCl as the reference electrode.
  • the present invention obtains wheat ear-shaped nanometal particle aggregates by limiting the time, potential and electrolyte composition of electrodeposited metal.
  • the electrodeposition after metal electrodeposition preferably further includes: sequentially washing and drying the electrodes after electrodepositing metal.
  • the washing solvent is preferably deionized water; the number of washings is preferably 2 to 4 times, and more preferably 3 times.
  • the drying is preferably freeze-drying; the freeze-drying temperature is preferably -20 to -60°C, and more preferably -30 to -50°C; the freeze-drying time is preferably 10 to 14 hours. More preferably, it is 11 to 13 hours.
  • the preparation method of the wettability control layer preferably includes the following steps:
  • a third catalyst is deposited on the surface of the primary macro array electrode to obtain the macro array electrode.
  • a non-catalytically active substance is secondly deposited on the surface of a conductive substrate to obtain a primary macro array electrode.
  • the second deposition is preferably a vapor deposition method.
  • the specific preparation method is: xylene is used as the carbon source, ferrocene is used as the catalyst, the mixture of the two is ultrasonically oscillated for 10 minutes as the precursor liquid, and the conductive matrix is used as the lining.
  • the bottom and the precursor solution were placed in a quartz boat, placed in the middle of the quartz tube and heated to 750°C. After 2 hours of reaction, it was cooled to room temperature.
  • the present invention deposits a third catalyst on the surface of the primary macro array electrode to obtain the macro array electrode.
  • the third deposition is preferably electrochemical deposition or hydrothermal deposition.
  • the third deposition is preferably electrochemical deposition; when the catalyst is a metal sulfide, nitride, carbide, oxide, hydroxide or metal phosphide, The third deposition is preferably hydrothermal deposition.
  • the electrochemical deposition preferably involves soaking the primary macro array electrode in a catalyst solution and performing electrochemical deposition to obtain the macro array electrode.
  • the molar concentration of the catalyst solution is preferably 0.5 to 15 mmol/L, and more preferably 2 to 9 mmol/L.
  • the catalyst solution preferably includes a metal salt solution, more preferably an H 2 PtCl 6 solution.
  • the electrochemical deposition time is preferably 1 to 240 min, more preferably 2 to 110 min, and most preferably 3 to 80 min.
  • the hydrothermal deposition preferably involves placing the primary macro array electrode and the catalyst solution in a reactor at the same time to obtain the macro array electrode.
  • the catalyst solution preferably includes a metal salt solution and a non-metal salt solution.
  • the non-metal salt in the non-metal salt solution preferably includes a carbon source, a sulfur source or a nitrogen source.
  • the sulfur source is preferably thiourea or elemental sulfur;
  • the carbon source is preferably molybdenum carbide, vanadium carbide or titanium carbide;
  • the nitrogen source is preferably iron nitride, cobalt nitride or tungsten nitride .
  • the molar concentration of the metal salt in the catalyst solution is preferably 1 to 30 mmol/L, more preferably 5 to 20 mmol/L; the molar concentration of the non-metal salt in the catalyst solution is preferably 4 to 35 mmol/L. , more preferably 7 to 25 mmol/L.
  • the hydrothermal deposition time is preferably 3 to 18 hours, more preferably 5 to 15 hours.
  • the temperature of the hydrothermal deposition is preferably 50 to 220°C, and more preferably 100 to 180°C.
  • the third post-deposition process preferably further includes: washing and drying the third post-deposition electrode in sequence.
  • the washing solvent is preferably deionized water; the number of washings is preferably 2 to 4 times, and more preferably 3 times.
  • the drying is preferably oven drying; the drying temperature is preferably room temperature, and the room temperature is preferably 20-35°C, more preferably 25-30°C; the drying time is preferably It is 15-60mins, and it is more preferable that it is 20-40mins.
  • the present invention also provides the application of the macro array electrode described in the above technical solution or the macro array electrode prepared by the preparation method described in the above technical solution as a gas evolution reaction electrode.
  • the present invention has no special limitations on the application, and conventional methods in this field can be used.
  • the distance between the cathode and the anode in the gas evolution reaction system is preferably 1 to 100 mm, and more preferably 1.5 to 50 mm.
  • the array electrode provided by the present invention as an electrode for the gas evolution reaction can continuously generate, directionally transport and efficiently collect the bubbles generated by the gas evolution reaction.
  • the invention can continuously generate, directionally transmit and efficiently collect bubbles through the integrated beam electrode, which greatly prevents bubbles from being directly released into the electrolyte. At the same time, it can also shorten the distance between the cathode and the anode. , minimizing the use of additional equipment.
  • the base of the electrode model is a cube of 1cm ⁇ 1cm ⁇ 0.5cm.
  • the cones are arranged in an array.
  • the diameter of the cones in direct contact with the base is 300 ⁇ m, the length of the cone is 0.84cm, the distance between the cone and adjacent cones is 200 ⁇ m, and the angle between the cone and the vertical direction of the substrate is 10°; import the electrode model file into UV Stereo
  • photo-curing UV photosensitive resin is used as the raw material and light with a wavelength of 405nm is used for photo-curing 3D printing;
  • the photo-curing 3D printing product is subjected to ultrasonic treatment (using ethanol as the solvent, power (290W, temperature: 19°C) for 5 minutes, repeat ultrasonic treatment three times to obtain a resin matrix;
  • the resin matrix was soaked in the sensitizing solution (10g L -1 SnCl 2 , 0.12mol/L HCl) at 50°C for 15 minutes, and washed three times with deionized water; the washed product was immersed in the activation solution (100mg L -1 PdCl 2 , soak in 0.03 mol/L HCl) at 50°C for 25 minutes, and wash with deionized water three times to obtain a pretreated resin matrix;
  • the array electrode was prepared according to the method of Example 1, except that the angle between the cone and the vertical direction of the substrate was 35°.
  • the array electrode was prepared according to the method of Example 1, except that the angle between the cone and the vertical direction of the substrate was 50°.
  • Example 3 Two pieces of the electrodes of Example 3 were placed in a single-cell electrolytic cell without a separator, and the distance between the cathode and the anode was about 1.5 mm.
  • Array electrodes were prepared according to the method of Example 1, except that an aqueous solution of sulfuric acid with a pH value of 2 and a concentration of nickel sulfate of 60 g ⁇ L -1 was used as the electrolyte. Electrodeposition on the substrate surface for 920s.
  • Array electrodes were prepared according to the method of Example 1, except that an aqueous solution of sulfuric acid with a pH value of 1, a concentration of nickel sulfate of 60 g ⁇ L -1 and a concentration of cobalt sulfate of 50 g ⁇ L -1 was used as the electrolyte. Electrodeposit on the surface of the nickel-phosphorus conductive substrate at a constant voltage of 0.8V for 800 seconds.
  • the preparation method includes the following steps: prepare a nickel-phosphorus conductive matrix according to Example 1; dry the nickel-phosphorus conductive matrix at 25°C, and then spray a layer of quality on the surface of the nickel-phosphorus conductive matrix.
  • PTFE solution polytetrafluoroethylene solution
  • PTFE solution polytetrafluoroethylene solution
  • a superaerophobic electrode was prepared according to Example 1; the difference is that the electrolyte for electrodeposition is copper sulfate with a concentration of 0.1 mol ⁇ L -1 and a pH value of 2. Aqueous solution of copper sulfate and sulfuric acid; the voltage of electrodeposition is -1V and the time is 1200s.
  • the electrode was prepared according to the method of Example 1, except that the substrate was a cube of 1 cm ⁇ 1 cm ⁇ 0.5 cm, and the surface of the substrate did not contain array cones.
  • Comparative Example 4 Two electrodes of Comparative Example 2 were placed in a single-cell electrolytic cell without a separator, and the distance between the two electrodes was about 1.5 mm.
  • the array electrode prepared in Example 2 was subjected to scanning electron microscopy to obtain an SEM image, as shown in Figure 4.
  • SEM image As can be seen from Figure 4, the finally obtained inclined conical structure is completely preserved, and the metal is uniformly deposited during the electroplating process.
  • the array electrodes prepared in Examples 1 to 3 were observed with a high-speed camera, and the bubble transport behavior at different tilt angles (10°, 35° and 50°) was obtained. As shown in Figure 5. It can be seen from Figure 5 that the bubbles directionally slide and desorb along the cone. During the bubble sliding process and after desorption, more active sites will be exposed to promote the gas evolution reaction.
  • Example Bubble desorption size ( ⁇ m) Percentage of bubble desorption (%) Example 1 155 ⁇ 10 49.5
  • Example 2 45.2 ⁇ 7 46.3
  • Example 3 36.5 ⁇ 5 51.2 Comparative example 3 167 ⁇ 8 47.9
  • a comparison chart of bubble slip rate and starting slip size at different tilt angles is drawn, as shown in Figure 6; according to the data in Table 1, the desorption of bubbles of various sizes from the surface of a single cone at different tilt angles is drawn.
  • the time statistics chart is shown in Figure 7.
  • a statistical graph of the proportion of bubble desorption size at different inclination angles is drawn, as shown in Figure 8.
  • a statistical graph of the proportion of bubbling desorption size in Comparative Example 3 is drawn, as shown in Figure 9.
  • the desorption size and desorption time of bubbles also vary with the change of the cone tilt angle.
  • the tilt angle is 10°
  • the desorption size of bubbles is mostly concentrated around 155 ⁇ m
  • the desorption time is about 267 ms
  • there are large bubbles (300-400 ⁇ m) deposited, which are not completely desorbed until t 2854 ms, causing severe coverage. Active site phenomena.
  • the tilt angle is 35°
  • the desorption size is reduced to 1/3 of the previous size, concentrated at around 45.2 ⁇ m, and the desorption time is shortened accordingly (53 ms).
  • the large bubble desorption time is shortened to 1671ms at this time, the siltation phenomenon still exists.
  • the cone inclination angle is crucial to the bubble transport process, which is mainly manifested in bubble slippage on a single cone and bubble desorption between adjacent cones. of two processes. Different tilt angles will affect different bubble slip speeds and fusion times; they will also affect the desorption size and desorption time of bubbles. On the same superaerophobic cone, the movement time of bubbles with different tilt angles is different. As shown in Example 1 in Figure 5, tiny bubbles near the tip began to slide after growing on a superhydrophobic cone with an inclination angle of 10° for 80 ms. During this process, the bubbles never left the electrode surface. After 85 ms, the two bubbles began to slide.
  • the electrical impedance test is performed at a voltage of 0.2V relative to the reversible hydrogen electrode (RHE), from 10 5 Hz to 0.1Hz.
  • the impedance test chart obtained is shown in Figure 13.
  • the current density diagram at constant potential is obtained, as shown in Figure 10; the electrochemical linear polarization curve (LSV) curve is obtained, as shown in Figure 11; the Tafel slope diagram is obtained, as shown in Figure 12; the electrochemical impedance diagram is obtained , as shown in Figure 13; the normalized ECSA curve of electric double layer capacitance and electrochemical active area is obtained, as shown in Figure 14; the normalized ECSA curve is obtained, as shown in Figure 15.
  • LSV electrochemical linear polarization curve
  • the peak overpotential is the same ( ⁇ 0V), but the difference is the current density growth rate.
  • the electrode surface exhibits the best HER catalytic activity.
  • the structure when only a Ni-P metal layer is deposited on the electrode surface and then a PTFE solution with a concentration of 0.6% is sprayed, the structure is particularly smooth.
  • the bubble contact angle is approximately 62°, and the electrode surface exhibits super aerophilic characteristics at this time.
  • the adhesion force is approximately 78 ⁇ N, showing strong adhesion.
  • the electrode is not suitable for gas production, but only for transporting gas. After energization, bubbles are generated on the surface and a gas film is quickly formed. Due to the Laplace pressure provided by the cone, coupled with the buoyancy component, the bubbles are directionally transported along the direction of the cone, from the tip to the root end.
  • the bubble contact angle at this time is about 131°, indicating that the surface is aerophobic, as shown in c in Figure 16, and it also ensures excellent conductivity as a conductive host.
  • the value is significantly reduced (16 ⁇ N).
  • part of the gas can be stuck in the gaps, forming a moderate adhesion state on the surface.
  • the formation of an aerophobic adhesive surface is not only conducive to the generation of bubbles, but a certain adhesion force also makes it difficult for the bubbles on the surface to detach directly from the surface under the action of buoyancy and move irregularly in the solution.
  • the adhesion force can overcome part of the buoyancy force, causing the bubbles below the cone to flip to the top of the cone without detaching.
  • the components of Laplace force and buoyancy force dominate. , making it slide well along the inclined direction from the tip of the cone to the wider end, and the bubble fusion effect occurs.
  • the special wheat ear-like structure of copper element will not only improve the conductivity of the substrate, but also achieve directional slip of bubbles.
  • the two electrode plates were placed in a single cell (the device of Example 4 is the same as that of Comparative Example 4 , the difference is that the electrode of Example 4 was replaced with the electrode of Comparative Example 4) to perform a hydrogen evolution reaction, and the bubble state was observed as shown in Figure 17. Continuously shorten the distance between them and observe the bubble state in the electrolyte. When the minimum distance reaches 1.5mm, the bubbles can still ensure orderly movement. As shown in Figure 18, a high-speed camera is used to magnify the observation.
  • the left side is the cone tilt array electrode (Example 4), and it can be seen that the bubbles are highly directionally transported; the right side is an ordinary superaerophobic flat electrode (Comparative Example 4), and the bubbles can be seen. Found in large amounts in electrolytes. It is concluded that the macrostructure of the cone and the microstructure of wheat ears jointly ensure the directional transport of bubbles.
  • Figure 19 is a gas chromatogram of the pyramidal tilted array electrode (Example 4) after 1 hour of reaction
  • Figure 20 is a gas chromatogram of the ordinary supergas-phobic flat electrode (Comparative Example 4) after 1 hour of reaction. It can be seen that the purity of hydrogen prepared using the electrode provided by the present invention can reach 99.999%, while the comparative electrode has an oxygen peak and the calculated purity is only 88.999%. It is concluded that the macrostructure of the cone and the microstructure of wheat ears jointly ensure the directional transport of bubbles.
  • the array electrode provided by the present invention is used for high-speed unidirectional bubble evolution and H 2 /O 2 product separation, and a downward-sloping 3D printed conical array with a viscous anaerobic surface is produced.
  • this method can control the unidirectional transport of bubbles along the electrode, with the driving forces being Laplace pressure and buoyancy.
  • the membrane-less water splitting device with a cathode-anode spacing of 1.5 mm, there was no significant gas mixing, indicating efficient collection of gas products.
  • the array electrodes prepared in Examples 5 and 6 are used for the hydrogen evolution reaction and the array electrodes with the copper metal layer prepared in Examples 1 to 3 are used for the hydrogen evolution reaction and have the same results, and the generated gas can be transported in a directional manner.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

本发明属于电催化、电极设计与制造技术领域，具体涉及一种宏观阵列电极及其制备方法和应用。本发明提供了一种宏观阵列电极，包括导电基体和沉积在所述导电基体表面的浸润性调控层；所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；所述浸润性调控层由纳米颗粒聚集体组成。在本发明中，阵列电极中锥体与基底垂直方向具有一定的角度，在形状梯度引起的拉普拉斯力和浮力分量的共同作用下提供良好的气泡牵引力，而浸润性调控层又使阵列电极具有粘附态的疏气表面，利用本发明提供的阵列电极进行析气反应电极能够使析气反应产生的气泡定向输运。

Description

一种宏观阵列电极及其制备方法和应用 技术领域
本发明属于电催化、电极设计与制造领域，具体涉及一种宏观阵列电极及其制备方法和应用。
背景技术
随着传统化石燃料的枯竭，寻找和开发替代一次能源的新型能量储存与转换系统是当前研究的重点所在。在众多能源转换体系中，析气反应是一个庞大且重要的分支，其中析氢反应、析氧反应及析氯反应作为典型的析气反应是化工产业中的重要组成部分。
析气反应系统中电极直接影响析气效率。传统的析气反应的电极为表面为超亲气的电极，利用这种电极进行析气反应容易使析气反应产生的气泡粘附在电极表面，从而阻止电极表面活性部位与电解液的直接接触，降低析气反应产气效率。为了提高产气效率科研人员研究开发了表面为超疏气的电极用于析气反应系统。表面为超疏气的电极对析气反应产生的气泡具有极小的粘附力能够快速释放析气反应产生的气泡，提高了析气反应的产气效率，但是由于电极表面的超疏气性质，导致析气反应产生的气泡无法有规则的运输，析气反应产生的气泡在电解质中进行无规则运动，降低了气体收集效率。
发明内容
有鉴于此，本发明提供了一种阵列电极及其制备方法和应用，本发明提供的阵列电极具有粘附态的疏气表面，将本发明提供的阵列电极用于析气反应电极能够使析气反应产生的气泡定向输运。
为了解决上述技术问题，本发明提供了一种宏观阵列电极，包括导电基体和沉积在所述导电基体表面的浸润性调控层；
所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
所述浸润性调控层由纳米颗粒聚集体组成。
优选的，所述圆锥体的母线长度为100～5000μm，所述圆锥体与所述基底接触部分的直径为10～5000μm，所述锥体阵列中单个圆锥体与相邻圆锥体 之间的间距为10～5000μm。
优选的，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当所述纳米颗粒聚集体为非催化活性物质时，所述锥体阵列还包括分布在浸润性调控层表面的催化剂。
优选的，所述纳米颗粒聚集体包括沿主干四周分布的若干列纳米分支，每列纳米分支中的单个纳米分支包括四周分布的次级纳米金属颗粒聚集体。
优选的，所述催化活性物质包括Cu、Ni、Co-Ni合金、Pt。
优选的，所述非催化活性物质包括碳纳米管。
优选的，所述催化剂包括电化学催化剂金属、金属硫化物、金属氮化物、金属碳化物、金属氧化物，金属氢氧化物，金属磷化物。
优选的，所述导电基体包括本征基体；所述本征基体包括导电物质或非导电物质；
当所述本征基体为非导电物质时，所述本征基体表面还包括导电层。
优选的，所述导电基体包括镍磷导电基体、铜导电基体或锌导电基体。
优选的，浸润性调控层与析气反应产生的气泡的接触角为120～150°。
本发明还提供了上述技术方案所述宏观阵列电极的制备方法，包括以下步骤：
制备导电基体，所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
在所述导电基体表面沉积浸润性调控层，得到所述宏观阵列电极；所述浸润性调控层由纳米颗粒聚集体组成。
优选的，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当所述纳米颗粒聚集体为催化活性物质时，所述浸润性调控层的制备方法包括以下步骤：
在导电基体表面第一沉积催化活性物质，得到所述宏观阵列电极。
优选的，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当纳米颗粒聚集体为非催化活性物质时，所述浸润性调控层的制备方法包括以下步骤：
在导电基体表面第二沉积非催化活性物质，得到初级宏观阵列电极；
在所述初级宏观阵列电极表面第三沉积催化剂，得到所述宏观阵列电极。
本发明还提供了上述技术方案所述宏观阵列电极或上述技术方案所述制备方法制备得到的宏观阵列电极作为析气反应电极的应用。
本发明提供了一种宏观阵列电极，包括导电基体和沉积在所述导电基体表面的浸润性调控层；所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；所述浸润性调控层由纳米颗粒聚集体组成。在本发明中，阵列电极中锥体与基底垂直方向具有一定的角度，在拉普拉斯力和浮力分量的共同作用下能够提供很好的气泡牵引力，而浸润性调控层又使阵列电极表面具有粘附态的疏气表面，利用本发明提供的阵列电极进行析气反应电极能够使析气反应产生的气泡定向输运。
附图说明
图1为实施例1制备得到的树脂基体、镍磷导电基体、初级阵列电极和阵列电极的实物图；
图2为实施例1制备得到的初级阵列电极表面的SEM图；
图3为实施例1制备得到的初级阵列电极表面铜的XRD谱图；
图4为实施例2制备得到的阵列电极表面的SEM图；
图5为对实施例1～3制备得到的阵列电极做HER反应，得到不同倾斜角度(10°，35°和50°)下的气泡输运行为图；
图6为不同倾斜角度下的气泡滑移速率和开始滑移尺寸的对比图；
图7为不同倾斜角度下，各尺寸气泡脱离单一锥体表面的脱附时间统计图；
图8为不同倾角度下，气泡脱附尺寸所占比例统计图；
图9为对比例3制备的平整电极，气泡脱附尺寸所占比例统计图；
图10为实施例1～3与对比例3制备得到的电极，做HER反应所对应的电流密度图；
图11为实施例1～3与对比例3制备得到的电极，做HER反应所对应的电流密度极化曲线(LSV)图；
图12为实施例1～3与对比例3制备得到的电极所对应的Tafel斜率图；
图13为实施例1～3与对比例3制备得到的电极所对应的交流阻抗图；
图14为实施例1～3与对比例3制备得到的电极所对应的双电层电容和电化学活性面积(ECSA)图；
图15为实施例1～3与对比例3制备得到的电极所对应的归一化电化学活性面积(ECSA)图；
图16为实施例2与对比例1、2制备得到的电极所对应的SEM图、粘附力图及相应的气泡行为图；
图17为实施例4和对比例4反应所用的单池电解池装置数码相机图；
图18为实施例4和对比例4反应中对应的气泡状态高速摄像机实拍图；
图19为对比例4反应1h后对应的气相色谱图；
图20为实施例4反应1h后对应的气相色谱图；
图21为实施例5制备得到的初级阵列电极表面的SEM图
图22为实施例6制备得到的初级阵列电极表面的SEM图。
具体实施方式
本发明提供了一种阵列电极，包括导电基体和沉积在所述导电基体表面的浸润性调控层；
所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
所述浸润性调控层由纳米颗粒聚集体组成。
在本发明中，所述圆锥体与基底垂直方向的夹角为0～85°优选为10～50°；所述圆锥体的母线长度优选为100～5000μm，更优选为300～1500μm；所述圆锥体与所述基底接触部分的直径优选为200～400μm，更优选为250～350μm；所述锥体阵列中单个锥体与相邻锥体之间的间距优选为150～300μm，更优选为200～250μm。本发明对所述导电基体的基底的尺寸无特殊限定，根据阵列电极的需要进行设计即可。
在本发明中，所述浸润性调控层由纳米颗粒聚集体组成；所述纳米颗粒聚集体优选包括沿主干四周分布的若干列纳米分支，每列纳米分支中的单个纳米分支包括四周分布的次级纳米金属颗粒聚集体。在本发明中，所述纳米 颗粒聚集体优选呈麦穗状；所述纳米颗粒聚集体的粒径优选为2～15μm，更优选为8μm。
在本发明中，所述纳米颗粒聚集体优选包括催化活性物质或非催化活性物质；所述催化活性物质优选包括Cu、Ni、Co-Ni合金或Pt，更优选为Cu、Ni或Co-Ni合金；所述非催化活性物质优选包括碳纳米管。
在本发明中，当所述纳米颗粒聚集体为催化活性物质时，所述浸润性调控层其两个作用，第一个作用为保证气泡与锥体的接触角为120～150°，以保证生成气泡的运动为粘附滚动；第二个作用为起催化剂的作用，催化析气反应的进行。
在本发明中，当所述纳米颗粒聚集体为非催化活性物质时，所述锥体阵列优选还包括分布在浸润性调控层表面的催化剂。在本发明中，所述催化剂优选包括电化学催化剂金属、金属硫化物、金属氮化物、金属碳化物、金属氧化物，金属氢氧化物，金属磷化物，更优选为电化学催化剂金属。在本发明中，所述电化学催化剂金属优选包括Pt、Pd、Ru、Au、Ag、Ir或Rh，更优选为Pt。本发明中，所述金属硫化物优选包括MoS x、FeS 2、NiS 2或CoS 2；所述金属氮化物优选包括Ni-SN@C、Ni 3N或Ni 3FeN；所述金属碳化物优选包括Mo 2C、CaC 2、Cr 3C 2；所述金属氧化物优选包括CuO或ZnO；所述金属氢氧化物优选包括Cu(OH) 2或二维层状双氢氧化物(LDHs)；所述金属磷化物优选包括FeP、CoP、NiP、FeCoP、FeNiP或CoNiP。
在本发明中，所述导电基体优选包括本征基体；所述本征基体优选包括导电物质或非导电物质。在本发明中，当所述本征基体为导电物质时，直接在本征基体表面沉积浸润性调控层。在本发明中，所述导电物质优选包括石墨碳或金属材料，更优选为石墨碳。在本发明中，所述金属材料优选包括铜、镍或铁，更优选为铜。在本发明中，当导电物质为石墨碳时，本发明制备石墨碳基体的方法优选包括机械微切割、化学气相沉积或氧化还原，更优选为机械微切割。当导电物质为金属材料时，本发明制备金属基体的方法优选为电化学腐蚀。
在本发明中，当所述本征基体为非导电物质时，所述本征基体表面还包括导电层。在本发明中，所述非导电物质优选包括树脂或聚甲基丙烯酸甲酯 (PMMA)，更优选为树脂。在本发明中，所述导电层优选包括镍磷导电层、铜导电层、锌导电层。在本发明中，当非导电物质物树脂时，本发明制备树脂基体的方法优选包括光固化、热固化或3D打印，更优选为3D打印。本发明优选在树脂基体表面化学沉积导电层。
在本发明中，所述导电基体优选包括镍磷导电基体、铜导电基体、锌导电基体，更优选为镍磷导电基体。在本发明中，所述镍磷导电基体以树脂基体为本征基体，以沉积在所述树脂基体表面的镍磷层为导电层。在本发明中，所述镍磷导电基体的制备方法优选包括以下步骤：
通过3D打印制备树脂基体；
在所述树脂基体表面化学沉积镍磷金属层，得到所述镍磷导电基体。
本发明通过3D打印制备树脂基体。本发明在3D打印前还优选包括：利用计算机辅助设计软件设计树脂基体的模型；将所述模型导入3D打印机中的的定制软件中。在本发明中，所述模型的尺寸和形状与导电基体的尺寸和形状一致。
在本发明中，所述3D打印优选为光固化3D打印，所述光固化3D打印用原料优选为光敏树脂，所述光敏树脂优选为UV光敏树脂。在本发明中，所述光固化3D打印用光的波长优选为350～450nm，更优选为405nm。在本发明中，所述3D打印用设备优选为UV立体光刻3D打印机，所述UV立体光刻3D打印机的型号优选为BMF nanoArch P140。
在本发明中，所述3D打印后优选还包括：将3D打印完成后产品进行超声处理。在本发明中，所述超声处理用溶剂优选为乙醇；所述超声处理的功率优选为200～300W，更优选为290W；所述超声处理的温度优选为10～25℃，更优选为19℃；所述超声处理的时间优选为1～10min，更优选为5min；所述超声处理的次数优选为1～5次，更优选为3次。在本发明中，所述超声处理能够除去3D打印产品表面未固化的光敏树脂。
得到树脂基体后，本发明在所述树脂基体表面化学沉积镍磷金属层，得到所述镍磷导电基体。在本发明中，所述化学沉积前优选还包括：将所述树脂基体依次在敏化液和活化液中浸泡。在本发明中，所述敏化液优选包括可溶性锡盐、酸液和水的混合溶液。在本发明中，所述可溶性锡盐优选包括氯 化锡、硫酸锡、乙酸锡、四氯化锡、二氯化锡和溴化锡中的一种或多种，更优选为氯化锡。在本发明中，当可溶性锡盐为两种以上上述具体物质时，本发明对具体物质的配比无特殊限定，采用任意配比即可。在本发明中，所述可溶性锡盐中锡离子在敏化液中的质量浓度优选为9～11g/L，更优选为10g/L。在本发明中，所述酸液优选包括盐酸、硫酸、硝酸、磷酸、醋酸或次氯酸，更优选为盐酸；所述酸液中氢离子在敏化液中的摩尔浓度优选为0.11～0.13mol/L，更优选为0.12mol/L。在本发明中，在敏化液中浸泡的时间优选为5～450min，更优选为13～100min，最优选为15～30min；在敏化液中浸泡的温度优选为10～400℃，更优选为40～100℃，最优选为50～80℃。
在本发明中，所述活化液优选包括可溶性钯盐、酸液和水的混合溶液。本发明在敏化液中浸泡后优选将所述浸泡后的样品进行洗涤，所述洗涤用溶剂优选为去离子水，所述洗涤的次数优选为2～4次，更优选为3次。
在本发明中，所述可溶性钯盐优选包括硝酸钯、硫酸钯、醋酸钯、氯化钯和二溴化钯中的一种或多种，更优选为氯化钯或醋酸钯。在本发明中，当可溶性锡盐为两种以上上述具体物质时，本发明对具体物质的配比无特殊限定，采用任意配比即可。在本发明中，所述可溶性钯盐中钯离子在活化液中的质量浓度优选为30～150mg/L，更优选为100mg/L。在本发明中，所述酸液优选包括盐酸、硫酸、硝酸、磷酸、醋酸或次氯酸，更优选为盐酸；所述酸液中氢离子在活化液中的摩尔浓度优选为0.01～0.1mol/L，更优选为0.02mol/L。在本发明中，在活化液中浸泡的时间优选为5～450min，更优选为20～100min，最优选为25～50min；在活化液中浸泡的温度优选为10～400℃，更优选为40～100℃，最优选为50～80℃。
本发明在活化液中浸泡后优选将所述浸泡后的样品进行洗涤，所述洗涤用溶剂优选为去离子水，所述洗涤的次数优选为2～4次，更优选为3次。
在本发明中，所述树脂基体经过敏化溶液和活化溶液浸泡增加了树脂基体表面的亲水性，利于后继镍磷金属层与树脂基体更好的结合。
在本发明中，所述化学沉积优选为将所述树脂基体于化学沉积溶液中浸泡。在本发明中，所述化学沉积溶液的pH值优选为9～11，更优选为10。在本发明中，所述化学沉积溶液优选为NiSO 4·6H 2O、C 6H 8O 7·H 2O和 NaH 2PO 2·H 2O的水溶液。在本发明中，所述NiSO 4在化学沉积溶液中的质量浓度优选为2～20g/L，更优选为10～15g/L；所述C 6H 8O 7在化学沉积溶液中的质量优选为15～25g/L，更优选为18～21g/L；所述NaH 2PO 2在化学沉积溶液中的质量优选为5～25g/L，更优选为8～15g/L。
在本发明中，所述浸泡前优选还包括：将所述化学沉积溶液和络合剂溶液混合。在本发明中，所述络合剂溶液中的络合剂优选包括柠檬酸钠、酒石酸钠、苹果酸、氨基乙酸、庚糖酸盐、葡萄糖酸钠、海藻酸钠或氨水；所述络合剂溶液中络合剂的质量浓度优选为5～30％，更优选为25％。在本发明中，所述化学沉积溶液和络合剂溶液的体积比优选为3～6:1，更优选为4:1。在本发明中，所述络合剂能控制可供反应的游离镍离子的浓度，抑制亚磷酸镍的沉淀，提高镍液的稳定性，延长镍液的使用寿命；起到缓冲剂和促进剂的作用，提高镍液的沉积速度。
本发明在化学沉浸溶液中浸泡的温度优选为10～400℃，更优选为80～300℃，最优选为100～200℃；在化学沉浸溶液中浸泡的时间优选为5～450min，更优选为28～300min，最优选为50～150min。
在本发明中，以钯为催化剂以次磷酸钠为还原剂以还原反应过程中生成的氢离子为氧化剂为例，所述化学沉积包括还原反应和氧化反应；所述还原反应的离子反应方程式如式1所示：
2H 2PO 2 -+2H 2O+Ni 2+→Ni 0+H2↑+4H ++2HPO 3 2-   式1。
在本发明中，所述氧化反应的离子反应方程式如式2所示：
H 2PO 2-+[H +]→P+H 2O+OH -    式2。
在本发明中，所述树脂基体表面化学沉积的镍磷金属为非晶态薄片结构。
在本发明中，所述化学沉积后优选还包括：将化学沉积后产品进行洗涤。在本发明中，所述洗涤用溶剂优选为去离子水，所述洗涤的次数优选为2～4次，更优选为3次。
本发明提供的宏观阵列电极具有粘气疏气表面；锥体阵列能够提供足够 的拉普拉斯压力和浮力的分量使在阵列电极表面产生的气泡不易在浮力的作用下直接从表面脱附，在溶液中无规则运动。在本发明中，阵列电极表面产生的尺寸很小的气泡，粘附力可以克服部分浮力，使锥体下端的气泡翻转到锥体上端而不脱附，随着气泡增大拉普拉斯力和浮力也逐渐增大，在纳米颗粒组成的聚集体和锥体阵列共同作用下大尺寸的气泡沿着锥体倾斜的方向脱附并定向输运。在本发明中，气泡在翻转过程中和脱附后还能暴露出更多的活性位点(催化剂)提高了产气效率。采用本发明提供的阵列电极作为析气反应的电极不仅能够提高气体产率还能提高产气效率。
本发明还提供了上述技术方案所述阵列电极的制备方法，包括以下步骤：
制备导电基体，所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
在所述导电基体表面沉积浸润性调控层，得到所述宏观阵列电极；所述浸润性调控层由纳米颗粒聚集体组成。
本发明制备导电基体，所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°。本发明对制备导电基体的方法无特殊要求，只要能够使圆锥体与基底垂直方向的夹角满足上述要求即可。
在本发明中，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当纳米颗粒聚集体为催化活性物质时，所述浸润性调控层的制备方法包括以下步骤：
在导电基体表面第一沉积催化活性物质，得到所述宏观阵列电极。
在本发明中，所述第一沉积优选为电沉积；所述电沉积的时间优选为100～950s，更优选为200～900s，最优选为300～800s；所述电沉积的电压优选为-0.08～10.60V，更优选为-0.58～8.60V，最优选为-0.7～2.60V。
所述电沉积用电解液为金属的硫酸盐和H 2SO 4的水溶液；所述电解液中金属的硫酸盐的浓度优选为6～90g·L -1，更优选为16～70g·L -1，最优选为20～40g·L -1；所述电解液的pH值优选为0.8～6，更优选为1.5～4。在本发明中，所述电解液优选将金属硫酸盐溶解于硫酸水溶液中得 到。在本发明中，当金属为铜时电解液优选为将硫酸铜溶解于硫酸水溶液中得到。在本发明中，所述电沉积金属的电压为-0.1～1.6V，优选为-0.6V～1.6V；所述电沉积金属的时间优选为200～950s，更优选为300～860s。在本发明中，电沉积铜时电沉积用电解液为CuSO 4和H 2SO 4的水溶液；所述电解液中硫酸铜的浓度优选为0.05～0.9mol·L -1，更优选为0.1～0.6mol·L -1；所述电解液的pH值优选为0.5～5.2，更优选为1～4；所述电沉积铜的电压优选为-0.05～-0.95V，更优选为-0.3～-0.8V；所述电沉积铜的时间优选为200～850s，更优选为240～700s。
在本发明中，所述电沉积金属优选以铂丝作为对电极，以Ag/AgCl作为参比电极。
本发明通过限定电沉积金属的时间、电位以及电解液的组成得到了麦穗状纳米金属颗粒聚集体。
在本发明中，所述电沉积金属后优选还包括：将电沉积金属后电极依次进行洗涤和干燥。在本发明中，所述洗涤用溶剂优选为去离子水；所述洗涤的次数优选为2～4次，更优选为3次。在本发明中，所述干燥优选为冷冻干燥；所述冷冻干燥的温度优选为-20～-60℃，更优选为-30～-50℃；所述冷冻干燥的时间优选为10～14h，更优选为11～13h。
在本发明中，当纳米颗粒聚集体为非催化活性物质时，所述浸润性调控层的制备方法优选包括以下步骤：
在导电基体表面第二沉积非催化活性物质，得到初级宏观阵列电极；
在所述初级宏观阵列电极表面第三沉积催化剂，得到所述宏观阵列电极。
本发明在导电基体表面第二沉积非催化活性物质，得到初级宏观阵列电极。在本发明中，所述第二沉积优选为用气相沉积法。
在本发明中，当非催化活性物质为碳纳米管时，具体制备方法为：以二甲苯为碳源，二茂铁作为催化剂，将两者混合液超声振荡10min作为前驱液，导电基体作为衬底与前驱液一并置于石英舟中，放入石英管中部升温至750℃，反应2h后，降至室温。
得到初级宏观阵列电极后，本发明在所述初级宏观阵列电极表面第三沉 积催化剂，得到所述宏观阵列电极。在本发明中，所述第三沉积优选为电化学沉积或水热沉积。在本发明中，当催化剂为电化学催化剂金属时，所述第三沉积优选为电化学沉积；当催化剂为金属硫化物、氮化物、碳化物、氧化物、氢氧化物或金属磷化物时，所述第三沉积优选为水热沉积。在本发明中，所述电化学沉积优选为将所述初级宏观阵列电极浸泡于催化剂溶液中，进行电化学沉积，得到所述宏观阵列电极。在本发明中，所述催化剂溶液的摩尔浓度优选为0.5～15mmol/L，更优选为2～9mmol/L。在本发明中，所述催化剂溶液优选包括金属盐溶液，更优选为H 2PtCl 6溶液。在本发明中，所述电化学沉积的时间优选为1～240min，更优选为2～110min，最优选为3～80min。
在本发明中，所述水热沉积优先为将所述初级宏观阵列电极与催化剂溶液同时放在反应釜中，得到所述宏观阵列电极。在本发明中，所述催化剂溶液优选包括金属盐溶液、非金属盐溶液。在本发明中，所述非金属盐溶液中非金属盐优选包括碳源、硫源或氮源。在本发明中，所述硫源优选为硫脲、或硫单质；所述碳源优选为碳化钼、碳化钒或碳化钛；所述氮源优选为氮化铁、氮化钴或氮化钨。在本发明中，所述催化剂溶液中金属盐的摩尔浓度优选为1～30mmol/L，更优选为5～20mmol/L；所述催化剂溶液中非金属盐的摩尔浓度优选为4～35mmol/L，更优选为7～25mmol/L。在本发明中，所述水热沉积的时间优选为3～18h，更优选为5～15h。在本发明中，所述水热沉积的温度优选为50～220℃，更优选为100～180℃。
在本发明中，所述第三沉积后优选还包括：将所述第三沉积后电极依次进行洗涤和干燥。在本发明中，所述洗涤用溶剂优选为去离子水；所述洗涤的次数优选为2～4次，更优选为3次。在本发明中，所述干燥优选为烘干；所述烘干的温度优选为室温，所述室温的温度优选为20～35℃，更优选为25～30℃；所述烘干的时间优选为15～60mins，更优选为20～40mins。
本发明还提供了上述技术方案所述宏观阵列电极或上述技术方案所述制备方法制备得到的宏观阵列电极作为析气反应电极的应用。本发明对所述应用无特殊限定，采用本领域常规的方式即可。
在本发明中，当所述阵列电极作为析气反应电极时，所述析气反应系统中阴极和阳极间的距离优选为1～100mm，更优选为1.5～50mm。
将本发明提供的阵列电极作为析气反应的电极能够连续产生、定向传输和高效收集析气反应生成的气泡。本发明凭借阵列电极的润湿梯度和锥形形态，集成束电极能够连续产生、定向传输和高效收集气泡，大大防止气泡直接释放到电解液中，同时，也可以缩短阴极和阳极之间的距离，最大限度地减少额外设备的使用。
为了进一步说明本发明，下面结合实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
利用计算机辅助设计软件设计电极模型，电极模型的基底为1cm×1cm×0.5cm的正方体，基底表面有289个锥体，所述锥体成阵列排布，所述锥体与基底直接接触的直径为300μm，所述锥体的长度为0.84cm，所述锥体与相邻锥体之间的间距为200μm，锥体与基底垂直方向的夹角为10°；将电极模型文件导入到UV立体光刻3D打印机(BMF nanoArch P140)的定制软件中，以光固化UV光敏树脂为原料利用波长为405nm的光进行光固化3D打印；将光固化3D打印产品进行超声处理(以乙醇为溶剂，功率为290W，温度为19℃)5min，重复超声处理3次，得到树脂基体；
将所述树脂基体在敏化液(10g L -1 SnCl 2，0.12mol/L HCl)中50℃浸泡15min，用去离子水洗涤3次；将洗涤后产品在活化溶液(100mg L -1PdCl 2，0.03mol/L HCl)中50℃浸泡25min，去离子水洗涤3次，得到预处理树脂基体；
将40mL的pH为10.0的化学沉积溶液(13g L -1 NiSO 4，21g L -1 C 6H 8O 7，10.6g L -1 NaH 2PO 2)和10mL质量浓度为25％的氨水混合，得到混合液；将预处理树脂基体在所述混合液中80℃浸泡30min后用去离子水洗涤三次，得到镍磷导电基体；
以pH为2 CuSO 4浓度为0.1mol·L -1的硫酸铜和硫酸的水溶液为电解液，以铂丝作为对电极，Ag/AgCl作为参比电极，在-0.6V恒定电压下在所述镍磷导电基体表面电沉积800s，利用去离子水对电沉积得到的电极进行洗涤3次，-33.7℃冷冻干燥12h，得到初级阵列电 极，其纳米金属颗粒聚集体的粒径为8μm；
将所述初级阵列电极浸泡在3mmol/L的H 2PtCl 6溶液中，电化学沉积2mins，将电化学沉积得到的电极去离子水洗涤3次，25℃烘干30mins，得到阵列电极；阵列电极中最外层催化剂纳米铂的粒径为1μm。
实施例2
按照实施例1的方法制备阵列电极，不同之处在于，锥体与基底垂直方向的夹角为35°。
实施例3
按照实施例1的方法制备阵列电极，不同之处在于，锥体与基底垂直方向的夹角为50°。
实施例4
将两片实施例3的电极放置在无隔膜的单池电解池中，阴极和阳极两电极间距离约1.5mm。
实施例5
按照实施例1的方法制备阵列电极，不同之处在于，以pH值为2硫酸镍的浓度为60g·L -1的硫酸的水溶液为电解液，在1.5V恒定电压下在所述镍磷导电基体表面电沉积920s。
实施例6
按照实施例1的方法制备阵列电极，不同之处在于，以pH值为1硫酸镍的浓度为60g·L -1和硫酸钴的浓度为50g·L -1的硫酸的水溶液为电解液，在0.8V恒定电压下在所述镍磷导电基体表面电沉积800s。
对比例1
以传统的超亲气电极为对比例；制备方法包括以下步骤：按照实施例1制备得到镍磷导电基体；将所述镍磷导电基体25℃干燥后，在镍磷导电基体表面喷涂一层质量浓度为0.1％的PTFE溶液(聚四氟乙烯溶液)，60°的真空烘干2h，得到超亲气电极)
对比例2
以传统的超疏气电极为对比例；按照实施例1制备得到超疏气电极；不 同之处在于，电沉积用电解液为硫酸铜的浓度为0.1mol·L -1，pH值为2的硫酸铜和硫酸的水溶液；电沉积的电压为-1V，时间为1200s。
对对比例2制备得到的超疏气电极进行扫描电镜检测(SEM)，如图16中b所示，由图16b得知对比例2制备得到的阵列电极中的铜层中的纳米铜聚集体并非麦穗状，而是纳米花状。
对比例3
按照实施例1的方法制备电极，不同之处在于，基底为1cm×1cm×0.5cm的正方体，基底表面不含有阵列锥体。
对比例4：将两片对比例2的电极放置在无隔膜的单池电解池中，两电极间距离约1.5mm。
实施例1制备得到的树脂基体、镍磷导电基体、初级阵列电极和阵列电极的实物图如图1所示。
对实施例1制备得到的初级阵列电极的表面进行扫描电镜检测，得到SEM图，如图2所示。由图2可知，初级阵列电极铜层中的铜为麦穗状。
对实施例1制备得到的初级阵列电极中的铜进行XRD检测，得到铜的XRD谱图，如图3所示。由图3可知，电镀上的金属确为铜单质，并且在很长一段时间内没有被氧化，说明此方法可以得到稳定性很好的阵列电极。
对实施例2制备得到的阵列电极进行扫描电镜检测，得到SEM图，如图4所示。由图4可知，最终得到的倾斜的锥形结构完整保留，且电镀过程中金属均匀沉积。
对实施例1～3制备得到的阵列电极进行高速摄像机的观察，得到不同倾斜角度(10°，35°和50°)下的气泡输运行为。如图5所示。由图5可以看出气泡沿着锥体定向滑移和脱附，起泡滑移过程中和脱附后会暴露更多的活性位点促进析气反应的进行。
为了进一步评估气泡定向运动的行为，统计了微小气泡在单一锥体上滑 移的尺寸及速率，展示了气泡脱离锥体的尺寸和时间，其结果列于表1中。
表1起泡运动数据
Figure PCTCN2022116536-appb-000001
对拍摄的气泡进行统计得到气泡在一定尺寸脱附的百分比，其结果列于表2。
表2气泡脱附尺寸所占比例数据
实施例 气泡脱附尺寸(μm) 气泡脱附的百分比(％)
实施例1 155±10 49.5
实施例2 45.2±7 46.3
实施例3 36.5±5 51.2
对比例3 167±8 47.9
根据表1中数据绘制不同倾斜角对气泡滑移速率和开始滑移尺寸的对比图，如图6所示；根据表1数据绘制不同倾斜角下，各尺寸气泡脱离单一锥体表面的脱附时间统计图，如图7所示。根据表2中数据绘制不同倾角下，气泡脱附尺寸所占比例统计图，如图8所示。根据表2中数据绘制对比例3起泡脱附尺寸所占比例统计图，如图9所示。
由图6可以看出气泡的平均滑移尺寸和平均滑移速率随着锥体倾斜角的变化，随之锥体倾斜角的增大滑移尺寸是呈逐渐减小的趋势，相对应的，滑移速率是呈逐渐增大的趋势。也就是说，倾斜角增大对气泡在单一锥体上的滑移过程是有很大帮助的。10°、35°和50°的阵列电极上，实验平均速度分别为4.2±2.1、12.3±1.4和24.6±0.9μm ms -1。而实验平均滑移尺寸分别为 37.5±2.1、24.5μL±2.9和16.7±1.6μm。此外，由图7～9也可以看出，气泡的脱附尺寸和脱附时间也随着锥体倾斜角变化而有所不同。当倾斜角为10°时，气泡的脱附尺寸大部分集中在155μm左右，脱附时间约为267ms，而且有大气泡(300～400μm)淤积，直到t＝2854ms后才完全脱附，严重覆盖活性位点的现象。当倾斜角为35°时，脱附尺寸缩小至之前的1/3，集中在45.2μm左右，脱附时间也相应缩短(53ms)。虽然此时大气泡脱附时间缩短至1671ms，但淤积的现象仍然存在。最终，将倾斜度调整为50°，52％的气泡脱附尺寸只有36.5μm，相应的，脱附时间达到最短，t＝15ms，所有气泡在600ms内完全脱离电极表面，完成更新，基本消除了大气泡聚集带来的恶劣后果，运输效率得到明显的提升。而对于平整基底来说，气泡几乎不会在表面滑移，而是直接进行脱附，脱附尺寸大部分集中在167μm，这样产生的后果是气泡杂乱运动，可能会损坏电极。可以得出结论，锥体的高倾斜角赋予了气泡在超疏气锥体上杰出的自发和定向传输性能。
根据图5～8可以看出，在电极阵列上，锥体倾斜角对气泡的运输过程是至关重要的，主要表现在单一锥体上的气泡滑移和相邻锥体之间气泡脱附的两个过程。不同的倾斜角会影响不同的气泡滑移速度，融合时间；还会影响气泡的脱附尺寸和脱附时间。在同一个超疏气锥体上，不同倾斜角的气泡的运动时间是不同的。如图5中实施例1所示，针尖附近微小气泡在倾斜角为10°的超疏水锥体上生长80ms后开始滑移，这一过程中气泡始终没有离开电极表面，85ms后两个气泡进行融合，形成一个更大的气泡。因为一直有电流通过，气泡体积开始原位增大，最终依靠浮力脱附锥体表面，弹跳至另一根锥体表面。而当倾斜角增加至α＝35°时，如图5中实施例2所示，气泡的运动过程是不变的，但滑移时间缩短至49ms，并在53ms时发生气泡间的融合，最终在73s后发生脱附。更进一步的说，当锥体倾斜角增加至α＝50°时，如图5中实施例3所示，滑移时间达到最小，约为34ms，在t＝39ms时发生气泡与气泡间的融合，不断生长，当t＝55ms时，气泡脱离表面，暴露出新的活性位点，以确保电化学析氢反应高效进行。
按照如下方法对阵列电极的电化学性能进行测试：
利用电化学工作站(CHI660e)进行检测，采用三电极体系，用碳棒、甘汞电极和Cu-Pt工作电极在pH＝1的H 2SO 4溶液中组装而成的。在实验之前，先对电极用去离子水冲洗三次，保证表面干净。
恒电位反应的E＝-0.3V vs.RHE，HER反应恒电位下的电流密度图如图10所示。
电位：电解质溶液中通入氢气后达到氢饱和的状态，由0V到-1V进行线性扫描，扫速为0.005mV/s。电化学线性极化曲线(LSV)如图11所示
基于图10得到Tafel斜率如图12所示。
电阻抗测试是电压在0.2V相对于可逆氢电极(RHE)，从10 5Hz到0.1Hz。得到阻抗测试图如图13所示。
设定测试方法为线性扫描法(LSV)，分别以20,40,60,80,100,120mV/s的扫速，在电压范围0.15V-0.25V vs.RHE内测试，选择在0.2V电压下的电流密度计算双电层电容值，用来估算电解液与电极表面接触处的电化学活性比表面积(ECSA)。双电层电容和电化学活性面积如图14所示。
由电流密度与电化学活性面积的比值得出归一化ECSA曲线如图15所示。
得到不同倾斜角下，电化学性能测试相关数据列于表3中。
表3不同倾斜度下的电化学性能测试及对比
Figure PCTCN2022116536-appb-000002
Figure PCTCN2022116536-appb-000003
得到恒电位下的电流密度图，如图10所示；得到电化学线性极化曲线(LSV)曲线图，如图11所示；得到Tafel斜率图，如图12所示；得到电化学阻抗图，如图13所示；得到双电层电容和电化学活性面积归一化ECSA曲线图，如图14所示；得到归一化ECSA曲线图，如图15所示。
由图10～15可以看出，不同倾斜度会影响电极的电化学性能：电流密度，电流密度加速度，塔菲尔斜率和电化学阻抗。由图10可知在相同的电压下，锥体倾斜度越大电流密度更大。从图11曲线图可知，随着电压的增加，锥体倾斜度越大，电流加速度越大；由图12可以看出，锥体倾斜度大的，塔菲尔斜率越小，说明斜率越小说明增长相同的电流密度所需要的过电位越小，活化性能越好；由图13可以看出锥体倾斜度越大，阻抗越小，说明电荷转移电阻越小，电极性能好；由图14可以看出锥体倾斜度越大，双电层电容越大，电化学活性面积ECSA越大，电极表面活性位点越高。由图15归一化ECSA的(j ECSA＝j/ECSA)柱状图得知，电极本身结构的设计带来的活性位点是增多的，催化效应增大。
为了进一步探索阵列电极的电解水性能，选择三电极体系，对其电化学指标进行测试，在恒电位下利用实施例1～3制备得到的阵列电极进行HER反应。对于倾斜角为10°，35°，50°的阵列电极，其电流密度分别为23.6、68.1、91.2mA cm 2，这也与上面讨论的气泡运动状态所一致，气泡滑移和脱附速率更快，被遮挡的活性面积就越容易重新保留在电解液中，保证电路通畅，电流变大。图11给出了其线性扫描伏安曲线(LSV)，可见三种情况下，其起峰过电位是相同的(～0V)，不同的是电流密度增长速率。当倾斜角为50°时，电极表面表现出最好的HER催化活性。除此之外，最大倾斜角的电极也具有更小的塔菲尔斜率(47mV dec-1)，明显优于α＝10°(161mV dec -1)、α＝35°(87mV dec -1)，如图12所示。证明在催化HER过程中，这三个电极经历了相似的反应过程，均遵循Volmer-Heyrovsky步骤。为了进 一步证实倾斜角变化带来的催化活性不同，我们使用交流阻抗法研究电极反应动力学，图13的Nyquist图中显示了α＝50°时相比于其他的角度有着较小的传质阻力(～2.5Ω)，证明此时的电极表面在HER反应中，具有更快的电子传输速率，这也是由于活性位点的及时更新导致的。对于双电层电容来说(图14)，10°，35°，50°分别为13,23,26mF，电化学活性面积为142，371，657，742cm 2。对于归一化ECSA来说(图15)，10°，35°，50°分别为0.06，0.10，0.13mA·cm -2ECSA -1。总之，通过调控电极表面浸润性和倾斜角，对析气反应性能的提高有着很大的帮助。
将对比例1、2和实施例2的电极的表面结构、粘附力和气泡行为进行对比，得到图16，其中a为超亲气电极(对比例1)的SEM图(插图为气泡在水介质中的接触角)，d为超亲气电极对应的粘附力(粘附力测试使用粘附力力测试仪(DCAT21)进行试验)，g为超亲气电极对应的气泡行为；b为超疏气电极(对比例2)的SEM图(插图为气泡在水介质中的接触角)，e为超疏气电极对应的粘附力，h为超疏气电极对应的气泡行为；c为实施例2制备的粘附态疏气电极的SEM图(插图为气泡在水介质中的接触角)，f为粘附态疏气电极对应的粘附力，i为粘附态疏气电极对应的气泡行为
由图16中a可以看出，当只在电极表面沉积一层Ni-P金属层，并且再喷涂浓度为0.6％的PTFE溶液，其结构是特别平整的。气泡接触角大概是62°，此时电极表面表现出超亲气的特性。如图16中d所示，粘附力大概是78μN，表现出很强的粘附力。这种情况下电极不适合产气，只适合运输气体。通电后，表面产生气泡并很快形成气膜，由于锥体提供的拉普拉斯压力，再加上浮力的分量，使气泡沿着锥体的方向，从尖端向根部一端定向输运。但一定时间后，气泡容易淤积在根部，占据活性位点，不适合做HER反应，这种现象可以通过2g的高速显微镜照片清晰的表现出来。当改变修饰条件，即在电极表面沉积Ni-P金属层后，在E＝-1V的电压下，沉积1200s，此时形成Ni-Cu金属电极，但其结构变为了纳米花状，增加了电解液的接 触面积，气泡接触角变为169°，变现出超疏气的特性，如图16中b所示。而此时的粘附力基本可以忽略(4μN)，如图16中e所示。此时气泡又会表现出其他状态，通过图16中h可以看到，在很快的析出后，会进行无规则运动，导致溶液中气泡很乱，当运用于实际生产中时，若阴阳两极电极板距离较近，很大程度上会影响收集气体的纯度。而距离过远时，电子在两极间传输较慢，又会产生一定的电流浪费。继续改变电镀铜的电压及时间，即在Ni-P金属层表面，通入E＝-0.7V的电压800s，得到了均匀致密的Cu单质，形成Ni-Cu金属电极，其表面展现出类似于麦穗的尖状物组合体，此时的气泡接触角约为131°，说明表面是疏气的，如图16中c所示，同时也保证了作为导电宿主的优良导电性。再去测量它的粘附力，如图16中f所示，数值有明显的降低(16μN)。但因为特殊的纳米级结构，使一部分气体可以卡在其间隙中，表面形成适中的粘附态。这种情况下，形成疏气的粘附态表面，不仅有利于气泡的产生，一定粘附力又使得表面的气泡不易在浮力的作用下直接从表面脱附，在溶液中无规则运动。相反，对于一开始产生的尺寸很小的气泡，粘附力可以克服部分浮力，使锥体下面的气泡翻转到锥体上面而不脱附，随后拉普拉斯力和浮力的分量占主导部分，使其很好地沿着倾斜的方向，从锥体的尖端定向滑移到更宽的一端，并且发生气泡融合效应。随着气泡不断变大，浮力增加，逐渐克服了粘附力的作用，最终沿着竖直方向弹跳到另外一个锥上，暴露出新的活性位点，继续重复上述过程，如图16中i所示。总之，特殊的铜单质麦穗状结构，不仅会提高基底导电性，还会很好的实现气泡的定向滑移。
为了进一步验证两极板在距离较近的情况下气泡仍然进行严格的定向输运，并具有较高的纯度，将两个电极板放置于单池中，(实施例4和对比例4的装置一样，区别在于将实施例4的电极替换为对比例4的电极)进行析氢反应，观察气泡状态如图17所示。不断缩短其间距，并观察电解液中的气泡状态。当间距最小达到1.5mm时，气泡仍可保证有序运动。如图18， 用高速摄像机进行放大观察，左边是锥体倾斜阵列电极(实施例4)，可见气泡是高度定向输运的；右边是普通的超疏气平整电极(对比例4)，可见气泡大量存在于电解质中。由此得出结论，锥体的宏观结构和麦穗状微观结构共同保证了气泡的定向输运。
为了进一步来验证图18所述观点，对实施例4和对比例4析氢反应得到的气体进行气相检测，得到气相色谱图如图19和20所示。图19是锥体倾斜阵列电极(实施例4)反应1小时后的气相色谱图，图20是普通的超疏气平整电极(对比例4)反应1小时后的气相色谱图。可见利用本发明提供的电极制备得到的氢气纯度可以达到99.999％，而对比电极存在氧峰，经计算纯度只有88.999％。由此得出结论，锥体的宏观结构和麦穗状微观结构共同保证了气泡的定向输运。综上所述，本发明提供的阵列电极，用于高速单向气泡演化与H 2/O 2产物分离，并制成了一个向下倾斜、具有粘性厌氧表面的3d打印锥形阵列。与传统的气泡不规则地脱离到电解液中不同，这种方法可以控制气泡沿电极的单向传输，其驱动力是拉普拉斯压力和浮力。在阴极-阳极间距为1.5mm的无膜拆分水装置中，没有明显的气体混合，表明气体产物的有效收集。
对实施例5制备得到的初级阵列电极的表面进行扫描电镜检测，得到SEM图，如图21所示。由图21可知，初级阵列电极镍层中的铜纳米镍聚集体为狗尾巴草状。
对实施例6制备得到的初级阵列电极的表面进行扫描电镜检测，得到SEM图，如图22所示。由图22可知，初级阵列电极镍钴合金层中的纳米镍钴聚集体为类麦穗状。
利用实施例5和实施例6制备得到的阵列电极用于析氢反应和利用实施例1～3制备得到的铜金属层的阵列电极用于析氢反应具有相同的结果，能够使产生的气体定向运输。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下 获得其他实施例，这些实施例都属于本发明保护范围。

Claims (14)

  1. 一种宏观阵列电极，包括导电基体和沉积在所述导电基体表面的浸润性调控层；
    所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
    所述浸润性调控层由纳米颗粒聚集体组成。
  2. 根据权利要求1所述宏观阵列电极，其特征在于，所述圆锥体的母线长度为100～5000μm，所述圆锥体与所述基底接触部分的直径为10～5000μm，所述锥体阵列中单个圆锥体与相邻圆锥体之间的间距为10～5000μm。
  3. 根据权利要求1所述宏观阵列电极，其特征在于，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当所述纳米颗粒聚集体为非催化活性物质时，所述锥体阵列还包括分布在浸润性调控层表面的催化剂。
  4. 根据权利要求3所述宏观阵列电极，其特征在于，所述纳米颗粒聚集体包括沿主干四周分布的若干列纳米分支，每列纳米分支中的单个纳米分支包括四周分布的次级纳米金属颗粒聚集体。
  5. 根据权利要求3或4所述宏观阵列电极，其特征在于，所述催化活性物质包括Cu、Ni、Co-Ni合金、Pt。
  6. 根据权利要求3所述宏观阵列电极，其特征在于，所述非催化活性物质包括碳纳米管。
  7. 根据权利要求3或6所述宏观阵列电极，其特征在于，所述催化剂包括电化学催化剂金属、金属硫化物、金属氮化物、金属碳化物、金属氧化物，金属氢氧化物，金属磷化物。
  8. 根据权利要求3所述宏观阵列电极，其特征在于，所述导电基体包括本征基体；所述本征基体包括导电物质或非导电物质；
    当所述本征基体为非导电物质时，所述本征基体表面还包括导电层。
  9. 根据权利要求8所述宏观阵列电极，其特征在于，所述导电基体包括镍磷导电基体、铜导电基体或锌导电基体。
  10. 根据权利要求1～4任一项所述宏观阵列电极，其特征在于，浸润性 调控层与析气反应产生的气泡的接触角为120～150°。
  11. 权利要求1～10任一项所述宏观阵列电极的制备方法，包括以下步骤：
    制备导电基体，所述导电基体包括基底和所述基底表面的锥体阵列，所述锥体阵列由圆锥体组成；所述圆锥体与基底垂直方向的夹角为0～85°；
    在所述导电基体表面沉积浸润性调控层，得到所述宏观阵列电极；所述浸润性调控层由纳米颗粒聚集体组成。
  12. 权利要求11所述制备方法，其特征在于，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当所述纳米颗粒聚集体为催化活性物质时，所述浸润性调控层的制备方法包括以下步骤：
    在导电基体表面第一沉积催化活性物质，得到所述宏观阵列电极。
  13. 权利要求11所述制备方法，其特征在于，所述纳米颗粒聚集体包括催化活性物质或非催化活性物质；当纳米颗粒聚集体为非催化活性物质时，所述浸润性调控层的制备方法包括以下步骤：
    在导电基体表面第二沉积非催化活性物质，得到初级宏观阵列电极；
    在所述初级宏观阵列电极表面第三沉积催化剂，得到所述宏观阵列电极。
  14. 权利要求1～10任一项所述宏观阵列电极或权利要求11～13任一项所述制备方法制备得到的宏观阵列电极作为析气反应电极的应用。
PCT/CN2022/116536 2022-06-20 2022-09-01 一种宏观阵列电极及其制备方法和应用 WO2023245868A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210694723.0A CN114959763B (zh) 2022-06-20 2022-06-20 一种宏观阵列电极及其制备方法和应用
CN202210694723.0 2022-06-20

Publications (1)

Publication Number Publication Date
WO2023245868A1 true WO2023245868A1 (zh) 2023-12-28

Family

ID=82963740

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/116536 WO2023245868A1 (zh) 2022-06-20 2022-09-01 一种宏观阵列电极及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN114959763B (zh)
WO (1) WO2023245868A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114959763B (zh) * 2022-06-20 2023-06-13 北京化工大学 一种宏观阵列电极及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039018A1 (de) * 1990-12-04 1992-06-11 Arnold Gallien Elektrolysezelle fuer gasentwickelnde bzw. gasverzehrende elektrolytische prozesse sowie verfahren zur herstellung der elektrolysezelle
CN111188056A (zh) * 2020-02-24 2020-05-22 北京化工大学 一种具有二级结构的多孔阵列电极及其制备方法和用途
CN112853392A (zh) * 2021-01-11 2021-05-28 清华大学深圳国际研究生院 一种碱性电解水阳极及其制备方法
CN113215604A (zh) * 2021-04-30 2021-08-06 北京航空航天大学 一种仿生浸润性梯度锥簇电极
CN114134528A (zh) * 2021-10-21 2022-03-04 中国空间技术研究院 微米阵列电极结构、制备方法及其用途
CN114177961A (zh) * 2021-12-28 2022-03-15 北京航空航天大学 一种水下超疏气微纤毛阵列定向气泡输送器及其制备方法和应用
CN114959763A (zh) * 2022-06-20 2022-08-30 北京化工大学 一种宏观阵列电极及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039018A1 (de) * 1990-12-04 1992-06-11 Arnold Gallien Elektrolysezelle fuer gasentwickelnde bzw. gasverzehrende elektrolytische prozesse sowie verfahren zur herstellung der elektrolysezelle
CN111188056A (zh) * 2020-02-24 2020-05-22 北京化工大学 一种具有二级结构的多孔阵列电极及其制备方法和用途
CN112853392A (zh) * 2021-01-11 2021-05-28 清华大学深圳国际研究生院 一种碱性电解水阳极及其制备方法
CN113215604A (zh) * 2021-04-30 2021-08-06 北京航空航天大学 一种仿生浸润性梯度锥簇电极
CN114134528A (zh) * 2021-10-21 2022-03-04 中国空间技术研究院 微米阵列电极结构、制备方法及其用途
CN114177961A (zh) * 2021-12-28 2022-03-15 北京航空航天大学 一种水下超疏气微纤毛阵列定向气泡输送器及其制备方法和应用
CN114959763A (zh) * 2022-06-20 2022-08-30 北京化工大学 一种宏观阵列电极及其制备方法和应用

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CUNMING YU ET AL.: "Spontaneous and Directional Transportation of Gas Bubbles on Superhydrophobic Cones", ADVANCED FUNCTIONAL MATERIALS, vol. 26, no. 19, 30 March 2016 (2016-03-30), pages 3236 - 3243, XP072411397, ISSN: 1616-301X, DOI: 10.1002/adfm.201505234 *
SHENG JINHUA; XU WENWEN; LU ZHIYI; SUN XIAOMING: "Recent Progress in the Use of Superwetting Nano Array Electrodes for Gas-Involved Electrocatalysis", JOURNAL OF BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY (NATURAL SCIENCE EDITION), BEIJING HUAGONG DAXUE, CN, vol. 45, no. 5, 29 October 2018 (2018-10-29), CN , pages 54 - 63, XP009551314, ISSN: 1671-4628, DOI: 10.13543/j.bhxbzr.2018.05.007 *
XUE XIUZHAN, YU CUNMING, WANG JINGMING, JIANG LEI: "Superhydrophobic Cones for Continuous Collection and Directional Transportation of CO 2 Microbubbles in CO 2 Supersaturated Solutions", ACS NANO, AMERICAN CHEMICAL SOCIETY, US, vol. 10, no. 12, 27 December 2016 (2016-12-27), US , pages 10887 - 10893, XP093119239, ISSN: 1936-0851, DOI: 10.1021/acsnano.6b05371 *
YINGJIE LI ET AL.: "Under-Water Superaerophobic Pine-Shaped Pt Nanoarray Electrode for Ultrahigh-Performance Hydrogen Evolution", ADVANCED FUNCTIONAL MATERIALS, vol. 25, no. 11, 10 February 2015 (2015-02-10), pages 1737 - 1744, XP072292072, ISSN: 1616-301X, DOI: 10.1002/adfm.201404250 *
ZHAO YAN, ZHANG YALI: "Advances in Nano-array Electrode Research", DAXUE HUAXUE, vol. 19, no. 5, 31 October 2004 (2004-10-31), pages 1 - 7, XP009551284, ISSN: 1000-8438 *

Also Published As

Publication number Publication date
CN114959763B (zh) 2023-06-13
CN114959763A (zh) 2022-08-30

Similar Documents

Publication Publication Date Title
Wang et al. Surface roughening of nickel cobalt phosphide nanowire arrays/Ni foam for enhanced hydrogen evolution activity
Yu et al. Carbon-coated nickel phosphide nanosheets as efficient dual-electrocatalyst for overall water splitting
Gao et al. Three-dimensional dendritic structures of NiCoMo as efficient electrocatalysts for the hydrogen evolution reaction
Darband et al. Three-dimensional porous Ni-CNT composite nanocones as high performance electrocatalysts for hydrogen evolution reaction
Zhang et al. General synthesis of NiCo alloy nanochain arrays with thin oxide coating: a highly efficient bifunctional electrocatalyst for overall water splitting
Liang et al. Self-supported FeP nanorod arrays: a cost-effective 3D hydrogen evolution cathode with high catalytic activity
Wang et al. Large-area synthesis of a Ni2P honeycomb electrode for highly efficient water splitting
CN109837558B (zh) 一种水热电沉积结合的羟基氧化铁-镍铁水滑石析氧电极的制备方法
Zu et al. Bimetallic carbide as a stable hydrogen evolution catalyst in harsh acidic water
Ashassi-Sorkhabi et al. Fabrication of bridge like Pt@ MWCNTs/CoS2 electrocatalyst on conductive polymer matrix for electrochemical hydrogen evolution
Battiato et al. Superior performances of electroless-deposited Ni–P films decorated with an ultralow content of Pt for water-splitting reactions
Zhang et al. Oxygen-incorporated NiMoP2 nanowire arrays for enhanced hydrogen evolution activity in alkaline solution
Li et al. Electrodeposited PCo nanoparticles in deep eutectic solvents and their performance in water splitting
WO2023245868A1 (zh) 一种宏观阵列电极及其制备方法和应用
CN103259023B (zh) 一种氢燃料电池电极材料制备方法
Kong et al. Interface engineering of N-doped Ni3S2/CoS2 heterostructures as efficient bifunctional catalysts for overall water splitting
Sun et al. Superaerophobic CoP nanowire arrays as a highly effective anode electrocatalyst for direct hydrazine fuel cells
Gultom et al. Bimetallic cobalt–nickel electrode made by a sputtering technique for electrocatalytic hydrogen evolution reaction: effect of nickel ratios
Xiang et al. Preparation of Pd/ZnO/Ni hierarchical porous array film with enhanced electrocatalytic activity for methanol oxidation
Jeong et al. CoP2 Nanoparticles Deposited on Nanometer-Thick Pt-Coated Fluorine-Doped Tin Oxide Substrates as Electrocatalysts for Simultaneous Hydrogen Evolution and Oxygen Evolution
Fang et al. Electrochemical deposited high-crystallinity vertical platinum nanosheets onto the carbon nanotubes directly grown on carbon paper for methanol oxidation
Yang et al. Modulation of water dissociation kinetics with a “breathable” wooden electrode for efficient hydrogen evolution
Han et al. Electrochemical construction of Cu@ NF frameworks and synthesis of self-supported microflower Cu2S@ NF as bifunctional catalysts for overall water splitting
Zhang et al. Electrodeposited platinum with various morphologies on carbon paper as efficient and durable self-supporting electrode for methanol and ammonia oxidation reactions
Tang et al. Facile in situ synthesis of an ultrafine and defect-rich co-doped MoS2 nanocluster catalyst for efficient hydrogen evolution reaction in alkaline medium

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22947608

Country of ref document: EP

Kind code of ref document: A1