VC / BiVO4 / CC self-supporting photoelectric catalytic material as well as preparation method and application thereof
By preparing VC/BiVO4 heterostructured photoelectrocatalytic materials on CC substrates, the problems of photogenerated carrier recombination and electrode stability were solved, the energy conversion efficiency and stability of the photoelectrocatalytic materials were improved, the preparation process was simplified and the cost was reduced.
Patent Information
- Application Number
- CN202510714031.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-30
- Publication Date
- 2025-09-16
AI Technical Summary
The rapid recombination of photogenerated carriers, insufficient stability of electrode materials and complex reaction kinetics in existing PEC photoelectrocatalytic technology lead to low energy conversion efficiency, limiting its large-scale application.
VC/BiVO4 heterostructures were prepared on CC substrates using hydrothermal deposition and slurry coating technology to form self-supporting photoelectrocatalytic materials with enhanced electronic interactions. The unique heterostructure of BiVO4 and VC was combined to improve conductivity and stability.
It achieves high conductivity, excellent reaction kinetics and high stability, improves the hydrogen evolution ability of photoelectrocatalytic materials, simplifies the preparation process and reduces costs.
Smart Images
Figure CN120649071A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of functional materials and relates to photoelectrocatalytic materials, and specifically to a VC / BiVO4 / CC self-supporting photoelectrocatalytic material and a preparation method and application thereof. Background Art
[0002] Today, the global energy landscape faces severe challenges, with the imbalance between energy supply and demand becoming increasingly severe. As a renewable, clean energy source, the development and utilization of hydrogen is closely linked to ecological conservation and air pollution control. Under the dual pressures of climate change and resource shortages, developing a green, low-carbon, and sustainable energy system, along with compatible energy storage and conversion technologies, is crucial for achieving long-term, stable energy supply and sustainable development. Among the many renewable energy sources, biomass, solar energy, wind energy, and hydropower all play a vital role in energy restructuring. Compared to other energy sources, hydrogen, with its significant advantages of high energy density and low carbon emissions, is considered an important energy source that can effectively alleviate the energy crisis and meet future energy needs. It holds great potential for addressing large-scale, stable energy supply. Among various hydrogen production technologies, PEC photoelectrocatalysis exhibits unique advantages. It can directly convert solar energy and electrical energy into chemical energy without generating additional pollutants. Specifically, PEC photoelectrocatalysis can theoretically achieve efficient and low-cost energy conversion for converting solar energy into hydrogen, making it a promising solution for addressing future energy needs. However, PEC photoelectrocatalysis currently faces numerous challenges. The rapid recombination of photogenerated carriers significantly reduces energy conversion efficiency; the instability of electrode materials limits the lifespan of equipment; and the complex reaction kinetics complicate the control of reaction conditions. These issues result in low actual solar-to-chemical energy conversion efficiency, severely restricting the large-scale application of PEC photoelectrocatalytic technology. Summary of the Invention
[0003] In response to the shortcomings of the existing technology, the purpose of the present invention is to provide a VC / BiVO4 / CC self-supporting photoelectrocatalytic material and its preparation method and application. The material has high conductivity, excellent reaction kinetics, high stability and efficient hydrogen evolution ability, showing great application potential in the field of photoelectrocatalysis. The preparation process is simple and controllable, the reaction conditions are mild, and the cost is low.
[0004] In order to achieve the above object, the present invention adopts the following technical solutions:
[0005] A method for preparing a VC / BiVO4 / CC self-supporting photoelectrocatalytic material comprises the following steps:
[0006] Step 1: Take the CC substrate and cut and clean it;
[0007] Step 2, weighing 0.5-2.0 g of bismuth nitrate pentahydrate, dissolving it in 3-15 mL of concentrated nitric acid, ultrasonically oscillating it to completely dissolve it, then adding 10-30 mL of deionized water, stirring evenly, and preparing solution A, then weighing 0.3-1.0 g of ammonium metavanadate, adding 10-30 mL of deionized water, stirring until completely dissolved, and preparing solution B; under magnetic stirring conditions, slowly adding solution B dropwise to solution A. After the addition is complete, continue stirring to fully mix the solution to obtain a mixed solution;
[0008] Step 3: Transfer the mixed solution prepared in step 2 to the polytetrafluoroethylene liner of the reactor, and place the CC substrate treated in step 1 into it. Seal the reactor, place it in an oven, and heat it to 140-180°C at a heating rate of 5°C / min. Maintain this temperature for 8-12 hours. After the reaction is completed, take it out and dry it to obtain a BiVO4 / CC composite precursor.
[0009] Step 4: Weigh vanadium trioxide powder and carbon black, mix them in a mass ratio of 0.75:0.1-1.0, place them in a white magnetic boat, place them in a tube furnace, and under an inert atmosphere, heat them from room temperature to 1000-1400°C at a rate of 5-20°C / min, keep them warm for 2-6 hours, and after the product cools with the furnace, take it out and grind it to obtain VC powder; weigh 0.2-1.0g of VC powder and place it in a beaker, then add 5-20mL of 75% ethanol solution and 0.001-0.02g of polyvinylidene fluoride, and ultrasonicate until uniformly dispersed to obtain VC precursor slurry;
[0010] Step 5: Evenly coat the VC precursor slurry on each side of the BiVO4 / CC composite precursor, and then dry it to obtain the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
[0011] The present invention also has the following technical features:
[0012] Preferably, the density of the CC substrate in step 1 is 1.3-1.5 g / cm 3 .
[0013] The CC substrate described in step 1 is cut to a length of 2 to 7 cm and a width of 1 to 3 cm.
[0014] The cleaning method of the CC substrate described in step 1 includes completely immersing the CC substrate in acetone for 12 to 48 hours, then immersing it in a 20% mass concentration hydrogen peroxide solution for 2 to 10 hours, and then ultrasonically treating it with deionized water and anhydrous ethanol for 15 to 30 minutes respectively.
[0015] Preferably, the drying in step 3 and step 5 is carried out in an oven at 60-100° C. for 4-12 hours.
[0016] The present invention also protects a VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared by the method as described above and its use as a photocathode in the photoelectrocatalytic water decomposition hydrogen production reaction.
[0017] Compared with the prior art, the present invention has the following technical effects:
[0018] The present invention combines hydrothermal deposition with slurry coating technology to load BiVO4 and VC on CC materials, forming a unique heterogeneous structure between BiVO4 and VC. This structure can strengthen the electronic interaction at the two-phase heterogeneous interface. VC has good electrical conductivity, and the overall electrical conductivity of the material can be improved after compounding. Compounding BiVO4 and VC on a CC substrate can further effectively enhance electron transport. At the same time, CC is acid and alkali resistant, which can make the VC / BiVO4 / CC self-supporting photoelectrocatalytic material have good stability under different conditions. The prepared VC / BiVO4 / CC self-supporting photoelectrocatalytic material has high electrical conductivity, excellent reaction kinetics, high stability and efficient hydrogen evolution ability, showing great application potential in the field of photoelectrocatalysis.
[0019] The present invention first prepares BiVO4 / CC by a hydrothermal deposition method, prepares VC powder by a one-step calcination method, and finally grows VC on BiVO4 / CC by a slurry coating method to prepare a VC / BiVO4 / CC self-supporting photoelectrocatalytic material. The slurry coating method can obtain a coating with uniform thickness, which is beneficial to improving the consistency of the overall performance of the coating. At the same time, the equipment and process are simple, the reaction conditions are mild, and it is easy to operate and master. It does not require complex technology and high-end equipment, which reduces the production threshold and cost, has high production efficiency, and is cost-effective. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 This is the X-ray diffraction analysis diagram of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2;
[0021] Figure 2 This is a scanning electron microscope image of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2;
[0022] Figure 3 This is a diagram of the oxygen evolution performance of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2. DETAILED DESCRIPTION
[0023] The specific contents of the present invention are further explained in detail below with reference to the embodiments.
[0024] The average molecular weight of the polyvinylidene fluoride used in the following examples is 400,000.
[0025] Example 1
[0026] This embodiment provides a method for preparing a VC / BiVO4 / CC self-supporting photoelectrocatalytic material, comprising the following steps:
[0027] Step 1: Take the density as 1.3g / cm 3 The medium-density CC substrate was cut into 2 cm in length and 1 cm in width. A 50 mL beaker was then used to completely immerse the CC substrate in acetone for 12 h, then in a 20% hydrogen peroxide solution for 2 h, and then ultrasonically treated with deionized water and anhydrous ethanol for 15 min, respectively.
[0028] Step 2, weigh 0.5g of bismuth nitrate pentahydrate, dissolve it in 5mL of concentrated nitric acid, ultrasonically oscillate it to completely dissolve it, then add 10mL of deionized water, stir evenly, and prepare solution A, then weigh 0.3g of ammonium metavanadate, add 10mL of deionized water, stir until completely dissolved, and prepare solution B; under magnetic stirring, slowly add solution B dropwise to solution A, after completion of the addition, continue stirring for 0.5h to fully mix the solution to obtain a mixed solution;
[0029] Step 3: Transfer the mixed solution prepared in step 2 to the polytetrafluoroethylene liner of the reactor, and place the CC substrate treated in step 1 into it. Seal the reactor, place it in an oven, and heat it to 140°C at a heating rate of 5°C / min and maintain it at this temperature for 8 hours. After the reaction is completed, take it out and dry it in an oven at 60°C for 12 hours to obtain a BiVO4 / CC composite precursor.
[0030] Step 4: Weigh vanadium trioxide powder and carbon black, mix them in a mass ratio of 0.75:0.4, place them in a white magnetic boat, place them in a tube furnace, and under an inert atmosphere, heat them from room temperature to 1000°C at a rate of 5°C / min, keep them warm for 2 hours, and after the product cools with the furnace, take it out and grind it to obtain VC powder; weigh 0.2g of VC powder and place it in a beaker, then add 5mL of 75% mass concentration ethanol solution and 0.001g of polyvinylidene fluoride, and ultrasonicate until uniformly dispersed to obtain VC precursor slurry;
[0031] Step 5: Evenly coat the VC precursor slurry on each side of the BiVO4 / CC composite precursor, and then dry it in an oven at 60°C for 12 hours to obtain the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
[0032] Example 2
[0033] This embodiment provides a method for preparing a VC / BiVO4 / CC self-supporting photoelectrocatalytic material, comprising the following steps:
[0034] Step 1: Take the density as 1.4g / cm 3 The medium-density CC substrate was cut into 5 cm in length and 2 cm in width. A 50 mL beaker was then used to completely immerse the CC substrate in acetone for 24 h, then in a 20% hydrogen peroxide solution for 6 h, and then ultrasonically treated with deionized water and anhydrous ethanol for 20 min respectively.
[0035] Step 2: Weigh 1.0 g of bismuth nitrate pentahydrate, dissolve it in 10 mL of concentrated nitric acid, and ultrasonically oscillate it to completely dissolve it. Then, add 20 mL of deionized water and stir evenly to prepare solution A. Then, weigh 0.6 g of ammonium metavanadate, add 20 mL of deionized water, and stir until completely dissolved to prepare solution B. Under magnetic stirring, slowly add solution B dropwise to solution A. After the addition is complete, continue stirring for 2 h to fully mix the solution to obtain a mixed solution.
[0036] Step 3: Transfer the mixed solution prepared in step 2 to the polytetrafluoroethylene liner of the reactor, and place the CC substrate treated in step 1 into it. Seal the reactor, place it in an oven, and heat it to 160°C at a heating rate of 5°C / min and maintain it at this temperature for 10 hours. After the reaction is completed, take it out and dry it in an oven at 80°C for 10 hours to obtain a BiVO4 / CC composite precursor.
[0037] Step 4: Weigh vanadium trioxide powder and carbon black, mix them in a mass ratio of 0.75:0.5, place them in a white magnetic boat, place them in a tube furnace, and under an inert atmosphere, heat them from room temperature to 1200°C at a rate of 10°C / min, keep them warm for 4 hours, and after the product cools with the furnace, take it out and grind it to obtain VC powder; weigh 0.6g of VC powder and place it in a beaker, then add 10mL of 75% ethanol solution and 0.01g of polyvinylidene fluoride, and ultrasonicate until uniformly dispersed to obtain VC precursor slurry;
[0038] Step 5: Evenly coat the VC precursor slurry on each side of the BiVO4 / CC composite precursor, and then dry it in an oven at 80°C for 8 hours to obtain the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
[0039] Figure 1This is the X-ray diffraction analysis of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2, where the horizontal axis is the 2θ angle and the vertical axis is the diffraction peak intensity. The VC / BiVO4 supported on the CC substrate corresponds to BiVO4 PDF#14-0688, and the (-121) and (040) crystal planes of BiVO4 at 28° and 30°, respectively. It also corresponds to VC PDF#35-0786, and the (222) and (400) crystal planes of VC at 37° and 43°, respectively, indicating the successful preparation of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
[0040] Figure 2 This is a scanning electron microscope image of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2; Figure 2 As shown, it presents a structure of staggered stacking of BiVO4 nanosheets and VC nanoparticles.
[0041] Figure 3 This is the oxygen evolution performance diagram of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared in Example 2; Figure 3 As shown in Figure 2, the VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared by the present invention exhibits excellent hydrogen evolution performance as a photocathode, and the photocurrent density reaches -2.46 mA / cm under a bias voltage of 0.0 V. 2 .
[0042] Example 3
[0043] This embodiment provides a method for preparing a VC / BiVO4 / CC self-supporting photoelectrocatalytic material, comprising the following steps:
[0044] Step 1: Take the density as 1.5g / cm 3 The medium-density CC substrate was cut into 7 cm in length and 3 cm in width. A 50 mL beaker was used to completely immerse the CC substrate in acetone for 48 h, then in a 20% hydrogen peroxide solution for 10 h, and then ultrasonically treated with deionized water and anhydrous ethanol for 30 min respectively.
[0045] Step 2: Weigh 2.0 g of bismuth nitrate pentahydrate, dissolve it in 15 mL of concentrated nitric acid, and ultrasonically oscillate it to completely dissolve it. Then, add 30 mL of deionized water and stir evenly to prepare solution A. Then, weigh 1.0 g of ammonium metavanadate, add 30 mL of deionized water, and stir until completely dissolved to prepare solution B. Under magnetic stirring, slowly add solution B dropwise to solution A. After the addition is complete, continue stirring for 3 hours to fully mix the solution to obtain a mixed solution.
[0046] Step 3: Transfer the mixed solution prepared in step 2 to the polytetrafluoroethylene liner of the reactor, and place the CC substrate treated in step 1 into it. Seal the reactor, place it in an oven, and heat it to 180°C at a heating rate of 5°C / min. Maintain this temperature for 12 hours. After the reaction is completed, take it out and dry it in an oven at 100°C for 4 hours to obtain a BiVO4 / CC composite precursor.
[0047] Step 4: Weigh vanadium trioxide powder and carbon black, mix them in a mass ratio of 0.75:1.0, place them in a white magnetic boat, place them in a tube furnace, and under an inert atmosphere, heat them from room temperature to 400°C at a rate of 20°C / min, keep them warm for 6 hours, and after the product cools with the furnace, take it out and grind it to obtain VC powder; weigh 1.0g of VC and place it in a beaker, then add 20mL of 75% ethanol solution and 0.02g of polyvinylidene fluoride, and ultrasonicate until uniformly dispersed to obtain VC precursor slurry;
[0048] Step 5: Evenly coat the VC precursor slurry on each side of the BiVO4 / CC composite precursor, and then dry it in an oven at 100°C for 4 hours to obtain the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
[0049] Those skilled in the art will appreciate that the embodiments described herein are intended to help readers understand the principles of the present invention, and it should be understood that the scope of protection of the present invention is not limited to such specific descriptions and embodiments. Those skilled in the art can make various other specific variations and combinations based on the technical teachings disclosed in the present invention without departing from the essence of the present invention, and they are still within the scope of protection of the present invention.
Claims
1. A method for preparing a VC / BiVO4 / CC self-supporting photoelectrocatalytic material, characterized in that: The following steps are involved: Step 1: Take the CC substrate and cut and clean it; Step 2, weighing 0.5-2.0 g of bismuth nitrate pentahydrate, dissolving it in 3-15 mL of concentrated nitric acid, ultrasonically oscillating it to completely dissolve it, then adding 10-30 mL of deionized water, stirring evenly, and preparing solution A, then weighing 0.3-1.0 g of ammonium metavanadate, adding 10-30 mL of deionized water, stirring until completely dissolved, and preparing solution B; under magnetic stirring conditions, slowly adding solution B dropwise to solution A. After the addition is complete, continue stirring to fully mix the solution to obtain a mixed solution; Step 3: Transfer the mixed solution prepared in step 2 to the polytetrafluoroethylene liner of the reactor, and place the CC substrate treated in step 1 into it. Seal the reactor, place it in an oven, and heat it to 140-180°C at a heating rate of 5°C / min. Maintain this temperature for 8-12 hours. After the reaction is completed, take it out and dry it to obtain a BiVO4 / CC composite precursor. Step 4: Weigh vanadium trioxide powder and carbon black, mix them in a mass ratio of 0.75:0.1-1.0, place them in a white magnetic boat, place them in a tube furnace, and under an inert atmosphere, heat them from room temperature to 1000-1400°C at a rate of 5-20°C / min, keep them warm for 2-6 hours, and after the product cools with the furnace, take it out and grind it to obtain VC powder; weigh 0.2-1.0g of VC powder and place it in a beaker, then add 5-20mL of 75% ethanol solution and 0.001-0.02g of polyvinylidene fluoride, and ultrasonicate until uniformly dispersed to obtain VC precursor slurry; Step 5: Evenly coat the VC precursor slurry on each side of the BiVO4 / CC composite precursor, and then dry it to obtain the VC / BiVO4 / CC self-supporting photoelectrocatalytic material.
2. The method for preparing the VC / BiVO4 / CC self-supporting photoelectrocatalytic material according to claim 1, characterized in that: The density of the CC substrate described in step 1 is 1.3-1.5 g / cm 3 .
3. The method for preparing the VC / BiVO4 / CC self-supporting photoelectrocatalytic material according to claim 1, characterized in that: The CC substrate described in step 1 is cut to a length of 2 to 7 cm and a width of 1 to 3 cm.
4. The method for preparing the VC / BiVO4 / CC self-supporting photoelectrocatalytic material according to claim 1, wherein: The cleaning method of the CC substrate described in step 1 includes completely immersing the CC substrate in acetone for 12 to 48 hours, then immersing it in a 20% mass concentration hydrogen peroxide solution for 2 to 10 hours, and then ultrasonically treating it with deionized water and anhydrous ethanol for 15 to 30 minutes respectively.
5. The method for preparing the VC / BiVO4 / CC self-supporting photoelectrocatalytic material according to claim 1, wherein: The drying in step 3 and step 5 is carried out in an oven at 60-100° C. for 4-12 hours.
6. A VC / BiVO4 / CC self-supporting photoelectrocatalytic material prepared by the method according to any one of claims 1 to 5.
7. Use of the VC / BiVO4 / CC self-supporting photoelectrocatalytic material as claimed in claim 6 as a photocathode in the photoelectrocatalytic water decomposition reaction to produce hydrogen.