CN113976165A - Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material - Google Patents
Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000000463 material Substances 0.000 title abstract description 17
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 11
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- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
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- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation and application of a bismuth tungstate and carbon nitride composite photocatalytic material, relates to a bismuth tungstate and carbon nitride photocatalytic composite material, and aims to solve the problems that a photocatalytic hydrogen production material synthesized by the prior art is wide in forbidden bandwidth, easy to compound photoproduction electron holes and poor in light absorption capacity, so that the hydrogen production efficiency of the conventional photocatalytic hydrogen production material is low and the like9[BiW11O38]/g‑C3N4(abbreviation BiW)11/g‑C3N4). The synthesis method comprises the following steps: sodium tungstate dihydrate and bismuth nitrate are stirred at normal temperature to prepare polyacid Na9[BiW11O38]Then with g-C3N4Compounding to obtain BiW11/g‑C3N4A composite photocatalytic material. The semiconductor composite photocatalytic material obtained by the invention is used for preparing hydrogen by water decomposition under normal temperature and normal pressure photocatalysis.
Description
Technical Field
The invention relates to a bismuth tungstate and carbon nitride composite nano material.
Background
Fossil energy is an essential energy base for human development and survival. However, the human beings develop and utilize non-renewable energy sources such as coal, petroleum and natural gas excessively and unlimitedly, which causes serious damage to the natural environment and causes the problems of fossil energy shortage and the like. Therefore, the future energy direction will turn to the development of clean and sustainable new energy. The hydrogen has high combustion value, and the combustion product is pollution-free water, is environment-friendly, and is green and renewable. The photocatalysis technology can utilize solar energy to carry out energy conversion, realize photocatalytic water decomposition to generate hydrogen, and convert the solar energy into pure pollution-free hydrogen energy, thereby providing a new strategy for solving the human energy shortage and realizing energy conversion.
Polyoxometalates (POMs), polyacid for short, are nanometer-sized oxygen-containing cluster compounds of inorganic metals composed of early transition metals coordinated with oxygen atoms. The polyacid has adjustable composition and structure, and reversible redox ability. The polyacid has an energy band structure similar to that of a metal oxide semiconductor, has a proper forbidden band width, and is often used for compounding with other semiconductor materials to form a polyacid-based composite material with a novel structure and strong functions.
Carbon nitride (g-C)3N4) The material is a novel non-metal semiconductor material, has good visible light capturing capability and electron transmission capability, and has stable structure. g-C3N4Simple preparation, high yield, large specific surface area and capability of providing more reactive sites. g-C compared with conventional semiconductor materials such as titanium dioxide3N4Has wider energy band structure, good thermal stability and environmental protection, and becomes one of the research hotspots in the field of photocatalysis. Thus, POM was reacted with g-C3N4The two are combined to form the polyacid-carbon nitride composite semiconductor photocatalytic material, so that the catalytic capability of the semiconductor photocatalytic material can be enhanced, and the photocatalyst has a good photocatalytic application prospect.
Disclosure of Invention
The invention aims to provide a method for preparing single-vacancy bismuth tungstate Na by heating and stirring at normal temperature9[BiW11O38](abbreviated as BiW11) And g-C3N4Is compounded withMaterials: BiW11/g-C3N4It is used for preparing hydrogen by photocatalytic water decomposition.
The invention relates to BiW for photocatalytic hydrogen evolution11/g-C3N4The composite photocatalytic material has triethanolamine as sacrificial agent, and electrochemical working electrode for testing electrochemical property of the photocatalyst consists of ITO conductive glass and BiW coated on the surface of the ITO conductive glass11/g-C3N4A composite material. BiW11/g-C3N4The synthesis of the composite material and the preparation of the working electrode are completed according to the following steps:
firstly, preparing single-vacancy bismuth tungstate: mixing sodium tungstate dihydrate (NaWO)4·2H2O), sodium hydroxide powder (NaOH) was dissolved in deionized water and glacial acetic acid (CH)3COOH, HAc for short) to regulate the pH value, heating the mixed solution to boiling, slowly dripping a bismuth nitrate solution into the boiling solution, heating and stirring, cooling and crystallizing, evaporating and concentrating, and drying to obtain a product, namely the single-vacancy bismuth tungstate: na (Na)9[BiW11O38](abbreviated as BiW11)。
Di, g-C3N4The preparation of (1): mixing melamine and ammonium hydrogen carbonate (NH)4HCO3) Putting into a porcelain boat, putting into a tube furnace, calcining under argon atmosphere, and cooling. Centrifuging, drying and grinding. The product g-C is obtained3N4。
Composite material BiW11/g-C3N4The preparation of (1): BiW will be mixed11And g-C3N4Dissolving in deionized water, adding 3-Aminopropyltriethoxysilane (APTES), stirring, centrifuging, washing, and drying to obtain final product BiW11/g-C3N4。
Fourthly, preparing an electrochemical working electrode: subjecting ITO conductive glass to ultrasonic treatment for 30 minutes respectively with xylene, acetone and ethanol, air drying, and then subjecting BiW11/g-C3N4And uniformly dripping the composite material, Nafion and ethanol suspension on one surface of the ITO glass, and airing at room temperature.
The adjusted pH of 6.5 as described in step one;
the temperature for heating to boiling in the step one is 100 ℃, the reaction temperature of the final mixture is 95 ℃, and the reaction time is 2 hours;
the bismuth nitrate solution in the first step is prepared from 0.67g of bismuth nitrate pentahydrate (BiNO)3·5H2O) dissolved in 1mL of concentrated HNO3Then adding 10mL of deionized water, stirring uniformly and preparing;
the cooling crystallization in the step one is to volatilize for 48 hours at room temperature and separate out colorless needle crystals;
the evaporation concentration in the step one is 1/5 from room temperature evaporation concentration solution to original solution;
the drying in the step one is vacuum drying, the drying temperature is 60 ℃, and the drying time is 8 hours;
the calcination temperature in the step two is 550 ℃, and the calcination time is 4 hours;
the temperature rise speed of the calcination in the step two is 5 ℃ min-1Raising to the final temperature;
stirring at room temperature for 24 hours in the step three, and washing once by using deionized water;
the drying in the third step is oven drying, the drying temperature is 60 ℃, and the drying time is 10 hours;
the suspension in the fourth step is prepared from 5mg of BiW11/g-C3N4The composite material is prepared by mixing 20 mu L of Nafion and 300 mu L of ethanol and carrying out ultrasonic treatment for 30 minutes.
The invention has the following characteristics:
the invention takes sodium tungstate dihydrate and bismuth nitrate as raw materials, and the raw materials are stirred and synthesized at room temperature to BiW11Then calcining the mixture with a tube furnace to obtain g-C3N4Compounding to obtain BiW11/g-C3N4A composite material. BiW in the invention11/g-C3N4The composite material is in a laminated structure, and the electron transmission capability of the catalyst is enhanced. The invention compounds bismuth tungstate with good photosensitivity and carbon nitride with good electron transport capability, thereby avoiding BiW11Easy to decompose. Impedance (L)Potential test and photocurrent response test results show that the composite material has a proper forbidden band width and shows a good effect of photocatalytic water decomposition to hydrogen production. The invention has the advantages of cheap and easily obtained raw materials, environmental protection, simple preparation process and low raw material cost, and is expected to realize large-scale industrial application.
Drawings
BiW in FIG. 111/g-C3N4A PXRD pattern for the semiconductor composite;
BiW in FIG. 211/g-C3N4Scanning electron micrographs of the semiconductor composite;
BiW in FIG. 311/g-C3N4An infrared spectrum of the semiconductor composite;
BiW in FIG. 411/g-C3N4A photocurrent response diagram of the semiconductor composite material at normal temperature and normal pressure;
BiW in FIG. 511/g-C3N4Performing electrochemical alternating current impedance spectroscopy on the semiconductor composite material;
BiW in FIG. 611/g-C3N4The hydrogen production rate of the semiconductor composite material is shown in a 6-hour hydrogen production rate diagram under normal temperature and normal pressure by taking triethanolamine as a sacrificial reagent.
Detailed Description
(1) 5g of NaWO4·2H2O and 1g NaOH are dissolved in 20mL of deionized water, glacial acetic acid is added dropwise to adjust the pH value to 6.5, and the solution is heated to 100 ℃ and cooled to room temperature to form a solution A. 0.67g of BiNO was weighed3·5H2O dissolved in 1mL concentrated HNO3And adding deionized water, and uniformly stirring to form a bismuth nitrate solution B. And dropwise adding the solution B into the solution A in a stirring state till the solution B is completely added. Heating is started, the mixed solution is heated to 95 ℃, and the temperature is kept, heated and stirred for 2 h. After 2h, the heating is stopped, the mixture is cooled to room temperature, the mixture is evaporated at room temperature for 48h, and the solution is concentrated to the original solution 1/5, so that colorless needle crystals are separated out. Vacuum drying at 60 ℃ for 8h to obtain single-vacancy bismuth tungstate: BiW11。
(2) 1.75g of melamine and 0.75g of NH4HCO3Put in porcelainIn the boat, 5 ℃ min-1The temperature is raised to 550 ℃ and the mixture is heated for 4 hours. Cooling, air drying, grinding to obtain g-C3N4。
(3) 0.075g of BiW is weighed out11And 0.075g g-C3N4Dissolving in 30mL deionized water, adding 150 μ L3-aminopropyltriethoxysilane, stirring for 24 hr to generate precipitate, centrifuging, washing with deionized water, oven drying at 60 deg.C for 10 hr, and grinding to obtain BiW11/g-C3N4A composite material.
(4) And (3) carrying out ultrasonic treatment on the ITO conductive glass for 30min by using dimethylbenzene, acetone and ethanol respectively. Weighing 5mg of composite material, adding 20 mu L of Nafion and 300 mu L of ethanol, mixing, and performing ultrasonic treatment for 30min to prepare a suspension; using a liquid transfer gun to transfer 150 mu L of the suspension, uniformly dripping the suspension on ITO glass (the suspension is required to be uniformly dispersed on the glass), and drying at room temperature to form the catalyst working electrode.
The invention is further described with reference to the following drawings and examples:
BiW shown in FIG. 111/g-C3N4The PXRD pattern of the semiconductor composite material is shown in the figure, and through an X-ray powder diffraction experiment, a relatively strong diffraction peak is observed at 27.4 ° of 2 θ of the composite material, which indicates that the composite material has a lamellar interlayer stacking structure.
BiW shown in FIG. 211/g-C3N4Scanning Electron microscopy of semiconductor composites BiW11And g-C3N4The nano-sheet structures are stacked layer by layer to form a flaky interlayer stacking shape.
BiW shown in FIG. 311/g-C3N4The infrared spectrogram of the semiconductor composite material is observed to be 700-1100 cm-1Within the range of the polyacid salt compound BiW11And g-C3N4Characteristic peak of (2).
BiW shown in FIG. 411/g-C3N4And a photocurrent response diagram of the semiconductor composite material at normal temperature and normal pressure. Generally, the stronger the instantaneous photocurrent intensity, the higher the separation ratio of photogenerated electrons and photogenerated holes. BiW11/g-C3N4The instantaneous photocurrent intensity of the composite material is 0.4-0.5 muA, and the separation efficiency of photo-generated electrons and photo-generated holes is high.
BiW shown in FIG. 511/g-C3N4Electrochemical ac impedance spectrum of the semiconductor composite. The composite material does not show an obvious semicircular structure in a high-frequency region, the intersection point of the curve and the X axis is used as the impedance of the composite material and represents the electron conductivity of the material, and the higher the slope of the curve is, the better the electron conductivity is. As shown, BiW11/g-C3N4The composite material has good electron conductivity and good separation effect of photogenerated electrons and photogenerated holes.
BiW shown in FIG. 611/g-C3N4The hydrogen production rate of the semiconductor composite material is shown in a 6-hour hydrogen production rate diagram under normal temperature and normal pressure by taking triethanolamine as a sacrificial reagent. As shown, BiW11/g-C3N4The average hydrogen production efficiency of the composite material is 2117 mu mol g-1·h-1The material has good photocatalytic hydrogen production activity, so the bismuth tungstate and carbon nitride composite photocatalytic material is a high-efficiency photocatalyst for photocatalytic water decomposition.
In summary, the present example uses a normal temperature stirring method to compound single-site bismuth tungstate with carbon nitride synthesized from melamine and ammonium bicarbonate to obtain BiW11/g-C3N4The composite material has good application prospect in photocatalytic water decomposition and hydrogen evolution.
Claims (8)
1. BiW for catalytic decomposition of water by normal temperature and pressure light11/g-C3N4The preparation method of the composite photocatalyst comprises the following steps:
(1) mixing NaWO4·H2Dissolving O and NaOH in deionized water, dropwise adding glacial acetic acid to adjust the pH value to 6.5, and heating the solution to a boiling solution. The prepared bismuth nitrate solution was then added dropwise. The reaction was heated to 95 ℃ with stirring for 2 hours. Cooling to room temperature, precipitating colorless needle crystal, naturally volatilizing at room temperature for 48 hr, concentrating the solution to 1/5 of the original solution, and vacuum drying at 60 deg.C to obtain single-defect productBismuth tungstate: na (Na)9[BiW11O38]；
(2) Reacting melamine with NH4HCO3Placing in a porcelain boat at 5 deg.C for min-1The temperature is raised to 550 ℃ and the mixture is heated for 4 hours. Cooling and grinding to obtain g-C3N4。
(3) BiW will be mixed11And g-C3N4Dissolving in deionized water, adding 3-aminopropyltriethoxysilane, stirring for 24 hr, centrifuging, washing with deionized water, oven drying, and grinding to obtain BiW11/g-C3N4A composite material.
2. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that the NaWO in the step (1)4·2H2O、NaOH、BiNO3·5H2The mass ratio of O is 7.46:1.50: 1.
3. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that the bismuth nitrate solution is required to be dropwise added into a system in the step (1) for full reaction; the reaction temperature was 95 ℃ and the reaction time was 2 hours.
4. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that after the heating in the step (1) is finished, the solution is cooled at room temperature, when colorless needle-shaped crystals are precipitated, the solution is continuously evaporated at room temperature for 48 hours until the solution is about 1/5, and the solution is dried; the drying is carried out for 8 hours under vacuum at 60 ℃.
5. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that the melamine and NH in the step (2)4HCO3The mass ratio of (A) to (B) is 2.33: 1.
6. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that BiW in the step (3)11And g-C3N4The mass ratio of (A) to (B) is 1: 1.
7. BiW according to claim 111/g-C3N4The preparation method of the composite photocatalyst is characterized in that BiW is added into 30mL of deionized water in the step (3)11And g-C3N4Then adding 3-aminopropyl triethoxysilane, stirring for 24 hours at room temperature, centrifuging, washing once with deionized water, and drying.
8. BiW of claim 111/g-C3N4The application method of the composite material comprises the following steps: triethanolamine is used as a sacrificial agent and is applied to photocatalytic decomposition water-out hydrogen reaction under normal temperature and pressure.
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