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
- Publication number
- CN113976165A CN113976165A CN202111418933.9A CN202111418933A CN113976165A CN 113976165 A CN113976165 A CN 113976165A CN 202111418933 A CN202111418933 A CN 202111418933A CN 113976165 A CN113976165 A CN 113976165A
- Authority
- CN
- China
- Prior art keywords
- biw
- solution
- preparation
- hours
- composite
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 title abstract description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title abstract description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011941 photocatalyst Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 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
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- -1 salt compound Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111418933.9A CN113976165B (en) | 2021-11-26 | 2021-11-26 | Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111418933.9A CN113976165B (en) | 2021-11-26 | 2021-11-26 | Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113976165A true CN113976165A (en) | 2022-01-28 |
| CN113976165B CN113976165B (en) | 2023-08-11 |
Family
ID=79731975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111418933.9A Active CN113976165B (en) | 2021-11-26 | 2021-11-26 | Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113976165B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917919A (en) * | 2022-06-10 | 2022-08-19 | 哈尔滨理工大学 | Bismuth-tungsten-cobalt polyoxometalate and carbon nitride composite photocatalytic material as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011057730A1 (en) * | 2009-11-13 | 2011-05-19 | Vidres S.A. | Composition and process for obtaining materials for coating ceramic bodies and the articles thus obtained |
| CN106753371A (en) * | 2016-11-28 | 2017-05-31 | 大连工业大学 | A kind of holmium ytterbium codope bismuth tungstate fluorescent material and preparation method thereof |
| CN107456991A (en) * | 2017-08-30 | 2017-12-12 | 江苏大学 | A kind of g C3N4Quantum dot loads the preparation method of Bismuth tungstate nano-sheet photochemical catalyst |
| CN113181900A (en) * | 2021-04-14 | 2021-07-30 | 中国科学院过程工程研究所 | Bi2WO6Protonated g-C3N4Nanosheet heterojunction photocatalyst and preparation method and application thereof |
-
2021
- 2021-11-26 CN CN202111418933.9A patent/CN113976165B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011057730A1 (en) * | 2009-11-13 | 2011-05-19 | Vidres S.A. | Composition and process for obtaining materials for coating ceramic bodies and the articles thus obtained |
| CN106753371A (en) * | 2016-11-28 | 2017-05-31 | 大连工业大学 | A kind of holmium ytterbium codope bismuth tungstate fluorescent material and preparation method thereof |
| CN107456991A (en) * | 2017-08-30 | 2017-12-12 | 江苏大学 | A kind of g C3N4Quantum dot loads the preparation method of Bismuth tungstate nano-sheet photochemical catalyst |
| CN113181900A (en) * | 2021-04-14 | 2021-07-30 | 中国科学院过程工程研究所 | Bi2WO6Protonated g-C3N4Nanosheet heterojunction photocatalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Synthesis and Crystal Structure of the Heteropolymate Compound Na3H2[Ce3(H2O)18Bi2W22O76]・23H2O", 结构化学, no. 08 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917919A (en) * | 2022-06-10 | 2022-08-19 | 哈尔滨理工大学 | Bismuth-tungsten-cobalt polyoxometalate and carbon nitride composite photocatalytic material as well as preparation method and application thereof |
| CN114917919B (en) * | 2022-06-10 | 2024-01-26 | 哈尔滨理工大学 | Bismuth tungsten cobalt polyacid salt and carbon nitride composite photocatalytic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113976165B (en) | 2023-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105817253B (en) | The preparation method of graphite phase carbon nitride nanometer sheet/Nano tube array of titanium dioxide catalysis material | |
| CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
| CN111203262B (en) | Method for rapidly preparing carbon nitride nanosheet loaded nano-copper, product and application thereof | |
| CN110961133B (en) | Nonmetal BCN/g-C3N4Van der Waals heterojunction photocatalyst and preparation method and application thereof | |
| CN102698728A (en) | Titanium dioxide nanotube/ graphene composite material and preparation method thereof | |
| CN107601557A (en) | One kind prepares 1T@2H MoS2/ black TiO2Method | |
| CN112871186A (en) | Nickel diselenide/sulfur indium zinc composite photocatalyst and preparation method and application thereof | |
| CN113976165B (en) | Preparation and application of bismuth tungstate and carbon nitride composite photocatalytic material | |
| CN113086950B (en) | Catalytic synthesis of H2O2Method (2) | |
| CN112569924B (en) | Preparation method of star-shaped bismuth vanadate/borane composite material | |
| CN107857308B (en) | Nickel-cobalt composite hydroxide ultra-long nanobelt, nickel-cobalt composite oxide ultra-long nanobelt and preparation method thereof | |
| CN106925306B (en) | Two-dimensional ultrathin ZnO/BiOBr0.9I0.1Hybrid solar catalyst and preparation method thereof | |
| CN107233897B (en) | A kind of visible-light photocatalyst and its preparation method and application of novel Z-type structure | |
| CN112786853A (en) | High-rate composite negative electrode material of sodium ion battery and preparation method thereof | |
| CN109926070B (en) | Mn (manganese)0.5Cd0.5S/WO3Preparation method of Au supported photocatalyst | |
| CN110743583A (en) | 0D/2D iron phosphide/cadmium sulfide composite photocatalyst and preparation method and application thereof | |
| CN108031481B (en) | Ultrathin bismuth oxyhalide nanosheet photocatalyst stripped by silver intercalation and preparation method thereof | |
| CN110327926B (en) | Preparation method of iron ion doped titanium dioxide nano material | |
| CN114917919B (en) | Bismuth tungsten cobalt polyacid salt and carbon nitride composite photocatalytic material and preparation method and application thereof | |
| CN105384187A (en) | Preparation method of stannous oxide with single-phase flower-sheet structure | |
| CN111905795A (en) | Simple and convenient environment-friendly Ta preparation method3N5Method for preparing photocatalyst | |
| CN113385167A (en) | Preparation method of stannic oxide nanosheet loaded cubic sodium tantalate | |
| CN110918104A (en) | Ternary heterojunction graphene-bismuth oxide/bismuth oxyhalide visible light photocatalyst and preparation method thereof | |
| CN113274998B (en) | Three-phase blended calcium titanate photocatalytic material and preparation method and application thereof | |
| CN114950397B (en) | Trifluoroacetic acid modified silicon surface TFA-Si photocatalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |