CN114177928A - Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof - Google Patents
Composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4Preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 10
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- 238000001354 calcination Methods 0.000 claims description 9
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012153 distilled water Substances 0.000 claims description 3
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- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
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- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000007858 starting material Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/33—
-
- 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
-
- 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
Composite photocatalyst Bi @ H-TiO with visible light response2/B‑C3N4The preparation method and the application thereof in hydrogen production by photocatalytic water decomposition belong to the technical field of energy storage and conversion. The invention firstly passes NaBH4High-temperature reduction treatment is carried out to obtain the dark brown B-C containing boron doping and nitrogen defects3N4And containing Ti3+Defective black TiO2And the response range of the visible light is expanded. The invention uses two materials to form a II type heterojunction (H-TiO)2/B‑C3N4) Simultaneously, a non-noble metal cocatalyst Bi is introduced to form the composite photocatalyst Bi @ H-TiO2/B‑C3N4. Thus, the triple means of heterojunction structure, surface defect and metal cocatalyst can be utilized to effectively promote photogeneration carrierThe separation and transfer of the flow and the reduction of the recombination efficiency of the flow, thereby improving the performance of photocatalytic hydrogen production.
Description
Technical Field
The invention belongs to the technical field of energy storage and conversion, and particularly relates to a composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4A preparation method and application thereof in hydrogen production by photocatalytic water decomposition.
Background
With the increasing world population, the global energy crisis and environmental pollution problems will become more serious, and the development of carbon-free clean energy becomes more and more important. Solar energy is the world's most abundant renewable, carbon-free energy source, and thus the utilization of solar energy has become a consensus in response to fossil fuel consumption and its severe pollution. In recent years, semiconductor-based photocatalytic technologies have received much attention due to their great application prospects in the field of solar energy utilization, such as water decomposition, carbon dioxide reduction, environmental purification, and the like. Since professor Fujishima and Honda found the photoelectrocatalytic water splitting phenomenon in 1972, how to efficiently convert solar energy into hydrogen energy and realize industrial production has become a major challenge for researchers. H2Is also a carbon-free fuel, the mass energy density of which is the highest (141.9MJ/kg) compared to any other known fuel. At present, there are two main ways of converting solar energy into hydrogen energy: the hydrogen is produced by decomposing water through photocatalysis and electrolysis of water driven by solar photovoltaic. At present, in a laboratory, the energy conversion efficiency of a solar hydrogen production device for connecting a solar cell and an electrolysis system is as high as about 30%. The energy conversion efficiency of photocatalytic water decomposition is obviously lower and is only about 1%, but the system is simpler, cheaper and easier to scale. Exciting, the Domen topic group (Nature 2021,598,304-3A hydrogen production device by photocatalytic water decomposition of Al photocatalyst. The device is composed of 100m2The panel array reactor of (a) is composed of,having H2The automatic recovery function, the system has been operated safely for several months, and the maximum energy conversion efficiency is 0.76%. This work shows that commercial production of solar energy into hydrogen energy by photocatalytic water splitting is feasible. However, the photocatalyst used in this device can only absorb ultraviolet light, and thus its energy conversion efficiency is low. How to utilize visible light with more energy in solar spectrum is one of effective ways for improving the performance of hydrogen preparation by photocatalytic water decomposition. In the past decades, researchers have prepared a large number of photocatalyst materials and explored various catalytic mechanisms to study and improve the activity of photocatalytic water splitting to produce hydrogen. Despite these efforts, the development of high performance photocatalysts under visible light remains a major challenge.
Black TiO2Since 2011 was discovered by the Mao project group (Science 2011,331,746-2Can absorb visible light, and reduces the recombination of photo-generated carrier pairs. g-C3N4(metal-free two-dimensional polymer semiconductor material) since 2009 reported by the wang new morning topic group (nat. mater.2009,8,76-80), extensive research has been conducted in the field of photocatalysis. g-C3N4Has a layered structure and has good absorption in the visible region. In addition, the method also has the advantages of good stability, no toxicity, high reduction potential, stable photoelectrochemical property and the like. However, original g-C3N4The photocatalytic performance of (a) is still not high, which is limited by factors such as light absorption, charge separation rate, rapid recombination of photogenerated carriers, and the like. In recent years, black TiO has been used2Or g-C3N4The research on the application of the basic photocatalytic material in photocatalytic hydrogen production is gradually advanced (int. J. hydrogen Energy 2020,45, 629-. There are three main effective means to increase the transfer rate of photogenerated carriers and to reduce their recombination efficiency, so that the photocatalytic activity of the photocatalyst can be increased: 1) constructing a heterojunction; 2) introducing surface defects; 3) a metal promoter is supported on the surface of the photocatalyst. To date, many studies have been madeIt is reported that photocatalytic activity can be effectively improved using only one of the strategies, and there are few attempts to effectively combine these three strategies. Therefore, combining these three strategies organically creates a new, inexpensive, stable photocatalyst system (that will have Ti)3+Defective TiO2And nitrogen defect B-C3N4After the heterojunction is constructed, the non-noble metal catalyst promoter Bi) is loaded on the surface of the heterojunction, and the composite catalyst has important significance in realizing hydrogen production by photocatalytic decomposition of water by visible light.
Disclosure of Invention
The invention aims to provide a novel composite photocatalyst Bi @ H-TiO with visible light response2/B-C3N4A preparation method and application thereof. The composite material is black in color and has good absorption in the whole visible light region. First we pass NaBH4High-temperature reduction treatment is carried out to obtain the dark brown B-C containing boron doping and nitrogen defects3N4And containing Ti3+Defective black TiO2And the response range of the visible light is expanded. In the formation of type II heterojunctions (H-TiO) using two materials2/B-C3N4) Meanwhile, a non-noble metal cocatalyst Bi is introduced to form the composite photocatalyst Bi @ H-TiO2/B-C3N4. Therefore, triple means of a heterojunction structure, surface defects and a metal cocatalyst can be utilized, so that the separation and transfer of photo-generated carrier pairs are effectively promoted, the recombination efficiency of the photo-generated carrier pairs is reduced, and the performance of photocatalytic hydrogen production is improved. In addition, Bi @ H-TiO2/B-C3N4The composite material can also be made into an electrode material, and has good photoelectric response under the irradiation of simulated sunlight.
The invention utilizes a hydrothermal method to construct II type heterojunction Bi @ H-TiO2/B-C3N4A photocatalytic material. Under the irradiation of simulated sunlight, in a type II heterojunction Bi @ H-TiO2/B-C3N4The inside of the photocatalytic material is mainly provided with two electron moving routes. On the one hand, due to B-C3N4Has a work function (3.30eV) less than that of H-TiO2Of (3.55eV) and less than BiWork function (4.22eV), so B-C3N4Part of photo-generated electrons on the conducting strip are easily transferred to H-TiO2Then transferred to metal Bi (electron capture centers) and H is photo-reduced+Generation of H2. In another aspect, B-C3N4The other part of electrons on the conducting belt are directly transferred to metal Bi to reduce H+Generation of H2. And B-C3N4The photo-generated holes on the valence band are consumed by triethanolamine serving as a sacrificial agent in the solution, so that the recombination with photo-generated electrons is avoided, and the hydrogen production efficiency is improved. Thus, Bi @ H-TiO2/B-C3N4The heterojunction composite material can effectively carry out photocatalytic decomposition on water to produce hydrogen. Because the film has strong light absorption capability in a visible light region and can enhance the photoelectric conversion performance, the Bi @ H-TiO2/B-C3N4The composite material also has a certain application prospect in the field of solar cells.
The photoelectric material has good visible light response and high photoelectric conversion efficiency, and has the performance of hydrogen production by photocatalytic decomposition of water by visible light. The invention designs and prepares II type heterojunction Bi @ H-TiO2/B-C3N4Photocatalytic material for increasing Bi @ H-TiO2/B-C3N4The main reasons for the performance of the heterojunction composite material in the photocatalytic hydrogen production are three: 1) dark brown B-C3N4(boron-doped and nitrogen-deficient) and black TiO2(containing Ti)3+Defects) expands the photoresponse range; 2) H-TiO2And B-C3N4The matched energy band structure can form a II-type heterojunction, so that the separation rate of photo-generated carrier pairs is improved, and the recombination efficiency of the photo-generated carrier pairs is reduced; 3) the load of the cocatalyst Bi can provide more electron capture sites and surface plasmon resonance effect thereof, and can improve the separation and transfer rate of photon-generated carriers. Therefore, the II type heterojunction Bi @ H-TiO designed by us2/B-C3N4The photocatalyst can effectively improve the separation and transfer rate of photo-generated carrier pairs from multiple aspects, and reduce the composite efficiency of the photo-generated carrier pairs, thereby improving the performance of photocatalytic hydrogen production.
The II type heterojunction has visible lightResponsive Bi @ H-TiO2/B-C3N4The preparation method of the photocatalytic material comprises the following steps (if not specified, the solution of the invention is aqueous solution):
1) black TiO 22Preparation of the photocatalyst
First, 0.7-1.4 mL of Ti (C)4H9O)4Adding the mixture into 15-30 mL of 1mol/L NaOH solution, magnetically stirring for 20-40 minutes, and then carrying out ultrasonic treatment for 3-8 minutes to obtain a suspension; then, adding 0.3-0.6 g of urea and 25-50 mL of an alcohol solvent which is easily dissolved in water into the suspension, magnetically stirring for 20-40 minutes to form a white suspension, transferring the white suspension into an autoclave, and carrying out hydrothermal treatment at 180-190 ℃ for 13-20 hours; centrifuging to collect a white product, sequentially centrifuging and washing the white product for several times by using dilute acetic acid, distilled water and absolute ethyl alcohol, drying the obtained sample at 40-80 ℃, grinding the dried sample, and calcining 0.1-0.2 g of the ground sample in an argon atmosphere at 600-700 ℃ for 2.0-3.0 hours (the temperature rise speed is 3-5 ℃/min); cooling to room temperature, and mixing 0.1-0.2 g of the sample with 0.1-0.2 g of NaBH4Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours at 350-400 ℃ in an argon atmosphere (the heating rate is 3-5 ℃/min); soaking the obtained black powder in deionized water for 4-8 hours until no bubbles are generated, so as to ensure that unreacted NaBH is completely removed4(ii) a Finally, centrifugally washing the mixture for several times by using deionized water and absolute ethyl alcohol, and drying the mixture overnight at the temperature of 40-80 ℃ to obtain the black TiO2A photocatalyst;
2) B-C doped with B (boron) element3N4Preparation of the photocatalyst
First, g-C is prepared by a thermal polymerization method3N4: calcining 2-10 g of melamine in an air atmosphere at 530-580 ℃ for 4-4.5 hours (the heating rate is 3-5 ℃/min), cooling to room temperature, and obtaining faint yellow g-C3N4Grinding into powder; secondly, 0.1-0.2 g g-C is prepared3N4And 0.05 to 0.1g of NaBH4Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours at the temperature of 300-350 ℃ in an argon atmosphere (the temperature rise speed is 3-5 ℃/min); then, the obtained depthSoaking the brown powder in water for 4-8 hours until no bubbles are generated to ensure complete removal of unreacted NaBH4(ii) a Finally, the brown powder is centrifugally washed for several times by deionized water and absolute ethyl alcohol, and dried overnight at the temperature of 40-80 ℃ to obtain B (boron) element doped B-C3N4A photocatalyst;
3)Bi@H-TiO2/B-C3N4preparation of composite photocatalytic material
Mixing 10-50 mg Bi (NO)3)3·5H2O dissolved in 10mL of 1mol/L diluted HNO3Sequentially adding 20-40 mL of water-soluble alcohol solvent and 20-30 mg of polyvinylpyrrolidone under continuous magnetic stirring; then sequentially adding 10-50 mg of black TiO2Photocatalyst and 40-80 mg of B-C3N4Adding a photocatalyst into the solution, continuously magnetically stirring for 3-8 minutes, and ultrasonically treating for 20-40 minutes; transferring the obtained black turbid liquid into an autoclave, and performing hydrothermal treatment at 160-180 ℃ for 10-15 hours; after the reaction is finished, sequentially centrifugally washing the obtained sample for a plurality of times by using deionized water and absolute ethyl alcohol; finally, drying the sample at 40-80 ℃ to obtain Bi @ H-TiO2/B-C3N4The composite photocatalytic material (recorded as Bi @ Ti-BCN).
4) Hydrogen production by photocatalyst
The photocatalytic hydrogen production experiment was performed using an on-line photocatalytic hydrogen production system (CEL-PAEM-D8, zhongzhi gold source company) with a temperature controlled at 6 ℃. Sunlight was simulated using 300W Xe lamps (covered CUT-off filters: JB 300(300-1100nm) or CUT 400(400-780nm)) as the light source. 20mg of the photocatalyst was dispersed in a mixed solution containing 6mL of triethanolamine (sacrificial agent) and 24mL of deionized water. Before turning on the xenon lamp, the reaction environment was kept under vacuum by using a vacuum pump for 30 minutes. Hydrogen was extracted every hour and analyzed by an on-line gas chromatograph (GC 7920-DTA).
The alcohol solvent which is easily dissolved in water in the step 1) can be one of isopropanol, absolute ethyl alcohol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol and glycerol; the magnetic stirring speed is 200-400 rpm, and the centrifugal operation speed is 8000-10000 rpm.
The polyvinylpyrrolidone in the step 3) can be one of K30 and K60; the water-soluble alcohol solvent can be one of isopropanol, anhydrous ethanol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol, and glycerol; the magnetic stirring speed is 200-400 rpm; the rotation speed of the centrifugal operation is 8000 rpm-10000 rpm.
Drawings
FIG. 1 shows graphs (a, b, f) of g-C in example 13N4、B-C3N4And Bi @ H-TiO2/B-C3N4(Bi @ Ti-BCN) photocatalyst, FIG. (c) is a photomicrograph of the metal Bi of example 4; FIG. d shows H-TiO in example 52A photo of the photocatalyst; FIG. e shows H-TiO in example 62/B-C3N4Photo of a real object of the (Ti-BCN) photocatalyst. Wherein the sample colors in the graphs (c, d, e, f) are all black, indicating that we obtained black TiO2And these samples have absorption in the visible region.
FIG. 2 shows examples g to C3N4Example 1, B-C3N4Example 1, Bi (example 4), H-TiO2X-ray diffraction patterns of (example 5), Ti-BCN (example 6) and Bi @ Ti-BCN (example 1) photocatalysts indicate that we successfully designed and prepared Bi @ H-TiO2/B-C3N4A composite photocatalyst is provided.
In FIG. 3, the graphs (a, b, f) are g-C in example 1, respectively3N4、B-C3N4And the scanning electron micrograph of the Bi @ Ti-BCN photocatalyst shows that the Bi @ H-TiO photocatalyst is successfully designed and prepared2/B-C3N4A composite photocatalyst is provided. FIG. (c) is a SEM photograph of the metal Bi spheres of example 4; FIG. d shows H-TiO in example 52Scanning electron micrographs of nanoparticles; FIG. (e) is a scanning electron micrograph of the Ti-BCN photocatalyst of example 6, comparing FIG. 3B with B-C in FIG. 3e3N4Having a layer of H-TiO on the surface2Nano particles, indicating successful preparation of H-TiO2/B-C3N4A composite photocatalyst is provided.
FIG. 4 shows examples of g-C3N4Example 1, B-C3N4Example 1H-TiO2(example 5), Ti-BCN (example 6) and Bi @ Ti-BCN (example 1) photocatalysts. Wherein B-C3N4In the infrared spectrum of 2177cm-1Has a new peak, which can be attributed to the asymmetric stretching vibration of the N.ident.C group, and is shown in B-C3N4The N defect is introduced. H-TiO2The infrared spectrograms of the Ti-BCN and Bi @ Ti-BCN samples have wider Ti-O stretching vibration absorption peaks (400-800 cm)-1) This also shows H-TiO2The nanoparticles are successfully loaded in B-C3N4A surface.
FIG. 5 shows examples g to C3N4Example 1, B-C3N4Example 1H-TiO2Histograms of hydrogen production rates for (example 5), Ti-BCN (example 6), Bi @ Ti-GCN (example 7), and Bi @ Ti-BCN (example 1) photocatalysts. Under the irradiation of ultraviolet and visible light (lambda)>300nm), the photocatalytic hydrogen production rate of Bi @ Ti-BCN is highest and can reach 223.08 mu mol g-1h-1. Under the irradiation of visible light (lambda)>400nm), the photocatalytic hydrogen production rate of Bi @ Ti-BCN is also the highest and reaches 18.84 mu mol g-1h-1Is H-TiO respectively2、B-C3N4And 67.3 times, 37.7 times, and 6.8 times of Ti-BCN.
FIG. 6 shows examples g to C3N4Example 1, B-C3N4Example 1, Bi (example 4), H-TiO2(example 5), Ti-BCN (example 6) and Bi @ Ti-BCN (example 1) photocatalysts. First, the light absorption of the Bi @ Ti-BCN sample was the strongest consistent with its highest photocatalytic hydrogen production rate in all samples. In addition, the Bi sample has a strong absorption peak at 279nm and a wide and weak peak at 350-600 nm (FIG. 6), which can be attributed to the Surface Plasmon Resonance (SPR) effect of Bi metal.
FIG. 7 shows examples of g-C3N4Example 1, B-C3N4Example 1H-TiO2(example 5), Ti-BCN (example 6) and Bi @ Ti-BCN (example 1) photocatalysts. Under the light irradiation, the strongest photocurrent of the Bi @ Ti-BCN is consistent with the highest photocatalytic hydrogen production rate of the Bi @ Ti-BCN in all samples, which indicates that the separation and transfer rate of a photon-generated carrier on the surface of the Bi @ Ti-BCN is highest, and the photocatalytic hydrogen production rate is favorably improved.
FIG. 8 shows B-C3N4And H-TiO2Calculating B-C by using UPS energy spectrum in the low binding energy region (a and C) and the high binding energy region (B and d) of the ultraviolet photoelectron spectrum of the sample3N4And H-TiO2The work functions of the samples were 3.30 and 3.55eV, respectively.
Detailed Description
The technical solution of the present invention is described in more detail with reference to the following specific examples, which are not intended to limit the present invention.
Example 1
1) Black TiO 22Preparation of the photocatalyst
First, 0.7mL of Ti (C)4H9O)4Adding into 15mL of 1mol/L NaOH solution, magnetically stirring for 30 minutes, and then carrying out ultrasonic treatment for 5 minutes. Subsequently, 0.3g of urea and 25mL of ethylene glycol were added to the above suspension. Magnetic stirring was carried out for another 30 minutes to form a white suspension, which was transferred to an autoclave and hydrothermal treated at 180 ℃ for 15 hours. Centrifuging to collect white product, sequentially centrifuging and washing with dilute acetic acid, distilled water and anhydrous ethanol for several times, and drying the obtained sample at 60 deg.C. The sample was then ground and divided into portions of 0.1g each, which were held in a tube furnace at 600 ℃ for 2 hours under argon atmosphere (rate of temperature rise 4 ℃/min). After cooling to room temperature, 0.18g of the above sample and 0.18g of NaBH were added4The mixture was ground for 30 minutes and then kept in a tube furnace at 350 ℃ for 1 hour under an argon atmosphere (the temperature rise rate was 4 ℃/min). The resulting black powder was then soaked in deionized water for 4 hours until no bubbles were generated to ensure complete removal of unreacted NaBH4. Finally, the mixture was washed several times by centrifugation with deionized water and absolute ethanol and dried overnight at 60 ℃.
2) Doping with B (boron) elementB-C of3N4Preparation of the photocatalyst
First of all, g-C is prepared by a thermal polymerization process3N4. Calcining at 550 deg.C for 4 hr (heating rate of 4 deg.C/min) in 10g melamine tube furnace, cooling to room temperature, and collecting light yellow g-C3N4Grinding into powder. Secondly, the prepared 0.2g g-C3N4And 0.1g NaBH4The mixture was ground for 30 minutes and then calcined in a tube furnace at 350 ℃ for 1 hour under argon atmosphere (rate of temperature rise 4 ℃/min). The resulting dark brown powder was then soaked in water for 4 hours until no bubbles were generated to ensure complete removal of unreacted NaBH4. The brown powder was then washed several times by centrifugation with deionized water and absolute ethanol and dried overnight at 60 ℃.
20mg of g-C are taken3N4The sample is used for photocatalytic hydrogen production experiment under the irradiation of ultraviolet and visible light (lambda)>300nm) of hydrogen production activity of 5.05 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production activity of 0.24 mu mol g-1h-1.20 mg of B-C was taken3N4The sample is used for photocatalytic hydrogen production experiment under the irradiation of ultraviolet and visible light (lambda)>300nm) of 1.65 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production activity of 0.50 mu mol g-1h-1。
3)Bi@H-TiO2/B-C3N4Preparation of composite photocatalytic material
20mg of Bi (NO)3)3·5H2O dissolved in 10mL of diluted HNO of 1mol/L3In (1), 30mL of ethylene glycol and 25mg of polyvinylpyrrolidone were added sequentially with continuous magnetic stirring. Then 10mg of black TiO are added in turn2And 40mg of B-C3N4Added to the above solution and magnetic stirring continued for 5 minutes. And after further ultrasonic treatment for 30 minutes, transferring the black turbid liquid into an autoclave, carrying out hydrothermal treatment for 12 hours at 160 ℃, and after the reaction is finished, sequentially carrying out centrifugal washing on the obtained sample for several times by using deionized water and absolute ethyl alcohol. Finally, the sample was dried at 60 ℃ to yield about 20mg Bi @ H-TiO2/B-C3N4(Bi @ Ti-BCN) catalyst. Under the irradiation of ultraviolet and visible light (lambda)>300nm) of 223.08 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production activity of 18.84 mu mol g-1h-1。
Example 2
The procedure is as in example 1 except that Bi (NO) is present in the starting material of step 3) in example 23)3·5H2O is 10mg, and about 20mg of Bi @ H-TiO is finally obtained2/B-C3N4(Bi @ Ti-BCN). Under the irradiation of ultraviolet and visible light (lambda)>300nm) of 217.23 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) hydrogen production rate of 15.46 mu mol g-1h-1。
Example 3
The procedure is as in example 1 except that Bi (NO) is present in the starting material of step 3) in example 33)3·5H2O is 50mg, and about 20mg of Bi @ H-TiO is finally obtained2/B-C3N4(Bi @ Ti-BCN). Under the irradiation of ultraviolet and visible light (lambda)>300nm) of 173.27 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production rate of 3.54 mu mol g-1h-1。
Example 4
Example 4 preparation of Bi Metal spheres, step 3) of example 1 is only required, and the starting material of step 3) is only 0.1g Bi (NO)3)3·5H2And O, finally obtaining the Bi metal ball. In addition, the Bi sample has a strong absorption peak at 279nm and a wide and weak absorption peak at 350-600 nm in the ultraviolet-visible diffuse reflectance spectrum (FIG. 6), which can be attributed to the characteristic peak of the SPR effect typical of Bi metal. The SPR characteristic of the cocatalyst Bi is beneficial to enhancing the visible light capture and charge separation, thereby improving the activity of the photocatalyst.
Example 5
EXAMPLE 5 preparation of H-TiO2Nanoparticles, only step 1) and step 3) of example 1), except that the starting material of step 3) is the only one50mg of Black TiO2Finally, about 30mg of H-TiO is obtained2And (3) nanoparticles. Under the irradiation of ultraviolet and visible light (lambda)>300nm) of hydrogen production rate of 86.53 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production rate of 0.28 mu mol g-1h-1。
Example 6
The procedure is as in example 1, except that the starting material for step 3) in example 6 is only 10mg of black TiO2And 40mg of B-C3N4Finally, about 15mg of H-TiO is obtained2/B-C3N4(Ti-BCN). Under the irradiation of ultraviolet and visible light (lambda)>300nm) of hydrogen production rate of 60.20 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production rate of 2.79 mu mol g-1h-1。
Example 7
The procedure is as in example 1, except that 20mg of Bi (NO) is used as the starting material in step 3) in example 73)3·5H2O, 10mg of Black TiO2And 40mg g-C3N4To obtain about 20mg of Bi @ H-TiO2/g-C3N4(Bi @ Ti-GCN). Under the irradiation of ultraviolet and visible light (lambda)>300nm) of 178.43 mu mol g-1h-1(ii) a Under the irradiation of visible light (lambda)>400nm) of hydrogen production rate of 5.98 mu mol g-1h-1。
Claims (5)
1. Bi @ H-TiO with visible light response2/B-C3N4The preparation method of the photocatalytic material comprises the following steps:
1) black TiO 22Preparation of the photocatalyst
First, 0.7-1.4 mL of Ti (C)4H9O)4Adding the mixture into 15-30 mL of 1mol/L NaOH solution, magnetically stirring for 20-40 minutes, and then carrying out ultrasonic treatment for 3-8 minutes to obtain a suspension; then, 0.3-0.6 g urea and 25-50 mL water-soluble alcohol solvent are added into the suspension, and magnetic stirring is performed for 20-40 minutes to form white suspension, which is transferred into an autoclave at 180-190 ℃ hydrothermal 13 ℃20 hours; centrifuging to collect a white product, sequentially centrifuging and washing the white product for several times by using dilute acetic acid, distilled water and absolute ethyl alcohol, drying the obtained sample at 40-80 ℃, grinding the dried sample, calcining 0.1-0.2 g of the ground sample in an argon atmosphere at 600-700 ℃ for 2.0-3.0 hours, and raising the temperature at 3-5 ℃/min; cooling to room temperature, and mixing 0.1-0.2 g of the sample with 0.1-0.2 g of NaBH4Mixing and grinding for 20-40 minutes, and calcining for 1-1.5 hours at 350-400 ℃ in an argon atmosphere, wherein the heating rate is 3-5 ℃/min; soaking the obtained black powder in deionized water for 4-8 hours until no bubbles are generated, so as to ensure that unreacted NaBH is completely removed4(ii) a Finally, centrifugally washing the mixture for several times by using deionized water and absolute ethyl alcohol, and drying the mixture overnight at the temperature of 40-80 ℃ to obtain the black TiO2A photocatalyst;
2) B-C doped with boron3N4Preparation of the photocatalyst
First, g-C is prepared by a thermal polymerization method3N4: calcining 2-10 g of melamine in an air atmosphere at 530-580 ℃ for 4-4.5 hours at a heating rate of 3-5 ℃/min, cooling to room temperature, and obtaining faint yellow g-C3N4Grinding into powder; secondly, 0.1-0.2 g g-C is prepared3N4And 0.05 to 0.1g of NaBH4Mixing and grinding for 20-40 minutes, and calcining for 1-1.5 hours at the temperature of 300-350 ℃ in an argon atmosphere, wherein the heating rate is 3-5 ℃/min; subsequently, the dark brown powder obtained is soaked in water for 4-8 hours until no bubbles are generated to ensure complete removal of unreacted NaBH4(ii) a Finally, the brown powder is centrifugally washed for several times by deionized water and absolute ethyl alcohol, and dried at 40-80 ℃ overnight to obtain boron element doped B-C3N4A photocatalyst;
3)Bi@H-TiO2/B-C3N4preparation of composite photocatalytic material
Mixing 10-50 mg Bi (NO)3)3·5H2O dissolved in 10mL of 1mol/L diluted HNO3Sequentially adding 20-40 mL of water-soluble alcohol solvent and 20-30 mg of polyvinylpyrrolidone under continuous magnetic stirring; however, the device is not suitable for use in a kitchenThen sequentially adding 10-50 mg of black TiO2Photocatalyst and B-C doped with 40-80 mg of boron element3N4Adding a photocatalyst into the solution, continuously magnetically stirring for 3-8 minutes, and ultrasonically treating for 20-40 minutes; transferring the obtained black turbid liquid into an autoclave, and performing hydrothermal treatment at 160-180 ℃ for 10-15 hours; after the reaction is finished, sequentially centrifugally washing the obtained sample for a plurality of times by using deionized water and absolute ethyl alcohol; finally, drying the sample at 40-80 ℃ to obtain the Bi @ H-TiO with visible light response2/B-C3N4A composite photocatalytic material.
2. The visible light responsive Bi @ H-TiO of claim 12/B-C3N4The preparation method of the photocatalytic material is characterized by comprising the following steps: the alcohol solvent which is easily dissolved in water in the step 1) is one of isopropanol, absolute ethyl alcohol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol and glycerol; the magnetic stirring speed is 200-400 rpm, and the centrifugal operation speed is 8000-10000 rpm.
3. The visible light responsive Bi @ H-TiO of claim 12/B-C3N4The preparation method of the photocatalytic material is characterized by comprising the following steps: the polyvinylpyrrolidone in the step 3) is one of K30 and K60; the water-soluble alcohol solvent is one of isopropanol, anhydrous ethanol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol and glycerol; the magnetic stirring speed is 200-400 rpm; the rotation speed of the centrifugal operation is 8000 rpm-10000 rpm.
4. Bi @ H-TiO with visible light response2/B-C3N4A photocatalytic material characterized by: is prepared by the method of any one of claims 1 to 3.
5. The visible light responsive Bi @ H-TiO of claim 42/B-C3N4Photocatalytic decomposition of photocatalytic materialsApplication in hydrogen production from water.
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