CN114177928B - Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof - Google Patents
Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof Download PDFInfo
- Publication number
- CN114177928B CN114177928B CN202111612860.7A CN202111612860A CN114177928B CN 114177928 B CN114177928 B CN 114177928B CN 202111612860 A CN202111612860 A CN 202111612860A CN 114177928 B CN114177928 B CN 114177928B
- Authority
- CN
- China
- Prior art keywords
- tio
- visible light
- photocatalyst
- preparation
- water
- 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.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000004298 light response Effects 0.000 title claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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
- 238000000034 method Methods 0.000 claims description 19
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 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
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 238000001354 calcination Methods 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
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 34
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000000969 carrier Substances 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 3
- 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 12
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 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
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 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
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
- 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
-
- 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
- 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
- B01J35/33—Electric or magnetic properties
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Composite photocatalyst Bi@H-TiO with visible light response 2 /B‑C 3 N 4 The preparation method and the application thereof in preparing hydrogen by photocatalytic water splitting belong to the technical field of energy storage and conversion. The invention firstly passes through NaBH 4 High-temperature reduction treatment to obtain dark brown B-C containing boron doping and nitrogen defects 3 N 4 And contains Ti 3+ Defective black TiO 2 Expanding their response range in visible light. The invention uses two materials to form a II type heterojunction (H-TiO 2 /B‑C 3 N 4 ) Meanwhile, a non-noble metal promoter Bi is also introduced to form a composite photocatalyst Bi@H-TiO 2 /B‑C 3 N 4 . Therefore, triple means of a heterojunction structure, surface defects and a metal cocatalyst can be utilized, so that the separation and transfer of photon-generated carriers are effectively promoted, the composite efficiency of the photon-generated carriers is reduced, and the photocatalytic hydrogen production performance is improved.
Description
Technical Field
The invention belongs to the technical field of energy storage and conversion, and in particular relates to a composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 A preparation method and application thereof in preparing hydrogen by photocatalytic decomposition of water.
Background
With the increasing population of the world, global energy crisis and environmental pollution problems will become more and more serious, and development of carbon-free clean energy becomes more and more important. Solar energy is the most abundant renewable carbon-free energy source in the world, so the utilization of solar energy has become a countermeasureConsensus on fossil fuel consumption and its serious pollution. In recent years, semiconductor-based photocatalytic technology has received attention due to its great application prospect in the field of solar energy utilization, such as water decomposition, carbon dioxide reduction, environmental purification, and the like. Since the discovery of the photocatalytic water splitting phenomenon in 1972 by the professor Fujishima and Honda, a japanese scientist, how to efficiently convert solar energy into hydrogen energy and realize industrial production has become a major challenge for researchers. H 2 Also a carbon-free fuel, the mass energy density was highest (141.9 MJ/kg) compared to any other known fuel. At present, two main ways of converting solar energy into hydrogen energy exist: photocatalytic water splitting to produce hydrogen and solar photovoltaic driven electrolysis to split water to produce hydrogen. Currently, in the laboratory, the energy conversion efficiency of a solar hydrogen production device connecting a solar cell and an electrolysis system is as high as about 30%. The energy conversion efficiency of photocatalytic water splitting is obviously lower, and is only about 1%, but the system is simpler, cheaper and easier to scale. It is exciting that a SrTiO-based solution has recently been reported by the document task force (Nature 2021,598,304-307) of university of Tokyo, japan 3 An Al photocatalyst photocatalytic water splitting hydrogen production device. The device is composed of 100m 2 Is composed of panel array reactor with H 2 The automatic recovery function, the system is safely operated for several months, and the highest energy conversion efficiency is 0.76%. This work shows that commercial production of solar energy into hydrogen energy by photocatalytic decomposition of water is possible. However, the photocatalyst used in this device can only absorb ultraviolet light, and thus its energy conversion efficiency is low. How to use the visible light with more energy in the solar spectrum is one of the effective ways to improve the performance of preparing hydrogen by photocatalytic decomposition of water. During the last decades, researchers have prepared a large number of photocatalyst materials and explored a variety of catalytic mechanisms to investigate and enhance 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 TiO 2 Has been found by the Mao group of topics (Science 2011,331,746-750) to be one of the most popular photocatalysts since 2011For it can overcome white TiO 2 Is capable of absorbing visible light and reducing recombination of photogenerated carrier pairs. g-C 3 N 4 (two-dimensional Polymer semiconductor materials free of metals) since being reported by the Wang Xinchen subject group (Nat. Mater.2009,8,76-80) in 2009, extensive research has been conducted in the field of photocatalysis. g-C 3 N 4 Has a layered structure and good absorption in the visible region. In addition, the fluorescent dye has the advantages of good stability, no toxicity, high reduction potential, stable photoelectrochemical property and the like. However, the original g-C 3 N 4 The photocatalytic performance of (c) is still not high, which is limited by factors such as light absorption, charge separation rate, fast recombination of photogenerated carriers, etc. In recent years, in black TiO 2 Or g-C 3 N 4 The research on the use of the base photocatalytic material for photocatalytic hydrogen production is gradually in progress (int.j. Hydrogen Energy 2020,45,629-639;J.Mater.Chem.A 2021,9,4687-4691). There are three main effective means to increase the transfer rate of photogenerated carriers and 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. So far, many studies report that photocatalytic activity can be effectively improved using only one of the strategies, and few attempts have been made to effectively combine the three strategies. Thus, combining these three strategies organically, a new, inexpensive, stable photocatalyst system was constructed (will have Ti 3+ Defective TiO 2 And nitrogen defects B-C 3 N 4 After the heterojunction is constructed, the non-noble metal promoter Bi is loaded on the surface, and the composite catalyst is used for realizing the hydrogen production by the 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 response 2 /B-C 3 N 4 A preparation method and application thereof. The color of the composite material is black, and the composite material has good absorption in the whole visible light region. First we pass NaBH 4 High temperature reduction treatment to obtain boron-containingDark brown B-C with doping and nitrogen defects 3 N 4 And contains Ti 3+ Defective black TiO 2 Expanding their response range in visible light. In the case of using two materials to form a type II heterojunction (H-TiO 2 /B-C 3 N 4 ) Meanwhile, a non-noble metal promoter Bi is also introduced to form a composite photocatalyst Bi@H-TiO 2 /B-C 3 N 4 . Therefore, triple means of a heterojunction structure, surface defects and a metal cocatalyst can be utilized, so that separation and transfer of photo-generated carrier pairs are effectively promoted, the composite efficiency of the photo-generated carrier pairs is reduced, and the photocatalytic hydrogen production performance is improved. In addition, bi@H-TiO 2 /B-C 3 N 4 The composite material can also be made into an electrode material, and has good photoelectric response under the irradiation of simulated sunlight.
The invention constructs the II heterojunction Bi@H-TiO by utilizing a hydrothermal method 2 /B-C 3 N 4 Photocatalytic material. Under the irradiation of simulated sunlight, the II-type heterojunction Bi@H-TiO 2 /B-C 3 N 4 Two electron moving routes are mainly arranged in the photocatalytic material. On the one hand due to B-C 3 N 4 Work function (3.30 eV) is smaller than H-TiO 2 Work function of (3.55 eV) and less than Bi is (4.22 eV), so B-C 3 N 4 A part of photo-generated electrons on the guide belt are easily transferred to H-TiO 2 On, then transferred to a metal Bi (electron trapping center) for H reduction by light + Production of H 2 . On the other hand, B-C 3 N 4 The other part of electrons on the conducting belt are directly transferred to the metal Bi to reduce H + Production of H 2 . And B-C 3 N 4 The photo-generated hole on the valence band is consumed by the sacrificial agent triethanolamine in the solution, so that the recombination of the photo-generated hole and photo-generated electrons is avoided, and the hydrogen production efficiency is improved. Therefore, bi@H-TiO 2 /B-C 3 N 4 The heterojunction composite material can effectively decompose water to produce hydrogen by photocatalysis. The light-absorbing material has strong light absorption capacity in the visible light region, and can enhance the photoelectric conversion performance to ensure that Bi@H-TiO 2 /B-C 3 N 4 The composite material also has a certain application prospect in the field of solar cells.
The photoelectric material has good visible light response, high photoelectric conversion efficiency and hydrogen production performance by decomposing water through visible light photocatalysis. The invention designs and prepares II heterojunction Bi@H-TiO 2 /B-C 3 N 4 Photocatalytic material for improving Bi@H-TiO 2 /B-C 3 N 4 The main reasons for the photocatalytic hydrogen production performance of heterojunction composite materials are three: 1) Dark brown B-C 3 N 4 (boron-containing doping and nitrogen defects) and black TiO 2 (containing Ti) 3+ Defects) expands the light response range; 2) H-TiO 2 With B-C 3 N 4 The matched energy band structure can form a II-type heterojunction, so that the separation rate of photo-generated carrier pairs is improved, and the composite efficiency of the photo-generated carrier pairs is reduced; 3) The loading of the cocatalyst Bi can provide more electron trapping sites and the surface plasmon resonance effect thereof, and can improve the separation and transfer rate of the photon-generated carriers. Therefore, the II type heterojunction Bi@H-TiO designed by us 2 /B-C 3 N 4 The photocatalyst can effectively improve the separation and transfer rate of the photo-generated carrier pairs from multiple aspects, and reduce the composite efficiency of the photo-generated carrier pairs, thereby improving the photocatalytic hydrogen production performance.
The II-type heterojunction has the Bi@H-TiO with visible light response 2 /B-C 3 N 4 The preparation method of the photocatalytic material comprises the following steps (if not specified, the solutions in the invention are all aqueous solutions):
1) Black TiO 2 Preparation of photocatalyst
First, 0.7 to 1.4mL of Ti (C 4 H 9 O) 4 Adding the mixture into 15-30 mL of 1mol/L NaOH solution, magnetically stirring the mixture for 20-40 minutes, and then performing ultrasonic treatment for 3-8 minutes to obtain suspension; then adding 0.3-0.6 g of urea and 25-50 mL of alcohol solvent which is easy to dissolve in water into the suspension, magnetically stirring for 20-40 minutes to form white suspension, transferring into an autoclave, and carrying out hydrothermal treatment at 180-190 ℃ for 13-20 hours; centrifuging to collect white product, centrifuging and washing with dilute acetic acid, distilled water and absolute ethyl alcohol for several times, stoving the obtained sample at 40-80 deg.c, grinding 0.1-0.2 g of the ground sample at 600-700 deg.cCalcining for 2.0-3.0 hours in argon atmosphere (the heating speed is 3-5 ℃/min); cooling to room temperature, adding 0.1-0.2 g of the sample and 0.1-0.2 g of NaBH 4 Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours in argon atmosphere at 350-400 ℃ (the heating rate is 3-5 ℃/min); soaking the obtained black powder in deionized water for 4-8 hr until no bubbles are generated to ensure complete removal of unreacted NaBH 4 The method comprises the steps of carrying out a first treatment on the surface of the Finally, centrifugal washing is carried out for a plurality of times by deionized water and absolute ethyl alcohol, and drying is carried out overnight at 40-80 ℃ to obtain black TiO 2 A photocatalyst;
2) B-C doped with B (boron) 3 N 4 Preparation of photocatalyst
First, g-C is prepared by a thermal polymerization method 3 N 4 : calcining 2-10 g melamine in air atmosphere at 530-580 deg.C for 4-4.5 hr at 3-5 deg.C/min, cooling to room temperature, and obtaining yellowish g-C 3 N 4 Grinding into powder; secondly, the prepared 0.1 to 0.2. 0.2g g-C 3 N 4 And 0.05 to 0.1g NaBH 4 Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours in an argon atmosphere at 300-350 ℃ (the heating rate is 3-5 ℃/min); subsequently, the dark brown powder obtained is immersed in water for 4 to 8 hours until no bubbles are generated, to ensure complete removal of unreacted NaBH 4 The method comprises the steps of carrying out a first treatment on the surface of the Finally, the brown powder is centrifugally washed by deionized water and absolute ethyl alcohol for a plurality of times, and is dried overnight at 40-80 ℃ to obtain B-C doped with B (boron) 3 N 4 A photocatalyst;
3)Bi@H-TiO 2 /B-C 3 N 4 preparation of composite photocatalytic material
10-50 mg Bi (NO) 3 ) 3 ·5H 2 O is dissolved in 10mL, 1mol/L of dilute HNO 3 Sequentially adding 20-40 mL of an alcohol solvent which is easy to dissolve in water and 20-30 mg of polyvinylpyrrolidone under continuous magnetic stirring; then sequentially adding 10-50 mg of black TiO 2 Photocatalyst and 40-80 mg B-C 3 N 4 Adding a photocatalyst into the solution, continuously magnetically stirring for 3-8 minutes, and performing ultrasonic treatment for 20-40 minutes; and then the obtained blackTransferring the color turbid liquid into an autoclave, and performing hydrothermal treatment for 10-15 hours at 160-180 ℃; after the reaction is finished, sequentially centrifugally washing the obtained sample with deionized water and absolute ethyl alcohol for a plurality of times; finally, drying the sample at 40-80 ℃ to obtain Bi@H-TiO 2 /B-C 3 N 4 Composite photocatalytic material (noted 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, medium teaching gold source company) at a temperature of 6 ℃. A300W Xe lamp (covering cutoff filters: JB 300 (300-1100 nm) or CUT 400 (400-780 nm)) was used as a light source to simulate sunlight. 20mg of photocatalyst was dispersed in a mixed solution containing 6mL of triethanolamine (sacrificial agent) and 24mL of deionized water. Before the xenon lamp is turned on, the reaction environment is ensured to be in a vacuum state by using a vacuum pump to vacuum for 30 minutes. Hydrogen was extracted once an hour and analyzed by an on-line gas chromatograph (GC 7920-DTA).
The alcohol solvent easily soluble in water in the step 1) can be one of isopropanol, absolute ethanol, 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, absolute ethanol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol, and glycerol; the magnetic stirring rotating speed is 200-400 rpm; the rotational speed of the centrifugal operation is 8000 rpm-10000 rpm.
Drawings
FIG. 1 shows graphs (a, b, f) of g-C in example 1 3 N 4 、B-C 3 N 4 And Bi@H-TiO 2 /B-C 3 N 4 (Bi@Ti-BCN) photocatalyst, and the graph (c) is a physical photograph of the metal Bi in example 4; FIG. (d) is the H-TiO of example 5 2 A physical photograph of the photocatalyst; FIG. (e) is the H-TiO of example 6 2 /B-C 3 N 4 (Ti-BCN) photo of photocatalyst. Wherein, the graph (c, d, e, f)The color of the sample is black, which shows that we obtain black TiO 2 And these samples all absorb in the visible region.
FIG. 2 shows the g-C values in the examples 3 N 4 (example 1), B-C 3 N 4 (example 1), bi (example 4), H-TiO 2 X-ray diffraction patterns of the photo-catalysts of (example 5), ti-BCN (example 6) and Bi@Ti-BCN (example 1) show that we successfully designed and prepared Bi@H-TiO 2 /B-C 3 N 4 A composite photocatalyst.
FIG. 3 shows graphs (a, b, f) of g-C in example 1, respectively 3 N 4 、B-C 3 N 4 And a scanning electron microscope photograph of a Bi@Ti-BCN photocatalyst, which shows that we successfully design and prepare Bi@H-TiO 2 /B-C 3 N 4 A composite photocatalyst. FIG. (c) is a scanning electron micrograph of the metal Bi balls in example 4; FIG. (d) is the H-TiO of example 5 2 Scanning electron microscope pictures of the nano particles; FIG. (e) is a scanning electron micrograph of the Ti-BCN photocatalyst of example 6, B-C of FIG. 3e compared with FIG. 3B 3 N 4 The surface is provided with a layer of H-TiO 2 Nanoparticles, indicating successful preparation of H-TiO 2 /B-C 3 N 4 A composite photocatalyst.
FIG. 4 shows the values g-C in the examples 3 N 4 (example 1), B-C 3 N 4 (example 1), H-TiO 2 Infrared spectra of (example 5), ti-BCN (example 6) and bi@ti-BCN (example 1) photocatalysts. Wherein B-C 3 N 4 Is 2177cm in the infrared spectrum of (C) -1 There is a new peak which can be ascribed to an asymmetric stretching vibration of the N.ident.C group, indicating that in B-C 3 N 4 N defects are introduced. H-TiO 2 The infrared spectrograms of the Ti-BCN sample and the Bi@Ti-BCN sample have wider Ti-O stretching vibration absorption peaks (400-800 cm -1 ) This also indicates H-TiO 2 Successful nanoparticle loading in B-C 3 N 4 A surface.
FIG. 5 shows the values of g-C in the examples 3 N 4 (example 1), B-C 3 N 4 (example 1), H-TiO 2 (example 5), ti-BCN (example6) Hydrogen production rate histogram of bi@ti-GCN (example 7) and bi@ti-BCN (example 1) photocatalysts. Under irradiation of ultraviolet and visible light (lambda)>300 nm), the highest photocatalytic hydrogen production rate of Bi@Ti-BCN can reach 223.08 mu mol g -1 h -1 . Under irradiation of visible light (lambda)>400 nm), the photocatalytic hydrogen production rate of Bi@Ti-BCN is also highest and reaches 18.84 mu mol g -1 h -1 Respectively H-TiO 2 、B-C 3 N 4 And 67.3 times, 37.7 times and 6.8 times of Ti-BCN.
FIG. 6 shows g-C in the examples 3 N 4 (example 1), B-C 3 N 4 (example 1), bi (example 4), H-TiO 2 (example 5), ti-BCN (example 6) and Bi@Ti-BCN (example 1). First, the strongest light absorption of the Bi@Ti-BCN sample is consistent with its highest photocatalytic hydrogen production rate in all samples. In addition, bi samples have a strong absorption peak at 279nm and a broad and weak peak at 350-600 nm (FIG. 6), which can be attributed to Bi metal surface plasmon resonance effect (SPR effect).
FIG. 7 is a graph of g-C in the examples 3 N 4 (example 1), B-C 3 N 4 (example 1), H-TiO 2 Photoelectric response curves of the photocatalysts of (example 5), ti-BCN (example 6) and Bi@Ti-BCN (example 1) under UV-visible light irradiation. Under the irradiation of light, the strongest photocurrent of Bi@Ti-BCN is consistent with the highest photocatalytic hydrogen production rate of the light in all samples, which shows that the separation and transfer rate of photo-generated carriers on the surface of the Bi@Ti-BCN is highest, and the photo-generated carriers are beneficial to improving the photocatalytic hydrogen production rate.
FIG. 8 is B-C 3 N 4 And H-TiO 2 The low binding energy region (a and C) and the high binding energy region (B and d) of the ultraviolet electron spectrum of the sample are used for calculating B-C by using the UPS energy spectrum 3 N 4 And H-TiO 2 The work functions of the samples were 3.30 and 3.55eV, respectively.
Detailed Description
The technical scheme of the present invention will be described in more detail with reference to specific examples, but the examples do not limit the present invention.
Example 1
1) Black TiO 2 Preparation of photocatalyst
First, 0.7mL of Ti (C 4 H 9 O) 4 To 15mL of 1mol/L NaOH solution, magnetically stirred for 30 minutes and then sonicated for 5 minutes. Subsequently, 0.3g of urea and 25mL of ethylene glycol were added to the above suspension. And magnetically stirring for 30 min to form white suspension, transferring to an autoclave, and hydrothermal treating at 180 ℃ for 15 h. The white product was collected by centrifugation, washed with dilute acetic acid, distilled water and absolute ethanol by centrifugation in sequence for several times, and then the obtained sample was dried at 60 ℃. The samples were then ground and divided into portions, each of which was held at 0.1g in a tube furnace at 600℃under argon for 2 hours (heating rate 4 ℃/min). After cooling to room temperature, 0.18g of the above sample and 0.18g of NaBH were added 4 The mixture was milled for 30 minutes and then maintained in a tube furnace at 350 c under argon atmosphere for 1 hour (heating rate 4 c/min). The resulting black powder was then immersed in deionized water for 4 hours until no bubbles were generated to ensure complete removal of unreacted NaBH 4 . Finally, the mixture was washed with deionized water and absolute ethanol by centrifugation several times and dried overnight at 60 ℃.
2) B-C doped with B (boron) 3 N 4 Preparation of photocatalyst
First, g-C is prepared by a thermal polymerization process 3 N 4 . Calcining in air atmosphere at 550deg.C for 4 hr (heating rate of 4deg.C/min) in 10g melamine tube furnace, cooling to room temperature, and collecting yellowish g-C 3 N 4 Grinding into powder. Next, the prepared 0.2. 0.2g g-C 3 N 4 And 0.1g NaBH 4 The mixture was milled for 30 minutes and then calcined in a tube furnace at 350 c under argon atmosphere for 1 hour (at a rate of 4 c/min). The dark brown powder obtained was then soaked in water for 4 hours until no bubbles were generated to ensure complete removal of unreacted NaBH 4 . The brown powder was then washed several times with deionized water and absolute ethanol by centrifugation and dried overnight at 60 ℃.
20mg g-C 3 N 4 The sample is used for a photocatalysis hydrogen production experiment,which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen-generating activity of 5.05. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen-generating activity of 0.24. Mu. Mol g -1 h -1 . Taking 20mg of B-C 3 N 4 The sample is subjected to a photocatalytic hydrogen production experiment under irradiation of ultraviolet and visible light (lambda)>300 nm) hydrogen-generating activity of 1.65. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen-generating activity of 0.50. Mu. Mol g -1 h -1 。
3)Bi@H-TiO 2 /B-C 3 N 4 Preparation of composite photocatalytic material
20mg Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 10mL of 1mol/L dilute HNO 3 30mL of ethylene glycol and 25mg of polyvinylpyrrolidone were added sequentially with continuous magnetic stirring. Then sequentially adding 10mg of black TiO 2 And 40mg of B-C 3 N 4 Added to the above solution and magnetically stirred for 5 minutes. After ultrasonic treatment for 30 minutes, transferring the black turbid liquid into an autoclave, carrying out hydrothermal treatment at 160 ℃ for 12 hours, and after the reaction is finished, sequentially centrifugally washing the obtained sample with deionized water and absolute ethyl alcohol for a plurality of times. Finally, the sample is dried at 60 ℃ to obtain about 20mg Bi@H-TiO 2 /B-C 3 N 4 (Bi@Ti-BCN) catalyst. Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen-generating activity of 223.08. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen generating activity of 18.84. Mu. Mol g -1 h -1 。
Example 2
The procedure is as in example 1, except that Bi (NO) in the starting material of step 3) in example 2 3 ) 3 ·5H 2 O is 10mg, and finally about 20mg Bi@H-TiO is obtained 2 /B-C 3 N 4 (Bi@Ti-BCN). Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen production rate of 217.23. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen production rate of 15.46. Mu. Mol g -1 h -1 。
Example 3
As in each of example 1A step was carried out, except that Bi (NO) in the starting material of step 3) in example 3 3 ) 3 ·5H 2 O is 50mg, and finally about 20mg Bi@H-TiO is obtained 2 /B-C 3 N 4 (Bi@Ti-BCN). Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen production rate of 173.27. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen production rate of 3.54. Mu. Mol g -1 h -1 。
Example 4
EXAMPLE 4 preparation of Bi metal pellets only step 3) in example 1 was required, and the starting material for step 3) was only 0.1g Bi (NO) 3 ) 3 ·5H 2 O, finally obtaining the Bi metal ball. In addition, the uv visible diffuse reflectance spectrum of the Bi sample has a strong absorption peak at 279nm and a broad and weak absorption peak at 350-600 nm (fig. 6), which can be attributed to the characteristic peak of the SPR effect typical of Bi metals. The SPR characteristic of the promoter Bi is beneficial to enhancing visible light capture and charge separation, thereby improving the activity of the photocatalyst.
Example 5
EXAMPLE 5 preparation of H-TiO 2 Nanoparticles, only step 1) and step 3) of example 1 were needed, except that the starting material for step 3) was only 50mg of black TiO 2 About 30mg of H-TiO is finally obtained 2 And (3) nanoparticles. Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen production rate of 86.53. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen production rate of 0.28. Mu. Mol g -1 h -1 。
Example 6
The procedure is as in example 1, except that in example 6, step 3) the starting material is only 10mg of black TiO 2 And 40mg B-C 3 N 4 Finally, about 15mg of H-TiO is obtained 2 /B-C 3 N 4 (Ti-BCN). Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen production rate of 60.20. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen production rate of 2.79. Mu. Mol g -1 h -1 。
Example 7
As if it were realThe procedure of example 1 was followed except that the starting material for step 3) of example 7 was 20mg Bi (NO) 3 ) 3 ·5H 2 O, 10mg of black TiO 2 And 40mg g-C 3 N 4 Finally, about 20mg Bi@H-TiO is obtained 2 /g-C 3 N 4 (Bi@Ti-GCN). Which is irradiated with ultraviolet and visible light (lambda)>300 nm) hydrogen production rate of 178.43. Mu. Mol g -1 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Under irradiation of visible light (lambda)>400 nm) hydrogen production rate of 5.98. Mu. Mol g -1 h -1 。
Claims (5)
1. Bi@H-TiO with visible light response 2 /B-C 3 N 4 The preparation method of the photocatalytic material comprises the following steps:
1) Black TiO 2 Preparation of photocatalyst
First, 0.7 to 1.4mL of Ti (C 4 H 9 O) 4 Adding the mixture into 15-30 mL of 1mol/L NaOH solution, magnetically stirring the mixture for 20-40 minutes, and then performing ultrasonic treatment for 3-8 minutes to obtain suspension; then adding 0.3-0.6 g of urea and 25-50 mL of alcohol solvent which is easy to dissolve in water into the suspension, magnetically stirring for 20-40 minutes to form white suspension, transferring into an autoclave, and carrying out hydrothermal treatment at 180-190 ℃ for 13-20 hours; centrifuging to collect white products, sequentially centrifuging and washing for several times by using dilute acetic acid, distilled water and absolute ethyl alcohol, drying the obtained sample at 40-80 ℃, grinding, calcining 0.1-0.2 g of ground sample in an argon atmosphere at 600-700 ℃ for 2.0-3.0 hours, wherein the heating rate is 3-5 ℃/min; cooling to room temperature, adding 0.1-0.2 g of the sample and 0.1-0.2 g of NaBH 4 Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours in an argon atmosphere at 350-400 ℃ at a heating rate of 3-5 ℃/min; soaking the obtained black powder in deionized water for 4-8 hr until no bubbles are generated to ensure complete removal of unreacted NaBH 4 The method comprises the steps of carrying out a first treatment on the surface of the Finally, centrifugal washing is carried out for a plurality of times by deionized water and absolute ethyl alcohol, and drying is carried out overnight at 40-80 ℃ to obtain black TiO 2 A photocatalyst;
2) Boron-doped B-C 3 N 4 Preparation of photocatalyst
First, g-C is prepared by a thermal polymerization method 3 N 4 : calcining 2-10 g melamine in air atmosphere at 530-580 deg.c for 4-4.5 hr at the temperature raising rate of 3-5 deg.c/min, cooling to room temperature and obtaining yellowish g-C 3 N 4 Grinding into powder; secondly, the prepared 0.1 to 0.2. 0.2g g-C 3 N 4 And 0.05 to 0.1g NaBH 4 Mixing and grinding for 20-40 minutes, and then calcining for 1-1.5 hours in an argon atmosphere at 300-350 ℃ at a heating rate of 3-5 ℃/min; subsequently, the dark brown powder obtained is immersed in water for 4 to 8 hours until no bubbles are generated, to ensure complete removal of unreacted NaBH 4 The method comprises the steps of carrying out a first treatment on the surface of the Finally, the brown powder is centrifugally washed for a plurality of times by deionized water and absolute ethyl alcohol, and is dried overnight at 40-80 ℃ to obtain B-C doped with boron element 3 N 4 A photocatalyst;
3)Bi@H-TiO 2 /B-C 3 N 4 preparation of composite photocatalytic material
10-50 mg Bi (NO) 3 ) 3 ·5H 2 O is dissolved in 10mL, 1mol/L of dilute HNO 3 Sequentially adding 20-40 mL of an alcohol solvent which is easy to dissolve in water and 20-30 mg of polyvinylpyrrolidone under continuous magnetic stirring; then sequentially adding 10-50 mg of black TiO 2 Photocatalyst and 40-80 mg boron element doped B-C 3 N 4 Adding a photocatalyst into the solution, continuously magnetically stirring for 3-8 minutes, and performing ultrasonic treatment for 20-40 minutes; transferring the obtained black turbid liquid into an autoclave, and performing hydrothermal treatment for 10-15 hours at 160-180 ℃; after the reaction is finished, sequentially centrifugally washing the obtained sample with deionized water and absolute ethyl alcohol for a plurality of times; finally, drying the sample at 40-80 ℃ to obtain Bi@H-TiO with visible light response 2 /B-C 3 N 4 A composite photocatalytic material.
2. A bi@h-TiO having a visible light response according to claim 1 2 /B-C 3 N 4 The preparation method of the photocatalytic material is characterized by comprising the following steps: the alcohol solvent which is easy to dissolve in water in the step 1) is isopropanol, absolute ethanol, propanol, butanol,One of isobutanol, cyclohexanol, ethylene glycol, 1, 3-propanediol and glycerol; the magnetic stirring speed is 200-400 rpm, and the centrifugal operation speed is 8000-10000 rpm.
3. A bi@h-TiO having a visible light response according to claim 1 2 /B-C 3 N 4 The 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, absolute ethanol, propanol, butanol, isobutanol, cyclohexanol, ethylene glycol, 1, 3-propylene glycol and glycerol; the magnetic stirring rotating speed is 200-400 rpm; the rotational speed of the centrifugal operation is 8000 rpm-10000 rpm.
4. Bi@H-TiO with visible light response 2 /B-C 3 N 4 The photocatalytic material is characterized in that: is prepared by the method of any one of claims 1 to 3.
5. A Bi@H-TiO having a visible light response as defined in claim 4 2 /B-C 3 N 4 The application of the photocatalytic material in preparing hydrogen by photocatalytic water decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111612860.7A CN114177928B (en) | 2021-12-27 | 2021-12-27 | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111612860.7A CN114177928B (en) | 2021-12-27 | 2021-12-27 | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114177928A CN114177928A (en) | 2022-03-15 |
| CN114177928B true CN114177928B (en) | 2023-10-03 |
Family
ID=80606127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111612860.7A Active CN114177928B (en) | 2021-12-27 | 2021-12-27 | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114177928B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115814832A (en) * | 2022-11-09 | 2023-03-21 | 广西师范大学 | Defect-modified graphite-phase carbon nitride titanium dioxide heterojunction composite material and application thereof in photo-thermal catalytic reduction of carbon dioxide |
| CN116282122B (en) * | 2023-03-24 | 2024-09-06 | 吉林大学 | Strong optical absorption inducing material based on photoinduced blackbody effect and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008006328A (en) * | 2006-06-27 | 2008-01-17 | National Institute For Materials Science | Photocatalyst comprising visible light responsive composite oxide semiconductor |
| CN106563470A (en) * | 2016-11-14 | 2017-04-19 | 江苏大学 | NiS2 nano-particle/g-C3N4 mesoporous nanosheet composite and preparation method thereof |
| WO2018022926A1 (en) * | 2016-07-28 | 2018-02-01 | eXion labs Inc. | Polymer-based antimicrobial compositions and methods of use thereof |
| CN107983387A (en) * | 2017-12-05 | 2018-05-04 | 福州大学 | A kind of preparation method of carbonitride/selenic acid bismuth composite material and application |
| CN109759110A (en) * | 2019-01-03 | 2019-05-17 | 华南理工大学 | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof |
| CN110194865A (en) * | 2019-03-25 | 2019-09-03 | 成都新柯力化工科技有限公司 | A kind of plastic matrix and preparation method of road guard purification vehicle exhaust |
-
2021
- 2021-12-27 CN CN202111612860.7A patent/CN114177928B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008006328A (en) * | 2006-06-27 | 2008-01-17 | National Institute For Materials Science | Photocatalyst comprising visible light responsive composite oxide semiconductor |
| WO2018022926A1 (en) * | 2016-07-28 | 2018-02-01 | eXion labs Inc. | Polymer-based antimicrobial compositions and methods of use thereof |
| CN106563470A (en) * | 2016-11-14 | 2017-04-19 | 江苏大学 | NiS2 nano-particle/g-C3N4 mesoporous nanosheet composite and preparation method thereof |
| CN107983387A (en) * | 2017-12-05 | 2018-05-04 | 福州大学 | A kind of preparation method of carbonitride/selenic acid bismuth composite material and application |
| CN109759110A (en) * | 2019-01-03 | 2019-05-17 | 华南理工大学 | A kind of N doping porous carbon loaded titanium dioxide photocatalyst and the preparation method and application thereof |
| CN110194865A (en) * | 2019-03-25 | 2019-09-03 | 成都新柯力化工科技有限公司 | A kind of plastic matrix and preparation method of road guard purification vehicle exhaust |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114177928A (en) | 2022-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110152711B (en) | CeO (CeO)2@MoS2/g-C3N4Ternary composite photocatalyst and preparation method thereof | |
| CN114177928B (en) | Composite photocatalyst Bi@H-TiO with visible light response 2 /B-C 3 N 4 Preparation method and application thereof | |
| CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
| CN109985618B (en) | H occupies BiVO4-OVs photocatalytic material, preparation method and application thereof | |
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN109847780A (en) | A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material | |
| CN109225265B (en) | Preparation method of all-solid-state Z-type heterojunction photocatalyst | |
| CN107824173A (en) | A kind of titanous auto-dope titania nanoparticles partial reduction stannic oxide/graphene nano piece composite and preparation method thereof | |
| CN114618537A (en) | Red phosphorus/strontium titanate heterojunction photocatalyst and preparation method and application thereof | |
| CN114950402A (en) | TiO 2 /CeO 2 Heterojunction photocatalyst and preparation method thereof | |
| CN113769764B (en) | CdS/Cu 7 S 4 /CdMoO 4 Preparation method and application of nano heterostructure | |
| CN109261203B (en) | Covalent triazine organic polymer photocatalyst capable of efficiently producing methane, and preparation and application thereof | |
| CN110102326B (en) | Nano-gold-loaded porous carbon modified carbon nitride composite photocatalytic material and preparation method and application thereof | |
| CN116920911A (en) | Preparation method and application of boron-doped carbon nitride nano-composite photocatalyst modified by ferric hydroxide | |
| CN103506116A (en) | Preparation and application of visible-light photocatalytic material of silver vanadate nanotube | |
| CN108554427B (en) | In2O3/BiOI semiconductor composite photocatalyst and preparation method and application thereof | |
| CN114210315B (en) | Preparation and application of rare earth erbium modified pollen carbon composite photocatalyst | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof | |
| CN112916014B (en) | All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof | |
| CN115090318A (en) | Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area | |
| CN114452998A (en) | Preparation method and application of multi-walled carbon nanotube and graphitized carbon nitride composite material | |
| CN110075879B (en) | Carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material and preparation method and application thereof | |
| Ali et al. | Clean production of lactic acid by selective carbon-carbon bond cleavage of biomass feedstock over a novel carbon-bismuth oxychloride photocatalyst | |
| CN114984965B (en) | P-n heterojunction composite photocatalyst Cu 2 O/MTiO 3 Preparation method and application thereof | |
| CN110876945A (en) | ZnIn grown in limited area in carbon nano hollow sphere2S4Photocatalyst and preparation method 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 |