CN113209987B - Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water - Google Patents
Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water Download PDFInfo
- Publication number
- CN113209987B CN113209987B CN202110423589.6A CN202110423589A CN113209987B CN 113209987 B CN113209987 B CN 113209987B CN 202110423589 A CN202110423589 A CN 202110423589A CN 113209987 B CN113209987 B CN 113209987B
- Authority
- CN
- China
- Prior art keywords
- bismuth
- mno
- photocatalyst
- oxide semiconductor
- bivo
- 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
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000002950 deficient Effects 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 230000004048 modification Effects 0.000 title abstract description 13
- 238000012986 modification Methods 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 230000007547 defect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 230000001699 photocatalysis Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003426 co-catalyst Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-M thiophene-2-carboxylate Chemical compound [O-]C(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-M 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a photocatalyst composed of a defective oxide semiconductor and a bismuth-based modification component and application thereof in hydrogen production by decomposing water. The catalyst is expressed as R/Bi/O, wherein the defective oxide O can be MnO 2 /MnO x 、WO 3 /WO x 、BiOI/BiO x I x BiVO (BiVO) 4 /BiVO 4‑x And semiconductor oxides with anionic surface defects, wherein R in the bismuth-based modifying component R/Bi is Bi 2 S 3 、Bi/Bi 2 S 3 Or Bi/ZnFe 2 O 4 A semiconductor with equal high reduction potential or a semiconductor with high reduction potential and a co-catalyst Bi compound. The R/Bi/O photocatalyst has the characteristics of simple synthesis process, low cost and easy obtainment of raw materials, wide spectral response, high efficient carrier separation efficiency, high oxidation-reduction potential, good surface activity and the like, and has the advantages of high hydrogen production rate by catalytic decomposition of water under the mild condition of visible light irradiation and high efficiency of converting solar energy into hydrogen energy.
Description
Technical Field
The invention relates to a photocatalyst composed of a defective oxide semiconductor and a bismuth-based modification component and application thereof in hydrogen production by decomposing water, belonging to the technical field of photocatalytic energy conversion.
Background
The photocatalysis hydrogen production technology has the characteristics of low energy consumption, mild reaction condition, environment friendliness and the like, and is one of the technologies with the most application prospect in the field of energy catalytic conversion. The catalyst is the core of the photocatalysis hydrogen production technology. The performance of the photocatalyst is mainly affected by the four aspects: photo-responsive range, photo-generated carrier separation efficiency, redox potential and interfacial properties. At present, those skilled in the art have mainly devised and modified catalytic materials around these improvements in performance in order to further increase the efficiency of light energy conversion to hydrogen energy (STH) and the catalytic hydrogen production rate.
Constructing heterojunction catalysts by compounding semiconductors with different energy gap structures is an effective way to obtain the above-described desired four-way properties. The energy gap staggered compound catalyst composed of energy gap staggered semiconductors such as Z type, S type, II type and I type has been shown to be superior to the photocatalytic hydrogen production rate and STH of single semiconductor componentAdv. Mater. 2017, 29, 1601694；Chem, 2020, 6, 1543-1559). Such as core-shell structured Z-schema Ru/La, rh-SrTiO 3 /Ir/Ta 3 N 5 Hydrogen production rate of/Co (1.68 mmol/g/h) and STH (0.037%) were Ru/SrTiO 3 Rh 3 times that of RhChem. Mater. 2014, 26, 4144-4150). However, the fixed bandgap staggering property of the bandgap staggering type composite catalyst results in a limited space for improvement in performance due to the interrelation between the photoresponse range, the redox potential and the separation efficiency of the photogenerated carriers, despite the co-catalyst Pt, niP x ，CoO x The optimization of the composite and crystal structures and the morphology structures can improve the catalytic activity of the energy gap staggered heterojunction catalyst to a certain extentSol. Energy, 2020, 206, 8-17; New J. Chem. 2020, 44, 4332-4339）。
In addition, although the loading, doping, etc. of noble metals Pt, pd, etc. have obtained excellent photocatalytic hydrogen production performance, for example, 1% Pt- (PPy-TiO) 2 ) The hydrogen production rate of (2) reaches 125.1 mmol h -1 g -1 （Appl. Catal. B: Environ. 2021, 281, 119457) However, noble metal catalysts are expensive, have high commercial costs, and are difficult to realize for a wide range of commercial applications.
Disclosure of Invention
Aiming at the problems faced by the catalytic materials in the field of photocatalytic hydrogen production, the invention provides a method for oxidizing by defectsPhotocatalyst composed of a compound semiconductor and a bismuth-based modification component and application thereof in hydrogen production by decomposing water. The photocatalyst material composed of the defective oxide semiconductor and the bismuth-based modifying component obtained by the present invention can be expressed as R/Bi/O. Wherein the defective oxide semiconductor O having a high oxidation potential may be MnO 2 /MnO x 、WO 3 /WO x 、BiOI/BiO x I x 、BiVO 4 /BiVO 4-x And one of the semiconductor oxides having anionic surface defects. R in the bismuth-based modified component R/Bi is Bi 2 S 3 、Bi/Bi 2 S 3 Or Bi/ZnFe 2 O 4 A semiconductor with equal high reduction potential or a semiconductor with high reduction potential and a co-catalyst Bi compound. The metallic Bi in the middle of the molecular formula can be used as a bridge for the transfer of photogenerated carriers of bridging energy gap split semiconductor components R and O. In terms of composition, the molar ratio of R to O of the R/Bi/O component is 0.01 to 10, preferably 0.05 to 1.
The preparation method of the photocatalyst material composed of the R/Bi/O defect oxide semiconductor and the bismuth-based modification component comprises the following steps:
(1) Synthesizing a defective oxide O;
(2) Uniformly mixing O obtained in the step (1) with bismuth precursor, and roasting in hydrogen-containing atmosphere or dispersing in liquid by ultrasonic wave, and carrying out illumination reduction to obtain Bi/O;
(3) The component R is supported on the Bi/O of the compound obtained in the step (2).
The defective oxide O in the above step (1) is obtained by calcining MnO in air, an inert gas or a hydrogen-containing gas 2 、WO 3 Semiconductor oxides such as BiOI and the like are obtained, and the roasting temperature is 80-600 o C. The preparation method of the semiconductor oxide is a prior art, including but not limited to a coprecipitation method, a hydrothermal method, etc., and can be obtained according to various preparation methods disclosed in the prior art by a person skilled in the art.
The bismuth precursor in the step (2) is preferably bismuth nitrate, and may be soluble bismuth salts such as bismuth acetate, bismuth sulfate or bismuth chloride.
The step (3) is carried out by a coprecipitation methodBi loading on Bi/O by hydrothermal method and/or in-situ reduction method 2 S 3 、Bi/Bi 2 S 3 Or Bi/ZnFe 2 O 4 . The reaction temperature of the hydrothermal method is 80-200 o The in-situ reduction method may be a chemical reduction method such as in-situ light reduction or heat treatment in a hydrogen-containing atmosphere.
Compared with the prior art, the photocatalyst R/Bi/O composed of the defective oxide semiconductor and the bismuth-based modified component has the following characteristics: (1) Simultaneously, the wide spectral response, the high-efficiency carrier separation efficiency, the high oxidation-reduction potential and the good surface-interface activity property are realized; (2) The device has high-efficiency photocatalytic water splitting hydrogen production capacity and solar energy conversion efficiency; the raw materials used in the step (3) are cheap, and the synthesis conditions are mild.
Detailed Description
The present invention will be further described with reference to specific examples, but the implementation method of the present invention is not limited to the specific operation modes described in the examples, and any other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principle of the present invention should be equivalent to the substitution modes, and are included in the protection scope of the present invention.
Comparative example 1
Manganese oxide powder in N 2 Atmosphere 400 o Calcining C for 2 hours to obtain MnO 2 。
Comparative example 2
Taking 0.05 mol/L CH 3 CSNH 2 And 0.03 mol/L Bi (NO) 3 ) 3 ·5H 2 The 30 mL portions of the O-glycol and glycerol mixed (2:1) solutions were mixed and then stirred to precipitate. The obtained product is centrifugally separated and dried to obtain Bi 2 S 3 。
Comparative example 3
Manganese oxide powder in N 2 Atmosphere 400 o Calcining C for 2 hours to obtain MnO 2 . MnO is added to 2 Ultrasonic dispersion in 60 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 O ethylene glycol and water were mixed (1:11) in solution. The resulting solution mixture was illuminated at 300W Xe lampStirring under irradiation to obtain Bi/MnO 2 . 0.025g Bi/MnO 2 Ultrasonic dispersing in 9 mL water, adding to 30 mL of 0.004 mol/L Bi (NO) 3 ) 3 ·5H 2 O, ethanol and glycerol are mixed (2:1) and stirred uniformly, and then 30 mL of CH with the concentration of 0.006 mol/L is added 3 CSNH 2 The solution was mixed (2:1) with glycerol and the precipitate was stirred. The obtained product is centrifugally separated and dried to obtain Bi 2 S 3 /Bi/MnO 2 。
Example 1
Photocatalyst Bi/Bi composed of defective oxide semiconductor and bismuth-based modification component 2 S 3 /Bi/MnO 2 /MnO x : manganese oxide powder was subjected to an air atmosphere 400 o Calcining C for 4 hours to obtain MnO rich in oxygen defect sites 2 /MnO x . MnO is added to 2 /MnO x Ultrasonic dispersion in Bi (NO) 3 ) 3 ·5H 2 O ethylene glycol and water were mixed (1:11) and the resulting solution mixture was stirred for a certain period of time under the Xe lamp illumination of 300W. The obtained product is centrifugally separated and dried to obtain Bi/MnO 2 /MnO x . 0.025g Bi/MnO is taken 2 /MnO x Ultrasonic dispersing in 9 mL water, adding to 30 mL of 0.004 mol/L Bi (NO) 3 ) 3 ·5H 2 O, ethanol and glycerol are mixed (2:1) and stirred uniformly, and then 30 mL of CH with the concentration of 0.006 mol/L is added 3 CSNH 2 Mixing (2:1) ethanol and glycerol, stirring and precipitating to obtain Bi 2 S 3 /Bi/MnO 2 /MnO x . 0.025g Bi 2 S 3 /Bi/MnO 2 /MnO x Ultrasonic dispersion in 60 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 The solution was mixed (1:11) with ethylene glycol and water, and the resulting solution mixture was stirred under 300W Xe lamp irradiation to react. The obtained product is centrifugally separated and dried to obtain Bi/Bi 2 S 3 /Bi/MnO 2 /MnO x Wherein Bi/Bi 2 S 3 And MnO 2 /MnO x The molar ratio of (2) is 0.1.
Example 2
The method comprises the following steps ofPhotocatalyst Bi composed of defective oxide semiconductor and bismuth-based modification component 2 S 3 /Bi/MnO 2 /MnO x : manganese oxide powder was subjected to an air atmosphere of 500 o Calcining C for 2 hours to obtain MnO rich in oxygen defect sites 2 /MnO x . MnO is added to 2 /MnO x Ultrasonic dispersion in Bi (NO) 3 ) 3 ·5H 2 O ethylene glycol and water were mixed (1:11) and the resulting solution mixture was stirred for a certain period of time under the Xe lamp illumination of 300W. The obtained product is centrifugally separated and dried to obtain Bi/MnO 2 /MnO x . 0.025g Bi/MnO 2 /MnO x Ultrasonic dispersing in 9 mL water, adding to 30 mL of 0.008 mol/L Bi (NO) 3 ) 3 ·5H 2 O, ethanol and glycerol are mixed (2:1) and stirred uniformly, and then 30 mL of CH with the concentration of 0.006 mol/L is added 3 CSNH 2 The solution was mixed (2:1) with glycerol and the precipitate was stirred. The obtained product is centrifugally separated and dried to obtain Bi 2 S 3 /Bi/MnO 2 /MnO x Wherein Bi is 2 S 3 And MnO 2 /MnO x The molar ratio of (2) is 0.2.
Example 3
Photocatalyst Bi/Bi composed of defective oxide semiconductor and bismuth-based modification component 2 S 3 /Bi/MnO 2 /MnO x : manganese oxide powder was subjected to an air atmosphere 400 o Calcining C for 2 hours to obtain MnO rich in oxygen defect sites 2 /MnO x . MnO is added to 2 /MnO x Ultrasonic dispersion in Bi (NO) 3 ) 3 ·5H 2 O ethylene glycol and water were mixed (1:11) and the resulting solution mixture was stirred for a certain period of time under the Xe lamp illumination of 300W. The obtained product is centrifugally separated and dried to obtain Bi/MnO 2 /MnO x . 0.025g Bi/MnO is taken 2 /MnO x Ultrasonic dispersing in 9 mL water, adding 0.002 mol/L Bi (NO) 30 mL 3 ) 3 ·5H 2 O, ethylene glycol and glycerol are mixed (2:1) and stirred uniformly, and then CH of 30 mL and 0.006 mol/L is added 3 CSNH 2 Mixing (2:1) the solution with glycerol, stirringAnd (5) stirring and precipitating. The obtained product is centrifugally separated and dried in air atmosphere to obtain Bi 2 S 3 /Bi/MnO 2 /MnO x . 0.025g Bi 2 S 3 /Bi/MnO 2 /MnO x Ultrasonic dispersion in 60 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 The resulting solution mixture was stirred in a (1:11) solution of O-ethylene glycol and water under the irradiation of a 300W Xe lamp. The obtained product is centrifugally separated and dried to obtain Bi/Bi 2 S 3 /Bi/MnO 2 /MnO x Wherein Bi/Bi 2 S 3 And MnO 2 /MnO x The molar ratio of (2) is 0.05.
Example 4
Photocatalyst Bi/Bi composed of defective oxide semiconductor and bismuth-based modification component 2 S 3 /Bi/WO 3 /WO 3-x : tungsten oxide powder in air atmosphere 80 o C drying for 10 hours to obtain WO rich in oxygen defect sites 3 /WO 3-x . WO is incorporated into 3 /WO 3-x Ultrasonic dispersion in 5 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 Mixing O ethylene glycol and ethanol (1:11) solution, drying, and placing in hydrogen atmosphere 300 o Roasting C to 0.5. 0.5 h to obtain Bi/WO 3 /WO 3-x . 0.025g Bi/WO 3 /WO 3-x Ultrasonic dispersing in 9 mL water, adding to 30 mL of 0.013 mol/L Bi (NO) 3 ) 3 ·5H 2 O, ethanol and glycerol are mixed (2:1) and stirred uniformly, and then 30 mL of 0.019 mol/L CH is added 3 CSNH 2 The solution was mixed (2:1) with glycerol and the precipitate was stirred. The obtained product is centrifugally separated and dried to obtain Bi 2 S 3 /Bi/WO 3 /WO 3-x . Bi is mixed with 2 S 3 /Bi/WO 3 /WO 3-x In a hydrogen atmosphere 350 o Roasting C to 0.5. 0.5 h to obtain Bi/Bi 2 S 3 /Bi/WO 3 /WO 3-x 。Bi/Bi 2 S 3 /Bi/WO 3 /WO 3-x Middle Bi/Bi 2 S 3 And WO 3 /WO 3-x The molar ratio of (2) is 1.0.
Example 5
Photocatalyst Bi/Bi composed of defective oxide semiconductor and bismuth-based modification component 2 S 3 /Bi/BiOI/BiO x I x : 30.003 mol/L Bi (NO) 3 ) 3 ·5H 2 The mixture was stirred uniformly in an ethylene glycol solution of O, and then a 0.0048 mol/L KI solution of 20. 20 mL was added thereto and stirred at room temperature for 6 hours. The resulting product was centrifuged and then placed in a forced air oven 80 o C drying for 8 hr to obtain BiOI/BiO x I x . BiOI was ultrasonically dispersed in 5 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 Mixing O ethylene glycol and ethanol (1:11) solution, drying, and then adding into hydrogen atmosphere 300 o Roasting 1 h to obtain Bi/BiOI/BiO x I x . Taking 0.025g Bi/BiOI/BiO x I x Ultrasonic dispersing in 9 mL water, adding to 30 mL of 0.013 mol/L Bi (NO) 3 ) 3 ·5H 2 O, ethanol and glycerol are mixed (2:1) and stirred uniformly, and then 30 mL of 0.019 mol/L CH is added 3 CSNH 2 The solution was mixed (2:1) with glycerol and the precipitate was stirred. The obtained product is centrifugally separated and dried to obtain Bi 2 S 3 /Bi/BiOI/BiO x I x . Bi is mixed with 2 S 3 /Bi/BiOI/BiO x I x 300 in hydrogen atmosphere o Roasting 1. 1 h to obtain Bi/Bi 2 S 3 /Bi/BiOI/BiO x I x 。Bi/Bi 2 S 3 /Bi/BiOI/BiO x I x Middle Bi/Bi 2 S 3 And BiOI/BiO x I x The molar ratio of (2) is 0.6.
Example 6
Photocatalyst Bi/ZnFe composed of defective oxide semiconductor and bismuth-based modification component 2 O 4 /Bi/BiVO 4 /BiVO 4-x : bismuth vanadate powder in Hydrogen atmosphere 300 o Roasting C to 0.5. 0.5 h to obtain Bi/BiVO 4 /BiVO 4-x . Bi/BiVO 4 /BiVO 4-x Ultrasonic dispersion of 0.01 mol/L Fe (NO) in 30 mL 3 ) 3 ·9H 2 After the O solution, 30.005 mol/L Zn (NO) of mL was added 3 ) 2 ·6H 2 O is stirred uniformly, thenAt 180 o Hydrothermal reaction under C to obtain ZnFe 2 O 4 /Bi/BiVO 4 /BiVO 4-x . ZnFe (ZnFe) 2 O 4 /Bi/BiVO 4 /BiVO 4-x Ultrasonic dispersion in 60 mL of 0.005 mol/L Bi (NO) 3 ) 3 ·5H 2 The reaction was stirred in a mixed (1:11) solution of O-ethylene glycol and water under the irradiation of a 300W Xe lamp. The obtained product is centrifugally separated and dried to obtain Bi/ZnFe 2 O 4 /Bi/BiVO 4 /BiVO 4-x Wherein Bi/ZnFe 2 O 4 And BiVO 4 /BiVO 4-x The molar ratio of (2) is 0.05.
The catalyst 1.5-5.0. 5.0 mg was respectively dispersed in 50 mL glass bottles containing a mixed solution of 4. 4 mL deionized water and 1. 1 mL methanol. The obtained reaction system is bubbled with Ar gas for 15 min to remove O 2 Then at 200 mW cm -2 And (3) reacting for 2-3 h under the light source of Xe. H obtained by the reaction 2 The yield of (2) was determined by gas chromatography.
TABLE 1 evaluation results of catalyst Activity
| Material | Reaction Rate (mmol g) -1 h -1 ） | Solar energy-hydrogen energy conversion (STH,%) |
| Comparative example 1 | 3.99 | 0.24 |
| Comparative example 2 | 7.30 | 0.43 |
| Comparative example 3 | 14.59 | 0.41 |
| Example 1 | 39.05 | 1.12 |
| Example 2 | 21.49 | 0.48 |
| Example 3 | 23.02 | 0.76 |
| Example 4 | 25.49 | 0.84 |
| Example 5 | 23.30 | 0.83 |
| Example 6 | 33.30 | 1.03 |
Claims (4)
1. A photocatalyst consisting of a defective oxide semiconductor and a bismuth-based modifying component, characterized in that the photocatalyst consists of a defective oxide semiconductor expressed as O and a bismuth-based modifying component expressed as R/Bi; the defective oxide semiconductor O is semiconductor oxide MnO with anionic surface defects 2 /MnO x 、WO 3 /WO x 、BiOI/BiO x I x Or BiVO 4 /BiVO 4-x One of the following; r in the bismuth-based modified component R/Bi is Bi 2 S 3 、Bi/Bi 2 S 3 Or Bi/ZnFe 2 O 4 One of them.
2. The photocatalyst composed of a defective oxide semiconductor and a bismuth-based modifying component according to claim 1, wherein the molar ratio of the composition R and O is 0.01 to 10.
3. The photocatalyst composed of a defective oxide semiconductor and a bismuth-based modifying component according to claim 1, which is prepared by a method comprising the steps of:
(1) Synthesizing a defective oxide semiconductor O;
(2) Uniformly mixing the defect oxide semiconductor O obtained in the step (1) with a bismuth precursor, and then roasting and reducing in a hydrogen-containing atmosphere to obtain a compound Bi/O, or dispersing the compound Bi/O in liquid by ultrasonic and carrying out illumination reduction to obtain the compound Bi/O;
(3) And (3) loading the component R on the Bi/O of the compound obtained in the step (2) to obtain the photocatalyst.
4. Use of a photocatalyst consisting of a defective oxide semiconductor and a bismuth-based modifying component according to claim 1 in a photocatalytic water splitting hydrogen production reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110423589.6A CN113209987B (en) | 2021-04-20 | 2021-04-20 | Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110423589.6A CN113209987B (en) | 2021-04-20 | 2021-04-20 | Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113209987A CN113209987A (en) | 2021-08-06 |
| CN113209987B true CN113209987B (en) | 2024-03-26 |
Family
ID=77088005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110423589.6A Active CN113209987B (en) | 2021-04-20 | 2021-04-20 | Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113209987B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN110252353A (en) * | 2019-07-02 | 2019-09-20 | 汕头大学 | A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application |
| CN111729671A (en) * | 2020-05-25 | 2020-10-02 | 华南理工大学 | Zinc ferrite/bismuth vanadate nano heterostructure composite material and preparation method and application thereof |
| CN112156770A (en) * | 2020-10-31 | 2021-01-01 | 湘潭大学 | Bismuth tungstate composite photocatalyst with bismuth and oxygen double vacancies as well as preparation method and application thereof |
| CN112452344A (en) * | 2020-12-14 | 2021-03-09 | 北京科技大学 | In-situ synthesis of monatomic Bi0Bridged TiO2Method for preparing @ BiOCl composite photocatalytic material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9379422B2 (en) * | 2012-06-13 | 2016-06-28 | The Regents Of The University Of California | Hydrogen-treated semiconductor metal oxides for photoelectrical water splitting |
-
2021
- 2021-04-20 CN CN202110423589.6A patent/CN113209987B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN110252353A (en) * | 2019-07-02 | 2019-09-20 | 汕头大学 | A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application |
| CN111729671A (en) * | 2020-05-25 | 2020-10-02 | 华南理工大学 | Zinc ferrite/bismuth vanadate nano heterostructure composite material and preparation method and application thereof |
| CN112156770A (en) * | 2020-10-31 | 2021-01-01 | 湘潭大学 | Bismuth tungstate composite photocatalyst with bismuth and oxygen double vacancies as well as preparation method and application thereof |
| CN112452344A (en) * | 2020-12-14 | 2021-03-09 | 北京科技大学 | In-situ synthesis of monatomic Bi0Bridged TiO2Method for preparing @ BiOCl composite photocatalytic material |
Non-Patent Citations (2)
| Title |
|---|
| Junqi Li等.Metallic Bi Nanocrystal-Modified Defective BiVO4 Photoanodes with Exposed (040) Facets for Photoelectrochemical Water Splitting.《ChemElectroChem》.2017,第4卷2852-2861. * |
| Metallic Bi Nanocrystal-Modified Defective BiVO4 Photoanodes with Exposed (040) Facets for Photoelectrochemical Water Splitting;Junqi Li等;《ChemElectroChem》;第4卷;2852-2861 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113209987A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109746022B (en) | Preparation method and use method of high-dispersion copper-zinc catalyst for carbon dioxide reduction | |
| WO2019137020A1 (en) | Transition metal and nitrogen co-doped carbon composite material for use in formaldehyde purification and preparation method therefor | |
| CN109453766B (en) | Ag-loaded TiO with atomic-level dispersion2Preparation method of mesoporous nanobelt photocatalyst | |
| CN109569695B (en) | Preparation method and use method of core-shell structure catalyst for carbon dioxide hydrogenation | |
| WO2022089669A1 (en) | Composite material of strontium-doped ordered mesoporous lanthanum manganite loaded with precious metal palladium, and preparation method therefor and use thereof in catalytic oxidation of toluene | |
| CN112023938A (en) | Bimetallic ion doped nano composite photocatalyst and preparation method thereof | |
| CN110721685B (en) | Composite photocatalytic material and preparation method and application thereof | |
| CN113908833A (en) | Reverse water gas shift catalyst and preparation method and application thereof | |
| CN111389409B (en) | Preparation method and application of bismuth vanadate photocatalyst with surface modified by cobalt-copper oxide | |
| CN113209987B (en) | Photocatalyst composed of defective oxide semiconductor and bismuth-based modification component and application of photocatalyst in hydrogen production by decomposing water | |
| CN110256230B (en) | Catalyst for efficiently catalyzing glycerol to prepare glyceric acid under alkali-free condition and preparation method thereof | |
| CN108069838B (en) | Method for preparing formaldehyde by photocatalytic oxidation of ethylene glycol | |
| CN114950439B (en) | High-efficiency photolysis water hydrogen production MOF TiO 2 NiO material and preparation method and application thereof | |
| CN110885683A (en) | Bi2MoO6Quantum dot and preparation method and application thereof | |
| CN112007663B (en) | MoS2@CrOx/La,Al-SrTiO3/CoOOH photocatalyst and preparation method thereof | |
| CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
| CN112390291A (en) | Preparation method of vanadate cocatalyst material | |
| CN114308034A (en) | Strontium titanate semiconductor catalyst co-doped with (III) and (V) valence double transition metal ions and preparation method thereof | |
| CN116174000A (en) | Preparation method and application of low-defect perovskite type tantalum-based oxynitride photocatalyst | |
| CN113398912A (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN112441884A (en) | Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling | |
| CN107159197B (en) | Solid solution photocatalyst with dodecahedron morphology and preparation method thereof | |
| CN112569961A (en) | Preparation method of MOF-derived hollow cobalt oxide-loaded manganese oxide catalyst, product and application thereof | |
| JP4264514B2 (en) | Dimethyl ether reforming catalyst and method for producing hydrogen-containing gas using the same | |
| CN114192142B (en) | Catalyst for dinonyl phenol hydrogenation 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 |