CN114588913B - CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst, and preparation and application thereof - Google Patents
CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst, and preparation and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 28
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 23
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 14
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000000969 carrier Substances 0.000 abstract description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 9
- 229940043267 rhodamine b Drugs 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
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- 238000005215 recombination Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 31
- 239000000047 product Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000012298 atmosphere Substances 0.000 description 14
- 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 13
- 230000001699 photocatalysis Effects 0.000 description 9
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
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- 150000003254 radicals Chemical class 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 230000027756 respiratory electron transport chain Effects 0.000 description 2
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- 239000004094 surface-active agent Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000010842 industrial wastewater Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000004065 wastewater treatment 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst, and preparation and application thereof. The invention prepares CuO/Bi/BiVO by a three-step method 4 The Z-type heterojunction photocatalyst has the advantages of low-cost and easily-obtained raw materials and simple and convenient reaction process. In the catalyst, cuO/BiVO 4 The heterojunction is constructed to promote the separation of photon-generated carriers and widen the light absorption range of the catalyst; the introduction of Bi simple substance is used as a bridge for guiding charge transfer to promote BiVO 4 And a Z-shaped heterojunction is formed between the silicon oxide and the CuO, electrons with stronger reducing capability and holes with stronger oxidizing capability are reserved, meanwhile, the recombination of carriers is inhibited, and the service life of photo-generated carriers is prolonged. CuO/Bi/BiVO 4 The Z-type heterojunction photocatalyst has excellent photocatalytic degradation performance on rhodamine B and good stability, and can be applied to the field of photocatalytic degradation.
Description
Technical Field
The invention belongs to the field of photocatalysts, and in particular relates to a CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst, and preparation and application thereof.
Background
In recent years, environmental pollution, particularly water resource pollution, has been increasing. With the progress of global industrialization, the amount of industrial wastewater discharged in the industries of daily life of residents, printing and dyeing medicines, papermaking and the like is increased year by year. The sewage contains a large amount of pathogenic microorganisms, various nutrient substances for promoting the growth of aquatic plants, toxic compounds and mutagenic and carcinogenic compounds. The direct discharge of these organic contaminants into the environment can reduce the dissolved oxygen in the body of water; anaerobic decomposition products have high toxicity and three-induced effects; the pollutant has high chromaticity, peculiar smell and ecological environment pollution. Therefore, in order to protect human health and the environment, sewage must be treated to be discharged to the environment or recycled.
Today, with the increase of population and production demands, the discharge amount of sewage is gradually increased, the available space is gradually reduced, the discharge standard is more strict, and the conventional sewage treatment process cannot meet the requirements. Among a plurality of organic wastewater treatment technologies, the photocatalysis advanced oxidation technology has the outstanding advantages of green energy conservation, economy and high efficiency, and has attracted wide attention.
Among various semiconductor photocatalysts, biVO 4 The band gap of the material is 2.4-2.5eV, has proper band gap and unique photocatalysis response in a visible light region, has lower valence band position and stronger oxidizing capability, and is a good photocatalysis semiconductor material. But BiVO 4 The specific surface area of the catalyst is small, the quantum utilization rate is low, the self-generated carriers are seriously compounded, and the catalytic activity of the catalyst serving as a photocatalyst is greatly reduced. Most scientific researchers perform BiVO on the material through methods such as element doping, metal loading or heterojunction construction 4 Modified but BiVO therein 4 The shape is mostly a truncated octahedral structure, the material size is larger, the migration of photo-generated carriers and the exposure of active sites are not facilitated, and the further improvement of the photocatalytic performance is limited. Patent application CN102600857A discloses a carbon sphere-supported CuO-BiVO 4 Preparation method of heterojunction composite photocatalyst, which uses carbon sphere as carrier and adsorbent to improve photocatalysis effect, lacks CuO-BiVO 4 And (3) regulating and controlling the heterojunction construction. Patent CN106498372B discloses the preparation of Bi/BiVO by photo-deposition 4 Method of compounding photoanode materials, the catalyst despite the expansion of BiVO 4 For the visible light absorption range, the performance of photoelectrochemical decomposition of water is improved, but a heterojunction is not constructed, so that the oxidation-reduction potential of the catalyst is severely limited. Therefore, how to further increase BiVO 4 The catalytic performance of the base photocatalyst is a problem to be solved urgently.
Disclosure of Invention
To solve the defects and shortcomings of the prior artIt is a primary object of the present invention to provide a CuO/Bi/BiVO 4 A preparation method of a Z-type heterojunction photocatalyst.
The invention prepares CuO/Bi/BiVO by a three-step method 4 Z-type heterojunction photocatalysts. CuO/BiVO 4 The heterojunction can promote the separation of photon-generated carriers and widen the light absorption range of the catalyst. The simple substance Bi is introduced to form a Schottky junction with the semiconductor material, so that the recombination of carriers is inhibited, and the service life of photo-generated carriers is prolonged; meanwhile, plays an important role in the construction of a Z-type heterojunction, and the Bi simple substance is taken as a bridge for electron transfer and transmission to promote BiVO 4 And CuO from the II type heterojunction to the Z type heterojunction, and electrons with stronger reducing capability and holes with stronger oxidizing capability are reserved.
Another object of the present invention is to provide a CuO/Bi/BiVO prepared by the above method 4 Z-type heterojunction photocatalysts.
It is still another object of the present invention to provide the above CuO/Bi/BiVO 4 Application of Z-type heterojunction photocatalyst in the field of photocatalysis.
The invention aims at realizing the following technical scheme:
CuO/Bi/BiVO 4 The preparation method of the Z-type heterojunction photocatalyst comprises the following steps:
(1) Uniformly mixing bismuth nitrate pentahydrate acid solution and vanadium source water solution, regulating pH to 2-9, performing hydrothermal reaction at 150-200 ℃ for 1-24 h, cooling, washing and drying to obtain BiVO 4 ；
(2) Copper nitrate trihydrate is dissolved in water and BiVO is added 4 Heating, stirring, evaporating the solvent, and calcining at 200-400 ℃ for 1-5 h to obtain CuO/BiVO 4 A heterojunction;
(3) CuO/BiVO 4 Dispersing the heterojunction in water, adding sodium borohydride solution, stirring, washing and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalysts.
The obtained CuO/Bi/BiVO 4 The Z-type heterojunction photocatalyst has a load of metal Bi and a heterojunction structure, and has excellent photocatalytic performanceCan be used.
Preferably, the acid solution in the bismuth nitrate pentahydrate acid solution in the step (1) is nitric acid solution, and the concentration is 0.5-2 mol/L; the concentration of bismuth nitrate pentahydrate in the bismuth nitrate pentahydrate acid solution is 0.0162-0.0323 g/mL.
Preferably, the vanadium source in the aqueous solution of the vanadium source in the step (1) is sodium metavanadate; the concentration of the vanadium source water solution is 0.0041-0.0081 g/mL.
Preferably, the mass ratio of bismuth nitrate pentahydrate to vanadium source in the step (1) is 4:1.
preferably, the uniform mixing in the step (1) means stirring for 30-60 min at normal temperature.
Preferably, the pH of the step (1) is adjusted by using sodium hydroxide solution with the concentration of 1-10 mol/L.
Preferably, the hydrothermal reaction in the step (1) is carried out for 12-20 hours.
Preferably, the washing in the step (1) means washing with water and ethanol for 3-5 times in sequence, namely washing with water for 3-5 times and then washing with ethanol for 3-5 times, and the drying is conventional drying.
Preferably, the copper nitrate trihydrate, water and BiVO of step (2) 4 The proportion of (3) is 12-243 mg:20mL:0.6g.
Preferably, the temperature of the heating and stirring in the step (2) is 60-90 ℃.
Preferably, the calcination in step (2) is performed in an air atmosphere, from room temperature to a set temperature at a rate of 2 ℃/min.
Preferably, step (3) the CuO/BiVO 4 And adding water into the heterojunction, and then performing ultrasonic dispersion for 10-30 min.
Preferably, the concentration of the sodium borohydride solution in the step (3) is 0.01-0.1 mol/L, and the solvent is water.
Preferably, step (3) the CuO/BiVO 4 The heterojunction, water and sodium borohydride solution were in a ratio of 0.3g:70mL: 1-20 mL.
Preferably, the stirring in the step (3) means stirring at normal temperature for 0.5-2 h.
Preferably, the washing in the step (3) refers to washing with water for 3 to 5 times in sequence, and the drying is conventional drying.
The CuO/Bi/BiVO prepared by the method 4 Z-type heterojunction photocatalysts.
The CuO/Bi/BiVO 4 The Z-type heterojunction photocatalyst not only introduces Bi simple substance, but also has a Z-type heterojunction structure.
The CuO/Bi/BiVO 4 The application of the Z-type heterojunction photocatalyst in the field of photocatalytic degradation.
The invention constructs the CuO/Bi/BiVO through a three-step method 4 The Z-type heterojunction photocatalyst can prepare CuO/Bi/BiVO without using a template agent and a surfactant 4 Z-type heterojunction photocatalyst, bi simple substance is taken as a bridge for electron transfer and transmission, and BiVO is promoted 4 And the transition between CuO from the II type heterojunction to the Z type heterojunction, the higher oxidation-reduction potential of the photocatalyst is reserved. The degradation rate of the catalyst to rhodamine B under full spectrum irradiation reaches 99 percent, and the reaction rate is 0.03841min -1 Is BiVO 4 The rate of photocatalytic degradation of rhodamine B is 16.8 times that of CuO/BiVO 4 The rate of the heterojunction photocatalytic degradation of rhodamine B is 1.8 times.
Compared with the prior art, the invention has the following advantages:
(1) The method prepares the CuO/Bi/BiVO for the first time by a three-step method 4 The Z-type heterojunction photocatalyst has the advantages of low cost and easy acquisition of raw materials, simple and convenient reaction process and no need of adding a surfactant and a template agent.
(2) The invention is controlled by components, and the CuO/BiVO 4 The simple substance Bi is introduced into the heterojunction, so that the transfer of photo-generated carriers is promoted, and the CuO/Bi/BiVO is constructed 4 Z-type heterojunction photocatalysts.
(3) The invention obtains CuO/Bi/BiVO through reasonable component regulation and structural design 4 The Z-type heterojunction photocatalyst has excellent photocatalytic degradation performance on rhodamine B.
(4)CuO/Bi/BiVO 4 The Z-type heterojunction photocatalyst has good stability and can be applied to the field of photocatalytic degradation.
Drawings
FIG. 1 is a BiVO of comparative example 1 of the present invention 4 (a) CuO (b) in comparative example 2, cuO/BiVO in comparative example 6 4 -5 (c) and CuO/Bi/BiVO in example 1 4 -SEM image of 1 (d); (e) CuO/Bi/BiVO in example 1 4 Mapping graph of-1.
FIG. 2 is a BiVO of comparative example 1 of the present invention 4 CuO in comparative example 2, cuO/BiVO in comparative example 6 4 -5 and CuO/Bi/BiVO in example 1 4 -1 (a) XRD; (b) CuO/Bi/BiVO in example 1 4 XPS spectrum of-1.
FIG. 3 is BiVO in comparative example 1 of the present invention 4 CuO in comparative example 2, cuO/BiVO in comparative example 6 4 -5 and CuO/Bi/BiVO in example 1 4 -XPS spectra of (a) Bi 4f of 1; (b) XPS spectra of V2 p; (c) XPS spectrum of O1 s; (d) XPS spectrum of Cu 2 p.
FIG. 4 is a BiVO of comparative example 1 of the present invention 4 CuO in comparative example 2, cuO/BiVO in comparative example 6 4 -5 and CuO/Bi/BiVO in example 1 4 -uv-vis diffuse reflectance pattern of 1.
FIG. 5 is BiVO in comparative example 1 of the present invention 4 CuO in comparative example 2, cuO/BiVO in comparative example 6 4 -5 and CuO/Bi/BiVO in example 1 4 -1 (a) EIS diagram; (b) I-t diagram.
FIG. 6 shows the CuO/Bi/BiVO in example 1 of the present invention 4 -1 (a) free radical quenching test pattern; (b) a free radical quenching performance profile; (c) BiVO (BiVO) 4 And VB-XPS map of CuO; (d) a corresponding band location map.
FIG. 7 is BiVO in comparative example 1 of the present invention 4 CuO in comparative example 2, bi/BiVO in comparative example 3 4 CuO/Bi/BiVO in comparative example 4 4 CuO/BiVO in comparative example 6 4 -5 and CuO/Bi/BiVO in example 1 4 -1 (a) a time profile of degradation product concentration; (b) degradation rate profile.
FIG. 8 is a diagram showing the CuO/Bi/BiVO in example 1 of the present invention 4 -1 cycle stability test pattern.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
The specific conditions are not noted in the examples of the present invention, and are carried out according to conventional conditions or conditions suggested by the manufacturer. The raw materials, reagents, etc. used, which are not noted to the manufacturer, are conventional products commercially available.
The preparation process of the invention is as follows:
synthesis of BiVO by hydrothermal process 4 Copper nitrate trihydrate (12-243 mg) was dissolved in 20mL of water, and 0.6g of BiVO was added 4 Heating and stirring at 80 ℃ until the solvent is evaporated to dryness, then heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min under an air atmosphere, and preserving heat for 1h to obtain the CuO/BiVO with different CuO loading amounts 4 Heterojunction, named CuO/BiVO 4 -x (x: mass percent of CuO added). 0.3g CuO/BiVO 4 Dispersing the heterojunction in 70mL of water, adding 0.05mol/L sodium borohydride solution (1-12 mL), stirring for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 Y (y: the volume of sodium borohydride solution added).
Test conditions:
rhodamine B is taken as a degradation object: 10mg of the catalyst+40 mL of rhodamine B aqueous solution (100 ppm) was irradiated with a full spectrum under a 500W xenon lamp.
Comparative example 1
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 。
Comparative example 2
2.0g of copper nitrate trihydrate is heated to 300 ℃ from room temperature under the air atmosphere at the heating rate of 2 ℃/min and is kept for 1h, so that CuO is obtained.
Comparative example 3
0.762g bismuth nitrate pentahydrate was dissolved in 30mL 2mol/LDissolving 0.191g of sodium metavanadate in 30mL of water in a dilute nitric acid solution, then dropwise adding the sodium metavanadate solution into a bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH to 2 with 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 0.3g BiVO was used 4 Dispersing in 70mL water, adding 1mL 0.05mol/L sodium borohydride solution, stirring at room temperature for 1h, washing the obtained product with water for 3 times, and drying to obtain Bi/BiVO 4 。
Comparative example 4
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate and 0.6g of BiVO 4 Directly mixing, heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min under an air atmosphere, and preserving heat for 1h to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 Dispersing the heterojunction in 70mL of water, adding 1mL of 0.05mol/L sodium borohydride solution, stirring for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 A composite material.
Comparative example 5
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 12mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent evaporatesThen heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min under the air atmosphere and preserving heat for 1h to obtain CuO/BiVO 4 Heterojunction, named CuO/BiVO 4 -1。
Comparative example 6
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate is dissolved in 20mL of water and 0.6g of BiVO is added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 Heterojunction, named CuO/BiVO 4 -5。
Comparative example 7
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 182mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 Heterojunction, named CuO/BiVO 4 -10。
Comparative example 8
Bismuth nitrate pentahydrate of 0.762g is dissolved in 30mL of 2mol/L dilute nitric acid solution, sodium metavanadate of 0.191g is dissolved in 30mL of water, then sodium metavanadate solution is dripped into bismuth nitrate solution, after mixing the two solutions, stirring is carried out for 30min, pH is adjusted to 2 by 10mol/L sodium hydroxide solution,transferring into a high-pressure reaction kettle, preserving heat at 180 ℃ for 15h, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 273mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 Heterojunction, named CuO/BiVO 4 -15。
Comparative example 9
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 364mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 Heterojunction, named CuO/BiVO 4 -20。
Example 1
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 The heterojunction was dispersed in 70mL of water and 1mL of 0.05mol/L borohydride was addedStirring the sodium solution for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 -1。
Example 2
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate is dissolved in 20mL of water and 0.6g of BiVO is added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 Dispersing the heterojunction in 70mL of water, adding 3mL of 0.05mol/L sodium borohydride solution, stirring for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 -3。
Example 3
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 The heterojunction was dispersed in 70mL of water, 6mL of a 0.05mol/L sodium borohydride solution was added, and the mixture was stirred at room temperature for 1h, and the resulting product was treated with waterWashing for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 -6。
Example 4
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 Dispersing the heterojunction in 70mL of water, adding 9mL of 0.05mol/L sodium borohydride solution, stirring for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 -9。
Example 5
Dissolving 0.762g of bismuth nitrate pentahydrate in 30mL of 2mol/L dilute nitric acid solution, dissolving 0.191g of sodium metavanadate in 30mL of water, then dropwise adding the sodium metavanadate solution into the bismuth nitrate solution, mixing the two solutions, stirring for 30min, adjusting the pH value to 2 by using 10mol/L sodium hydroxide solution, transferring into a high-pressure reaction kettle, preserving heat for 15h at 180 ℃, naturally cooling to room temperature, centrifugally washing the obtained product with water and absolute ethyl alcohol for 3 times respectively, and drying to obtain BiVO 4 . 91mg of copper nitrate trihydrate was dissolved in 20mL of water and 0.6g of BiVO was added 4 Heating and stirring at 80deg.C until the solvent is evaporated to dryness, heating from room temperature to 300deg.C at a heating rate of 2deg.C/min under air atmosphere, and maintaining for 1 hr to obtain CuO/BiVO 4 And a heterojunction. 0.3g CuO/BiVO 4 Dispersing the heterojunction in 70mL of water, adding 12mL of 0.05mol/L sodium borohydride solution, stirring for 1h at room temperature, washing the obtained product with water for 3 times, and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst named CuO/Bi/BiVO 4 -12。
BiVO prepared in the invention 4 、CuO、CuO/BiVO 4 Heterojunction and CuO/Bi/BiVO 4 The morphology of the prepared catalyst is BiVO wrapped by CuO through SEM and Mapping tests (figure 1) of the Z-type heterojunction photocatalyst 4 Fishbone structure, cuO is uniformly dispersed in BiVO 4 And (3) upper part. By XRD and XPS tests (FIG. 2), it is further demonstrated that CuO was successfully loaded into BiVO 4 And (3) upper part. As shown in FIG. 3a, cuO/Bi/BiVO 4 The XPS spectrum of Bi 4f of-1 shows a new Bi simple substance characteristic peak, which proves that CuO/Bi/BiVO is successfully prepared 4 Z-type heterojunction photocatalysts. As shown in FIG. 3d, cuO/BiVO 4 -5 and CuO/Bi/BiVO 4 Cu is present in XPS spectrum of Cu 2p of-1 2+ Is also demonstrated to successfully load CuO into BiVO 4 And (3) upper part. The ultraviolet-visible diffuse reflection diagram of fig. 4 shows that the absorption of the composite material prepared by the invention at 500-800nm is obviously enhanced, and the light absorption range is widened. As can be seen from EIS and I-t tests shown in FIG. 5, the compounded photocatalyst has the advantages of reduced charge transfer resistance, increased photocurrent and higher carrier transmission efficiency. The radical quenching test of FIGS. 6 a-b shows that EDTA-2Na and methanol both inhibit the photocatalytic degradation reaction, i.e., cuO/Bi/BiVO 4 The free radical of the Z-type heterojunction photocatalyst which plays a main role in photolysis is h + And OH. From FIG. 6c, biVO can be derived 4 And the valence band position of CuO, the band position of the composite is shown in FIG. 6 d. FIG. 7a is a graph showing photocatalytic degradation performance test of a sample in the present invention, cuO/Bi/BiVO 4 The degradation rate of the-1 pair rhodamine B reaches 99 percent. With pure CuO and Bi/BiVO 4 The sum of photodegradation properties is compared with that of CuO/Bi/BiVO 4 And (1) the performance of the photocatalytic degradation of rhodamine B is greatly improved. And CuO/BiVO 4 -5 (comparative example 6) and CuO/Bi/BiVO 4 The photocatalytic performance of-1 (example 1) is significantly better than that of CuO/Bi/BiVO 4 (comparative example 4), thereby illustrating copper nitrate trihydrate and BiVO 4 Direct mixing to prepare CuO/Bi/BiVO 4 The CuO agglomeration covers up the reactive sites, and simultaneously inhibits the subsequent Bi simple substance from being in CuO and BiVO 4 The introduction between interfaces is unfavorable for CuO/Bi/BiVO 4 Formation of a Z-type heterojunction. As can be seen from FIG. 7b, the reaction rate of the photocatalyst prepared by the present invention conforms to the first order reaction kinetics, cuO/BiVO 4 -5 reaction rate of BiVO 4 9.3 times of CuO/Bi/BiVO 4 -1 reaction rate of BiVO 4 Is 16.8 times as large as the above. FIG. 8 is CuO/Bi/BiVO 4 The cycle stability test chart of-1 shows that the photocatalytic degradation performance of the composite material is not reduced after 6 cycles, so that the composite photocatalyst prepared by the method has good photocatalytic stability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above 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 made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. CuO/Bi/BiVO 4 The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps of:
(1) Copper nitrate trihydrate is dissolved in water and BiVO is added 4 Heating, stirring, evaporating the solvent, and calcining at 200-400 ℃ for 1-5 h to obtain CuO/BiVO 4 A heterojunction;
(2) CuO/BiVO 4 Dispersing the heterojunction in water, adding sodium borohydride solution, stirring, washing and drying to obtain CuO/Bi/BiVO 4 Z-type heterojunction photocatalyst;
step (1) the copper nitrate trihydrate, water, and BiVO 4 The proportion of (3) is 12-243 mg:20mL:0.6g;
the concentration of the sodium borohydride solution in the step (2) is 0.01-0.1 mol/L; the CuO/BiVO 4 The heterojunction, water and sodium borohydride solution were in a ratio of 0.3g:70mL: 1-20 mL.
2. A CuO/Bi/BiVO as defined by claim 1 4 The preparation method of the Z-type heterojunction photocatalyst is characterized in that the heating and stirring temperature in the step (1) is 60-90 ℃;stirring in the step (2) means stirring at normal temperature for 0.5-2 h.
3. A CuO/Bi/BiVO as defined by claim 1 4 The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the following steps of (1) the BiVO 4 The preparation method comprises the following steps:
uniformly mixing bismuth nitrate pentahydrate acid solution and vanadium source water solution, regulating pH to 2-9, performing hydrothermal reaction at 150-200 ℃ for 1-24 h, cooling, washing and drying to obtain BiVO 4 。
4. A CuO/Bi/BiVO as defined by claim 3 4 The preparation method of the Z-type heterojunction photocatalyst is characterized in that an acid solution in the bismuth nitrate pentahydrate acid solution is a nitric acid solution, and the concentration is 0.5-2 mol/L; the concentration of bismuth nitrate pentahydrate in the bismuth nitrate pentahydrate acid solution is 0.0162-0.0323 g/mL; the vanadium source in the vanadium source aqueous solution is sodium metavanadate; the concentration of the vanadium source water solution is 0.0041-0.0081 g/mL; the mass ratio of the bismuth nitrate pentahydrate to the vanadium source is 4:1.
5. a CuO/Bi/BiVO as defined by claim 3 4 The preparation method of the Z-type heterojunction photocatalyst is characterized in that the regulator used for regulating the pH is sodium hydroxide solution, and the concentration is 1-10 mol/L; the hydrothermal reaction time is 12-20 h.
6. A CuO/Bi/BiVO as defined by claim 1 4 The preparation method of the Z-type heterojunction photocatalyst is characterized by comprising the step (2) of preparing the CuO/BiVO 4 And adding water into the heterojunction, and then performing ultrasonic dispersion for 10-30 min.
7. A CuO/Bi/BiVO prepared by the process as claimed in any one of claims 1 to 6 4 Z-type heterojunction photocatalysts.
8. A CuO/Bi/BiVO as defined by claim 7 4 Z-type heterojunction photocatalyst in photocatalytic degradation fieldIs used in the application of (a).
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