CN111389422B - Ag/BiOCl-OVs composite photocatalyst and preparation method and application thereof - Google Patents
Ag/BiOCl-OVs composite photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111389422B CN111389422B CN202010322992.5A CN202010322992A CN111389422B CN 111389422 B CN111389422 B CN 111389422B CN 202010322992 A CN202010322992 A CN 202010322992A CN 111389422 B CN111389422 B CN 111389422B
- Authority
- CN
- China
- Prior art keywords
- biocl
- ovs
- crystal face
- reaction
- deionized 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 61
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000013078 crystal Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 48
- 239000008367 deionised water Substances 0.000 claims abstract description 42
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- 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 claims abstract description 15
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 15
- 238000005286 illumination Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 229910052724 xenon Inorganic materials 0.000 claims description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 9
- 230000000593 degrading effect Effects 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000006552 photochemical reaction Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 26
- 239000007788 liquid Substances 0.000 description 14
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 230000031700 light absorption Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000003574 free electron Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 sodium-zinc-manganese oxide Chemical compound 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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 provides an Ag/BiOCl-OVs composite photocatalyst and a preparation method and application thereof, wherein the method comprises the following steps of 1: (0.05-0.3) by mass ratio, exposing the BiOCl-OVs powder with the (001) crystal face and Ag (NO) 3 ) 3 Dissolving in deionized water to obtain a mixed system; step 2, carrying out reduction reaction on the mixed system under a light source to obtain a reaction solution; and 3, separating and drying the product in the reaction solution to obtain the Ag/BiOCl-OVs composite photocatalyst. The invention adopts the illumination reduction method to make Ag attached to the oxygen vacancy + The Ag electrons can be transferred to BiOCl, the Fermi level of the BiOCl is raised, the reduction capability of the photo-generated electrons is improved, and the composite photocatalyst can effectively degrade an organic pollutant rhodamine B.
Description
Technical Field
The invention belongs to the field of semiconductor photocatalytic functional materials, and particularly relates to an Ag/BiOCl-OVs composite photocatalyst as well as a preparation method and application thereof.
Background
In recent years, semiconductor photocatalytic technology has received much attention because of its potential applications in relieving environmental pollution pressure and energy shortage.
BiOCl is a layered structure consisting of a bismuth oxide layer and a chlorine atomic layer, and photo-generated electrons and holes easily form excitons in the limited layered structure, so that the separation of current carriers in the BiOCl is not obvious, and the photocatalytic performance is not ideal. To facilitate exciton dissociation, oxygen vacancies can be introduced into the system, which can not only trap excitons as defects, but which can cause energy disorder of the system, while excitons tend to dissociate into free electrons and holes in the energy-disorder region. In addition, biOCl is a wide bandgap semiconductor that responds only to ultraviolet light. Aiming at the defects of weak visible light absorption of BiOCl, difficult separation of photon-generated carriers and the like, noble metal can be selectively loaded on the surface of the BiOCl for modification. Among the numerous noble metals, ag is the most economical noble metal with a strong surface plasmon resonance effect (SPR). SPR can be classified into two types, one is a transverse surface plasmon resonance effect (TSPR), and the other is a longitudinal surface plasmon resonance effect (LSPR). The TSPR is a propagation type plasma resonance effect, and can enable the plasma to propagate hundreds of microns along the metal surface; the LSPR can reduce the thickness of a semiconductor for absorbing incident light and shorten the distance of a photon-generated carrier to reach a reaction site, so that photon-generated charges can be effectively separated. In addition to this, LSPR can enhance the absorption of semiconductors in the visible region. Therefore, under the action of TSPR and LSPR of oxygen vacancy and Ag, the visible light absorption of BiOCl can be enhanced, the dissociation of excitons can be accelerated, and the effective separation of photo-generated charges can be realized.
So far, although there are many reports about loading Ag on the surface of BiOCl, only LSPR of Ag is mentioned in the report, TSPR is not mentioned, and there is no report in the prior art that Ag is deposited on oxygen vacancy of BiOCl.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the Ag/BiOCl-OVs composite photocatalyst, and a preparation method and application thereof, wherein the Ag/BiOCl-OVs composite photocatalyst is low in cost and simple to operate, and the reduction capability of photo-generated electrons is improved, so that the composite photocatalyst can effectively degrade organic pollutants.
The invention is realized by the following technical scheme:
a preparation method of an Ag/BiOCl-OVs composite photocatalyst comprises the following steps,
and 3, separating and drying the product in the reaction solution to obtain the Ag/BiOCl-OVs composite photocatalyst.
Preferably, in step 1, the powder and Ag (NO) are 3 ) 3 Adding the mixture into deionized water, and stirring the mixture for 30 to 35min at room temperature to obtain a mixed system.
Preferably, the time of the reduction reaction in the step 2 is 2.5 to 3.5 hours.
Preferably, in step 2, the mixed system is reacted in an XPA-3 photochemical reactor.
Preferably, in the step 3, the reaction solution is washed by deionized water and absolute ethyl alcohol for 3 to 5 times respectively, and then dried at 70 to 90 ℃ to obtain the Ag/BiOCl-OVs composite photocatalyst.
The Ag/BiOCl-OVs composite photocatalyst is prepared by the preparation method of the Ag/BiOCl-OVs composite photocatalyst.
The Ag/BiOCl-OVs composite photocatalyst is applied to degradation of rhodamine B.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method of the Ag/BiOCl-OVs composite photocatalyst, due to the layered structure of BiOCl, the BiOCl has a strong exciton effect, namely, most of photo-generated electrons and holes are combined to form a large number of primary excitons under illumination, and only a few photo-generated electrons can migrate to the (001) crystal face of the BiOCl; oxygen vacancies can trap excitons as defects on the one hand, and can cause energy disorder of the system on the other hand, and excitons tend to separate into free electrons and holes in an energy disorder region, so that the introduction of oxygen vacancies in the system is favorable for exciton separation; the SPR effect of Ag can not only enhance the light absorption of semiconductor, but alsoEffective separation of photo-generated charges can be promoted. Then utilizing the thermal electron pair Ag generated by oxygen vacancy under illumination + Depositing Ag on the exposed oxygen vacancies of the BiOCl (001) crystal face, and reducing the Ag attached to the oxygen vacancies by light + Reducing the solution into Ag to prepare the Ag/(001) crystal face BiOCl-OVs photocatalyst. The deposited Ag presents two shapes of nano particles and strips, so that the Ag has two SPR effects of a transverse surface plasma resonance effect (TSPR) and a longitudinal surface plasma resonance effect (LSPR), and the work function of the Ag is smaller than that of BiOCl, so that the electrons of the Ag can be transferred to the BiOCl, the Fermi level of the BiOCl is raised, the reduction capability of the photo-generated electrons is improved, and the composite photocatalyst can effectively degrade an organic pollutant rhodamine B.
Under the illumination of the composite photocatalyst, the TSPR of Ag promotes high-energy electrons of Ag to be transmitted to BiOCl, and the high-energy electrons compete for holes in a primary exciton in the BiOCl to form a secondary exciton and release electrons in the primary exciton; the secondary excitons are trapped by oxygen vacancies as defects, releasing holes from the secondary excitons. Electrons released from the primary excitons and holes released from the secondary excitons are effectively separated under the LSPR action. Finally, dissociation of excitons in the BiOCl and separation of photo-generated charges are accelerated under the action of transfer of Ag polarization charges and TSPR and LSPR effects.
The composite photocatalyst has higher mineralization degree on rhodamine B under simulated sunlight, so that organic pollutants can be effectively degraded, and the composite photocatalyst has a good application prospect.
Drawings
FIG. 1 is an XRD pattern of products prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2.
FIG. 2 is a Raman spectrum of products prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2.
Fig. 3 is an enlarged view of a dotted line portion in fig. 2.
FIG. 4 is an EPR spectrum of the products prepared in comparative example 1, comparative example 2 and example 2 of the present invention.
FIG. 5 is an SEM and HRTEM image of BiOCl prepared in comparative example 1 of the present invention.
Fig. 6 is an SEM image and a low power TEM image of BiOCl prepared in comparative example 2 of the present invention.
FIG. 7 is a HRTEM image of BiOCl prepared in comparative example 2 of the present invention.
FIG. 8 is an SEM photograph of the Ag/(001) plane BiOCl-OVs photocatalyst (10% Ag/BiOCl) prepared in example 1 of the present invention.
FIG. 9 is a HRTEM image of the Ag/(001) plane BiOCl-OVs photocatalyst (10% Ag/BiOCl) prepared in example 1 of the present invention.
FIG. 10 is an EDS graph of Ag/(001) -plane BiOCl-OVs photocatalysts (10% Ag/BiOCl) prepared in example 1 of the present invention.
FIG. 11 is a diagram of the forming mechanism of the Ag/(001) crystal face BiOCl-OVs photocatalyst prepared by the invention.
FIG. 12 is a graph of UV-Vis DRS of the products prepared in comparative examples 1-2 and examples 1-4 of the present invention.
FIG. 13 is a graph showing the removal rate of rhodamine B and the capture of active species in simulated sunlight (500W) for the products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention.
FIG. 14 is a graph showing the removal rate of the products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention under 385nm monochromatic light irradiation.
FIG. 15 is a graph showing the removal rate of the products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention under 365nm monochromatic light irradiation.
FIG. 16 is a graph showing the removal rate of the products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention under 535nm monochromatic light irradiation.
FIG. 17 is a diagram of work function and electron transfer of BiOCl, ag/BiOCl calculated by DFT theory.
FIG. 18 is a PL map of the products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention.
FIG. 19 is a photo-catalysis mechanism diagram of the Ag/(001) crystal face BiOCl-OVs photo-catalyst prepared by the invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention uses Bi (NO) 3 ) 3 ·5H 2 O is a Bi source, naCl is a Cl source, and BiOCl with an oxygen vacancy and an exposed (001) crystal face is prepared by a hydrothermal method; the Ag/(001) crystal face BiOCl-OVs composite photocatalyst is prepared by adopting an illumination reduction method.
The preparation method of the Ag/(001) crystal face BiOCl-OVs composite photocatalyst specifically comprises the following steps:
step 1: in a molar ratio of 1 3 ) 3 ·5H 2 Dissolving O and NaCl in deionized water, taking 48mL of the common deionized water, stirring for 2h at room temperature to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the reaction is finished and the temperature is reduced to room temperature, standing to remove supernatant, washing precipitates for 3-5 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70-90 ℃ to obtain oxygen vacancy-containing exposed (001) crystal face BiOCl powder, namely exposed (001) crystal face BiOCl-OVs;
step 2: dissolving the BiOCl-OVs powder obtained in the step 1 in 45-65 ml of deionized water, stirring at room temperature for 30-35 min to obtain a suspension aqueous solution A, and adding Ag (NO) 3 ) 3 Adding into the aqueous solution A to obtain a suspension mixed system A, wherein BiOCl-OVs and Ag (NO) with (001) crystal face exposed in the mixed system A 3 ) 3 The mass ratio of (1): (0.05-0.3);
in practice, the specific experiment was carried out with 5%,10%,20%,30% Ag on BiOCl-OVs, the total amount of BiOCl-OV added was 0.3g and Ag (NO) 3 ) 3 BiOCl-OVs and Ag (NO) exposing the (001) crystal face at 0.015g,0.03g,0.06g and 0.09g 3 ) 3 The concentration of the sodium-zinc-manganese oxide is respectively 4.62-6.67 g/L and 0.25-1.50 g/L;
placing the mixed system A in an XPA-3 photochemical reaction instrument for illumination reduction deposition reaction for 2.5-3.5 h to obtain reaction liquid, and adopting a light source with illumination being a xenon lamp as simulated sunlight, wherein the selected power is 350W;
when in illumination, the thermal electron generated by oxygen vacancy in BiOCl will attractLead Ag + And Ag attracted by thermal electrons of oxygen vacancies on the BiOCl (001) crystal plane + Reducing the Ag into Ag, depositing the Ag on the oxygen vacancy sites of the exposed BiOCl (001) crystal face, and forming the Ag/(001) crystal face BiOCl-OVs photocatalyst. Because the work function of Ag is less than that of BiOCl, the electrons of Ag can migrate to BiOCl, so that the Fermi level of the BiOCl is raised, and the reducing capability of photo-generated electrons is improved.
Ag deposited on oxygen vacancies of a BiOCl (001) crystal face is in two shapes of nano particles and strips, has a transverse surface plasmon resonance effect (TSPR) and a longitudinal surface plasmon resonance effect (LSPR), enhances the visible light absorption of the BiOCl, accelerates the separation of excitons in the BiOCl, and promotes the effective separation of carriers.
And then filtering the reaction solution, respectively washing the obtained precipitate with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 70-90 ℃ to obtain the photocatalyst of Ag loaded on the (001) crystal face oxygen vacancy exposing the (001) crystal face BiOCl, namely the Ag/(001) crystal face BiOCl-OVs composite photocatalyst.
The composite photocatalyst can be used for degrading organic pollutants.
The preparation method of the Ag/(001) crystal face BiOCl-OVs photocatalyst comprises the following steps:
example 1:
step 1: adding 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
step 2: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.015g of Ag (NO) 3 ) 3 Adding into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to irradiate for 2.5h to obtain a reaction solution, filtering the reaction solution,and washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 2:
step 1: adding 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL deionized water, stirring at room temperature for 2 hours to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting at 160 ℃ for 18 hours, cooling the reaction kettle to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove a supernatant, washing precipitates with deionized water and absolute ethyl alcohol for 3 times respectively, drying at 70 ℃, and grinding to obtain an exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
step 2: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.03g of Ag (NO) 3 ) 3 Adding the solution A into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 2.5 hours to obtain reaction liquid, filtering the reaction liquid, washing precipitates for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 3:
step 1: 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
and 2, step: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.06g of Ag (NO) 3 ) 3 Adding into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 2.5h to obtain a reaction solution, filtering the reaction solution, and respectively using deionized water and absolute ethyl alcohol for precipitationCleaning for 3 times, and drying at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 4:
step 1: 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL deionized water, stirring at room temperature for 2 hours to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting at 160 ℃ for 18 hours, cooling the reaction kettle to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove a supernatant, washing precipitates with deionized water and absolute ethyl alcohol for 4 times respectively, drying at 80 ℃, and grinding to obtain an exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
and 2, step: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.09g of Ag (NO) 3 ) 3 Adding the mixed solution into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 2.5 hours to obtain reaction liquid, filtering the reaction liquid, respectively cleaning precipitates for 3 times by using deionized water and absolute ethyl alcohol, and drying the precipitates at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 5:
step 1: 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
step 2: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 45mL of water, stirring at room temperature for 35min to obtain (001) crystal face BiOCl-OVs water solution A, and adding 0.06g of Ag (NO) 3 ) 3 Adding into solution A to obtain mixed system A, placing mixed system A in XPA-3 photochemical reactor, irradiating for 3h to obtain reaction solution, filtering reaction solution, washing precipitate with deionized water and anhydrous ethanol for 5 times, and drying at 90 deg.C to obtainAg/(001) crystal face BiOCl-OVs photocatalyst.
Example 6:
step 1: 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 4 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 85 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
and 2, step: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 65mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.09g of Ag (NO) 3 ) 3 Adding the mixed solution into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 3.5 hours to obtain reaction liquid, filtering the reaction liquid, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for 3 times, and drying the precipitates at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 7:
step 1: adding 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
step 2: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 50mL of water, stirring at room temperature for 35min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.03g of Ag (NO) 3 ) 3 Adding the mixed solution into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 3 hours to obtain reaction liquid, filtering the reaction liquid, washing precipitates for 3 times by deionized water and absolute ethyl alcohol respectively, and drying the precipitates at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Example 8:
step 1: adding 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
step 2: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain (001) crystal face BiOCl-OVs aqueous solution A, and adding 0.06g of Ag (NO) 3 ) 3 Adding the solution A into the solution A to obtain a mixed system A, placing the mixed system A in an XPA-3 photochemical reactor to be irradiated for 3.5 hours to obtain reaction liquid, filtering the reaction liquid, washing precipitates for 3 times by deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the Ag/(001) crystal face BiOCl-OVs photocatalyst.
Comparative example 1
BiOCl powder containing oxygen vacancy exposing (001) crystal face: adding 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL of deionized water, stirring for 2h at room temperature to obtain reaction precursor liquid, transferring the precursor liquid to a hydrothermal reaction kettle, reacting for 18h at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, drying and grinding at 70 ℃ to obtain the exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs.
Comparative example 2
Step 1: 8mmol of Bi (NO) 3 ) 3 ·5H 2 Dissolving O and 8mmol NaCl in 48mL deionized water, stirring at room temperature for 2h to obtain a reaction precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting at 160 ℃ for 18h, cooling to room temperature after the reaction is finished, taking out the reaction kettle, standing to remove a supernatant, washing the precipitate with deionized water and absolute ethyl alcohol for 3 times, drying at 70 ℃, filtering, and drying,Grinding to obtain exposed (001) crystal face BiOCl powder containing oxygen vacancies, namely (001) crystal face BiOCl-OVs;
and 2, step: dissolving 0.3g of (001) crystal face BiOCl-OVs powder in 60mL of water, stirring at room temperature for 30min to obtain a (001) crystal face BiOCl-OVs aqueous solution A, placing the solution A in an XPA-3 photochemical reactor to irradiate for 2.5h to obtain a reaction solution, filtering the reaction solution, washing precipitates for 3 times by using deionized water and absolute ethyl alcohol respectively, and drying at 70 ℃ to obtain the oxygen vacancy-containing exposed (001) crystal face BiOCl powder irradiated by a xenon lamp.
The above conclusions and mechanisms are specifically explained below.
FIG. 1, FIG. 2 and FIG. 3 are XRD and Raman spectra of the Ag/(001) crystal face BiOCl-OVs photocatalyst prepared by the invention. Wherein a and b are BiOCl and BiOCl-Xe synthesized according to comparative example 1 and comparative example 2, respectively, and c, d, e and f are XRD and Raman spectra of photocatalysts synthesized according to example 1, example 2, example 3 and example 4, respectively. As shown in FIG. 1, all diffraction peaks of BiOCl correspond to tetragonal BiOCl (JCPDS 82-0485), in which the diffraction peak intensities of (001), (002), and (003) planes are significantly higher than those of other diffraction peaks, indicating that the synthesized BiOCl exposes the (001) plane. After loading Ag, the diffraction peak intensities of the (001), (002), and (003) planes are significantly decreased (the dotted line box in fig. 2, i.e., fig. 3), which is attributed to the shielding effect of Ag. In addition, biOCl-Xe has diffraction peak intensities significantly lower than BiOCl, which is attributed to the rearrangement of the internal crystal structure of BiOCl after irradiation. 145cm in FIG. 2 -1 And 199cm -1 Two distinct bands at (A) each represent A 1g Stretching vibration mode and E of Bi-Cl inside of mold g The inside of the die is Bi-Cl stretching vibration mode. Further inspection of FIG. 3 revealed 396cm -1 B of (A) 1g The mode is due to the disappearance of oxygen atoms, which confirms the presence of oxygen vacancies in the sample. BiOCl at 396cm -1 The peak intensity is significantly weaker than that of BiOCl-Xe, since BiOCl is irradiated by a xenon lamp to introduce more oxygen vacancies. Oxygen vacancies can cause crystal breakage and reduce surface crystallinity. Therefore, it was shown that the decrease in intensity of BiOCl-Xe diffraction peak in the XRD spectrum is due to oxygen vacancies. But 396cm after loading Ag -1 The peak intensity is significantly reduced or substantially maintained, which proves that AgOccupying oxygen vacancies. In addition, the remaining samples were at 145cm compared to BiOCl -1 And 199cm -1 The intensity of the peak is obviously enhanced, and the enhancement of the Raman peak is related to oxygen vacancy as can be seen from the combination of FIG. 3.
FIG. 4 is an EPR spectrum of the Ag/(001) crystal face BiOCl-OVs photocatalyst prepared by the invention. Where a and b are BiOCl and BiOCl-Xe synthesized according to comparative examples 1 and 2, respectively, and c is the EPR curve of the Ag/(001) face BiOCl-OVs photocatalyst synthesized according to example 2. BiOCl has a weak EPR signal at g =2.003 due to the capture of lone pairs of electrons by oxygen vacancies. However, biOCl-Xe exhibits a strong EPR signal and 10% Ag/BiOCl has a peak EPR signal intensity that is weaker than BiOCl-Xe but still stronger than BiOCl. The order of the oxygen vacancy content is BiOCl-Xe > 10% >, ag/BiOCl > BiOCl. Illustrating the deposition of Ag in the oxygen vacancies in Ag/BiOCl.
FIGS. 5, 6, 7, 8, 9 and 10 show the microstructure and morphology of samples of the Ag/(001) face BiOCl-OVs photocatalyst prepared by the method. In FIG. 5, biOCl having good crystallinity has a disk-like morphology (length: 1.5 to 6 μm, width: 1.5 to 3 μm, thickness: 0.3 to 0.6 μm). BiOCl has a lattice fringe spacing of 0.276nm, which corresponds to the (110) plane of BiOCl (HRTEM at 5nm in the upper right corner of FIG. 5), indicating that BiOCl is produced with the (001) plane exposed and the (110) plane flanking it.
The side of the disk-shaped BiOCl exhibited a lamellar layer structure after xenon lamp irradiation, as shown in fig. 6, due to rearrangement of the crystal structure inside the BiOCl after xenon lamp irradiation, which is consistent with a decrease in intensity of the BiOCl-Xe diffraction peak in XRD.
Figure 7 HRTEM at 5nm shows that the lattice fringes of the lamellar structure emerging laterally to the BiOCl are 0.220nm, this fringe spacing corresponds to the (112) atomic plane of BiOCl, and that the BiOCl is still exposed to the (001) crystallographic plane.
The morphology of Ag deposited on the surface of BiOCl is shown in FIG. 8, which is a granular (20-50 nm) morphology and a striped (100-200 nm length, about 20nm width) morphology, and as can be seen from FIG. 9, the lattice fringes with a spacing of 0.276nm correspond to the (110) plane of BiOCl, which indicates that the disk-shaped BiOCl prepared by the present invention has an exposed (001) plane, while the intra-circle spacing on the disk-shaped BiOCl is 0.23The 6nm lattice fringes correspond to Ag nanoparticles, indicating that Ag is indeed deposited in the (001) plane of BiOCl. The EDS results demonstrate the presence of Ag and the Ag content is 3%, as shown in figure 10. The large difference between the actually deposited Ag content (3%) and the initially set 10% of the experiment is attributed to the fact that only a few electrons on the (001) plane of BiOCl donate Ag + Reducing the Ag into Ag.
FIG. 11 is a diagram of the forming mechanism of the Ag/(001) crystal face BiOCl-OVs photocatalyst prepared by the invention. Due to the layered structure, biOCl has a strong exciton effect. Under illumination, electrons and holes in the BiOCl form primary excitons immediately under the action of coulomb force, and therefore, almost no free electrons exist in the (001) crystal plane of the BiOCl. Meanwhile, more oxygen vacancies are generated in the BiOCl due to the rearrangement of the internal crystal structure of the BiOCl under the irradiation of the xenon lamp. The free electrons at the oxygen vacancy in BiOCl reach the high-energy state to generate hot electrons e h - Thermal electrons attract Ag due to electrostatic attraction + And immediately introduce Ag + Reducing the Ag into Ag. Finally, ag is deposited on oxygen vacancies of the BiOCl (001) crystal face to form the Ag/(001) crystal face BiOCl-OVs photocatalyst.
FIG. 12 is a UV-Vis DRS spectrogram of the Ag/(001) crystal face BiOCl-OVs photocatalyst prepared by the method. Where a and b are BiOCl and BiOCl-Xe synthesized according to comparative example 1 and comparative example 2, respectively, and c, d, e and f are UV-Vis DRS curves for photocatalysts synthesized according to example 1, example 2, example 3 and example 4, respectively. All photocatalysts have a pronounced absorption sideband at about 372nm, which corresponds to BiOCl. BiOCl was calculated to have a band gap of 3.33eV and conduction and valence band potentials of 0.475eV and 3.805eV, respectively. The light absorption of pure phase BiOCl is weak in the visible region, but the light absorption of BiOCl-Xe is significantly enhanced due to the generation of more oxygen vacancies after xenon lamp irradiation. After xenon lamp irradiation, the color of the pure phase BiOCl changed from white to light gray, indicating an increase in the oxygen vacancy concentration. After Ag is loaded, the light absorption of the Ag/BiOCl in visible light and even near infrared light regions is obviously enhanced. In the Ag/BiOCl photocatalyst, two obvious absorption peaks are generated at about 338nm and about 538nm, which are respectively attributed to the Transverse Surface Plasmon Resonance (TSPR) and Longitudinal Surface Plasmon Resonance (LSPR) of Ag, and the Ag deposited on the surface of the BiOCl has two SPR side bands because the Ag is in the shape of nano-sphere particles and stripes. When Ag is present as a nanosphere particle, free electrons are displaced from the nucleus and core electrons and resonate with incident light to produce LSPR. However, when Ag is in a stripe shape, free electrons generate a propagating surface plasmon resonance (TSPR) on the Ag surface.
FIG. 13, FIG. 14, FIG. 15 and FIG. 16 are the curves of degraded rhodamine B (RhB) prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention, and FIG. 13 also contains an active species capture map. In FIG. 13, a and b are BiOCl and BiOCl-Xe synthesized according to comparative example 1 and comparative example 2, respectively, and c, d, e and f are degradation curves of the photocatalysts synthesized according to example 1, example 2, example 3 and example 4, respectively, the photocatalytic performance of BiOCl is improved after Ag is loaded, and the degradation rate of RhB by Ag/BiOCl is 2.64 times that of pure-phase BiOCl after 120min of illumination. Moreover, similar results were obtained under monochromatic light irradiation (see fig. 14, 15, 16). When 385nm monochromatic light was chosen as the light source, only the TSPR (388 nm) of Ag was activated, the degradation rate of RhB by pure phase BiOCl after 40min of light irradiation was 28%, whereas 10% Ag/BiOCl could reach 75%. Similarly, the degradation rate of RhB by Ag/BiOCl (86%) was higher than that by BiOCl (49%) at 365nm, 10%. This suggests that the TSPR of Ag plays an important role in photocatalytic reactions. In addition, when 535nm was used as the light source, 10% of the degradation rate of Ag/BiOCl (degradation rate 36%) with respect to RhB was still higher than that of BiOCl (degradation rate 17%). This indicates that LSPR also plays an important role in photocatalytic reactions. In conclusion, both TSPR and LSPR of Ag make important contribution to the photocatalytic reaction.
To detect the active species, an active species capture experiment was performed again (see fig. 13). The experimental results show that O 2 - And h + Is the major active species and OH is the minor active species. The conduction band position of BiOCl is calculated to be 0.475eV, and the potential is lower than O 2 /·O 2 - Potential (-0.046V), in which case O cannot be generated 2 - The specific calculation result is shown in fig. 17. Work function of BiOCl(W F ) 7.37eV, greater than the work function of Ag (4.23 eV). Therefore, electrons flow from Ag to BiOCl. This will cause electrons to accumulate in the BiOCl and raise the fermi level of the BiOCl.
FIG. 18 is a PL spectrum of products prepared in comparative examples 1 to 2 and examples 1 to 4 of the present invention. Where a and b are BiOCl and BiOCl-Xe synthesized according to comparative example 1 and comparative example 2, respectively, and c, d, e and f are PL profiles for photocatalysts synthesized according to example 1, example 2, example 3 and example 4, respectively. As can be seen from the figure, the broad peak in the range of 542 to 580nm is due to recombination of photo-generated electrons and holes, while the emission peak at 538nm originates from a defect in BiOCl, i.e., oxygen vacancy, indicating the presence of oxygen vacancies in all photocatalysts. In addition, a significant defect-bound exciton peak at 557nm appears, i.e., the neutral exciton is bound by the defect, and oxygen vacancies coexist with excitons in the photocatalyst. As can be seen, the PL emission peak intensity of Ag/BiOCl is lower than that of pure phase BiOCl, which indicates that the carrier separation can be promoted after Ag is deposited on the surface of BiOCl.
FIG. 19 is a photo-catalytic mechanism diagram of the Ag/(001) crystal face BiOCl-OVs photo-catalyst prepared by the invention. Under light, a large number of primary excitons are generated in BiOCl (as indicated by the lower ellipse in fig. 9), and the generated energetic electrons in Ag are propagated to BiOCl through TSPR (as indicated by the solid arrow on the left side of fig. 9). Since the energetic electron energy of Ag is much larger than that of the electron in the primary exciton, the energetic electron of Ag competes for the hole in the primary exciton, thereby forming a new secondary exciton (e.g., upper ellipse in fig. 9). Finally, the electrons in the primary exciton are released and reach the conduction band of BiOCl, while the secondary exciton is trapped by the oxygen vacancy in BiOCl, releasing the hole therein, which migrates to the valence band of BiOCl. Electrons released by the primary excitons and holes released by the secondary excitons are accelerated and separated under the action of the LSPR effect of Ag, and a large number of holes and superoxide radicals participate in the photocatalytic reaction. In conclusion, the polarization charge of Ag lifts the energy band structure of BiOCl and the TSPR and LSPR effects of Ag accelerate exciton dissociation and promote carrier separation, so that Ag/BiOCl has excellent photocatalytic performance.
The above description is only one embodiment of the present invention, and not all or only one embodiment, and any equivalent alterations to the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (2)
1. A preparation method of an Ag/BiOCl-OVs composite photocatalyst applied to degrading rhodamine B is characterized by comprising the following steps,
step 1, dissolving BiOCl-OVs powder with exposed (001) crystal face in 45-65 ml of deionized water, stirring at room temperature for 30-35 min to obtain suspension-state aqueous solution, and adding Ag (NO) 3 ) 3 Adding the mixture into the aqueous solution to obtain a mixed system in a suspension state, wherein BiOCl-OVs powder with an exposed (001) crystal face and Ag (NO) are added into the mixed system 3 ) 3 The mass ratio of (1): (0.05-0.3);
the BiOCl-OVs powder with the exposed (001) crystal face is obtained according to the following process:
in a molar ratio of 1 3 ) 3 ·5H 2 Dissolving O and NaCl in deionized water, stirring for 2 hours at room temperature to obtain a precursor solution, transferring the precursor solution to a hydrothermal reaction kettle, reacting for 18 hours at 160 ℃, taking out the reaction kettle after the temperature is reduced to room temperature after the reaction is finished, standing to remove supernatant, washing precipitates for 3-5 times by using the deionized water and absolute ethyl alcohol respectively, drying and grinding at 70-90 ℃ to obtain BiOCl-OVs powder with exposed (001) crystal faces;
step 2, the mixed system is subjected to reduction deposition reaction for 2.5 to 3.5 hours in an XPA-3 photochemical reaction instrument by using 350W illumination, a light source with illumination as a xenon lamp is adopted as simulated sunlight, and Ag attached to an oxygen vacancy of BiOCl exposing a (001) crystal face is subjected to reduction deposition reaction + Reducing the Ag into Ag with two shapes of nano particles and strips, wherein the work function of the Ag is less than BiOCl, and the Ag has a transverse surface plasma resonance effect and a longitudinal surface plasma resonance effect to obtain a reaction solution;
and 3, washing the reaction liquid with deionized water and absolute ethyl alcohol for 3-5 times respectively, and then drying at 70-90 ℃ to obtain the Ag/BiOCl-OVs composite photocatalyst applied to degrading rhodamine B.
2. The Ag/BiOCl-OVs composite photocatalyst applied to degrading rhodamine B, which is obtained by the preparation method of the Ag/BiOCl-OVs composite photocatalyst applied to degrading rhodamine B, as recited in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322992.5A CN111389422B (en) | 2020-04-22 | 2020-04-22 | Ag/BiOCl-OVs composite photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010322992.5A CN111389422B (en) | 2020-04-22 | 2020-04-22 | Ag/BiOCl-OVs composite photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111389422A CN111389422A (en) | 2020-07-10 |
| CN111389422B true CN111389422B (en) | 2023-01-31 |
Family
ID=71417022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010322992.5A Active CN111389422B (en) | 2020-04-22 | 2020-04-22 | Ag/BiOCl-OVs composite photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111389422B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547100B (en) * | 2020-12-23 | 2022-06-24 | 昆明理工大学 | Silver/bismuth oxyhalide composite photocatalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069876A (en) * | 2014-06-24 | 2014-10-01 | 华中师范大学 | Ag-BiOCl compound photocatalyst prepared by depositing nanometer silver on [001] crystal face of BiOCl nanometer sheet and method |
| CN105709782A (en) * | 2016-03-09 | 2016-06-29 | 安徽工业大学 | Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material |
| CN107824202A (en) * | 2017-10-19 | 2018-03-23 | 哈尔滨理工大学 | A kind of chlorine bismuth oxybromide (010)/graphene hetero-junctions and its preparation method and application |
| CN108722407A (en) * | 2018-05-30 | 2018-11-02 | 陕西科技大学 | A kind of Ag- (010) crystal face BiVO4Photochemical catalyst and preparation method thereof |
| CN110064394A (en) * | 2019-05-20 | 2019-07-30 | 江南大学 | A kind of Ag@Ag with high catalytic degradation activity2O/BiOCl composite material and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9409791B2 (en) * | 2014-12-29 | 2016-08-09 | Council Of Scientific & Industrial Research | Photocatalytic degradation of pharmaceutical drugs and dyes using visible active biox photocatalyst |
-
2020
- 2020-04-22 CN CN202010322992.5A patent/CN111389422B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104069876A (en) * | 2014-06-24 | 2014-10-01 | 华中师范大学 | Ag-BiOCl compound photocatalyst prepared by depositing nanometer silver on [001] crystal face of BiOCl nanometer sheet and method |
| CN105709782A (en) * | 2016-03-09 | 2016-06-29 | 安徽工业大学 | Preparing method and application of Ag/AgBr/BiOCl-(001) nanometer composite material |
| CN107824202A (en) * | 2017-10-19 | 2018-03-23 | 哈尔滨理工大学 | A kind of chlorine bismuth oxybromide (010)/graphene hetero-junctions and its preparation method and application |
| CN108722407A (en) * | 2018-05-30 | 2018-11-02 | 陕西科技大学 | A kind of Ag- (010) crystal face BiVO4Photochemical catalyst and preparation method thereof |
| CN110064394A (en) * | 2019-05-20 | 2019-07-30 | 江南大学 | A kind of Ag@Ag with high catalytic degradation activity2O/BiOCl composite material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Zhao Zhang etal..Ag-BiOCl Nanocomposites Prepared by Oxygen Vacancy Induced Photodeposition Method with Improved Visible Light Photocatalytic Activity.《Materials Letters》.2015,(第150期),第97-100页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111389422A (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kaviyarasu et al. | Evaluation on La2O3 garlanded ceria heterostructured binary metal oxide nanoplates for UV/visible light induced removal of organic dye from urban wastewater | |
| Senasu et al. | CdS/BiOBr heterojunction photocatalyst with high performance for solar-light-driven degradation of ciprofloxacin and norfloxacin antibiotics | |
| Sahu et al. | Facile synthesis of ZnO nanoplates and nanoparticle aggregates for highly efficient photocatalytic degradation of organic dyes | |
| Hou et al. | 3D Bi12TiO20/TiO2 hierarchical heterostructure: synthesis and enhanced visible-light photocatalytic activities | |
| Liang et al. | Facile synthesis of Ag/ZnO micro-flowers and their improved ultraviolet and visible light photocatalytic activity | |
| Zha et al. | Ultraviolet photocatalytic degradation of methyl orange by nanostructured TiO 2/ZnO heterojunctions | |
| Xu et al. | Monodispersed Ag 3 PO 4 nanocrystals loaded on the surface of spherical Bi 2 MoO 6 with enhanced photocatalytic performance | |
| Li et al. | Synthesis, microstructure, and photocatalysis of ZnO/CdS nano-heterostructure | |
| Li et al. | Microwave hydrothermal synthesis of Sr2+ doped ZnO crystallites with enhanced photocatalytic properties | |
| Meng et al. | Synthesis of fullerene modified with Ag 2 S with high photocatalytic activity under visible light | |
| Gao et al. | Hierarchical Ag/ZnO micro/nanostructure: green synthesis and enhanced photocatalytic performance | |
| Dhal et al. | Hydrothermal synthesis and enhanced photocatalytic activity of ternary Fe 2 O 3/ZnFe 2 O 4/ZnO nanocomposite through cascade electron transfer | |
| Guo et al. | An oxygen-vacancy-rich Z-scheme g-C3N4/Pd/TiO2 heterostructure for enhanced visible light photocatalytic performance | |
| Ahmad et al. | Highly efficient visible light driven photocatalytic activity of graphene and CNTs based Mg doped ZnO photocatalysts: A comparative study | |
| Jiang et al. | Natural assembly of a ternary Ag–SnS–TiO 2 photocatalyst and its photocatalytic performance under simulated sunlight | |
| Wang et al. | Synthesis of tunable ZnS–CuS microspheres and visible-light photoactivity for rhodamine B | |
| Manivel et al. | CuO-TiO2 nanocatalyst for photodegradation of acid red 88 in aqueous solution | |
| CN109250755B (en) | Bismuth oxide photocatalyst containing different crystal phases with bismuth defects and preparation method thereof | |
| Sriwichai et al. | Effect of iron loading on the photocatalytic performance of Bi2WO6 photocatalyst | |
| Wei et al. | Synthesis of hierarchically structured ZnO spheres by facile methods and their photocatalytic deNOx properties | |
| Hu et al. | Photocatalytic property of a Bi 2 O 3 nanoparticle modified BiOCl composite with a nanolayered hierarchical structure synthesized by in situ reactions | |
| Yang et al. | CuO core–shell nanostructures: Precursor-mediated fabrication and visible-light induced photocatalytic degradation of organic pollutants | |
| Maiti et al. | An ambient condition, one pot route for large scale production of ultrafine (< 15 nm) ZnO nanowires from commercial zinc exhibiting excellent recyclable catalytic performance: Approach extendable to CuO nanostructures | |
| Mubeen et al. | Band structure tuning of ZnO/CuO composites for enhanced photocatalytic activity | |
| Kakhaki et al. | Optical properties of zinc oxide nanoparticles prepared by a one-step mechanochemical synthesis method |
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 |