CN110813276A - Preparation method and application of bismuth oxide-based photocatalyst - Google Patents
Preparation method and application of bismuth oxide-based photocatalyst Download PDFInfo
- Publication number
- CN110813276A CN110813276A CN201911049111.0A CN201911049111A CN110813276A CN 110813276 A CN110813276 A CN 110813276A CN 201911049111 A CN201911049111 A CN 201911049111A CN 110813276 A CN110813276 A CN 110813276A
- Authority
- CN
- China
- Prior art keywords
- bismuth oxide
- based photocatalyst
- metal salt
- temperature
- mixed solution
- 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.)
- Pending
Links
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 65
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000010355 oscillation Effects 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 13
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 20
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 15
- 239000002131 composite material Substances 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 230000000875 corresponding effect Effects 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 bismuth oxide compound Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a preparation method and application of a bismuth oxide-based photocatalyst, belonging to the technical field of photocatalysts. Under the condition of stirring, dissolving metal salt of an active component into deionized water to obtain an active metal salt solution; dispersing bismuth oxide into an active metal salt solution to obtain a precursor mixed solution; ultrasonically dipping the precursor mixed solution for 10-50 min, and then placing the precursor mixed solution at the temperature of 40-65 ℃ for oscillation treatment for 1-6 h to obtain a mixture; placing the mixture at the temperature of 70-110 ℃ for heat treatment for 10-24 h to obtain a catalyst precursor; and uniformly heating the catalyst precursor to 300-800 ℃, and roasting for 2-5 h to obtain the bismuth oxide-based photocatalyst. The bismuth oxide-based photocatalyst has large specific surface area and wide light absorption range, can simultaneously respond to visible light and ultraviolet light, and has the photocatalytic removal efficiency of gaseous mercury higher than 98 percent.
Description
Technical Field
The invention relates to a preparation method and application of a bismuth oxide-based photocatalyst, belonging to the technical field of photocatalysts.
Background
Mercury is a heavy metal pollutant with extremely strong biological toxicity, and can enter human bodies through food chains due to the characteristics of high toxicity, high volatility, accumulation in biological chains and the like, and the mercury has fatal influence on the nervous system and growth and development of people, so the mercury becomes a global circulating pollution element. Coal-fired mercury pollution has become another big pollution problem following coal-fired sulfur pollution. Most of mercury generated in the coal burning process is discharged into the atmosphere along with flue gas, and coal burning is the most main source of artificial mercury emission. The mercury in coal combustion flue gas is usually elemental mercury (Hg)0) Mercury (Hg) in its oxidized state2+) And particulate mercury (Hg)p) Three forms exist. Different forms of mercury have widely different physical and chemical properties. Compared with bivalent mercury and granular mercury, the elemental mercury is difficult to control and remove due to the characteristics of water insolubility, stable chemical property, strong volatility and diffusion capacity and the like.
The photocatalytic technology is considered to be one of the most potential green technical means for solving the problems of energy, environment and the like due to the unique advantages of environmental friendliness, mild conditions, strong oxidation performance, direct utilization of sunlight and the like. Conventional TiO2Although it has the advantages of low cost, no toxicity, stability, high catalytic activity, etc., it is considered as the most important photocatalyst in the field of photocatalytic research. However, due to its wider band gap (E)gAbout 3.2 eV), higher photogenerated charge recombination rate, and the like, and can only display optical activity in an ultraviolet region, thereby greatly restricting the practical application of the material in the environmental pollution treatment. It is therefore highly desirable to find photocatalysts that respond to visible light in order to maximize the use of sunlight as a light source in the future.
Bismuth oxide catalysts are relatively deficient in photocatalytic removal of gaseous contaminants in the gas phase, particularly gaseous elemental mercury (Hg), due to the ease with which photogenerated carriers recombine, their small specific surface area, their relatively low photocatalytic activity, and their relative lack of photocatalytic removal of gaseous contaminants in the gas phase0) The photocatalytic oxidation is adopted, and a gas-solid phase reaction photocatalyst is not reported.
Disclosure of Invention
The inventionThe bismuth oxide has the characteristic of wider band gap energy range, so that the bismuth oxide has relatively wider absorption range on light, has responsiveness in a visible light region, and can not only strongly absorb visible light, but also effectively transfer photoproduction hole-electron, thereby obviously improving the photocatalytic activity of the composite catalyst and being used for removing gaseous mercury (Hg) by photocatalysis0）。
A preparation method of a bismuth oxide-based photocatalyst comprises the following specific steps:
(1) under the condition of stirring, dissolving metal salt of the active component into deionized water to obtain an active metal salt solution;
(2) dispersing bismuth oxide into the active metal salt solution obtained in the step (1) to obtain precursor mixed solution;
(3) ultrasonically dipping the precursor mixed solution for 10-50 min, and then placing the precursor mixed solution at the temperature of 40-65 ℃ for oscillation treatment for 1-6 h to obtain a mixture;
(4) placing the mixture obtained in the step (3) at the temperature of 70-110 ℃ for heat treatment for 10-24 h to obtain a catalyst precursor;
(5) and (4) uniformly heating the catalyst precursor in the step (4) to the temperature of 300-800 ℃, and roasting for 2-5 h to obtain the bismuth oxide-based photocatalyst.
The active component in the step (1) is La2O3、Fe2O3、CeO2、CuO、Ag2O、V2O5、ZnO、Co3O4、WO3、MoO3、NiO、Cr2O3、Gd2O3、SnO2、ZrO2、Nd2O5、Er2O3One or more of (a).
The load capacity of the active component in the bismuth oxide-based photocatalyst is 3-15% by mass percent.
And (5) the constant-speed heating rate is 1.5-5 ℃/min.
The composite catalyst of the metal-loaded bismuth oxide is prepared by adopting an impregnation method, the specific surface area of the composite is increased, the recombination rate of photon-generated carriers is reduced, and the light absorption range is extended, so that the photocatalytic activity is effectively improved, and the composite catalyst can simultaneously respond to ultraviolet light and visible light.
The bismuth oxide-based photocatalyst can be used for removing gaseous mercury through photocatalysis, and the bismuth oxide-based photocatalyst is used for removing element mercury (Hg) through the photocatalysis0) The reaction mechanism of (a) is as follows:
Bi2O3+hv→h++e-（1）
H2O ↔ H++ OH-（2）
O2+ 4H++ 4e-↔ 2H2O （3）
O2+e-→.O2 -（4）
OH- ad+h+→.OHad（5）
H2Oad+ h+→.OHad+ H+（6）
Hg0 ad+h+→Hg2+（7）
Hg0 ad+OHad+H+→.Hg++ H2O （8）
Hg+ ad+OHad+H+→.Hg2++ H2O （9）
Hg0 ad+2.OH→ HgO + H2Oad（10）
Hg0 ad+.O2 -→ HgO （11）
Hg0 ad+2h++2OH- ad→HgOad+ H2Oad（12）
the invention adopts a metal negativeThe material formed by supported bismuth oxide has excellent photocatalytic activity, and supported metal ions can replace part of Bi in bismuth oxide crystal lattice3+The Bi-O-M bond is formed, the recombination rate of photon-generated carriers can be effectively reduced due to the existence of the composite oxide, and the formed composite can form a similar heterojunction with bismuth oxide, so that the effective separation of photon-generated electrons and holes is realized;
the loaded metal ions are also effective acceptors of electrons, and by capturing the photoproduction electrons formed in the bismuth oxide, the recombination of the photoproduction electrons and holes can be effectively reduced, the migration efficiency of the photoproduction electrons is improved, and more free radicals with photocatalytic activity are formed.O2-And.OH, further effectively promoting the activity of the catalyst and improving the demercuration efficiency;
the invention can further extend the light absorption to an infrared light region by loading metal ions and increasing the roasting temperature to a certain extent, thereby improving the utilization rate of the catalyst to light.
The invention has the beneficial effects that:
(1) the preparation method of the catalyst is simple in process and low in cost, and the metal-loaded bismuth oxide compound prepared by adopting the impregnation-roasting method has good photocatalytic activity in an ultraviolet-visible light region;
(2) the metal-loaded bismuth oxide composite catalyst has more positive valence band position, so a photoproduction hole on a semiconductor valence band has stronger oxidability;
(3) the metal-loaded bismuth oxide composite catalyst can capture photo-generated electrons through doping of metal ions, can effectively improve the separation efficiency of photo-generated carriers, and further leaves more photo-generated holes at the position of a semiconductor valence band to oxidize elemental mercury (Hg)0) More photo-generated electrons are collected at the position and the surface of a conduction band of the compound, and further more photo-catalytic active free radicals can be promoted2-Generation of OH;
(4) in the process of preparing the catalyst, any toxic and harmful surfactant, organic matter, chelating agent and the like are not used, so that the preparation process is economic and green;
(5) the bismuth oxide catalyst loaded with metal ions has more excellent physicochemical properties after being roasted, so that the efficiency of photocatalytic oxidation demercuration is effectively promoted.
Drawings
FIG. 1 shows the bismuth oxide-based photocatalyst of pure bismuth oxide and different active components of example 1 for gaseous mercury (Hg)0) The photocatalytic removal efficiency of (a);
FIG. 2 shows the example 2 of the different calcination temperatures of a bismuth oxide-based photocatalyst versus gaseous mercury (Hg)0) The photocatalytic removal efficiency of (a);
FIG. 3 is a graph of FE-SEM characterization results of pure bismuth oxide and the bismuth oxide-based photocatalyst of example 2;
FIG. 4 shows the different loading of La for pure bismuth oxide and example 32O3/Bi2O3UV-vis DRS diagram corresponding to the composite catalyst.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of a bismuth oxide-based photocatalyst comprises the following specific steps:
(1) under the stirring condition, according to the amount of 3 percent of loading amount of the active component, the metal salt La (NO) of the active component is added3)3·6H2O、AgNO3Or Cu (NO)3)2·3H2Dissolving O in deionized water to obtain an active metal salt solution;
(2) dispersing bismuth oxide into the active metal salt solution obtained in the step (1) to obtain precursor mixed solution;
(3) ultrasonically dipping the precursor mixed solution for 20min, and then placing the precursor mixed solution at the temperature of 45 ℃ for oscillation treatment for 3.5h to obtain a mixture; wherein the oscillation frequency is 50 r/min;
(4) placing the mixture obtained in the step (3) at the temperature of 90 ℃ for heat treatment for 18h to obtain a catalyst precursor;
(5) uniformly heating the catalyst precursor in the step (4) to 500 ℃ and roasting for 2h to obtain the bismuth oxide-based photocatalyst; wherein the heating rate is 3 ℃/min;
and (3) detecting the catalytic performance: grinding and sieving bismuth oxide-based photocatalyst, and weighing 0.2g of bismuth oxide-based photocatalyst for removing mercury (Hg) in simulated flue gas by photocatalytic oxidation under ultraviolet-visible Light Emitting Diode (LED)0) The total flow rate of the gas in the simulated flue gas is 700ml/min and 4 percent of O2，Hg0The inlet concentration is 1000ug/m3；
Pure bismuth oxide and bismuth oxide-based photocatalyst with different active components can be used for treating gaseous mercury (Hg) under ultraviolet LED irradiation0) The photocatalytic removal efficiency is shown in fig. 1, and as can be seen from fig. 1, the photocatalytic demercuration efficiency of the bismuth oxide-based composite loaded with different active components is remarkably improved compared with that of pure bismuth oxide, which shows that the catalyst has better physicochemical properties through loading metals, so that the activity of the catalyst can be effectively improved.
Example 2: a preparation method of a bismuth oxide-based photocatalyst comprises the following specific steps:
(1) under the stirring condition, according to the loading amount of the active component of 6 percent by mass, adding metal salt La (NO) of the active component3)3·6H2Dissolving O in deionized water to obtain an active metal salt solution;
(2) dispersing bismuth oxide into the active metal salt solution obtained in the step (1) to obtain precursor mixed solution;
(3) ultrasonically dipping the precursor mixed solution for 30min, and then placing the precursor mixed solution at the temperature of 65 ℃ for oscillation treatment for 1.5h to obtain a mixture; wherein the oscillation frequency is 70 r/min;
(4) placing the mixture obtained in the step (3) at the temperature of 80 ℃ for heat treatment for 24h to obtain a catalyst precursor;
(5) uniformly heating the catalyst precursor in the step (4) to 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃ and roasting for 3 hours to obtain the bismuth oxide-based photocatalyst; wherein the heating rate is 4 ℃/min;
and (3) detecting the catalytic performance: grinding and sieving bismuth oxide-based photocatalyst, and weighing 0.2g of bismuth oxide-based photocatalyst for photocatalytic oxidation and removal under ultraviolet-visible Light Emitting Diode (LED)Removing elemental mercury (Hg) from simulated flue gas0) The total flow rate of the gas in the simulated flue gas is 700ml/min and 4 percent of O2，Hg0The inlet concentration is 1000ug/m3；
Corresponding 6% La at different roasting temperatures2O3/Bi2O3The sample was used to remove elemental mercury (Hg)0) It was found that the corresponding efficiency of the samples calcined at 500 ℃ was relatively high, with bismuth oxide based photocatalysts at different calcination temperatures for gaseous mercury (Hg)0) The photocatalytic mercury removal efficiency is shown in fig. 2, and as can be seen from fig. 2, the photocatalytic mercury removal efficiency of the prepared composite is improved along with the increase of the roasting temperature within the roasting temperature range of 300-500 ℃, and an optimal roasting temperature value exists; the calcination temperature affects the crystallinity, grain size and specific surface area of the photocatalyst, thereby further affecting its activity; the roasting temperature can influence the appearance of the catalyst, and a sample roasted at the temperature of 500-800 ℃ can be agglomerated and sintered along with the temperature rise, so that the corresponding activity can be reduced;
pure bismuth oxide (a) and 6% of La2O3/Bi2O3（500℃）（b）、6%La2O3/Bi2O3(700 ℃ C.) (c) the corresponding FE-SEM characterization results are shown in FIG. 3, where a is pure bismuth oxide and b is 6% La2O3/Bi2O3(500 ℃ C.), c 6% La2O3/Bi2O3(700 ℃), as can be seen from fig. 3, the pure bismuth oxide has a significant difference from the morphology of the sample after calcination, and the morphology of the catalyst also changes with the increase of the calcination temperature, and the morphology of the catalyst gradually changes from a sphere-like shape to a sheet shape. As the firing temperature increases, the dispersibility of the material is better, exposing more active sites. But the higher roasting temperature causes serious agglomeration and recrystallization of the material; when the roasting temperature is 700 ℃, the catalyst is sintered, and agglomeration and recrystallization occur, so that the catalytic activity at the temperature is reduced; the catalyst calcined at 500 deg.c has excellent shape, high dispersivity and more exposed active area, so that the calcining temperature is highThe corresponding catalytic activity is also relatively high.
Example 3: a preparation method of a bismuth oxide-based photocatalyst comprises the following specific steps:
(1) under the stirring condition, according to the mass percentage, the metal salt La (NO) of the active component is added according to the loading amount of the active component being 3-15%3)3·6H2Dissolving O in deionized water to obtain an active metal salt solution;
(2) dispersing bismuth oxide into the active metal salt solution obtained in the step (1) to obtain precursor mixed solution;
(3) ultrasonically dipping the precursor mixed solution for 25min, and then placing the precursor mixed solution at the temperature of 55 ℃ for oscillation treatment for 2.5h to obtain a mixture; wherein the oscillation frequency is 60 r/min;
(4) placing the mixture obtained in the step (3) at the temperature of 80 ℃ for heat treatment for 24h to obtain a catalyst precursor;
(5) uniformly heating the catalyst precursor in the step (4) to 500 ℃ and roasting for 2h to obtain the bismuth oxide-based photocatalyst; wherein the heating rate is 4 ℃/min, and the bismuth oxide-based photocatalyst is respectively 3 percent of La2O3/Bi2O3、6%La2O3/Bi2O3、9%La2O3/Bi2O3、12%La2O3/Bi2O3、15%La2O3/Bi2O3；
And (3) detecting the catalytic performance: grinding and sieving bismuth oxide-based photocatalyst, and weighing 0.2g of bismuth oxide-based photocatalyst for removing mercury (Hg) in simulated flue gas by photocatalytic oxidation under ultraviolet-visible Light Emitting Diode (LED)0) The total flow rate of the gas in the simulated flue gas is 700ml/min and 4 percent of O2，Hg0The inlet concentration is 1000ug/m3；
Pure bismuth oxide and La with different loading amounts2O3/Bi2O3The graph of the UV-vis DRS corresponding to the composite catalyst is shown in FIG. 4, and as can be seen from FIG. 4, compared with pure bismuth oxide, the absorption of the supported lanthanum oxide in the ultraviolet-visible region is remarkably improved, and the absorption range of light can be further extended to the infrared regionThe maximum absorption edge is extended, so that the photocatalyst has good photocatalytic activity under the irradiation of a visible light LED.
Claims (5)
1. A preparation method of a bismuth oxide-based photocatalyst is characterized by comprising the following specific steps:
(1) under the condition of stirring, dissolving metal salt of the active component into deionized water to obtain an active metal salt solution;
(2) dispersing bismuth oxide into the active metal salt solution obtained in the step (1) to obtain precursor mixed solution;
(3) ultrasonically dipping the precursor mixed solution for 10-50 min, and then placing the precursor mixed solution at the temperature of 40-65 ℃ for oscillation treatment for 1-6 h to obtain a mixture;
(4) placing the mixture obtained in the step (3) at the temperature of 70-110 ℃ for heat treatment for 10-24 h to obtain a catalyst precursor;
(5) and (4) uniformly heating the catalyst precursor in the step (4) to the temperature of 300-800 ℃, and roasting for 2-5 h to obtain the bismuth oxide-based photocatalyst.
2. The method for preparing a bismuth oxide-based photocatalyst according to claim 1, characterized in that: the active component in the step (1) is La2O3、Fe2O3、CeO2、CuO、Ag2O、V2O5、ZnO、Co3O4、WO3、MoO3、NiO、Cr2O3、Gd2O3、SnO2、ZrO2、Nd2O5、Er2O3One or more of (a).
3. The method for preparing a bismuth oxide-based photocatalyst according to claim 1, characterized in that: the load capacity of the active component in the bismuth oxide-based photocatalyst is 3-15% by mass percent.
4. The method for preparing a bismuth oxide-based photocatalyst according to claim 1, characterized in that: and (5) the constant temperature rise rate is 1.5-5 ℃/min.
5. The use of the bismuth oxide-based photocatalyst prepared by the method of any one of claims 1 to 4 for the photocatalytic removal of gaseous mercury.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911049111.0A CN110813276A (en) | 2019-10-31 | 2019-10-31 | Preparation method and application of bismuth oxide-based photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911049111.0A CN110813276A (en) | 2019-10-31 | 2019-10-31 | Preparation method and application of bismuth oxide-based photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110813276A true CN110813276A (en) | 2020-02-21 |
Family
ID=69551469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911049111.0A Pending CN110813276A (en) | 2019-10-31 | 2019-10-31 | Preparation method and application of bismuth oxide-based photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110813276A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111701604A (en) * | 2020-06-10 | 2020-09-25 | 河南理工大学 | Preparation method of silver iodide-silver oxide-bismuth oxyhalide-cobalt ferrite magnetic visible-light-driven photocatalyst |
| CN112221496A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Catalyst for multi-metal oxide-based diesel oxidation catalyst and preparation method thereof |
| CN114433107A (en) * | 2022-01-11 | 2022-05-06 | 西安建筑科技大学 | Co3O4/Bi4O7/Bi2O3Heterojunction photocatalyst and application thereof |
| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658116A (en) * | 2012-04-14 | 2012-09-12 | 吉林大学 | Rare earth element-doped bismuth oxide photocatalyst and preparation method thereof |
| CN103816912A (en) * | 2014-03-05 | 2014-05-28 | 阜阳师范学院 | Preparing method for Bi2O3/Co3O4 compound photocatalyst and application thereof |
| CN107715860A (en) * | 2017-08-21 | 2018-02-23 | 中南大学 | A kind of preparation and its application of bismuth oxide photochemical catalyst |
-
2019
- 2019-10-31 CN CN201911049111.0A patent/CN110813276A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658116A (en) * | 2012-04-14 | 2012-09-12 | 吉林大学 | Rare earth element-doped bismuth oxide photocatalyst and preparation method thereof |
| CN103816912A (en) * | 2014-03-05 | 2014-05-28 | 阜阳师范学院 | Preparing method for Bi2O3/Co3O4 compound photocatalyst and application thereof |
| CN107715860A (en) * | 2017-08-21 | 2018-02-23 | 中南大学 | A kind of preparation and its application of bismuth oxide photochemical catalyst |
Non-Patent Citations (4)
| Title |
|---|
| XUE MEI QI等: "Fabrication of BiOIO3 nanosheets with remarkable photocatalytic oxidation removal for gaseous elemental mercury", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 曾俊等: "Cu2+掺杂的Bi2O3的制备及光催化性能的研究", 《化学研究与应用》 * |
| 朱琳等: "Ag2O/Bi2O3复合光催化剂的制备及其可见光催化性质研究", 《第十三届全国太阳能光化学与光催化学术会议学术论文集》 * |
| 杨迎春等: "La掺杂 Bi2O3的制备、表征与可见光催化活性", 《化学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111701604A (en) * | 2020-06-10 | 2020-09-25 | 河南理工大学 | Preparation method of silver iodide-silver oxide-bismuth oxyhalide-cobalt ferrite magnetic visible-light-driven photocatalyst |
| CN112221496A (en) * | 2020-10-13 | 2021-01-15 | 天津大学 | Catalyst for multi-metal oxide-based diesel oxidation catalyst and preparation method thereof |
| CN114433107A (en) * | 2022-01-11 | 2022-05-06 | 西安建筑科技大学 | Co3O4/Bi4O7/Bi2O3Heterojunction photocatalyst and application thereof |
| CN114433107B (en) * | 2022-01-11 | 2024-04-12 | 西安建筑科技大学 | Co (cobalt) 3 O 4 /Bi 4 O 7 /Bi 2 O 3 Heterojunction photocatalyst and application thereof |
| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
| CN114551828B (en) * | 2022-01-28 | 2023-06-02 | 同济大学 | Bi-MOF-derived bismuth oxide-based negative electrode material and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110813276A (en) | Preparation method and application of bismuth oxide-based photocatalyst | |
| CN108970613B (en) | Iron oxyhydroxide modified titanium dioxide composite photocatalyst and preparation method and application thereof | |
| CN109107567B (en) | M-MnOX-CeO2Catalyst and application thereof | |
| CN105642299A (en) | Nickel-doped lanthanum ferrite/clay nano-structure composite and preparation method and application thereof | |
| CN107376964B (en) | Preparation and application of composite photocatalyst with doped perovskite as carrier | |
| CN102350340A (en) | Composite smoke denitration catalyst capable of oxidizing zero-valence mercury | |
| CN110354840B (en) | Preparation of beta-Bi2O3/BiVO4Method for preparing composite photocatalytic material | |
| CN108816239B (en) | Supported catalyst, preparation method and application thereof | |
| CN111495352B (en) | Method for efficiently photo-catalytically oxidizing metal doped modified strontium titanate of elemental mercury | |
| CN107126959B (en) | A kind of attapulgite load CoTiO3-CeO2Hetero-junctions SCR low-temperature denitration catalyst and preparation method thereof | |
| CN113000046A (en) | Modified manganese-based mullite catalyst for synergistic purification of nitrogen oxides and volatile organic compounds, and preparation method and application thereof | |
| CN111097442A (en) | Flue gas synergistic denitration and demercuration catalyst and preparation method thereof | |
| CN110124710B (en) | Composite metal oxide catalyst and preparation method thereof | |
| CN102008964A (en) | Lanthanum vanadate-based visible light responsive photocatalyst and preparation method thereof | |
| CN1269568C (en) | Composite nano-photo-catalyst used for purifying air | |
| CN112958153B (en) | Heteropoly acid-containing denitration catalyst and preparation method and application thereof | |
| CN113877611A (en) | Phosphoric acid modified manganese oxide supported catalyst and preparation method thereof | |
| CN106732547B (en) | Demercuration catalyst for low-temperature oxidation of zero-valent mercury in coal-fired flue gas and preparation method thereof | |
| CN108067247B (en) | Preparation method of iron oxide pillared layered manganese oxide low-temperature denitration catalyst | |
| CN113522316B (en) | Gas phase cerium-titanium sulfide supported tin oxide catalyst and preparation method and application thereof | |
| CN113731445B (en) | Photocatalyst taking barium stannate as carrier to load cadmium sulfide quantum dots, and preparation method and application thereof | |
| CN114870879A (en) | Bimetal perovskite load graphene-like carbon nitride visible-light-induced photocatalyst and preparation method thereof | |
| CN102416318B (en) | Visible-light response calcium-bismuth composite oxide catalyst and preparation method thereof | |
| CN114471532A (en) | Preparation method and application of flower-like samarium-manganese composite oxide denitration catalyst | |
| CN115350704B (en) | Ag (silver) alloy 2 O cluster modified perovskite-like hydroxide visible light catalyst, preparation method and application |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200221 |
|
| RJ01 | Rejection of invention patent application after publication |