CN112251234A - Photocatalyst for degrading heavy metal ions in soil and preparation method thereof - Google Patents
Photocatalyst for degrading heavy metal ions in soil and preparation method thereof Download PDFInfo
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- CN112251234A CN112251234A CN202011132352.4A CN202011132352A CN112251234A CN 112251234 A CN112251234 A CN 112251234A CN 202011132352 A CN202011132352 A CN 202011132352A CN 112251234 A CN112251234 A CN 112251234A
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- heavy metal
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- 239000002689 soil Substances 0.000 title claims abstract description 65
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 150000002500 ions Chemical class 0.000 title claims abstract description 45
- 230000000593 degrading effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000001354 calcination Methods 0.000 claims description 34
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 30
- 239000004202 carbamide Substances 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 239000004201 L-cysteine Substances 0.000 claims description 15
- 235000013878 L-cysteine Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 150000001621 bismuth Chemical class 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000005067 remediation Methods 0.000 abstract description 16
- PJILMBYYVIXWTK-UHFFFAOYSA-N [Bi]=O.[Fe] Chemical compound [Bi]=O.[Fe] PJILMBYYVIXWTK-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 238000005303 weighing Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 7
- 239000012498 ultrapure water Substances 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ODHCTXKNWHHXJC-UHFFFAOYSA-N acide pyroglutamique Natural products OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005520 electrodynamics Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a photocatalyst for degrading heavy metal ions in soil and a preparation method thereof3N4Powder, modified molecular sieve with regular pore channel structure, Fe-Bi oxide, g-C3N4Loading the powder onto modified molecular sieve, passing through molecular sieve and g-C3N4The strong adsorption effect of the powder on heavy metal ions is matched with the high catalytic activity of the iron bismuth oxide, so that the reduction degradation rate of the catalyst on the heavy metal ions is greatly improved, the in-situ remediation on the soil surface can be realized, the heavy metal content in the soil is effectively reduced, and the photocatalyst provided by the invention can conveniently and conveniently adsorb the heavy metal ionsThe method is recovered from the repaired soil, does not produce secondary pollution, and has wide application prospect in the field of repairing the heavy metal polluted soil.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a photocatalyst for degrading heavy metal ions in soil and a preparation method thereof.
Background
According to survey data of national soil pollution conditions, the total overproof rate of the national polluted soil is 16.1%, wherein the proportion of slightly, moderately and severely polluted points is 11.2%, 2.3%, 1.5% and 1.1%, respectively. At present, the domestic pollution type is mainly inorganic type, secondly organic type and has smaller composite pollution proportion, wherein the number of the inorganic pollutant exceeding standard points accounts for 82.8 percent of all exceeding standard points. The national land survey results show that nearly 40% of farmland vegetable field soil heavy metal pollution in partial cities in Zhu triangular region exceeds the standard, and 10% of farmland vegetable field soil heavy metal pollution seriously exceeds the standard. The yield of the grains is reduced by over 1000 million tons each year in China due to heavy metal pollution, the yield of the grains polluted by the heavy metal reaches 1200 million tons, and the total economic loss is at least 200 hundred million yuan.
Soil remediation is a technical measure to restore normal function to contaminated soil. At present, the remediation method aiming at the heavy metal pollution of soil mainly comprises an immobilization method, a leaching method, a soil washing method, an electrodynamics remediation method, a chemical reduction method, a plant remediation method and a microorganism remediation method, and the problems of low remediation efficiency, high treatment cost and the like exist in the whole method. The traditional restoration methods such as landfill, leaching, electrochemistry and the like have large engineering quantity and high cost, and often cause the damage of soil structures and the loss of certain nutrient elements. The soil photocatalytic degradation is a novel soil in-situ remediation technology, and has a wide prospect in remediation of heavy metal contaminated soil. However, few studies on photocatalytic degradation of soil heavy metals are available, and the remediation effect of soil heavy metal pollution is difficult to further improve. Therefore, the development of a simple and efficient heavy metal photocatalyst has very important significance for soil remediation.
Disclosure of Invention
The invention aims to solve the technical problem of providing a photocatalyst for degrading heavy metal ions in soil and a preparation method thereof, and aims to solve the problem that the catalytic performance of the existing photocatalyst for degrading the heavy metal ions in the soil needs to be further improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a photocatalyst for degrading heavy metal ions in soil comprises the following steps:
step one, calcining urea and thiourea at the temperature of 540-3N4Powder;
step two, adding the molecular sieve, ethyl orthosilicate and citric acid into an ethanol solution, uniformly mixing, stirring for reaction, washing, drying, and calcining at 800 ℃ at 700-;
step three, adding soluble ferric salt, soluble bismuth salt, L-cysteine and urea into deionized water, and uniformly mixing to obtain a precursor solution; subjecting said g-C to3N4Adding the powder and the modified molecular sieve into the precursor solution, uniformly mixing, transferring to a high-pressure reaction kettle, and reacting at 160-180 ℃ for 10-15h to obtain a precursor;
and step four, calcining the precursor at the temperature of 550-650 ℃ to obtain the photocatalyst.
Compared with the prior art, the preparation method of the photocatalyst provided by the invention has the advantages that the urea and the thiourea are calcined at a specific temperature, and the g-C is controlled by different decomposition rates of the urea and the thiourea3N4So that g-C is produced3N4Powder bodyThe porous material has a more loose multilayer structure, so that doping of active components is facilitated; meanwhile, the pore channel structure of the molecular sieve is reconstructed by adopting tetraethoxysilane and citric acid, so that the modified molecular sieve has a more regular pore channel structure, the activity and the adsorption performance of the molecular sieve are improved, and the modified molecular sieve is a subsequent active component and g-C3N4The deposition provides a suitable reaction environment for the active components and g-C3N4More uniformly deposited on the pore structure and the surface of the molecular sieve; in addition, the growth of the iron bismuth oxide is regulated and controlled by L-cysteine to prepare the nanoscale iron bismuth oxide with uniform size, so that the specific surface area of the active component is improved, and meanwhile, due to the doping of bismuth ions, the crystal lattice of the iron oxide is distorted to generate defects and inhibit the recombination of photoproduction electrons and holes; and the doping of bismuth ions increases active sites of reaction, improves the absorption of visible light by the material, improves the conductivity of the material, accelerates the propagation rate of photo-generated electrons, and improves the photocatalytic efficiency of active components
The iron-bismuth oxide and g-C in the photocatalyst provided by the invention3N4Is uniformly and firmly adsorbed by the molecular sieve, avoids the agglomeration and loss of active components, and contains g-C in the photocatalyst3N4The modified molecular sieve can generate strong adsorption effect on heavy metal ions in soil, so that adsorption sites can keep high concentration of the heavy metal ions, a high-concentration reaction environment is provided for photocatalysis, the heavy metal ions at the adsorption sites are degraded under the action of sunlight by the photocatalyst loaded by the molecular sieve, and meanwhile, the molecular sieve has a regular pore structure and g-C3N4The loose multilayer structure is also beneficial to the migration of heavy metal ions, and the g-C is improved3N4The modified molecular sieve can adsorb heavy metal ions in soil, so that continuous and efficient photoreduction degradation of iron bismuth oxide to the heavy metal ions is maintained, the reducibility degradation rate of the heavy metal ions is greatly improved, in-situ remediation on the soil surface can be realized, the heavy metal content in the soil is effectively reduced, the material can be conveniently recovered from the remediated soil, no secondary pollution is generated, and the heavy metal pollution is avoidedThe method has wide application prospect in the field of soil remediation.
Preferably, in the step one, the temperature is raised to 540 ℃ and 580 ℃ at the speed of 4-6 ℃/min, and the calcination time is 3-5 h.
Preferably, in the step one, the ball milling speed is 700-900r/min, the ball milling time is 2-4h, and the ball-to-material ratio is 30-40: 1.
The method can prepare pure-phase irregular loose lamellar g-C3N4Powder, g-C favorable for iron-bismuth oxide to enter powder3N4A lamellar structure, avoiding the subsequent photocatalytic reaction process g-C3N4Agglomeration and is beneficial to ensure that photogenerated electrons flow between the iron bismuth oxide and g-C3N4The light-catalyzed degradation efficiency is further improved.
Preferably, in the first step, the mass ratio of the urea to the thiourea is 3-4: 1.
g-C prepared by the invention3N4The surface of the powder contains sulfur, oxygen and other atoms, and can adsorb heavy metal ions through surface complexation such as chemical adsorption and the like, so that a good adsorption site is provided for the heavy metal ions, and the iron bismuth oxide can be used for sufficiently degrading the heavy metal ions.
Preferably, in the second step, the mass ratio of the molecular sieve, the tetraethoxysilane, the citric acid and the ethanol solution is 1:0.5-0.8:0.4-0.6: 5-10; the mass concentration of the ethanol solution is 40-60 wt%.
Preferably, in the second step, the stirring reaction temperature is 50-60 ℃, and the reaction time is 2-3 h.
The preferred reaction temperature can fully reproduce the pore channel structure of the molecular sieve to obtain the pore channel structure with a regular structure, and the inner surface of the pore channel of the molecular sieve can be enriched with electron-rich atoms such as C, O, so that electron-hole recombination is effectively inhibited, heavy metal ions adsorbed and enriched by the molecular sieve are captured by active components, and the photocatalytic degradation activity of the iron-bismuth oxide is improved.
Preferably, in the second step, the temperature is raised to 700-800 ℃ at the temperature raising rate of 6-8 ℃/min, and the calcination time is 5-8 h.
The optimized calcination mode can fully activate the modified molecular sieve, improve the activity of the molecular sieve, and is more favorable for depositing active components in the pore structure of the molecular sieve and on the surface of the framework of the molecular sieve, so that the specific surface area of the active components is improved, the adsorption performance of the molecular sieve on moisture and heavy metal ions is improved, and the directional diffusion mobility of the heavy metal ions in soil is promoted.
Preferably, in the third step, the soluble ferric salt is one or more of ferric sulfate, ferric nitrate or ferric chloride.
Preferably, in the third step, the soluble bismuth salt is one or two of bismuth nitrate and bismuth chloride.
Preferably, in the third step, the mol ratio of the soluble ferric salt to the soluble bismuth salt to the L-cysteine to the urea is 2.5-3.5:1:0.3-0.5: 4-6.
Preferably, in the third step, the concentration of the soluble bismuth salt in the precursor solution is 0.2-0.3 mol/L.
Preferably, in the third step, the soluble ferric salt, the modified molecular sieve and the g-C in the precursor solution3N4The mass ratio of the powder is 1:80-120: 0.4-0.6.
The optimized material proportion is matched with the high-pressure reaction condition of an autoclave, which is favorable for leading the iron-bismuth oxide and the g-C3N4Fully enters the pore channel structure of the molecular sieve to prepare the high-efficiency photocatalyst with active components uniformly deposited in and on the pore channel structure of the molecular sieve.
Preferably, in the fourth step, the temperature is raised to 550 ℃ and 650 ℃ at the temperature raising rate of 4-6 ℃/min, and the calcination time is 5-8 h.
Preferably, the modified molecular sieve is a large-pore molecular sieve with the inner pore size larger than 150nm and the diameter of the molecular sieve is 2-3mm, the molecular sieve is a silicon-aluminum molecular sieve, and n isSiO2：nAl2O3＝50-100：1。
The invention also provides a photocatalyst for degrading heavy metal ions in soil, and the photocatalyst is prepared by the preparation method.
The photocatalyst for degrading heavy metal ions in soil provided by the invention can be used for in-situ remediation on the surface of soil, has high photocatalytic reaction speed, can be carried out under the irradiation of normal-temperature visible light, greatly improves the utilization rate of solar energy, is easy to separate from the soil, has no secondary pollution, is widely suitable for the treatment of the heavy metal ions in the soil, is particularly suitable for the remediation of the soil polluted by the heavy metal ions such as copper, cadmium, zinc, lead, arsenic and the like, has a simple preparation method, and has high popularization and application values.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
A preparation method of a photocatalyst for degrading heavy metal ions in soil comprises the following steps:
step one, weighing urea and thiourea according to a mass ratio of 4:1, heating to 580 ℃ at a speed of 6 ℃/min, calcining for 3h, cooling to room temperature, carrying out ball milling at a ball milling speed of 700r/min for 4h at a ball-to-material ratio of 30:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 20min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, tetraethoxysilane, citric acid and 60 wt% ethanol water solution according to the mass ratio of 1:0.8:0.5:10, uniformly mixing, stirring and reacting at 60 ℃ for 2 hours, washing, drying, heating to 700 ℃ at the heating rate of 6 ℃/min, and calcining for 8 hours to obtain the modified molecular sieve;
step three, weighing ferric nitrate nonahydrate, bismuth chloride, L-cysteine and urea according to the molar ratio of 2.5:1:0.4:5, adding the weighed materials into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth chloride is 0.2 mol/L; weighing the g-C3N4Powder, modified molecular sieve and precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:120:0.5, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 15 hours at 160 ℃ to obtain a precursor;
and step four, calcining the precursor at 650 ℃ for 5 hours at the heating rate of 5 ℃/min to obtain the photocatalyst.
Example 2
A preparation method of a photocatalyst for degrading heavy metal ions in soil comprises the following steps:
step one, weighing urea and thiourea according to a mass ratio of 3:1, heating to 540 ℃ at a speed of 5 ℃/min, calcining for 5h, cooling to room temperature, carrying out ball milling at a ball milling speed of 900r/min for 2h at a ball-to-material ratio of 40:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 30min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, ethyl orthosilicate, citric acid and 50 wt% ethanol water solution according to the mass ratio of 1:0.6:0.6:8, uniformly mixing, stirring and reacting at 50 ℃ for 3h, washing, drying, heating to 800 ℃ at the heating rate of 8 ℃/min, and calcining for 5h to obtain the modified molecular sieve;
step three, weighing anhydrous ferric chloride, bismuth chloride, L-cysteine and urea according to the molar ratio of 3.0:1:0.5:6, adding the anhydrous ferric chloride, the bismuth chloride, the L-cysteine and the urea into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth chloride in the precursor solution is 0.25 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:100:0.4, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 10 hours at 180 ℃ to obtain a precursor;
and step four, calcining the precursor at 600 ℃ for 6h, wherein the heating rate is 6 ℃/min, and obtaining the photocatalyst.
Example 3
A preparation method of a photocatalyst for degrading heavy metal ions in soil comprises the following steps:
step one, weighing urea and thiourea according to the mass ratio of 3.5:1, heating to 560 ℃ at the speed of 4 ℃/minCalcining for 4h, cooling to room temperature, ball milling at a ball milling rate of 800r/min for 3h at a ball-to-material ratio of 50:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 20min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, ethyl orthosilicate, citric acid and 40 wt% ethanol water solution according to the mass ratio of 1:0.5:0.4:5, uniformly mixing, stirring and reacting at 55 ℃ for 2.5h, washing, drying, and then heating to 750 ℃ at the heating rate of 7 ℃/min and calcining for 7h to obtain the modified molecular sieve;
step three, weighing anhydrous ferric chloride, bismuth nitrate pentahydrate, L-cysteine and urea according to the molar ratio of 3.5:1:0.3:4, adding the anhydrous ferric chloride, the bismuth nitrate pentahydrate, the L-cysteine and the urea into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth nitrate in the precursor solution is 0.3 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:80:0.6, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 12 hours at 170 ℃ to obtain a precursor;
and step four, calcining the precursor at 550 ℃ for 8 hours at the heating rate of 4 ℃/min to obtain the photocatalyst.
Example 4
A preparation method of a photocatalyst for degrading heavy metal ions in soil comprises the following steps:
step one, weighing urea and thiourea according to the mass ratio of 3.8:1, heating to 570 ℃ at the speed of 5.5 ℃/min, calcining for 3.5h, cooling to room temperature, and carrying out ball milling at the ball milling speed of 850r/min for 3.5h at the ball-to-material ratio of 45:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 40min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, tetraethoxysilane, citric acid and 55 wt% ethanol aqueous solution according to the mass ratio of 1:0.7:0.5:8, uniformly mixing, stirring and reacting at 58 ℃ for 2h, washing, drying, heating to 780 ℃ at the heating rate of 8 ℃/min, and calcining for 6h to obtain the modified molecular sieve;
step three, weighing anhydrous ferric chloride, bismuth nitrate pentahydrate, L-cysteine and urea according to the molar ratio of 3.3:1:0.4:5, adding the weighed anhydrous ferric chloride, bismuth nitrate pentahydrate, L-cysteine and urea into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth nitrate in the precursor solution is 0.25 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:90:0.4, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 11 hours at 175 ℃ to obtain a precursor;
and step four, calcining the precursor at 580 ℃ for 7 hours at the heating rate of 5 ℃/min to obtain the photocatalyst.
Comparative example 1
This comparative example provides a photocatalyst for degrading heavy metal ions in soil, the preparation method is exactly the same as example 1, except that in step one, only urea calcination is used to prepare g-C3N4The powder is prepared by the following specific steps:
weighing urea, heating to 580 ℃ at the speed of 6 ℃/min, calcining for 3h, cooling to room temperature, ball-milling at the ball-milling speed of 700r/min for 4h at the ball-material ratio of 30:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 20min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, tetraethoxysilane, citric acid and 60 wt% ethanol water solution according to the mass ratio of 1:0.8:0.5:10, uniformly mixing, stirring and reacting at 60 ℃ for 2 hours, washing, drying, heating to 700 ℃ at the heating rate of 6 ℃/min, and calcining for 8 hours to obtain the modified molecular sieve;
step three, weighing ferric nitrate nonahydrate, bismuth chloride, L-cysteine and urea according to the molar ratio of 2.5:1:0.4:5, adding the weighed materials into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth chloride is 0.2 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:120:0.5, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 15 hours at 160 ℃ to obtain a precursor;
and step four, calcining the precursor at 650 ℃ for 5 hours at the heating rate of 5 ℃/min to obtain the photocatalyst.
Comparative example 2
The comparative example provides a photocatalyst for degrading heavy metal ions in soil, the preparation method of the photocatalyst is completely the same as that of example 1, except that in the second step, tetraethoxysilane is not added in the molecular sieve modification process, and the preparation steps are as follows:
step one, weighing urea and thiourea according to a mass ratio of 4:1, heating to 580 ℃ at a speed of 6 ℃/min, calcining for 3h, cooling to room temperature, carrying out ball milling at a ball milling speed of 700r/min for 4h at a ball-to-material ratio of 30:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 20min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, citric acid and 60 wt% ethanol water solution according to the mass ratio of 1:0.5:10, uniformly mixing, stirring and reacting at 60 ℃ for 2h, washing, drying, and then heating to 700 ℃ at the heating rate of 6 ℃/min and calcining for 8h to obtain the modified molecular sieve;
step three, weighing ferric nitrate nonahydrate, bismuth chloride, L-cysteine and urea according to the molar ratio of 2.5:1:0.4:5, adding the weighed materials into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth chloride is 0.2 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:120:0.5, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 15 hours at 160 ℃ to obtain a precursor;
and step four, calcining the precursor at 650 ℃ for 5 hours at the heating rate of 5 ℃/min to obtain the photocatalyst.
Comparative example 3
The comparative example provides a photocatalyst for degrading heavy metal ions in soil, the preparation method is completely the same as that of example 1, except that in the third step, L-cysteine is replaced by L-pyroglutamic acid with the same amount, and the specific preparation steps are as follows:
step one, weighing urea and thiourea according to a mass ratio of 4:1, heating to 580 ℃ at a speed of 6 ℃/min, calcining for 3h, cooling to room temperature, carrying out ball milling at a ball milling speed of 700r/min for 4h at a ball-to-material ratio of 30:1 to obtain g-C3N4Powder;
step two, ultrasonically cleaning a molecular sieve with the diameter of 2-3mm in ultrapure water for 20min, and drying the molecular sieve until the molecular sieve is anhydrous for later use; weighing the molecular sieve, tetraethoxysilane, citric acid and 60 wt% ethanol water solution according to the mass ratio of 1:0.8:0.5:10, uniformly mixing, stirring and reacting at 60 ℃ for 2 hours, washing, drying, heating to 700 ℃ at the heating rate of 6 ℃/min, and calcining for 8 hours to obtain the modified molecular sieve;
step three, weighing ferric nitrate nonahydrate, bismuth chloride, L-pyroglutamic acid and urea according to the molar ratio of 2.5:1:0.4:5, adding the weighed materials into deionized water, and uniformly mixing to obtain a precursor solution, wherein the concentration of the bismuth chloride is 0.2 mol/L; weighing the g-C3N4Powder, a modified molecular sieve and a precursor solution, wherein the precursor solution contains ferric nitrate, the modified molecular sieve and g-C3N4The mass ratio of the powder is 1:120:0.5, the powder is uniformly mixed, transferred into a high-pressure reaction kettle and reacted for 15 hours at 160 ℃ to obtain a precursor;
and step four, calcining the precursor at 650 ℃ for 5 hours at the heating rate of 5 ℃/min to obtain the photocatalyst.
The molecular sieves used in examples 1 to 4 and comparative examples 1 to 3 described above each had a mean diameter of 2 to 3mm, nSiO2：nAl2O350-100: 1, and the modified molecular sieve prepared in the second step is a large-pore molecular sieve with the inner pore size larger than 150 nm.
Application examples
Selecting a land polluted by heavy metals in a place in Hebei province, taking 0-20cm soil on the surface layer of the land, naturally drying the soil, sieving the soil with a 30-mesh sieve, then weighing 4 parts of 500g of polluted soil as a sample, respectively weighing 10g of the photocatalytic materials prepared in the example 1 and the comparative examples 1-3, respectively and fully mixing the photocatalytic materials with 4 parts of the soil sample, carrying out a photodegradation experiment (with the average light intensity of 2350Lux) under simulated illumination, culturing for 10 days, wherein the illumination time is 8h every day, and keeping the water content of the soil to be 40% during the culture period. The soil samples which are not cultivated and are cultivated are subjected to a toxicity leaching test, the test method is shown in solid waste-leaching toxicity leaching method-horizontal oscillation method, the heavy metal content in the leaching solution is measured, and the results are shown in table 1.
TABLE 1
The photocatalysts prepared in the examples 2 to 4 can achieve the effect of photocatalytic degradation of heavy metal ions basically equivalent to that of the photocatalyst prepared in the example 1.
In conclusion, the photocatalyst for degrading heavy metal ions in soil provided by the invention can effectively reduce the content of heavy metal ions in soil, particularly divalent heavy metal (Pb)2+、Cr2+、Zn2+、Hg2+) The removal effect is obviously improved, the method can be used for repairing and treating heavy metal single pollution or compound pollution of various soils, and the preparation method is easy for large-scale production and has better application prospect in the field of soil remediation.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a photocatalyst for degrading heavy metal ions in soil is characterized by comprising the following steps:
step one, calcining urea and thiourea at the temperature of 540-3N4Powder;
step two, adding the molecular sieve, ethyl orthosilicate and citric acid into an ethanol solution, uniformly mixing, stirring for reaction, washing, drying, and calcining at 800 ℃ at 700-;
step three, adding soluble ferric salt, soluble bismuth salt, L-cysteine and urea into deionized water, and uniformly mixing to obtain a precursor solution; subjecting said g-C to3N4Adding the powder and the modified molecular sieve into the precursor solution, uniformly mixing, transferring to a high-pressure reaction kettle, and reacting at 160-180 ℃ for 10-15h to obtain a precursor;
and step four, calcining the precursor at the temperature of 550-650 ℃ to obtain the photocatalyst.
2. The method as claimed in claim 1, wherein in the step one, the temperature is increased to 580 ℃ at a rate of 4-6 ℃/min, and the calcination time is 3-5 h; and/or
In the first step, the ball milling speed is 700-.
3. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil according to claim 1, wherein in the first step, the mass ratio of the urea to the thiourea is 3-4: 1.
4. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil according to claim 1, wherein in the second step, the mass ratio of the molecular sieve, the tetraethoxysilane, the citric acid and the ethanol solution is 1:0.5-0.8:0.4-0.6: 5-10; the mass concentration of the ethanol solution is 40-60 wt%.
5. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil according to claim 1, wherein in the second step, the stirring reaction temperature is 50-60 ℃, and the reaction time is 2-3 h; and/or
In the second step, the temperature is raised to 700-800 ℃ at the temperature raising rate of 6-8 ℃/min, and the calcination time is 5-8 h.
6. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil according to claim 1, wherein in the third step, the soluble ferric salt is one or more of ferric sulfate, ferric nitrate or ferric chloride; and/or
In the third step, the soluble bismuth salt is one or two of bismuth nitrate or bismuth chloride.
7. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil as claimed in claim 6, wherein in the third step, the molar ratio of the soluble ferric salt to the soluble bismuth salt to the L-cysteine to the urea is 2.5-3.5:1:0.3-0.5: 4-6; and/or
In the third step, the concentration of the soluble bismuth salt in the precursor solution is 0.2-0.3 mol/L.
8. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil according to claim 7, wherein in the third step, the soluble iron salt, the modified molecular sieve and the g-C in the precursor solution3N4The mass ratio of the powder is 1:80-120: 0.4-0.6.
9. The method for preparing the photocatalyst for degrading the heavy metal ions in the soil as claimed in claim 1, wherein in the fourth step, the temperature is raised to 550-650 ℃ at the temperature raising rate of 4-6 ℃/min, and the calcination time is 5-8 h.
10. A photocatalyst for degrading heavy metal ions in soil, which is prepared by the preparation method of any one of claims 1 to 9.
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