CN115025789A - High-activity copper sulfide biochar catalyst CuSx @ BC in-situ preparation method and application thereof - Google Patents
High-activity copper sulfide biochar catalyst CuSx @ BC in-situ preparation method and application thereof Download PDFInfo
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 230000000694 effects Effects 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 51
- 241000051984 Blepharidachne Species 0.000 claims abstract description 39
- 241000223782 Ciliophora Species 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
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- 229930101283 tetracycline Natural products 0.000 claims abstract description 32
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 10
- 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 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 9
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 6
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- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 abstract description 8
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- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 22
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- 239000002028 Biomass Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- 241001465754 Metazoa Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 2
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- 241001428136 Grateloupia filicina Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
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- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a high-activity copper sulfide biochar catalyst CuS x The @ BC in-situ preparation method comprises the steps of screening strong ciliate desert-grass seedlings and transplanting the ciliate desert-grass seedlings into soil; ) Irrigation of CuSO 4 Solution: daily use of low-concentration CuSO 4 Irrigating with the solution once and continuously for 5-12 days; then using high-concentration CuSO every day 4 The solution is irrigated once and irrigated for 5 to 12 days continuously; after stopping irrigating and stably growing for 5-12 days, harvesting the roots of the ciliate desert-grass to obtain ciliate desert-grass rich in copper; cleaning and drying the ciliate desert-grass rich in copper, and then heating the ciliate desert-grass in inert atmospherePyrolysis is carried out for 1-3h at the temperature of 800-900 ℃ to obtain the high-activity copper sulfide biochar catalyst CuS x @ BC, where x =1, or 2. Discovery of CuS x @ BC @ Cu in charcoal is CuS and CuS 2 The morphology exists. CuS under visible light illumination x @ BC is able to activate H efficiently 2 O 2 。CuS x @BC/H 2 O 2 The constructed heterogeneous Fenton system has a wide application range of pH3-11 and anti-interference reaction characteristics, and can efficiently remove various organic pollutants such as tetracycline, rhodamine B, methylene blue, orange II and the like.
Description
Technical Field
The invention provides a preparation method of a high-activity copper sulfide biochar catalyst (CuSx @ BC) and the application field of the high-activity copper sulfide biochar catalyst in photocatalytic degradation.
Background
Biochar (BC) is a solid material obtained by thermochemical decomposition of biomass material under oxygen-limited conditions, and is defined by the international biochar organization as "solid material obtained by biomass carbonization". Biomass (bioglass) is an organic matter material obtained from living matter or organic and inorganic composites, including organisms such as plants and animals, as well as animal excreta, plant litter, waste wood, precipitated sludge, and the like. The preparation method of the biochar comprises the following steps: pyrolysis, gasification, hydrothermal carbonization, and the like. There has been extensive research in the thermochemical decomposition process to convert biomass materials into combustible gases, bio-oils and biochar, which can replace fossil fuels. Biochar has applications in many environmental fields, including adsorption of water pollutants and air pollutants, as a catalyst, environmental pollution control, and the like, and recently has a tendency to be studied in other fields, such as fuel cells, supercapacitors, hydrogen storage, and the like.
The biochar has a porous structure and rich functional groups, and has great application potential in many environmental fields. Recently, in order to improve the catalytic performance of the biochar, the biomass is soaked in a solution containing Mg, Fe, Al and other elements for 2-12h by a chemical soaking method and then pyrolyzed to prepare modified biochar, and the method effectively improves the catalytic capability of the biochar so as to improve the performance of removing target pollutants. For example, bamboo charcoal is ground and sieved, and copper ions are loaded by an impregnation method to prepare the Cu/C Fenton heterogeneous catalyst, wherein the catalyst is prepared from Cu, CuO and Cu 2 O composition capable of promoting H 2 O 2 OH is generated, and the degradation performance to organic pollutants is improved.
Copper sulfide (CuS) isA p-type semiconductor material is widely applied to photocatalytic degradation of toxic organic pollutants as a photocatalyst due to excellent optical, electrical and catalytic properties. Meanwhile, CuS is also considered as a catalyst for catalyzing Fenton-like reaction and can activate H 2 O 2 OH is generated by decomposition, thereby improving the removal of organic matters by the reaction system. However, the problems of easy inactivation, instability, undesirable catalytic activity and the like of CuS are caused by the high surface activity of CuS and the rapid recombination of photo-generated electron-hole pairs. The CuS is reported to be compounded with other carriers, so that the separation of carriers generated by separating photons can be promoted or the band gap of a semiconductor can be changed, and the catalytic efficiency of the CuS composite photocatalytic material is improved. The literature data show that the CuS is concentrated on the charcoal material in situ, which may effectively improve the CuS photocatalytic performance, but the similar research is rare.
Disclosure of Invention
Aiming at the technical problem, the invention uses CuSO 4 The method comprises the steps of stressing ciliate desert-grass with a solution, preparing ciliate desert-grass rich in copper and sulfur into an in-situ copper sulfide biochar material (CuSx @ BC), and performing physical property characterization on biochar by adopting an electron scanning microscope SEM, an EDS, an X-ray diffractometer (XRD), an X-ray photoelectron spectrometer (XPS), specific surface area analysis (BET), Atomic Absorption Spectroscopy (AAS) and the like. Tetracycline (TC) is used as a probe molecule, and a certain amount of H is added 2 O 2 Establishing a Fenton-like system and researching the catalytic performance of the CuSx @ BC heterogeneous Fenton system.
High-activity copper sulfide biochar catalyst CuS x The @ BC in-situ preparation method comprises the following steps:
(1) screening strong ciliate desert-grass seedlings and transplanting the ciliate desert-grass seedlings into soil;
(2) irrigation of CuSO 4 Solution: daily use of low-concentration CuSO 4 The solution is irrigated once and irrigated for 5 to 12 days continuously; then using high-concentration CuSO every day 4 The solution is irrigated once and irrigated for 5 to 12 days continuously; after stopping irrigation and stably growing for 5-12 days, harvesting the roots of the ciliate desert-grass to obtain ciliate desert-grass with enriched copper, wherein the whole process of blank control is irrigation by water;
(3) for enrichment of copperAfter being cleaned and dried, the ciliate desert-grass is heated to 800- x @ BC, where x ═ 1, or 2.
The low-concentration CuSO 4 The mass concentration of the solution is 0.05-0.2 g/L; high concentration of CuSO 4 The mass concentration of the solution is 1.0-2.0 g/L.
After transplanting into soil, CuSO with mass concentration of 0.1g/L is adopted every day 4 Irrigating the ciliate desert-grass seedlings with the solution for 10 days; then adopting 1g/L CuSO 4 Irrigating ciliate desert-grass seedlings with the solution for 6 days; then 2g/L CuSO is adopted 4 The solution is used for irrigating the ciliate desert-grass seedlings for 4 days.
As a preferred scheme, the ciliate desert-grass with enriched copper is cleaned and dried and then is treated with N 2 Raising the temperature to 900 ℃ at the speed of 17 ℃/min and preserving the temperature for 1 h.
According to the technical scheme, the stress method of the prepared high-activity copper sulfide biochar catalyst (CuSx @ BC) adopts a three-stage stress method, frequency division is carried out from low concentration to high concentration to stress ciliate desert-grass, and the obtained catalytic material is used for removing toxic organic pollutants in water. Specifically, the stress time is 30 days, the irrigation is carried out every day in the first 20 days, and the irrigation is stopped in the last 10 days. In the first 10 days, 1.965g of CuSO is irrigated every day 4 3.93g of CuSO is irrigated every day on days 10 to 20 4 . The application of removing tetracycline, rhodamine B, methylene blue and golden orange II under the condition of visible light.
The technical scheme of the invention is that the raw material of the high-activity copper sulfide biochar catalyst (CuSx @ BC) prepared by the method is a biochar product formed by pyrolyzing ciliate desert-grass under the condition of limited oxygen, has rich pore structures and larger specific surface area, contains more oxygen-containing active groups on the surface, and is a multifunctional material widely applied to the field of environmental management. Copper sulfide (CuS) is a p-type semiconductor material, and is widely used as a photocatalyst for photocatalytic degradation of toxic organic pollutants due to its excellent optical, electrical and catalytic properties. Meanwhile, CuS is also considered as a catalyst for catalyzing Fenton-like reaction and can activate H 2 O 2 Decompose to produce ·OH, thereby improving the removal of organic matters by the reaction system. However, the problems of easy inactivation, instability, undesirable catalytic activity and the like of CuS are caused by the high surface activity of CuS and the rapid recombination of photo-generated electron-hole pairs. The CuS is enriched on the biochar material in situ, so that the separation of carriers generated by photon separation can be promoted or the band gap of a semiconductor can be changed, the CuS photocatalysis performance can be effectively improved, and the CuS photocatalysis material is applied to the degradation and removal of toxic organic pollutants in water.
In the invention, the copper sulfide biochar is prepared, the biochar is physically characterized by adopting a scanning electron microscope SEM, an EDS, an X-ray diffractometer (XRD) and a specific surface area tester (BET), the content of copper element in the biochar is detected by atomic absorption, the catalytic activity of the biochar containing copper and sulfur element is researched by a photocatalytic experiment, and the result shows that:
through the physical characterization of the biochar such as SEM, BET, XRD, XPS and the like, the biochar is determined to have a certain specific surface area and aperture, copper ions and sulfur elements have a certain inhibiting effect on the growth of ciliate desert-grass, and the specific surface area and the aperture of the prepared biochar are reduced. After the enrichment of copper and sulfur elements, a diffraction peak of CuS was detected. Furthermore, XPS results indicate that Cu is present in biochar at 2+ valency and S is SO 4 2- 、S 2 2- And S 2- The storage form is in the biochar, which indicates that copper is expressed as CuS @ CuS 2 The main active ingredient exists in the biological carbon, and X in CuSx is 1 and 2.
The photocatalytic reaction of the biochar shows that the catalytic performance of the biochar is obviously improved after the biochar is enriched with copper and sulfur elements, and the biochar can be used for treating H 2 O 2 The catalytic activation efficiency of (2) is 10 times of that of the blank biochar, and the TC removal efficiency is 139 times of that of the blank biochar.
Drawings
Figure 1 blank biochar SEM characterization.
FIG. 2 SEM representation of in situ copper sulfide biochar.
Figure 3 blank biochar EDS detection map.
Figure 4 in situ copper sulphide biochar EDS detection map.
Figure 5 XRD patterns of blank biochar and in situ copper sulphide biochar.
FIG. 6 Cu-XPS plots of blank biochar and in situ copper sulfide biochar.
FIG. 7S-XPS plots of blank biochar and in situ copper sulfide biochar.
FIG. 8 Tetracycline (TC) degradation kinetics curves.
FIG. 9 kinetics curves of Tetracycline (TC) degradation at different pH.
FIG. 10 is a graph showing the kinetics of Tetracycline (TC) degradation in the presence of inorganic anions and humic acid.
FIG. 11 removal rates of copper sulfide biochar in situ for different substrates.
The abbreviations in the above figures have the following meanings:
fig. 12 is an XRD pattern of the comparative example.
In FIGS. 1-11, BC is blank biochar, CuSx @ BC is a high activity copper sulfide biochar catalyst, HA is humic acid, MB is methylene blue, RhB is rhodamine B, OrII is golden orange II.
Detailed Description
Example 1
An experimental instrument: electric heating constant temperature blast drying box (DGG-9123A type, Shanghai), tubular resistance furnace (SK 2, model number, manufactured by electric furnace of Jianli province, Hubei Yinshan county, Inc.), KSW-4D-11A type temperature controller, high speed centrifuge (TG16W type, Changsha), vacuum pump (Yuhua instrument, SHZ-DIII), XL30 scanning electron microscope (Philips, Netherlands), JW-BK112 type specific surface area aperture analyzer (BET, Beijing Jinggao Boke technology Inc.), Autosorb-1 type N 2 Physical adsorption apparatus (Quantachrome, USA), photoreactor (XPA series photochemical reaction apparatus, XPA series-7 type multi-tube stirrer), UV-1800PC ultraviolet-visible spectrophotometer (Hitachi, Japan), CHA-S constant temperature oscillation (China corporation), D/max2500 type ray diffractometer (Rigaku, Japan), Delta320 pH meter (Mettler-Toledo, Shanghai Co., Ltd.), Pinnacle 900T Perkin Elmer type atomic absorption spectrometer, X-ray photoelectron spectroscopy (XPS, ES-AB 220i-XL, Saimer Feishi science Co., USA).
The experimental reagent: CuSO 4 ·5H 2 O，H 2 O 2 (30%) methylene blue(MB), Tetracycline (TC), rhodamine B (RhB), golden orange II (OrII), other reagents are analytically pure, and water is secondary distilled water.
Plant cultivation and preparation of biochar
Screening and transplanting strong ciliate desert-grass from the outdoor without pollution environment, selecting seedlings (8-12cm long seedlings) with good growth condition in the same area, transplanting three seedlings in each pot, and using 4kg of soil with shredded coconut and shredded coconut (the mass ratio is 3:1) in each pot. Firstly, 0.1g/LCuSO is used 4 Irrigating with the solution for 10 days, and adopting 1g/L CuSO when the growth condition of the plant to be transplanted tends to be good 4 Irrigating the ciliate desert-grass seedlings with the solution for 6 days; then 2g/L CuSO is adopted 4 Irrigating ciliate desert-grass seedlings with the solution for 4 days to ensure that the copper content is 15g finally, stopping irrigating, starting to harvest ciliate desert-grass roots after continuously growing for 10 days, starting to harvest plants after enriching metals for one month, cleaning ciliate desert-grass rich in copper and sulfur, drying, heating to 900 ℃ at the heating rate of 17 ℃/min in nitrogen atmosphere, and sintering for 2 hours to prepare the high-activity copper sulfide biochar catalyst CuS x @ BC, results show CuSx biochar catalyst copper as CuS and CuS 2 Two components are present, wherein CuS 2 Has higher catalytic activity, so that CuS x Wherein X is 1 or 2.
In the comparative example 'preparation method of copper-enriched biochar' of ciliate desert-grass, the plant cultivation scheme is as follows: grateloupia filicina is transplanted from the outdoor without pollution environment, seedlings (8-12cm long seedlings) with good growth condition are selected in the same area, three seedlings are transplanted in each pot, and 4kg of soil with shredded coconut and shredded coconut (the mass ratio is 3:1) is used in each pot. A set of blank controls, two experimental groups enriched in copper metal ions, each of three replicates was set. Water irrigation of blank control, preparation of Cu for experimental group 2+ Metal solution (specifically CuSO) 4 Solution) to enrich the ciliate desert-grass with copper element, and the copper only exists in the form of CuS (see figure 12 with XRD result).
Example 2
High activity copper sulfide biochar catalyst CuS prepared according to example 1 x @ BC, referring to water body anions and humic acid in three gorges reservoirDesign different anion (Cl) in concentration - 、NO 3 - And HCO 3 - ) And an inhibition effect experiment of humic acid on degradation of TC by CuSx @ BC. CuS under the coexistence of inorganic anions and humic acid x @ BC catalytic degradation TC experiment:
Cl - the influence of (a): weighing 10mg of CuS x @ BC and 23mg NaCl 40mL of 1X 10 was added -5 mol/L TC solution (in this case Cl in solution) - The concentration of (1) is 10mmol/L), placing the mixture into a dark box, magnetically stirring the mixture for reaction for 90min, and sampling every 30 min. After the adsorption reaction, hydrogen peroxide (H) is added into the solution 2 O 2 ) In solution of (H) 2 O 2 ) When the concentration reaches 4mmol/L, placing the photoreaction test tube into a visible light photoreactor, sampling every 30min, measuring the absorbance value and calculating the degradation rate, wherein the total photoreaction time is 210 min.
NO 3 - The influence of (a): NaNO 3 The amount added was 34mg (to make NO in solution) 3 - At a concentration of 10mmol/L), the rest with the above Cl - The same effect was observed in the experiment.
HCO 3 - The influence of (a): KHCO 3 The amount added was 40mg (to make HCO in solution) 3 - At a concentration of 10mmol/L), the rest with the above Cl - The same effect was observed in the experiment.
Effect of HA: HA was added in an amount of 0.4mg (to give a HA concentration of 10mg/L in the solution), and the rest was combined with Cl as described above - The same effect was observed in the experiment.
Determination of physical Properties of biochar
And (3) SEM and EDS detection: and marking the sample, inspecting, and observing the pore and the appearance of the biochar.
BET determination of specific surface area of biochar: by using N 2 Determination of the specific surface area of the biochar by physical adsorption (BET) method, N at 77K 2 Under a certain pressure, the surface of a detected sample (adsorbent) has reversible physical adsorption effect on gas molecules (adsorbates) at ultralow temperature, and a determined equilibrium adsorption capacity exists corresponding to a certain pressure. By measuring the equilibrium adsorption capacity, the specific surface area, the surface area in the hole and the hole body of the sample to be measured are equivalently calculated by using a theoretical modelThe specific surface area is calculated by adopting a BET (Brunauer-Emmett-Teller) formula.
XRD determination of biochar crystalline phase: measuring the biochar crystalline phase by adopting an X-ray diffractometer (XRD), wherein 2 theta is 5-90 DEG, the scanning speed is 8 DEG/min, and the step length is as follows: 0.02 continuous scan.
Detecting the concentration of metal ions in the biochar by atomic absorption: weighing a certain amount of biochar in a digestion tank, recording the quality of a sample, adding 5mL of nitric acid and 1mL of hydrofluoric acid into the biochar sample, placing the biochar sample into a digestion furnace for digestion at 180 ℃ for 10 hours, taking out the biochar sample, placing the biochar sample into a fume hood for cooling, and using 5% HNO 3 The volume of the solution is determined to be 50mL, an atomic absorption spectrometer makes a standard curve through the standard solution of the copper element, the content of the total copper element in the digested sample is measured by a flame method, and the concentration of copper ions in the biochar is calculated.
Electron Scanning (SEM) and EDS characterization
Fig. 1 and fig. 2 are electron scanning micrographs of BC and CuSx @ BC, respectively, and it is apparent from the images that both biochar retain the tissue structure of the biomass raw material and have larger pores, but there is no significant difference in morphology, which indicates that Cu and S elements enriched in situ in the biochar in a stress manner do not produce significant changes in the morphology of the biochar. Although the morphology of the biochar was unchanged, the specific surface area, pore volume and pore interior surface area of CuSx @ BC were much smaller than BC (table 1), indicating that the CuSx @ BC sample had successfully loaded Cu and S elements.
TABLE 1 BC and CuSx @ BC specific surface area and pore size determination
EDS detection is carried out on BC and CuSx @ BC, and the detection results are shown in figure 3, figure 4 and table 2. As can be seen from fig. 3 and table 2, the BC sample detected only C, O elements, and did not detect Cu, S, P, and the like. Of CuSx @ BC samplesEDS detection results show that the CuSx @ BC contains Cu and S elements with the content of 12.19 percent and 6.62 percent respectively (figure 4 and table 2), which indicates that the CuS x Successfully enriches Cu and S elements in the @ BC sample.
TABLE 2 EDS element detection Table for BC and CuSx @ BC samples
a The content of Cu in the biochar detected by AAS.
XRD measurement
FIG. 5 is an XRD pattern of BC and CuSx @ BC, wherein SiO is the substance corresponding to each diffraction peak in BC 2 And CaCO 3 However, in addition to CaCO in CuSx @ BC 3 Besides the diffraction peak, the obvious characteristic diffraction peak of CuS is also shown, which indicates that the Cu element and the S element in the CuSx @ BC sample are simultaneously CuS and CuS 2 The form is loaded on biochar.
In the comparative example "preparation method of biological carbon with enriched copper element from ciliate desert-grass", the XRD result of the copper biological carbon shows that only CuS is contained in Cu in the copper biological carbon. The XRD characterization of the copper biochar is shown in figure 12.
FIG. 6 is a Cu-XPS energy spectrum of BC and CuSx @ BC, without any diffraction peak in the Cu 2p spectrum of the BC sample, indicating that the BC sample contains no Cu element or very low Cu element content, consistent with the results in combination with AAS in Table 2. Obvious Cu exists in Cu 2p map of CuSx @ BC sample 2+ Characteristic diffraction peaks (932.5eV and 952.2eV), and the appearance of Cu at 940.5eV 2+ The characteristic oscillating satellite peak of (b), therefore, the Cu element in CuSx @ BC can be determined to be +2 valent.
FIG. 7 is an S-XPS energy spectrum of BC and CuSx @ BC, without any diffraction peaks in the S2 p spectrum of the BC sample, indicating that the BC sample does not contain S element. The S2 p spectrum of the CuSx @ BC sample has 3 obvious diffraction peaks which respectively correspond to SO of an S element 4 2- 、S n 2- 、S 2-- And S 2 2 This indicates that the S element is in various forms, mainly CuS and CuS 2 Present in CuSx @ BC.
FIG. 8 shows BC and CuSxKinetics of degradation curve of @ BC versus TC. Under the action of visible light, the removal of TC by BC and CuSx @ BC is less than 10%, which shows that BC and CuSx @ BC do not have the capability of directly degrading TC by photocatalysis. In the presence of H 2 O 2 The latter BC has a certain degradation effect (16.4 percent, 210min) on TC, and CuSx @ BC is added with H 2 O 2 The degradation capability of the catalyst on TC is obviously improved (98.2 percent, 210 min). Experiments show that CuSx @ BC obtained by in-situ enrichment of Cu and S elements can efficiently activate low-concentration H under the condition of visible light 2 O 2 (4mmol/L), which can remove 98.2% of TC in 210min, is a good photo-Fenton catalyst.
FIG. 9 is a graph of the degradation kinetics of CuSx @ BC versus TC at various pH. It can be seen from the graph that there is no significant change in the degradation rate of TC over the pH range of 3.0-11.0, which indicates that CuSx @ BC/H 2 O 2 The photo-Fenton system has wide pH applicability.
FIG. 10 is a graph showing the degradation kinetics of TC by CuSx @ BC under the coexistence of different anions and humic acid. As can be seen from the figure, the anion (Cl) - 、NO 3 - And HCO 3 - ) HAs no obvious inhibition effect on the degradation of TC by CuSx @ BC, and simultaneously, the HA HAs no obvious inhibition effect on the degradation of the TC by CuSx @ BC/H 2 O 2 The inhibition effect of the photo-Fenton system is also small. This illustrates CuSx @ BC/H 2 O 2 The optical-Fenton system is a Fenton-like system with wide applicability and has high practical application value.
In the comparative example 'preparation method of biochar for enriching copper element by ciliate desert-grass', copper biochar is activated by photocatalysis 2 O 2 Degradation of MB did not show resistance to anions (Cl) - 、NO 3 - And HCO 3 - ) And HA properties.
FIG. 11 shows the removal rate of CuSx @ BC for various substrates within 210 min. It can be seen that CuSx @ BC/H is within 210min 2 O 2 The light-Fenton system not only has obvious TC degradation effect, but also can realize more than 98% removal effect on MB, RhB and OrII.
The technical scheme of the invention includes that the copper sulfate solution stresses ciliate desert-grass and anaerobic thermal cracking is adopted to obtain the synchronous in-situ enrichment Cu and SElemental biochar material CuS x @BC，CuS x @ BC x ═ 1 or 2. EDS, XRD, AAS and XPS characterization results show that Cu in the biochar is CuS and CuS 2 The morphology exists. Although due to the pore size of the biochar CuS x The specific surface area is reduced, the adsorption effect on the antibiotic Tetracycline (TC) is weakened, but CuS is generated under the visible light x @ BC is capable of efficiently activating H 2 O 2 (k＝4.44x10 -5 mmol/min) is a high activity heterogeneous Fenton catalyst. CuS x @BC/H 2 O 2 The constructed heterogeneous Fenton system has the characteristics of wide pH3-11 application range and anti-interference reaction, and can efficiently remove various organic pollutants such as tetracycline, rhodamine B, methylene blue, orange II and the like. The results show that the novel high-activity CuSx @ BC photocatalyst can be prepared by the in-situ enrichment way of the centipede grasses, and can be applied to removal of toxic organic pollutants such as antibiotics and the like.
Claims (9)
1. High-activity copper sulfide biochar catalyst CuS x The in-situ preparation method of @ BC is characterized by comprising the following steps:
(1) screening strong ciliate desert-grass seedlings and transplanting the ciliate desert-grass seedlings into soil;
(2) irrigation of CuSO 4 Solution: daily use of low-concentration CuSO 4 The solution is irrigated once and irrigated for 5 to 12 days continuously; then using high-concentration CuSO every day 4 The solution is irrigated once and irrigated for 5 to 12 days continuously; after stopping irrigating and stably growing for 5-12 days, harvesting the roots of the ciliate desert-grass to obtain ciliate desert-grass rich in copper;
(3) cleaning and drying the ciliate desert-grass rich in copper, heating to 800-900 ℃ in inert atmosphere, and pyrolyzing for 1-3h to obtain the high-activity copper sulfide biochar catalyst CuS x @ BC, where x =1, or 2.
2. The high activity copper sulfide biochar catalyst CuS as claimed in claim 1 x The in-situ preparation method of @ BC is characterized in that the CuSO with low concentration 4 The mass concentration of the solution is 0.05-0.2 g/L; high concentration of CuSO 4 The mass concentration of the solution is 1.0-2.0 g/L.
3. The high activity copper sulfide biochar catalyst CuS as claimed in claim 1 x The @ BC in-situ preparation method is characterized in that after the @ BC is transplanted into soil, CuSO with the mass concentration of 0.1g/L is adopted every day 4 Irrigating the ciliate desert-grass seedlings with the solution for 10 days; then 1g/L CuSO is adopted 4 Irrigating the ciliate desert-grass seedlings with the solution for 6 days; then 2g/L CuSO is adopted 4 The solution is used for irrigating the ciliate desert-grass seedlings for 4 days.
4. The high activity copper sulfide biochar catalyst CuS as claimed in claim 1 x The in-situ preparation method of @ BC is characterized in that ciliate desert-grass rich in copper is cleaned and dried and then is subjected to N 2 Raising the temperature to 900 ℃ at the speed of 17 ℃/min and preserving the temperature for 1 h.
5. The high-activity copper sulfide biochar catalyst CuS prepared according to any one of claims 1 to 4 x Application of @ BC in removing antibiotics and organic dyes.
6. The use of claim 5, wherein the antibiotic removed by the prepared CuSx @ BC under visible light conditions includes, but is not limited to, tetracycline.
7. The use of claim 5, wherein the dyes removed by the prepared CuSx @ BC under visible light conditions include, but are not limited to, rhodamine B, methylene blue, and gold orange II.
8. The use of claim 5, wherein the pH range for removing the antibiotic and the dye under visible light conditions of CuSx @ BC is 3.0-11.0.
9. The use of claim 5, wherein the water-coexisting anions of CuSx @ BC under visible light conditions for the removal of antibiotics and dyes include, but are not limited to Cl - 、NO 3 - 、HCO 3 - And humic acid.
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