CN113797890B - Method for preparing catalytic and adsorption material from deep sea clay - Google Patents
Method for preparing catalytic and adsorption material from deep sea clay Download PDFInfo
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- CN113797890B CN113797890B CN202111182192.9A CN202111182192A CN113797890B CN 113797890 B CN113797890 B CN 113797890B CN 202111182192 A CN202111182192 A CN 202111182192A CN 113797890 B CN113797890 B CN 113797890B
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- sea clay
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Abstract
The invention relates to a method for preparing a catalytic and adsorption material from deep-sea clay, which is a catalytic or adsorption material mainly made of clay and designed for different types of deep-sea clay according to the characteristics of chemical compositions, structures and the like of the deep-sea clay. The three kinds of deep sea clay are collected from different sea areas. The deep sea clay is divided into iron-manganese-rich deep sea clay, structurally active deep sea clay and silicon-aluminum-rich deep sea clay according to the composition and structural characteristics. For deep sea clay with relatively high content of iron and manganese, the deep sea clay can be directly used as a Fenton catalyst for water purification; for deep sea clay with structural activity, the deep sea clay and molybdenum disulfide can be symbiotically compounded to be used as a photocatalyst for water disinfection; the silicon-aluminum-rich deep sea clay can be used as raw material for preparing zeolite molecular sieve adsorbents such as analcime, faujasite, cancrinite and the like. The invention takes the deep-sea clay with huge resource reserves in world oceans as a raw material to prepare the catalytic and adsorptive material for environmental remediation, and has innovative significance.
Description
Technical Field
The invention relates to a technology for preparing a catalytic and adsorption material by using deep-sea clay and application thereof, and aims at the characteristics of the composition, structure and the like of different types of deep-sea clay, the catalytic and adsorption material which takes clay as a main body and is used for environmental remediation such as sewage purification, greenhouse gas treatment and the like is designed and prepared.
Background
The resource reserves of global marine sediments are huge, including clay, soft mud and the like, and according to the research results of the projects related to the 'fifteen-from-eleven' plan of the Chinese Atlantic society, the resource reserves of the clay in the world ocean are about 2.1 multiplied by 10 7 km 3 . At present, deep sea clay is mostly focused on the formation reason, distribution factors, the presumed ocean current and plate motion, and the geological researches on enriched metal sulfide and rare earth resources, and the like, but the application research on the clay is little. At present, the high-quality clay resources on the earth surface are increasingly exhausted, the deep-sea clay with rich reserves is utilized to prepare a catalytic and adsorbing material for sewage purification and disinfection, and greenhouse gas CO is treated 2 The application of high added value has important significance.
The deep-sea clay deposit mainly comprises I/M (I/M), contains fragments of feldspar, quartz, kaolinite, calcite and the like, partially contains amorphous iron-manganese micro-nodules, and the substances coexist in a relatively uniform physical mixing mode, and the chemical composition and the structure of the deep-sea clay deposit are different according to the sea area. The special environment of the ocean leads the deep sea clay to have unique composition and structural characteristics compared with the earth surface clay, such as the characteristics of fine particles, poor crystallinity, more structural defects, large specific surface area, high content of iron and manganese and the like. The iron element exists in a Fe (III) valence state mostly and contains a small amount of Fe (II) valence state, while the manganese element exists in a Mn (IV) valence state mainly, part of the iron-manganese compounds are contributed by symbiotic iron-manganese nodules, and part of the iron-manganese compounds are derived from structural ions in a clay mineral crystal lattice. The deep sea clay samples related to the invention are respectively collected from different sea areas and are divided into iron-manganese-rich deep sea clay #1, structural active deep sea clay #2 and silicon-aluminum-rich deep sea clay #3 according to the composition and structural characteristics of the deep sea clay samples. The chemical composition is shown in table 1.
TABLE 1 chemical composition of different types of deep sea Clay (% by weight)
In recent years, water pollution caused by organic dyes, heavy metal ions, bacteria and the like is increasingly serious, and CO is 2 The greenhouse effect caused by excessive emission is also in need of solution, and in the face of this environmental problem, adsorption technology, membrane filtration technology, biological treatment technology, photocatalytic degradation technology, advanced oxidation technology including fenton's catalysis, and the like have been successively developed. The clay and the composite catalytic or adsorption material taking the clay as the substrate are widely applied in the fields of Fenton catalysis, photocatalysis, adsorption and the like due to the characteristics of low price and easy obtaining, excellent pollutant treatment effect, environmental friendliness, low energy consumption in the experimental process and the like. Fenton catalysis is an advanced oxidation technology which utilizes Fe (II) or Fe (III) to catalyze H 2 O 2 Generating active oxygen components (ROS) such as hydroxyl free radical (. OH) and the like, thereby oxidizing pollutants such as organic dye and the like into CO 2 、H 2 O and other small molecular substances. At present, researchers have focused much on iron compound/clay composite heterogeneous fenton catalysts or fenton-like catalysts, such as majia super, dajiali, zhuoduo, dao zhao, mahong bamboo, xiaoyu, maqingliang, proceedings of university of tai principle engineering, 2015, 46:399-404, in the research of 'construction and application of magnetic bentonite multiphase Fenton system', fe is prepared by coprecipitation method 3 O 4 The bentonite is used as a Fenton catalyst to degrade methyl orange, and the decolorization rate can reach 96.72 percent at most. Xiaoyu qiang, chapter qingfang, qiao chen, ma qingliang, ma jian super, coal technology, 2017, 36:280-282, the carbon pillared magnetic bentonite composite water treatment agent is prepared by adopting a solvothermal method in the research of catalytic degradation of coking wastewater by carbon pillared magnetic bentonite, and the Fenton degradation rate of phenol can reach 95.59 percent at most. Masui, qi Liu Asia, zhan Xuan, yuan Peng Fei, and what disputes, university of Huaqiao (Nature science and science)Version), 2018, 39:844-850, loading nano Fe on' zirconium column support bentonite 3 O 4 Multiphase Fenton-like treatment of aged landfill leachate 3 O 4 The zirconium column supported bentonite catalyst has good effect of treating the old landfill leachate. Madder, wu tianwei, zhao ming yue, hou jian hua, royal sainseng, feng ke, wang xiao zhi, environmental engineering article, 2020, 14:2463-2473 at "ATP @" Fe 3 O 4 Composite material for catalyzing persulfate to degrade tetracycline, namely Fe is prepared by adopting coprecipitation method 3 O 4 The highest degradation rate of the catalyst on tetracycline of Attapulgite (ATP) fenton catalyst can reach 98.75%. At present, most of Fenton catalysts for degrading pollutants such as organic dyes in water are artificially synthesized iron-containing composite materials, but research on Fenton catalysis by utilizing naturally-produced iron-rich manganese clay, particularly deep sea clay, is not reported. The invention utilizes the fact that the deep-sea clay containing ferro-manganese (# 1 sample) is directly used for Fenton catalytic degradation of rhodamine B (RhB) without any purification and modification, except that Fenton action of iron species can generate OH, the inherent adsorption performance of the clay also greatly improves the degradation efficiency of RhB, mnO in the clay 2 To H 2 O 2 Will produce O 2 The bubbles, making them self-driven and acting as micro-motors, promote micro-mixing and mass transfer of the solution, thus contributing to the efficiency of RhB degradation. In the present invention, #1 has Fenton catalytic performance such that 10mg/L of RhB is completely degraded within 60 min. In addition, compared with the removal of RhB by four types of surface clay, namely halloysite, illite, montmorillonite and kawo soil, the removal efficiency of RhB under the same conditions is 17.4%, 38.6%, 89.5% and 92.4%, which are far less than that of deep sea clay.
The photocatalytic sterilization refers to that when a semiconductor photocatalyst is irradiated by light with energy larger than the band gap energy of the semiconductor photocatalyst, photo-generated electron-hole pairs are excited, one part of the electron-hole pairs are compounded, and the other part of the electron-hole pairs react with oxygen, hydroxyl (-OH) and other receptors adsorbed on the surface of a material to form ROS with oxidability, so that the purposes of environmental purification such as sterilization and the like are achieved. MoS 2 As a new type of lightCatalysts, which are receiving increasing attention by virtue of a layered structure and a narrow band gap, are in contact with TiO 2 (3.0-3.2 eV) in comparison with the band gap, moS 2 The band gap of (A) is only 1.3-1.9eV, so that visible light can be fully utilized. However, large size pure MoS 2 The nanosheets make diffusion distances of electrons and holes to the surface of the material longer, resulting in a high recombination rate of electron-hole pairs making it difficult to generate ROS, and in addition, moS 2 Hydrophobic and non-uniform dispersion in water, which greatly limits its photocatalytic sterilization activity in aqueous solutions. Thus, a single layer of MoS was prepared 2 Nanosheets, metal doping, and building heterostructures have been used to facilitate the separation of photogenerated electron-hole pairs to enhance antimicrobial activity. For example, zheng, wang Fang, zhao Di, chen Zhao Bao, zhongnan Pharmacology, 2021, 18:776-780 in "two-dimensional MoS loaded with Chitosan and eugenol 2 Preparation and research on bacteriostatic activity of the method 2 The nano-flake is loaded with chitosan and eugenol, and the result shows good antibacterial activity. Shu xu, mamoge, zhuicheng, hudengfeng, jiejikang, xu shikang, the journal of macromolecule, 2021, 52:1-9 in the form of "layered MoS 2 Preparation of composite membranes and study of nanofiltration and photothermal antibacterial Properties of the composite membranes 2 The nano sheets construct a thin-layer composite nanofiltration membrane, and the sterilization rate of the nano sheets to staphylococcus aureus and escherichia coli under near-infrared radiation can reach 90%. Wu-bang, hujiale, chen national honor, proceedings of the university of the southern china (nature science edition), 2021, 47:195-201 in the article of antibiotic load type molybdenum disulfide-glycosyl perylene bisimide self-assembly system construction and antibacterial research, perylene bisimide compound covalently conjugated with galactosyl or mannosyl is loaded on a sheet layer MoS 2 The surface of the bacillus pyocyaneus is further coated with an antibiotic ceftazidime to construct a targeted bacteria treatment system, and the efficient targeted antibacterial activity of the bacillus pyocyaneus under the irradiation of white light is very obvious. MoS 2 The compound is compounded with clay, and the current reports are less. Kunkang, zhao zhou fang, liujunsheng, the national academy of nonferrous metals (English edition), 2012, 22:2484-2490 inRice MoS 2 Synthesis of bentonite complex and its use in removing organic dye 2 Intermediate calcination of MoS deposited on the surface of bentonite 3 Preparation of Nano MoS 2 The bentonite compound has excellent methyl orange removing performance. Machilus pauhoi, laoshanxiang, liuwenjie, lissajou, yaoshan, modern chemical engineering, 2020, 40:122-132 in "HNTs/TiO 2 /MoS 2 Preparation of composite material and application thereof in chlortetracycline photocatalytic degradation 2 /MoS 2 The highest degradation efficiency of the composite material to the chlortetracycline can reach 93.13 percent. Charm jade, bow, chen yan, white comedo, zhuan, liudan, marjor, yanghong, non-metal mine, 2020, 43:103-106 in "TiO 2 /MoS 2 Preparation of @ diatomite photocatalyst and research on performance of the photocatalyst @ preparation of TiO by sol-gel method and hydrothermal method 2 /MoS 2 The @ diatomite composite photocatalyst has a good catalytic degradation effect on methylene blue. However, the antibacterial property of MoS was not studied 2 The research of preparing the antibacterial material by compounding the antibacterial material with the deep sea clay is not reported. The invention utilizes the structural activity of deep-sea clay to prepare the deep-sea clay (# 2 sample) and MoS by a hydrothermal method 2 Symbiotic complex (MoS) 2 /# 2) as photocatalyst for water disinfection, wherein the crystallinity of nearly amorphous I/M mineral in deep sea clay is significantly enhanced during symbiosis process to increase hydroxyl (-OH) in the clay, OH attracts photoproduction hole, inhibits recombination of electron-hole pair, and further increases the concentration of OH in solution, and furthermore, the hydrophilicity of deep sea clay promotes MoS 2 The dispersion in the aqueous solution and the symbiosis of the two also reduce MoS 2 The size of the nanosheets further shortens the distance that photogenerated carriers diffuse to the surface of the material. Thus, moS 2 /#2 shows excellent antibacterial activity with a bactericidal rate for E.coli as high as 99.95% for pure MoS prepared under the same conditions 2 (the sterilization rate is only 61.87%) shows excellent photocatalytic antibacterial capability in aqueous solution.
The zeolite molecular sieve is a silicon-aluminiumThe acid salt has the functions of molecular sieving, adsorption, ion exchange and catalysis, has a plurality of pore channels with uniform pore diameters and holes arranged and arranged on the structure, and can obtain molecular sieves with different pore diameters according to different silicon-aluminum ratios. The method is widely applied to the fields of organic chemical industry, petrochemical industry, gas dehydration, waste gas treatment and batteries. At present, the research on synthesizing molecular sieves by using natural clay as a raw material is more, such as: trade, cloudshan, mondshur, "chemical proceedings of higher schools," 2007, 28:816-820, in the term of "phase transition law of zeolite molecular sieve synthesized from kaolin as raw material", naX, naP and SOD zeolite are synthesized from kaolin, which is a natural clay mineral, by hydrothermal crystallization, and the influence of crystallization temperature and concentration reduction on zeolite crystallinity is discussed. Raynaud crystal, zhang daoyu, yao guang, sunjing, zheng Shuihu, nonmetal mineral, 2018, 41:20-23, in the 'hydrothermal synthesis of X-type molecular sieve by diatomite', the X-type molecular sieve is synthesized by hydrothermal synthesis by taking diatomite as a raw material, and the optimal preparation conditions are crystallization temperature of 110 ℃, crystallization time of 5h, aging temperature of 30 ℃, aging time of 30min, water-sodium ratio of 40 and sodium-silicon ratio of 1.4. Wanmann, shilin, zhangyangyang, "nonmetallic minerals", 2020, 43:25-29, mn in "illite-based zeolite phase composite for Water 2+ In the adsorption research of (1), illite is used as a raw material, calcium carbonate and gypsum are used as activating auxiliary materials, a zeolite phase composite material is prepared by adopting a roasting hydrothermal synthesis method, and Mn in the zeolite phase composite material is researched 2+ Adsorption of (2). However, the research on the preparation of the molecular sieve by taking deep-sea clay as a raw material is not reported, the invention takes the deep-sea clay (# 3) as the raw material for the first time, and utilizes the characteristic that the structure is loose and is easy to open, a hydrothermal method is adopted to extract silicon-aluminum from #3 as a precursor solution for synthesizing the zeolite molecular sieve, and the optimal process conditions for extracting the silicon-aluminum are that the alkaline-earth ratio is 2.0, the hydrothermal temperature is 90 ℃, and the hydrothermal time is 3 hours. The silicon-aluminum leaching solution of #3 is used as a raw material, three zeolite molecular sieves of analcime, faujasite and cancrinite are synthesized by continuously adopting a hydrothermal crystallization method, and the optimal process conditions for synthesizing the analcime are as follows: the silicon-aluminum ratio is 2. The best process conditions for synthesizing the faujasite are as follows: 1, the ratio of silicon to aluminum is 3, the crystallization temperature is 110 ℃, and the heat preservation time is 12 ℃h, naOH concentration 4.75mol/L. The optimal process conditions for synthesizing cancrinite are as follows: the volume ratio of the guiding agent to the silicon-aluminum leaching liquid is 2, the crystallization temperature is 160 ℃, the heat preservation time is 169h, and the NaOH concentration is 5mol/L. On the basis, three kinds of zeolites are researched for heavy metal ion Cu 2+ And CO 2 The adsorption of gas shows that the prepared three kinds of zeolite have good Cu 2+ And CO 2 And (4) adsorption capacity.
Disclosure of Invention
1. Fenton catalytic material prepared from iron-manganese-rich deep-sea clay #1
1. The invention utilizes the deep sea clay #1 rich in iron and manganese as the Fenton catalyst and the micromotor for degrading RhB dye in water in H 2 O 2 Various motion tracks such as a spiral type, a circle type, a random type and the like are displayed in the solution, and RhB (10 mg/L) can be completely removed within 60 min.
2. To achieve the effect in 1, the following conditions need to be adopted. Catalyst #1:0.1g/L, oxidant H 2 O 2 :0.5wt%, surfactant Sodium Dodecyl Sulfate (SDS): 0.5wt%, target contaminant RhB:10mg/L, reaction pH: 2, reaction temperature: at 60 deg.C.
2. MoS 2 Photocatalytic material prepared by compounding deep sea clay #2
1. The invention mixes deep sea clay #2 and MoS under hydrothermal condition 2 The nano sheets are compounded according to different proportions to prepare the composite photocatalyst with a symbiotic structure, which is used for killing escherichia coli in water. Wherein 20% of MoS 2 /#2 exhibited 99.95% bactericidal efficacy.
2. To achieve the effect in 1, the following steps need to be completed: preparation of MoS compounded in different proportions 2 /#2, escherichia coli was cultured at the same time, and MoS was prepared in different proportions 2 And/# 2 adding into the Escherichia coli bacterial liquid, applying visible light illumination, after the illumination is finished, diluting the bacterial liquid, counting, and calculating the concentration, thereby obtaining the sterilization rate.
3. To prepare MoS compounded in different proportions in 2 2 /#2, the following procedure is required: one-step preparation of MoS by hydrothermal method 2 /#2, #2 was first added to cetyltrimethylammonium bromide (CTAB)Deionized water to make into suspension to activate clay, and adding sodium molybdate (Na) into suspension after activation 2 MoO 4 ·2H 2 O) and thioacetamide (CH) 3 CSNH 2 ) After ultrasonic treatment and stirring, the mixture is moved into a reaction kettle with a polytetrafluoroethylene lining and is placed in an oven for reaction. After the reaction is finished, centrifugally washing and vacuum drying to obtain a final product MoS 2 /#2. Adjusting the adding amount of sodium molybdate and thioacetamide to obtain MoS compounded in different proportions 2 /#2。
3. Zeolite molecular sieve prepared from deep sea clay #3 and adsorption performance
1. The invention takes deep sea clay #3 as raw material, utilizes the characteristic of high loose activity of deep sea clay structure, and adopts a hydrothermal method to synthesize three zeolite molecular sieves of analcime, faujasite and cancrinite for removing CO 2 Heavy metal Cu in gas and water 2 + An adsorbent for ions. Amount of analcime added 1.5g/L for Cu 80mg/L 2+ The maximum adsorption rate of ions can reach 97.63 percent in 4h, and the adsorption rate to CO is high 2 Has a maximum adsorption amount of 48.271m 2 (iv) g;1.0g/L faujasite addition for 60mg/L Cu 2+ The maximum adsorption rate of ions can reach 98.38 percent in 3h, and the adsorption rate of the ions to CO is 2 Has a maximum adsorption capacity of 17.965m 2 (ii)/g; 1.5g/L Cabernet addition for 80mg/L Cu 2+ The maximum adsorption rate of ions can reach 98.90 percent in 3h, and the adsorption rate to CO is high 2 Has a maximum adsorption amount of 32.520m 2 /g。
2. To achieve the effect in 1, the following steps need to be completed: taking 100mL of Cu with a certain concentration 2+ Putting the ionic solution into a 200mL conical flask, then putting a certain amount of zeolite molecular sieve into the conical flask, then putting the conical flask into a vibration box, setting the rotation speed at 200rpm, and measuring Cu in the solution by using an ultraviolet-visible spectrophotometer after the adsorption balance is achieved 2+ The absorbance of the ions is calculated, and then the zeolite molecular sieve to Cu is calculated 2+ The adsorption rate of ions. For CO 2 The adsorption of (2) needs to dry the zeolite for 12h in an environment of 100 ℃ to remove the influence of moisture in the zeolite. Before testing, the sample is put into a U-shaped pipe for preheating, and after treatment, CO is connected 2 Gas cylinder, test boilingMolecular sieve of stone in CO 2 BET specific surface area under atmosphere to obtain its para-CO 2 The amount of adsorption of (3).
3. In order to prepare the zeolite molecular sieve in 2, the following method is adopted: and extracting silicon and aluminum in the deep sea clay #3 under the conditions that the alkaline earth ratio is 2.0, the hydrothermal temperature is 90 ℃ and the hydrothermal time is 3h. Taking 100mL of silicon-aluminum leaching solution, adjusting the silicon-aluminum ratio and the alkalinity of the solution, standing for 1h, transferring the solution into a reaction kettle containing a polytetrafluoroethylene lining, and putting the reaction kettle into an oven for heating. And taking out the reaction kettle after the reaction is finished, and cooling at room temperature. And (3) carrying out suction filtration on the solid-liquid mixture in the kettle until the solid product is washed to be neutral, and drying the product at 80 ℃ for 2h to obtain the zeolite molecular sieve. 1, the ratio of silicon to aluminum is 2, the crystallization temperature is 180 ℃, the heat preservation time is 1693 h, and the analcime molecular sieve is synthesized when the concentration of NaOH is 0.6mol/L. And (2) synthesizing the faujasite molecular sieve when the silicon-aluminum ratio is 3. : the volume ratio of the guiding agent to the silicon-aluminum leaching solution is 2, the crystallization temperature is 160 ℃, the heat preservation time is 1693 hours, and the cancrinite molecular sieve is synthesized when the NaOH concentration is 5mol/L
Advantageous effects
1. The invention utilizes the deep-sea clay widely existing in world oceans as a resource, enlarges the resource amount and has great significance.
2. Deep sea clay #1 rich in iron manganese oxide was used directly as Fenton catalyst and micromotor for degradation of RhB dye in water in H 2 O 2 When the catalyst exists, the Fenton catalytic performance and the self-driving capability are excellent, and 10mg/L of RhB can be completely degraded within 60 min. Is superior to most of high-quality clay for land, such as halloysite, illite, montmorillonite, black cotton soil, etc.
3. Deep sea clay #2 and MoS with iron having structural activity 2 The symbiotic composition is used as a photocatalyst for water disinfection, and the I/M crystallinity in the #2 after the symbiotic composition and the photocatalyst are compounded is enhanced, so that the-OH content is increased, the separation of photo-generated electrons and holes is promoted, and the MoS is improved 2 Original disinfection activity. By controlling MoS 2 The mass ratio of the clay to the clay is 20% MoS 2 /#2 reached the best E.coli disinfection rate of 99.95% due to pure MoS 2 Medicine for treating chronic gastritisToxicity rate (61.87%).
4. Extracting silicon-aluminum-rich deep-sea clay #3 with silicon-aluminum, and preparing analcime, faujasite and cancrinite zeolite molecular sieves by a hydrothermal method, wherein the prepared three zeolites have good CO adsorption capacity 2 Heavy metal Cu in gas and water 2+ The ion capacity is an adsorption material with practical application significance and prospect.
Detailed Description
The purpose of the invention is realized by the following technical scheme:
1. deep sea clay #1 Fenton catalytic material
1.#1 at H 2 O 2 Self-driven observation in solution: different concentrations (0.1 wt%, 0.2wt%, 0.3wt%, 0.5wt%, 1 wt%) of H were prepared 2 O 2 Solutions, 0.5wt% SDS was added thereto and sufficiently dissolved, respectively. When observing, firstly, 2-3 drops of H are added by a dropper 2 O 2 The solution was spread evenly on a glass slide to form a thin liquid layer, then a very small amount of #1 was dipped into the liquid layer by a capillary tube, and H at various concentrations of #1 was photographed by a stereomicroscope in combination with Tpcapture software 2 O 2 Movement in solution.
2. Fenton degradation experiments: preparing 11.11mg/L RhB aqueous solution, putting 18mL into a 20mL glass bottle with a cover, adding H 2 O 2 (30 wt%) and deionized water (2 mL), adjusting pH with 0.5mol/L HCl solution, covering the bottle, shaking, placing in an electric heating constant temperature water bath at 60 deg.C, measuring absorbance curve with ultraviolet-visible spectrophotometer at 700-400nm after the temperature of the liquid in the bottle is raised to 60 deg.C, recording the absorbance value at 554nm as initial absorbance C 0 . Then adding 0.1g SDS and 0.0020g deep sea clay #1 into the solution, screwing down the bottle cap, placing in a water bath kettle for heating, taking 3mL liquid every 5min to measure an absorbance curve, and recording the absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing the degradation till 60 min. The method for calculating the degradation rate (eta) of the deep-sea clay #1 to RhB at different time t in the reaction process comprises the following steps:
η(％)＝100(C 0 -C t )/C 0
2. MoS 2 Deep sea clay #2 composite photocatalytic material
1. MoS with different composite proportions 2 Preparation of/# 2: 3g of deep sea clay #2 and 0.35g of CTAB were first weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h. Then 1.2100g of sodium molybdate and 1.5030g of thioacetamide are added into the suspension, and then the suspension is placed in an ultrasonic machine for ultrasonic treatment for 30min, taken out and stirred at 50 ℃ for 24h. The suspension was then transferred to a teflon lined reactor and placed in an oven at 220 ℃ for 24h to react. And after the reaction is finished, centrifuging the solution by using a centrifugal machine, pouring out supernatant to obtain a product, respectively centrifuging and washing the product three times by using deionized water and absolute ethyl alcohol, and then placing the product in a vacuum drying oven to carry out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the final product. According to MoS 2 The ratio between the theoretical yield of #2 and the charged mass of #2 designates the sample as 20% MoS 2 /#2. Under otherwise identical conditions and procedures, the amounts of sodium molybdate and thioacetamide added were adjusted to 0.3025g and 0.3758g,0.6050g and 0.7515g,1.8150g and 2.2545g and 2.4200g and 3.0060g, respectively, to give a batch of product, and the contents of MoS was calculated to be 20% based on the total weight of the product 2 The same naming convention as/# 2 was designated in turn as 5% 2 /#2，10％MoS 2 /#2，30％MoS 2 /#2 and 40% MoS 2 /#2。
2. Testing the photocatalytic sterilization performance: coli (e.coli 8739) was first activated at 37 ℃ for 24 hours and cultured to log phase, and then its concentration was measured by an aerobic count plate. Then diluting the bacterial liquid to about 10 6 c.f.u.mL -1 And determining the concentration C thereof 0 And (4) standby. To ensure MoS in all added samples 2 Mass equal, respectively adding 24mg 5% MoS 2 /#2，12mg 10％MoS 2 /#2，6mg 20％MoS 2 /#2，4mg 30％MoS 2 /#2 and 3mg 40% MoS 2 /#2 was added to 100mL of E.coli suspension, which was then left to stand under visible light for 18h. After the illumination is finished, diluting the bacterial liquid according to gradient, and then using an aerobic meterThe plurality of plates respectively measure the concentration of the bacteria liquid in the diluted solution, and finally the dilution times meeting the counting requirement are selected to calculate the concentration (C) of the bacteria liquid in the original solution 1 ). Two parallel experiments were performed on each sample and the average of the two parallel experiments was taken to obtain the final result. The calculation method of the sterilization rate (a) comprises the following steps:
a(％)＝100(C 0 -C 1 )/C 0
3. preparation of zeolite molecular sieve from deep sea clay #3
1. Purification of deep sea clay # 3: purifying #3 by natural settling method, pulping clay, breaking up, disintegrating, and adding a certain amount of anhydrous sodium carbonate (NaCO) as dispersant 3 ) Stirring for a certain time by adopting a strong stirrer, and standing for separation. Can remove impurities such as feldspar and calcite in #3.
2. Silicon and aluminum extraction of deep sea clay # 3: preparing 100mL of clay suspension by taking the purified #3 as a raw material according to the alkaline earth ratio of 2.0, transferring the clay suspension into a reaction kettle containing a polytetrafluoroethylene lining, putting the clay suspension into an oven, heating the clay suspension at the set temperature of 90 ℃ for 3 hours to obtain the silicon-aluminum leachate.
3. Preparation of analcime: taking 100mL of silicon-aluminum leaching solution, adjusting the silicon-aluminum ratio in the solution to be 2, then adding 0.6mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1h. And then transferring the mixture into a reaction kettle containing a polytetrafluoroethylene lining, putting the reaction kettle into an oven for heating, setting the temperature at 180 ℃, taking the reaction kettle out after 16 hours, and cooling at room temperature. And (3) carrying out suction filtration on the solid-liquid mixture in the kettle until the solid product is washed to be neutral, and drying the product at 80 ℃ for 2 hours to obtain the analcime.
4. Preparation of faujasite: taking 100mL of silicon-aluminum leaching solution, adjusting the silicon-aluminum ratio in the solution to be 3, then adding 4.75mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1h. And then transferring the mixture into a reaction kettle containing a polytetrafluoroethylene lining, putting the reaction kettle into an oven for heating, setting the temperature at 110 ℃, taking the reaction kettle out after 12 hours, and cooling at room temperature. And (3) carrying out suction filtration on the solid-liquid mixture in the kettle until the solid product is washed to be neutral, and drying the product at 80 ℃ for 2 hours to obtain the faujasite.
5. Preparation of cancrinite: 1.27g of aluminum hydroxide powder and 4.5g of sodium hydroxide particles are weighed and placed in a 250mL beaker, 30mL of deionized water is weighed and poured in, the beaker is sealed by a preservative film, and the beaker is magnetically stirred and heated to be dissolved into colorless solution. The clear solution was poured slowly into 19.2g of water glass and the inner wall of the beaker was rinsed with a small amount of deionized water. The mixture was magnetically stirred at room temperature for 3h to give a white sol-like directing agent. And (3) taking 100mL of silicon-aluminum leaching solution, adding 20mL of guiding agent, then adding 5mol/L of NaOH solution to adjust the alkalinity of the solution, and standing the solution for 1h. And then transferring the mixture into a reaction kettle containing a polytetrafluoroethylene lining, putting the reaction kettle into an oven for heating, setting the temperature to be 160 ℃, taking the reaction kettle out after 16 hours, and cooling the reaction kettle at room temperature. And repeatedly washing the obtained powder with deionized water until the solution on the surface of the powder is completely washed away, and drying the product at 80 ℃ for 2h to obtain cancrinite.
6. Cu adsorption of analcite, faujasite and cancrinite 2+ Ion performance test: for all adsorption experiments, a concentration of 100mL was taken (C) 0 ) Cu of (2) 2+ Putting the ionic solution into a 200mL conical flask, then putting a certain amount of prepared zeolite molecular sieve into the conical flask, then putting the conical flask into a vibration box, setting the rotation speed at 200rpm, and measuring Cu in the solution by using an ultraviolet-visible spectrophotometer after the adsorption balance is achieved 2+ The absorbance of the ion is measured according to a standard curve to obtain the concentration C 2 . Zeolite molecular sieve pair Cu 2+ The ion adsorption rate (w) is calculated by:
w(％)＝100(C 0 -C 2 )/C 0
7. adsorption of CO by analcime, faujasite and cancrinite 2 Performance testing of the gas: for CO 2 The adsorption of (2) needs to dry zeolite for 12h in an environment of 100 ℃ to remove the influence of moisture in the zeolite. Before testing, the sample is put into a U-shaped pipe for preheating, and after treatment, CO is connected 2 Gas cylinders, testing zeolite molecular sieves in CO 2 BET specific surface area under atmosphere to obtain its para-CO 2 The amount of adsorption of (3).
Example 1
(1) 0.1wt%, 0.2wt%, 0.3wt%, 0.5wt%, 1wt% of H was prepared 2 O 2 The solutions were dissolved by adding 0.5wt% SDS and stirring.
(2) For one concentration of H 2 O 2 The solution was applied evenly to the slide by 2-3 drops using a dropper to form a thin liquid layer, then a very small amount of #1 was added to the liquid layer by capillary dipping, and the slide was placed on the stage of a stereomicroscope.
(3) During observation, the magnification and the focal length of the microscope are adjusted, and the Tpcapture software is combined to shoot H of #1 in different concentrations 2 O 2 Movement in solution.
Example 2
(1) 18mL of 11.11mg/L RhB aqueous solution was placed in a 20mL glass bottle with a cap, and 0.60mL of H was added 2 O 2 (30 wt%) and 1.40mL of deionized water, adjusting the pH value to 1 with 0.5mol/L HCl solution, covering the bottle, shaking up, placing in an electric heating constant-temperature water bath kettle at 60 ℃ to raise the temperature of the liquid in the bottle to 60 ℃.
(2) Taking 3mL of liquid, placing the liquid in a quartz cuvette, measuring an absorbance curve of the quartz cuvette in a 700-400nm range by using an ultraviolet-visible spectrophotometer, and recording an absorbance value at 554nm as initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) Taking 3mL of liquid every 5min to measure an absorbance curve, recording the absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 94.5%.
Example 3
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.60mL of H was added 2 O 2 (30 wt%) and 1.40mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking uniformly, placing the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ and raising the temperature of liquid in the bottle to 60 ℃.
(2) Taking 3mL of liquidMeasuring the absorbance curve in a quartz cuvette in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nm t And quickly returning after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 100%.
Example 4
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.06mL of H was added 2 O 2 (30 wt%) and 1.94mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking uniformly, placing the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ and raising the temperature of liquid in the bottle to 60 ℃.
(2) Taking 3mL of liquid, placing the liquid in a quartz cuvette, measuring an absorbance curve of the quartz cuvette in a 700-400nm range by using an ultraviolet-visible spectrophotometer, and recording an absorbance value at 554nm as initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nm t And quickly returning after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 67.7%.
Example 5
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.12mL of H was added 2 O 2 (30 wt%) and 1.88mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking uniformly, placing the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ and raising the temperature of liquid in the bottle to 60 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, and using ultraviolet visible light spectroscopyThe absorbance curve of the photometer is measured in the range of 700 to 400nm, and the value of absorbance at 554nm is recorded as initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 88.8%.
Example 6
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.18mL of H was added 2 O 2 (30 wt%) and 1.82mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking up, placing the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ to ensure that the temperature of liquid in the bottle is raised to 60 ℃.
(2) Taking 3mL of liquid, placing the liquid in a quartz cuvette, measuring an absorbance curve of the quartz cuvette in a 700-400nm range by using an ultraviolet-visible spectrophotometer, and recording an absorbance value at 554nm as initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) Taking 3mL of liquid every 5min to measure an absorbance curve, recording the absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 97.8%.
Example 7
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.30mL of H was added 2 O 2 (30 wt%) and 1.70mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking the bottle evenly, and putting the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ to ensure that the temperature of liquid in the bottle is raised to 60 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, and measuring the absorbance curve of the liquid in the 700-400nm range by using an ultraviolet-visible spectrophotometerLine, recording the absorbance value at 554nm as the initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and placed in a water bath and heated.
(4) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing degradation until 60min, wherein the degradation rate of #1 to RhB is calculated to be 100%.
Example 8
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.30mL of H was added 2 O 2 (30 wt%) and 1.70mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle cap, shaking up, and placing in a room-temperature environment at 20 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in a 700-400nm range by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle and the cap was tightened.
(4) Taking 3mL of liquid every 5min to measure an absorbance curve, recording the absorbance C at 554nm t And quickly pouring back after the measurement is finished, and finishing degradation until 60min, wherein the degradation rate of #1 to RhB is calculated to be 23.2%.
Example 9
(1) 18mL of 11.11mg/L RhB aqueous solution was taken and placed in a 20mL glass bottle with a cap, and 0.30mL of H was added 2 O 2 (30 wt%) and 1.70mL of deionized water, adjusting the pH value to 2 by using 0.5mol/L HCl solution, covering the bottle, shaking up, placing the bottle in an electric heating constant-temperature water bath kettle at 40 ℃ to ensure that the temperature of liquid in the bottle is raised to 40 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in a 700-400nm range by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C 0 And the liquid was poured back into the bottle.
(3) 0.1g SDS and 0.0020g catalyst #1 were added to the bottle, the cap was tightened and the flask was placed in a water bath and heated.
(4) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nm t And quickly returning after the measurement is finished, and finishing the degradation till 60min, wherein the degradation rate of #1 to RhB is calculated to be 43.3%.
Example 10
(1) 3g of deep sea clay #2 and 0.35g of CTAB were weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h.
(2) 0.3025g of sodium molybdate and 0.3758g of thioacetamide were added to the suspension, and the mixture was sonicated in a sonicator for 30min, and then taken out and stirred at 50 ℃ for 24 hours.
(3) Transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at 220 ℃ for reaction for 24 hours.
(4) After the reaction was completed, the solution was centrifuged by a centrifuge, the supernatant was decanted to obtain a product, the product was centrifuged and washed three times with deionized water and absolute ethanol, respectively, and then placed in a vacuum drying oven to be vacuum-dried at 60 ℃ for 24 hours to obtain a final product 5% MoS 2 /#2。
(5) Taking 24mg 5 percent 2 /#2 was added to 100mL of E.coli suspension (concentration C) 0 ) Then, the bacterial liquid was placed under visible light for 18 hours. After the illumination is finished, the bacterial liquid is diluted, and the concentration (C) of the bacterial liquid in the solution after the illumination is finished is calculated 1 ). The antibacterial experiments were done in two groups, taking the average of the two parallel experiments to obtain the final result, 5% 2 The sterilization rate of/# 2 was 76.25%.
Example 11
(1) 3g of deep sea clay #2 and 0.35g of CTAB were weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h.
(2) 0.6050g of sodium molybdate and 0.7515g of thioacetamide are added into the suspension, the suspension is placed in an ultrasonic machine for ultrasonic treatment for 30min, and then the suspension is taken out and stirred for 24h at 50 ℃.
(3) Transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at 220 ℃ for reaction for 24 hours.
(4) After the reaction, the solution was centrifuged by a centrifuge, the supernatant was decanted to obtain a product, the product was centrifuged and washed three times with deionized water and absolute ethanol, and then placed in a vacuum oven for vacuum drying at 60 ℃ for 24 hours to obtain a final product 10% mos 2 /#2。
(5) 12mg 10% MoS 2 /#2 was added to 100mL of E.coli suspension (concentration C) 0 ) Then, the bacterial solution was placed under visible light for 18 hours. After the illumination is finished, the bacterial liquid is diluted, and the concentration (C) of the bacterial liquid in the solution after the illumination is finished is calculated 1 ). The antibacterial experiments were done in two groups, taking the average of the two parallel experiments to obtain the final result, 10% 2 The sterilization rate of/# 2 was 78.47%.
Example 12
(1) 3g of deep sea clay #2 and 0.35g of CTAB were weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h.
(2) 1.2100g of sodium molybdate and 1.5030g of thioacetamide are added into the suspension, the suspension is subjected to ultrasonic treatment in an ultrasonic machine for 30min, and the suspension is taken out and stirred at 50 ℃ for 24h.
(3) Transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at 220 ℃ for reaction for 24 hours.
(4) After the reaction is finished, centrifuging the solution by using a centrifugal machine, pouring out supernatant to obtain a product, centrifuging and washing the product three times by using deionized water and absolute ethyl alcohol respectively, and then placing the product in a vacuum drying oven to carry out vacuum drying for 24 hours at 60 ℃ to obtain the final product 20% MoS 2 /#2。
(5) 6mg 20% of MoS 2 /#2 was added to 100mL of E.coli suspension (concentration C) 0 ) Then, the bacterial solution was placed under visible light for 18 hours. After the illumination is finished, the bacterial liquid is diluted, and the concentration (C) of the bacterial liquid in the solution after the illumination is finished is calculated 1 ). The antibacterial tests were done in two groups, taking the average of the two parallel tests to obtain the final result, 20% MoS 2 The sterilization rate of/# 2 was 99.95%.
Example 13
(1) 3g of deep sea clay #2 and 0.35g of CTAB were weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h.
(2) 1.8150g of sodium molybdate and 2.2545g of thioacetamide are added into the suspension, the suspension is placed in an ultrasonic machine for ultrasonic treatment for 30min, and then the suspension is taken out and stirred for 24h at 50 ℃.
(3) Transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at 220 ℃ for reaction for 24 hours.
(4) After the reaction, the solution was centrifuged by a centrifuge, the supernatant was decanted to obtain a product, the product was centrifuged and washed three times with deionized water and absolute ethanol, respectively, and then placed in a vacuum drying oven to be vacuum-dried at 60 ℃ for 24 hours to obtain a final product 30% MoS 2 /#2。
(5) Taken 4mg 30% of MoS 2 /#2 was added to 100mL of E.coli suspension (concentration C) 0 ) Then, the bacterial liquid was placed under visible light for 18 hours. After the illumination is finished, the bacterial liquid is diluted, and the concentration (C) of the bacterial liquid in the solution after the illumination is finished is calculated 1 ). The antibacterial experiments were performed in two groups, and the average of the two parallel experiments was taken to obtain the final result, 30% MoS 2 The sterilization rate of/# 2 was 79.65%.
Example 14
(1) 3g of deep sea clay #2 and 0.35g of CTAB were weighed, 60mL of deionized water was added thereto, and the suspension was stirred at 60 ℃ for 24h.
(2) 2.4200g of sodium molybdate and 3.0060g of thioacetamide were added to the suspension, and the mixture was sonicated in a sonicator for 30min, and after removal, it was stirred at 50 ℃ for 24h.
(3) Transferring the suspension into a reaction kettle with a polytetrafluoroethylene lining, and placing the reaction kettle in an oven at 220 ℃ for reaction for 24 hours.
(4) After the reaction, the solution was centrifuged by a centrifuge, the supernatant was decanted to obtain a product, the product was centrifuged and washed three times with deionized water and absolute ethanol, respectively, and then placed in a vacuum drying oven to be vacuum-dried at 60 ℃ for 24 hours to obtain a final product 40% MoS 2 /#2。
(5) 3mg 40% of MoS 2 /#2 was added to 100mL of E.coli suspension (concentration C) 0 ) Then placing the bacteria solution inAnd (5) illuminating for 18h under visible light. After the illumination is finished, the bacterial liquid is diluted, and the concentration (C) of the bacterial liquid in the solution after the illumination is finished is calculated 1 ). The antibacterial experiments were performed in two groups, and the average of the two parallel experiments was taken to obtain the final result, 40% MoS 2 The sterilization rate of/# 2 was 72.27%.
Example 15
(1) Taking 100mL of deep sea clay #3 silicon-aluminum leaching solution obtained under the conditions that the alkaline earth ratio is 2.0, the hydrothermal temperature is 90 ℃ and the hydrothermal time is 3h, adjusting the silicon-aluminum ratio in the solution to be 2.
(2) Transferring the solution into a reaction kettle containing a polytetrafluoroethylene lining, and putting the reaction kettle into an oven to heat for 16 hours at 180 ℃.
(3) And taking out the reaction kettle after the reaction is finished, and cooling at room temperature. And (3) carrying out suction filtration on the solid-liquid mixture in the kettle until the solid product is washed to be neutral, and drying the product at 80 ℃ for 2 hours to obtain the analcime.
(4) Taking 80mg/L (C) 0 ) Cu of (2) 2+ 100mL of the ionic solution was placed in a 200mL Erlenmeyer flask, and then 1.5g/L analcime was added thereto, and the Erlenmeyer flask was put in a shaking chamber at a rotation speed set at 200rpm.
(5) After adsorbing for 4h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer 2+ The absorbance of the ion is measured according to a standard curve to obtain the concentration C 2 Calculated adsorption was 97.63%.
(6) Drying analcime at 100 deg.C for 12 hr to remove water influence. Before testing, the tube is put into a U-shaped tube for preheating.
(7) After the treatment, CO is connected 2 Gas cylinders, test analcime in CO 2 BET specific surface area under atmosphere to obtain its para-CO 2 The amount of adsorption of the zeolite is calculated to obtain the amount of adsorption of the analcime to CO 2 Has a maximum adsorption capacity of 48.271m 2 /g。
Example 16
(1) Taking 100mL of deep sea clay #3 silicon-aluminum leaching solution obtained under the conditions that the alkaline earth ratio is 2.0, the hydrothermal temperature is 90 ℃ and the hydrothermal time is 3h, adjusting the silicon-aluminum ratio in the solution to be 3.
(2) Transferring the solution into a reaction kettle containing a polytetrafluoroethylene lining, and putting the reaction kettle into an oven to heat for 12 hours at 110 ℃.
(3) And taking out the reaction kettle after the reaction is finished, and cooling at room temperature. And (3) carrying out suction filtration on the solid-liquid mixture in the kettle until the solid product is washed to be neutral, and drying the product at 80 ℃ for 2h to obtain the faujasite.
(4) Taking 60mg/L (C) 0 ) Cu of (2) 2+ 100mL of the ionic solution was placed in a 200mL Erlenmeyer flask, and then 1.0g/L faujasite was put into the Erlenmeyer flask, which was put into a shaking box at a rotation speed of 200rpm.
(5) After adsorbing for 3h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer 2+ The absorbance of the ion is measured according to a standard curve to obtain the concentration C 2 Calculated adsorption was 98.38%.
(6) Drying the faujasite for 12h in an environment of 100 ℃ to remove the influence of moisture in the faujasite. Before testing, the tube was placed in a U-tube and preheated.
(7) After the treatment, CO is connected 2 Gas cylinders, testing faujasite in CO 2 BET specific surface area under atmosphere to obtain its para-CO 2 Calculating the adsorption amount of the faujasite to CO 2 Has a maximum adsorption capacity of 17.965m 2 /g。
Example 17
(1) Taking 100mL of deep sea clay #3 silicon-aluminum leaching solution obtained under the conditions that the alkaline earth ratio is 2.0, the hydrothermal temperature is 90 ℃ and the hydrothermal time is 3h, adding 20mL of guiding agent, adding 5.00mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1h.
(2) The solution was transferred to a teflon lined reactor and heated in an oven at 160 ℃ for 16h.
(3) And taking out the reaction kettle after the reaction is finished, and cooling at room temperature. And repeatedly washing the obtained powder with deionized water until the solution on the surface of the powder is completely washed away, and drying the product at 80 ℃ for 2h to obtain cancrinite.
(4) Taking 80mg/L (C) 0 ) Cu of (2) 2+ 100mL of the ion solution was placed in a 200mL Erlenmeyer flask, and 1.5g/L cancrinite was added thereto, and the Erlenmeyer flask was set to 200rpm in a shaking box.
(5) After adsorbing for 3h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer 2+ The absorbance of the ion is measured according to a standard curve to obtain the concentration C 2 Calculated adsorption was 98.90%.
(6) The cancrinite is dried for 12h in an environment of 100 ℃ to remove the influence of moisture in the cancrinite. Before testing, the tube was placed in a U-tube and preheated.
(7) After the treatment, CO is connected 2 Gas cylinder, testing cancrinite in CO 2 BET specific surface area under atmosphere to obtain its para-CO 2 Calculating the amount of adsorption of cancrinite to CO 2 Has a maximum adsorption capacity of 32.520m 2 /g。
Claims (1)
1. The application of the deep-sea clay is characterized in that: iron-manganese-rich deep-sea clay #1 as Fenton catalyst for degrading rhodamine B dye in water and micromotor 2 O 2 The solution shows spiral, circular and irregular movement tracks, and the degradation rate of 10mg/L rhodamine B in 60min is 100%; the chemical composition of the iron-manganese-rich deep sea clay #1 comprises K 2 O is 1.52 wt%, na 2 7.37 wt% of O, 9.87 wt% of CaO, and Al 2 O 3 9.67 wt% SiO 2 30.56 wt% Fe 2 O 3 21.68 wt% and MnO 6.17 wt%.
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