CN113797890A - 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 PDF

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CN113797890A
CN113797890A CN202111182192.9A CN202111182192A CN113797890A CN 113797890 A CN113797890 A CN 113797890A CN 202111182192 A CN202111182192 A CN 202111182192A CN 113797890 A CN113797890 A CN 113797890A
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clay
deep sea
sea clay
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deep
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CN113797890B (en
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张培萍
孙雪
孙启玮
彭怡锦
郭健康
何越洋
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Jilin University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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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. According to the composition and the structural characteristics, the deep sea clay is divided into iron-manganese-rich deep sea clay, structural activity deep sea clay and silicon-aluminum-rich deep sea clay. For deep sea clay with relatively high content of iron and manganese, the catalyst 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 deep sea clay with huge resource reserves in world oceans as a raw material to prepare the catalytic and adsorption material for environmental restoration, and has innovative significance.

Description

Method for preparing catalytic and adsorption material from deep sea clay
Technical Field
The invention relates to a technology for preparing a catalytic and adsorption material by using deep sea clay and application thereof, wherein the catalytic and adsorption material which takes the 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 for different types of deep sea clay according to the characteristics of the deep sea clay such as composition, structure and the like.
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 relevant projects of the 'fifteen-eleven' plan of the Chinese ocean Association, the resource reserves of the clay in the world ocean are about 2.1 multiplied by 107km3. 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 treated2The 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. Wherein the iron element exists in a valence state of Fe (III) and contains a small amount of Fe (II), while the manganese element exists in a valence state of Mn (IV), the iron-manganese compounds are partly contributed by symbiotic iron-manganese nodules, and partly 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 (wt%) of different types of deep sea clays
Figure BDA0003297743420000011
In recent years, water pollution caused by organic dyes, heavy metal ions, bacteria and the like is increasingly serious, and CO is2The 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 H2O2The generated hydroxyl free radical (OH) and other Reactive Oxygen Species (ROS) to contaminate organic dyes and the likeOxidation of substances to CO2、H2O 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 the construction and application of a magnetic bentonite multiphase Fenton system, Fe is prepared by a coprecipitation method3O4The bentonite is used as a Fenton catalyst to degrade methyl orange, and the decolorization rate can reach 96.72 percent at most. Xiaoyuqiang, chapter qingfang, qiao chen, horse clear, ma jian chao, coal technology, 2017, 36: 280 plus 282, in the research of the catalytic degradation of coking wastewater by the carbon pillared magnetic bentonite, the carbon pillared magnetic bentonite composite water treatment agent is prepared by a solvothermal method, and the Fenton degradation rate of phenol can reach 95.59 percent at most. Masui, laeachen, zhang xu, yuanpengfei, and what was disputed, university of chinese school (nature science edition), 2018, 39: 844 and 850, loading nano Fe on the zirconium pillared bentonite3O4Multiphase Fenton-like treatment of aged landfill leachate3O4The zirconium pillared bentonite catalyst has good effect on treating old garbage leachate. Madder, wu tianwei, zhao ming yue, hou jian hua, royal sainseng, feng ke, wang xiao zhi, environmental engineering article, 2020, 14: 2463-3O4Composite material for catalyzing persulfate to degrade tetracycline, namely Fe is prepared by adopting coprecipitation method3O4The 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 that the deep-sea clay contains ferro-manganese (sample No. 1) without any purification and modification and is directly used for Fenton catalytic degradation of rhodamine B (RhB), 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, and the clay has the advantages thatMnO of medium2To H2O2Will produce O2The 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 ability such that 10mg/L of RhB is completely degraded within 60 min. In addition, comparing the removal of RhB by four kinds of surface clay, namely halloysite, illite, montmorillonite and black cotton, the removal efficiency of RhB under the same conditions is 17.4%, 38.6%, 89.5% and 92.4%, respectively, which is 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. MoS2As a new type of photocatalyst, there is increasing interest in the layered structure and narrow band gap, in combination with TiO2(3.0-3.2eV) in comparison with the band gap, MoS2The band gap of the light source is only 1.3-1.9eV, so that the light source can fully utilize visible light. However, large size pure MoS2The 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, MoS2Hydrophobic and non-uniform dispersion in water, which greatly limits its photocatalytic sterilization activity in aqueous solutions. Thus, a single layer of MoS was prepared2Nanosheets, 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 eugenol2Preparation and research on bacteriostatic activity of the method2The nano-flake is loaded with chitosan and eugenol, and the result shows good antibacterial activity. Shu xu, Ma Meng Qi, Zhu city, Hu Deng Feng, Ji Jian, Xu Zhi kang, macromolecule science and newspaper, 2021,52: 1-9 in the form of "layered MoS2Preparation of composite membranes and study of nanofiltration and photothermal antibacterial Properties of the composite membranes2The 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 supported molybdenum disulfide-glycosyl perylene bisimide self-assembly system construction and antibacterial research, a perylene bisimide compound covalently conjugated with galactosyl or mannosyl is supported on a lamellar MoS2The 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. MoS2The compound is compounded with clay, and the current reports are less. Hukun hong, Zhao and guang fang, liu jun sheng, chinese non ferrous metal student newspaper (english edition), 2012, 22: 2484 doping 2490 at "nano MoS2Synthesis of bentonite complex and its use in removing organic dye2Calcining MoS deposited on the surface of bentonite3Preparation of Nano MoS2The bentonite compound has excellent methyl orange removing performance. Machilus pauhoi, laoshanxiang, liuwenjie, lissajou, yaoshan, modern chemical engineering, 2020, 40: 122, 132 at "HNTs/TiO2/MoS2Preparation of composite material and application thereof in chlortetracycline photocatalytic degradation2/MoS2The 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 "TiO2/MoS2Preparation of @ diatomaceous earth photocatalyst and study of Properties thereof @ preparation of TiO by Sol-gel method and hydrothermal method2/MoS2The @ diatomite composite photocatalyst has a good catalytic degradation effect on methylene blue. However, the antibacterial property of MoS was not studied2Research on preparation of antibacterial material by compounding with deep sea clayEven more, it 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 method2Symbiotic 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 MoS2The dispersion in the aqueous solution and the symbiosis of the two also reduce MoS2The size of the nanosheets further shortens the distance that photogenerated carriers diffuse to the surface of the material. Thus, MoS2/#2 shows excellent antibacterial activity with a bactericidal rate for E.coli as high as 99.95% for pure MoS prepared under the same conditions2(the sterilization rate is only 61.87%) shows excellent photocatalytic antibacterial capability in aqueous solution.
The zeolite molecular sieve is aluminosilicate, has the functions of molecular sieving, adsorption, ion exchange and catalysis, has many pore passages with uniform pore diameter and holes arranged and arranged in 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, cloudstar, montage, "chemical proceedings of higher schools," 2007, 28: 816-820, in the article "phase transition law of zeolite molecular sieve synthesized from kaolin", NaX, NaP and SOD zeolite were synthesized from kaolin, which is a natural clay mineral, by hydrothermal crystallization, and the influence of crystallization temperature and concentration reduction on zeolite crystallinity was discussed. Raynaud, Zhang Xiao Yu, Yao Guang Yu, Sun Zhiming, 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, in "Illite-based zeolite phase composite material for Mn in water2+In the article, illite is used as a raw material, calcium carbonate and gypsum are used as activating auxiliary materials, a roasting hydrothermal synthesis method is adopted to prepare a zeolite phase composite material, and Mn of the zeolite phase composite material is researched2+Adsorption of (3). 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 ratio of silicon to aluminum is 2:1, the crystallization temperature is 180 ℃, the heat preservation time is 16h, and the NaOH concentration is 0.6 mol/L. The best process conditions for synthesizing the faujasite are as follows: the ratio of silicon to aluminum is 3:1, the crystallization temperature is 110 ℃, the heat preservation time is 12h, and the NaOH concentration is 4.75 mol/L. The optimal process conditions for synthesizing cancrinite are as follows: the volume ratio of the guiding agent to the silicon-aluminum leaching solution is 2:10, the crystallization temperature is 160 ℃, the heat preservation time is 16h, and the NaOH concentration is 5 mol/L. On the basis, three kinds of zeolites are researched for heavy metal ion Cu2+And CO2The adsorption of gas shows that the prepared three kinds of zeolite have good Cu2+And CO2Adsorption capacity.
Disclosure of Invention
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 H2O2Various motion tracks such as a spiral type, a circle type, a random type and the like are displayed in the solution, and RhB (10mg/L) can be completely removed within 60 min.
2. To achieve the effect in 1, the following conditions are required. Catalyst # 1: 0.1g/L, oxidant H2O2: 0.5 wt%, surfactant Sodium Dodecyl Sulfate (SDS): 0.5 wt%, target contaminant RhB: 10mg/L, reaction pH: 2, reaction temperature: at 60 ℃.
Two, MoS2Preparation of photocatalytic material by compounding deep sea clay #2
1. The invention mixes deep sea clay #2 and MoS under hydrothermal condition2The 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% MoS2/#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 proportions2/#2, Escherichia coli was cultured at the same time, and MoS was prepared in different proportions2And/# 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 22/#2, the following procedure was followed: one-step preparation of MoS by hydrothermal method2/#2, clay was activated by suspending #2 with cetyltrimethylammonium bromide (CTAB) in deionized water, and after activation, sodium molybdate (Na) was added to the suspension2MoO4·2H2O) and thioacetamide (CH)3CSNH2) 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 MoS2/# 2. Adjusting the adding amount of sodium molybdate and thioacetamide to obtain MoS compounded in different proportions2/#2。
Preparation of zeolite molecular sieve from deep sea clay #3 and its adsorption property
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 CO2Heavy metal Cu in gas and water2 +An adsorbent for ions. Amount of analcime added 1.5g/L for Cu 80mg/L2+The maximum adsorption rate of the ions can reach 97.63 percent in 4h, and the adsorption rate to CO is high2Has a maximum adsorption amount of 48.271m2(ii)/g; 1.0g/L faujasite addition for 60mg/L Cu2+Maximum absorption of ionsThe adsorption rate can reach 98.38 percent within 3h, and the adsorption rate to CO is up to 98.38 percent2Has a maximum adsorption amount of 17.965m2(ii)/g; 1.5g/L Cacancrinite addition for 80mg/L Cu2+The maximum adsorption rate of ions can reach 98.90 percent in 3h, and the adsorption rate to CO is high2Has a maximum adsorption amount of 32.520m2/g。
2. To achieve the effect in 1, the following steps need to be completed: taking 100mL of Cu with a certain concentration2+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 achieved2+The absorbance of the ions is calculated, and then the zeolite molecular sieve to Cu is calculated2+The adsorption rate of ions. For CO2The 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 connected2Gas cylinders, testing zeolite molecular sieves in CO2BET specific surface area under atmosphere to obtain its para-CO2The 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 3 h. 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. The ratio of silicon to aluminum is 2:1, the crystallization temperature is 180 ℃, the heat preservation time is 16h, and the analcime molecular sieve is synthesized when the concentration of NaOH is 0.6 mol/L. The silicon-aluminum ratio is 3:1, the crystallization temperature is 110 ℃, the heat preservation time is 12h, and the faujasite molecular sieve is synthesized when the NaOH concentration is 4.75 mol/L. : the volume ratio of the guiding agent to the silicon-aluminum leaching solution is 2:10, the crystallization temperature is 160 ℃, the heat preservation time is 16h, 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 resources, 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 H2O2When 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. Mixing deep sea clay #2 with MoS2The 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 improved2Original disinfection activity. By controlling MoS2The mass ratio of the composite material to the clay is 20 percent of MoS2/#2 optimal E.coli Sterilization of 99.95% was achieved due to pure MoS2Sterilization rate of (61.87%).
4. Extracting silicon-aluminum-rich deep-sea clay #3 with silicon-aluminum, and preparing analcime, faujasite and cancrinite zeolite molecular sieves by hydrothermal method, wherein the prepared three zeolites have good CO adsorption2Heavy metal Cu in gas and water2+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:
one, deep sea clay #1 Fenton catalytic material
1.#1 at H2O2Self-driven observation in solution: different concentrations (0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 1 wt%) of H were prepared2O2Solutions to which 0.5 wt% SDS was added and sufficiently dissolved, respectively. When observing, firstly, 2-3 drops of H are added by a dropper2O2The 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 software2O2Movement in solution.
2. Fenton degradation experiments: preparing 11.11mg/L RhB aqueous solution, putting 18mL into a 20mL glass bottle with a cover, adding H2O2(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 at 700-400nm with an ultraviolet-visible spectrophotometer after the temperature of the liquid in the bottle is raised to 60 deg.C, recording the absorbance value at 554nm as initial absorbance C0. Adding 0.1g SDS and 0.0020g deep sea clay #1 into the solution, screwing the bottle cap, placing in a water bath kettle for heating, taking 3mL liquid every 5min to measure the absorbance curve, and recording the absorbance C at 554nmtAnd 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(C0-Ct)/C0
two, MoS2Deep sea clay #2 composite photocatalytic material
1. MoS with different composite proportions2Preparation 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 24 h. 1.2100g of sodium molybdate and 1.5030g of thioacetamide are added into the suspension, then the suspension is placed in an ultrasonic machine for ultrasonic treatment for 30min, and is taken out and stirred at 50 ℃ for 24 h. The suspension was then transferred to a teflon lined reactor and placed in an oven at 220 ℃ for 24 h. 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 MoS2Ratio between theoretical yield of (1) and charged mass of #2 the sample was named 20% MoS2/# 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 0g, respectively7515g, 1.8150g and 2.2545g and 2.4200g and 3.0060g, to give a batch of products, and mixing these products with 20% MoS2The same naming convention of/# 2 was named 5% MoS in turn2/#2，10％MoS2/#2，30％MoS2/#2 and 40% MoS2/#2。
2. Testing the photocatalytic sterilization performance: coli (e.coli 8739) was first activated at 37 ℃ for 24h and cultured to log phase, and then its concentration was measured by an aerobic counting plate. Then diluting the bacterial liquid to about 10%6c.f.u.mL-1And determining the concentration C thereof0And (5) standby. To ensure MoS in all added samples2The same mass, respectively adding 24mg of 5% MoS2/#2，12mg 10％MoS2/#2，6mg 20％MoS2/#2，4mg 30％MoS2/#2 and 3mg 40% MoS2/#2 was added to 100mL of E.coli suspension, which was then left to stand under visible light for 18 h. After the illumination is finished, the bacterial liquid is diluted according to gradient, then the bacterial liquid concentration in the diluted solution is respectively measured by using an aerobic counting plate, and finally the bacterial liquid concentration (C) in the original solution is calculated by selecting the dilution times meeting the counting requirements1). Two parallel experiments were performed on each sample, and the average of the two parallel experiments was taken to obtain the final result. The sterilization rate (a) is calculated by the following method:
a(％)＝100(C0-C1)/C0
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 dispersant3) 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 2:1, then adding 0.6mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1 h. 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 2h 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 3:1, then adding 4.75mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1 h. 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 2h 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 beaker wall 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 1 h. 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 160 ℃, taking the reaction kettle out after 16 hours, 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.
6. Cu adsorption of analcite, faujasite and cancrinite2+Ion performance test: for all adsorption experiments, a concentration of 100mL (C) was taken0) Cu of (2)2+Putting the ionic solution into a 200mL conical flask, and then putting a certain amount of ionic solution into the conical flaskMeasuring the prepared zeolite molecular sieve, then placing the conical flask into an oscillation box, setting the rotating speed to be 200rpm, and measuring Cu in the solution by using an ultraviolet-visible spectrophotometer after the adsorption balance is achieved2+The absorbance of the ion is measured according to a standard curve to obtain the concentration C2. Zeolite molecular sieve pair Cu2+The ion adsorption rate (w) was calculated by:
w(％)＝100(C0-C2)/C0
7. adsorption of CO by analcime, faujasite and cancrinite2Performance testing of the gas: for CO2The 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 connected2Gas cylinders, testing zeolite molecular sieves in CO2BET specific surface area under atmosphere to obtain its para-CO2The amount of adsorption of (3).
Example 1
(1) 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 1 wt% of H was prepared2O2The solutions were dissolved by adding 0.5 wt% SDS and stirring.
(2) For one concentration of H2O2The 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 the #1 in different concentrations2O2Movement in solution.
Example 2
(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 added2O2(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) 3mL of the liquid was placed in a quartz cuvette and an ultraviolet-visible spectrophotometer was used at 700 deg.FMeasuring the absorbance curve in the range of-400 nm, recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 added2O2(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 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) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 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 added2O2(30 wt%) and 1.94mL of deionized water, adjusting the pH value to 2 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) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance curveThe value of the absorbance at 554nm was taken as the initial absorbance C0And 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 554nmtAnd 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 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 added2O2(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 up, placing the bottle in an electric heating constant-temperature water bath kettle at 60 ℃ to ensure that the temperature of the liquid in the bottle is raised to 60 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 added2O2(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) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 added2O2(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 60 ℃ to ensure that the temperature of liquid in the bottle is raised to 60 ℃.
(2) Placing 3mL of liquid in a quartz cuvette, measuring the absorbance curve of the liquid in the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 added2O2(30 wt%) and 1.70mL of deionized water, adjusting the pH value to 2 with 0.5mol/L HCl solution, covering the bottle, 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 the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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) The absorbance curve was measured by taking 3mL of liquid every 5min and recording its absorbance C at 554nmtAnd 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 added2O2(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 the range of 700-400nm by using an ultraviolet-visible spectrophotometer, and recording the absorbance value at 554nm as the initial absorbance C0And 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 554nmtAnd 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 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 24 h.
(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 after taking out, it was 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 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 be dried in vacuum at 60 DEG CDrying for 24h to obtain the final product of 5% MoS2/#2。
(5) 24mg of 5% MoS was taken2/#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 calculated1). The antibacterial experiments were done in two groups, and the average of the two parallel experiments was taken to obtain the final result, 5% MoS2The 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 24 h.
(2) 0.6050g of sodium molybdate and 0.7515g 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 24 h.
(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, 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 a final product of 10% MoS2/#2。
(5) 12mg of 10% MoS was taken2/#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 calculated1). The antibacterial experiments were done in two groups, and the average of the two parallel experiments was taken to obtain the final result, 10% MoS2The 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 24 h.
(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 24 h.
(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, 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 a final product of 20% MoS2/#2。
(5) Taking 6mg of 20% MoS2/#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 calculated1). The antibacterial experiments were done in two groups, and the average of the two parallel experiments was taken to obtain the final result, 20% MoS2The 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 24 h.
(2) 1.8150g of sodium molybdate and 2.2545g 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 24 h.
(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, 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 a final product of 30% MoS2/#2。
(5) Taking 4mg of 30% MoS2/#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 calculated1). The antibacterial experiments were done in two groups, and the average of the two parallel experiments was taken to obtain the final result, 30% MoS2The 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 24 h.
(2) 2.4200g of sodium molybdate and 3.0060g 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 24 h.
(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, 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 a final product of 40% MoS2/#2。
(5) 3mg of 40% MoS was taken2/#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 calculated1). The antibacterial experiments were done in two groups, and the average of the two parallel experiments was taken to obtain the final result, 40% MoS2The 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 2:1, adding 0.60mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1 h.
(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 2h 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, 1.5g/L of analcime was added thereto, and the Erlenmeyer flask was filled with the ionic solutionPut into an oscillation box and set at 200 rpm.
(5) After adsorbing for 4h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer2+The absorbance of the ion is measured according to a standard curve to obtain the concentration C2Calculated adsorption was 97.63%.
(6) Drying analcime at 100 deg.C for 12h to remove water influence. Before testing, the tube was placed in a U-tube and preheated.
(7) After the treatment, CO is connected2Gas cylinders, test analcime in CO2BET specific surface area under atmosphere to obtain its para-CO2The amount of adsorption of the zeolite is calculated to obtain the amount of adsorption of the analcime to CO2Has a maximum adsorption amount of 48.271m2/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 3:1, adding 4.75mol/L NaOH to adjust the alkalinity of the solution, and standing the solution for 1 h.
(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 of faujasite was put into the Erlenmeyer flask, and the Erlenmeyer flask was set to 200 rpm.
(5) After adsorbing for 3h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer2+The absorbance of the ion is measured according to a standard curve to obtain the concentration C2Calculated 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, connectingCO2Gas cylinders, testing faujasite in CO2BET specific surface area under atmosphere to obtain its para-CO2The adsorption amount of the faujasite is calculated to obtain the CO2Has a maximum adsorption amount of 17.965m2/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 1 h.
(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 160 ℃.
(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+The ionic solution (100 mL) was placed in a 200mL Erlenmeyer flask, and 1.5g/L cancrinite was added to the Erlenmeyer flask, which was set at 200rpm in a shaker.
(5) After adsorbing for 3h, measuring Cu in the solution by using an ultraviolet-visible spectrophotometer2+The absorbance of the ion is measured according to a standard curve to obtain the concentration C2Calculated 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 connected2Gas cylinder, testing cancrinite in CO2BET specific surface area under atmosphere to obtain its para-CO2Calculating the amount of absorption of cancrinite to CO2Has a maximum adsorption amount of 32.520m2/g。

Claims (7)

1. The deep sea clay is used for preparing a catalyzing and adsorbing material, and the method is characterized in that: iron-manganese-rich deep sea clay #1 as Fenton catalyst and micromotor for degrading rhodamine B dye in water in H2O2The solution shows various motion tracks of spiral, round, random and the like, and the degradation rate of 10mg/L rhodamine B in 60min is 100%.
2. The use of deep sea clay for the preparation of catalytic and adsorbent materials according to claim 1, characterized by: the following formula is adopted: iron and manganese rich deep sea clay # 1: 0.1g/L, H2O2: 0.1 wt% -1 wt%, sodium dodecyl sulfate: 0.5 wt%, rhodamine B: 10mg/L, pH: 1-2, temperature: 20-60 ℃.
3. The deep sea clay is used for preparing a catalyzing and adsorbing material, and the method is characterized in that: structurally active deep sea Clay #2 and MoS2Obtaining photocatalyst MoS with symbiotic structure by compounding nanosheets2/#2, the composite photocatalyst had a bactericidal rate of 99.95% against E.coli in water.
4. The use of deep sea clay for the preparation of catalytic and adsorbent materials according to claim 3, characterized in that: the following formula is adopted: 3g of structurally active deep sea clay #2, 0.35g of hexadecyl trimethyl ammonium bromide, 0.3025-2.4200g of sodium molybdate, 0.3758-3.0060g of thioacetamide.
5. The use of deep sea clay for the preparation of catalytic and adsorbent materials according to claim 4, characterized by: the formulation of claim 4, wherein 3g of structurally active deep sea clay #2 is mixed with 0.35g of cetyltrimethylammonium bromide, 60mL of deionized water is added thereto, the suspension is stirred at 60 ℃ for 24 hours, then 0.3025 to 2.4200g of sodium molybdate and 0.3758 to 3.0060g of thioacetamide are added thereto, then the suspension is placed in an ultrasonic machine for 30min of ultrasonic treatment, after being taken out and stirred at 50 ℃ for 24 hours, then the suspension is transferred to a polytetrafluoroethylene-lined reaction vessel and placed in a 220 ℃ oven for reaction for 24 hours, after that, the solid-liquid mixture in the vessel is centrifuged by a centrifuge, the supernatant is decanted to obtain a product, the product is centrifuged and washed three times with deionized water and absolute ethanol, and then the product is placed in a vacuum drying oven for vacuum drying at 60 ℃ for 24 hours to obtain the final product MoS2/#2。
6. The deep sea clay is used for preparing a catalyzing and adsorbing material, and the method is characterized in that: Si-Al-rich deep-sea clay #3 is used as a material for preparing three zeolite molecular sieves, namely analcime and cancrinite, by a hydrothermal method, and the prepared three zeolites have good Cu adsorption performance2+Ions and CO2Capacity of gas, wherein Cu2+The adsorption rate of ions is 97.63% -98.90%, and CO2The maximum adsorption amount of the adsorbent is 17.965-48.271m2/g。
7. The use of deep sea clay for the preparation of catalytic and adsorbent materials according to claim 6, characterized by: the following method is adopted: obtaining silicon-aluminum leaching solution of silicon-aluminum-rich deep sea clay #3 according to the alkaline earth ratio of 2.0, the hydrothermal temperature of 90 ℃ and the hydrothermal time of 3h, taking 100mL of the leaching solution, adding no guiding agent, and adjusting the silicon-aluminum ratio in the solution to be 2:1-3: 1; or adding 20mL of guiding agent, not adjusting the silicon-aluminum ratio, then adding 0.60-5.00mol/L NaOH to adjust the alkalinity of the solution, standing for 1h, transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating for 12-16h at 110-180 ℃, after finishing, 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 for 2h at 80 ℃ to obtain the product zeolite molecular sieve.
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