CN116037078A - A novel polymetallic MOF material and its preparation method and application - Google Patents

A novel polymetallic MOF material and its preparation method and application Download PDF

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CN116037078A
CN116037078A CN202310022267.XA CN202310022267A CN116037078A CN 116037078 A CN116037078 A CN 116037078A CN 202310022267 A CN202310022267 A CN 202310022267A CN 116037078 A CN116037078 A CN 116037078A
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王君雅
朱敏
温石坤
苑雯雯
魏娅玲
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Kunming University of Science and Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/226Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a novel multi-metal MOF material, which comprises the components of M (I) x (nM) y-MOF-74, wherein M (I) is an alkali metal with a valence of I, M is an alkali metal with a valence of I, II or III, and n represents the type of the M metal. The invention has the advantages that: the metal I is added as a secondary metal site, so that the pore diameter structure of the MOF material can be regulated, and the specific surface area of the MOF material is increased; meanwhile, the components of the material have structural diversity due to the electrostatic effect of Lewis acid and metal ions; an aliovalent-state multi-metal MOF material formed by using an I-valent alkali metal as a secondary metal site is excellent in acid-base property and electrostatic effect on the material; therefore, the carbon dioxide adsorption performance is stronger, the optimal CO2 adsorption performance is as high as 8.5mmol/g under the dynamic adsorption condition, the performance is improved by nearly 15% on the basis of the MOF material Mg-MOF-74 with the optimal adsorption effect at present, and is nearly 10 times that of commercial activated carbon, and compared with a bimetallic MOF material taking II metal as a secondary metal site, the performance is more excellent.

Description

一种新型多金属MOF材料及其制备方法及其应用A novel polymetallic MOF material and its preparation method and application

技术领域technical field

本发明涉及一种新型多金属MOF材料及其制备方法及其应用,属于CO2吸附技术领域。The invention relates to a novel polymetallic MOF material, a preparation method and an application thereof, and belongs to the technical field of CO2 adsorption.

背景技术Background technique

工业化的不断发展,全球气候变化成为人们关注的主要问题。在全球气候变化中,温室效应属于热点问题,温室效应的出现不仅会导致全球的海陆表面出现上升现象,还会使得冰川融化,海水的温度变高海平面上升。据研究表明,在近十年时间里,冰川融化速度相较于之前已加快了很多倍,对环境造成了不利影响而造成全球气温变化的主要因素就是温室气体(GHGs)的出现。人们常见到的温室气体包括臭氧、甲烷、CO2、氟化物等。其中,CO2属于对全球气候变化影响最大的气体,相比于其他气体,CO2会占据所有温室气体所导致温室效应的百分之六十以上,且CO2气体在空气中停留时间也最长。大气中CO2浓度升高的主要原因为化石燃料的使用,再加上人们生活水平的不断提升,社会对于能源的使用量越来越大,故CO2的排放量也在呈现逐渐上升的趋势。根据美国国家海洋和大气管理局(NOAA)测量的数据,目前大气中的CO2浓度从1980年的340ppm急剧上升到2022年的420.99ppm。With the continuous development of industrialization, global climate change has become a major concern of people. In global climate change, the greenhouse effect is a hot issue. The emergence of the greenhouse effect will not only lead to the rise of the global sea and land surfaces, but also cause the melting of glaciers, the temperature of the sea water will rise, and the sea level will rise. According to research, in the past ten years, the melting rate of glaciers has accelerated many times compared to before, and the main factor that has caused adverse effects on the environment and caused global temperature changes is the emergence of greenhouse gases (GHGs). Common greenhouse gases include ozone, methane, CO2, fluoride, etc. Among them, CO2 is the gas that has the greatest impact on global climate change. Compared with other gases, CO2 will account for more than 60% of the greenhouse effect caused by all greenhouse gases, and CO2 gas stays in the air for the longest time. The main reason for the increase of CO2 concentration in the atmosphere is the use of fossil fuels. Coupled with the continuous improvement of people's living standards, society uses more and more energy, so CO2 emissions are also showing a gradual upward trend. According to data measured by the National Oceanic and Atmospheric Administration (NOAA), the current concentration of CO2 in the atmosphere has risen sharply from 340ppm in 1980 to 420.99ppm in 2022.

要实现经济的持续发展,就需要找到适合的CO2捕集技术及CO2吸附剂,也就是说找到吸附量大、新型高效的CO2吸附剂属于热点问题。To achieve sustainable economic development, it is necessary to find a suitable CO2 capture technology and CO2 adsorbent, that is to say, finding a new type of high-efficiency CO2 adsorbent with a large adsorption capacity is a hot issue.

目前主流低温吸附剂材料主要有碳质吸附材料,沸石分子筛,金属有机框架(MOFs)等,该类材料的主要特点是能在相对低温下(通常在200℃以下)吸附二氧化碳。碳质吸附材料是以煤或有机物制成的高比表面的多孔含碳物质。包括活性炭及活性碳纤维、碳纳米管等纯碳结构的吸附剂。活性炭主要以高含碳物质为原料,经碳化和活化制备而成的碳质吸附材料,具有孔隙结构发达、比表面积大、化学性质稳定、耐酸耐碱、选择性吸附能力强、失效后容易再生等特点。活性炭由于具有微孔、中孔和大孔结构,是很好的潜在的吸附材料。目前实验室中改性后活性炭的二氧化碳吸附量可达2-3mmol/g。而未经改性商业活性炭的二氧化碳吸附量相对较低,只有0.89mmol/g。沸石分子筛是含碱金属和碱土金属氧化物的结晶硅铝酸盐的水合物,是一类由硅铝氧桥连接组成的空旷骨架结构的微孔晶体材料(孔道尺寸为0.5-1.2nm),对氮和二氧化碳的混合物具有选择性吸收,对二氧化碳具有较强的吸附能力,再生循环吸附性能良好,可作为一种高效、经济的CO2捕集吸附剂。金属有机骨架(Metal-Organic Frameworks,MOFs),主要是指使用无机金属离子和有机配体进行混合而制备的具有特定网络结构的多孔材料。在MOFs材料所使用的材料中,无机金属离子主要作用为多孔材料构成节点,常用到的无机金属离子包括价态不高的过渡金属种类,以及常见碱金属其他过渡金属等。与沸石分子筛相比,高比表面积提高了MOFs对二氧化碳捕获能力。别是压力小于10bar时,沸石的最大存储容量只有MOFs的三分之一。At present, mainstream low-temperature adsorbent materials mainly include carbonaceous adsorbent materials, zeolite molecular sieves, metal-organic frameworks (MOFs), etc. The main feature of these materials is that they can adsorb carbon dioxide at relatively low temperatures (usually below 200 °C). Carbonaceous adsorption materials are porous carbonaceous substances with high specific surface area made of coal or organic matter. Including activated carbon and activated carbon fibers, carbon nanotubes and other pure carbon-structured adsorbents. Activated carbon is mainly a carbonaceous adsorption material prepared by carbonization and activation with high carbon content as raw material. It has developed pore structure, large specific surface area, stable chemical properties, acid and alkali resistance, strong selective adsorption capacity, and easy regeneration after failure. Features. Activated carbon is a good potential adsorption material due to its microporous, mesopore and macroporous structure. At present, the carbon dioxide adsorption capacity of modified activated carbon in the laboratory can reach 2-3mmol/g. The carbon dioxide adsorption capacity of unmodified commercial activated carbon is relatively low, only 0.89mmol/g. Zeolite molecular sieves are hydrates of crystalline aluminosilicates containing alkali metal and alkaline earth metal oxides. It has selective absorption for the mixture of nitrogen and carbon dioxide, has strong adsorption capacity for carbon dioxide, and has good regeneration cycle adsorption performance, and can be used as an efficient and economical CO2 capture adsorbent. Metal-organic frameworks (Metal-Organic Frameworks, MOFs) mainly refer to porous materials with specific network structures prepared by mixing inorganic metal ions and organic ligands. Among the materials used in MOFs materials, inorganic metal ions mainly function as porous materials to form nodes. Commonly used inorganic metal ions include transition metals with low valence states, and common alkali metals and other transition metals. Compared with zeolite molecular sieves, the high specific surface area improves the carbon dioxide capture ability of MOFs. Especially when the pressure is less than 10bar, the maximum storage capacity of zeolite is only one-third of that of MOFs.

MOFs材料具有多样化的不饱和金属位点,使得MOFs在吸附过程中可与吸附质产生较大的作用力,故MOFs材料在气体吸附及分离方面具有较好的发展前景。然而目前MOF材料在常温常压的条件下,二氧化碳吸附量主要为4-6mmol/g,且材料稳定性较差,循环性能不佳。MOFs materials have a variety of unsaturated metal sites, so that MOFs can generate a large force with the adsorbate during the adsorption process, so MOFs materials have good development prospects in gas adsorption and separation. However, at present, under the conditions of normal temperature and pressure, the carbon dioxide adsorption capacity of MOF materials is mainly 4-6mmol/g, and the material stability is poor, and the cycle performance is not good.

于是研究者对MOFs材料进行改性,制成MOF-74材料,然而目前MOF-74材料的制备时所添加的无机金属离子主要为II价金属离子,如添加Mg2+,Ni2+,Co2+,Cu2+,Zn2+等。如在公开号CN103992339A中,刘福等人使用六水合硝酸镁制得Mg-MOF-74材料。在公开号CN105037444A中,刘英等人使用六水合硝酸钴制得纯相棒状的Co-MOF-74晶体材料。在MOF多金属合成方面,主要也是采用II金属元素复合,对母体MOF材料进行改性。如在公开号为:CN111393664A的专利中,邹吉军等人在铁源中掺杂其他II价金属Cr、Mn、Co、Ni、Cu等,使金属活性中心能100%暴露,能极大提高金属中心利用率,催化活性优异。在公开号为CN111848972A的专利中,罗旭彪等人以MOF-808合成条件为基础,在Zr源中加入不同比例的铁离子通过原位掺杂形成吸附材料,提高了材料的吸附性能和稳定性。安晓银,鲁金明,刘毅,杨建华,张艳,张雯.双金属MOF-74的合成及其气体吸附分离性能研究[J].化工新型材料,2020,48(04):185-190.DOI:10.19817/j.cnki.issn1006-3536.2020.04.042,作者采用II金属Co和Ni所合成的双金属MOF材料为Ni25Co-MOF-74,在常温常压下CO2吸附性能为4.77mmol/g。So researchers modified MOFs materials to make MOF-74 materials. However, the inorganic metal ions added in the preparation of MOF-74 materials are mainly II-valent metal ions, such as adding Mg2+, Ni2+, Co2+, Cu2+, Zn2+ wait. For example, in the publication number CN103992339A, Liu Fu et al. used magnesium nitrate hexahydrate to prepare Mg-MOF-74 material. In the publication number CN105037444A, Liu Ying et al. used cobalt nitrate hexahydrate to prepare a pure-phase rod-shaped Co-MOF-74 crystal material. In terms of MOF multi-metal synthesis, the compounding of II metal elements is mainly used to modify the parent MOF material. For example, in the patent with the publication number: CN111393664A, Zou Jijun and others doped other II-valent metals Cr, Mn, Co, Ni, Cu, etc. in the iron source, so that the metal active center can be 100% exposed, which can greatly improve the metal center. Excellent utilization rate and catalytic activity. In the patent with the publication number CN111848972A, Luo Xubiao et al. based on the synthesis conditions of MOF-808, added different proportions of iron ions to the Zr source to form an adsorption material through in-situ doping, which improved the adsorption performance and stability of the material. An Xiaoyin, Lu Jinming, Liu Yi, Yang Jianhua, Zhang Yan, Zhang Wen.Synthesis of bimetallic MOF-74 and its gas adsorption and separation properties[J].New Chemical Materials,2020,48(04):185-190 .DOI: 10.19817/j.cnki.issn1006-3536.2020.04.042, the bimetallic MOF material synthesized by the author using II metal Co and Ni is Ni25Co-MOF-74, and the CO2 adsorption performance is 4.77mmol/g at normal temperature and pressure.

可见引入不同的次级金属位点的可以对材料的性能有所改善,但目前多金属MOF领域研究主要为两种II价金属进行掺杂,CO2吸附性能、稳定性、循环性还是有待提高。It can be seen that the introduction of different secondary metal sites can improve the performance of the material. However, the current research in the field of multi-metallic MOFs mainly focuses on the doping of two valent metals, and the CO2 adsorption performance, stability, and cycleability still need to be improved.

发明内容Contents of the invention

本发明要解决的技术问题,在于提供一种新型多金属MOF材料及其在CO2吸附方面的应用,采用添加I价碱金属作为次级金属位点的方法,制备多金属MOF材料,此方法操作方便,且I价碱金属价格便宜,制备的多金属MOF材料二氧化碳吸附性能极佳,循环性好、稳定性强。The technical problem to be solved in the present invention is to provide a novel polymetallic MOF material and its application in CO2 adsorption. The polymetallic MOF material is prepared by adding I-valent alkali metals as secondary metal sites. It is convenient, and the I-valent alkali metal is cheap, and the prepared multi-metallic MOF material has excellent carbon dioxide adsorption performance, good cycle performance and strong stability.

本发明通过下述方案实现:一种新型多金属MOF材料,其成分为M(I)x(nM)y-MOF-74,其中,M(I)为I价碱金属,M为I价或者II价或者III价的碱金属,n表示M金属的种类,x+y=1,x>0,y>0,n≥1。The present invention is realized by the following scheme: a novel polymetallic MOF material, its composition is M(I)x(nM)y-MOF-74, wherein, M(I) is I-valent alkali metal, and M is I-valent or Alkali metal with valence II or valence III, n represents the type of metal M, x+y=1, x>0, y>0, n≥1.

一种新型多金属MOF材料的制备方法,其按照以下步骤进行:A kind of preparation method of novel polymetallic MOF material, it carries out according to the following steps:

步骤一、分别定量称取一种I价碱金属盐和一种或多种II价金属盐和2,5-二羟基对苯二甲酸,制得药品A;Step 1. Quantitatively weighing one I-valent alkali metal salt, one or more II-valent metal salts, and 2,5-dihydroxyterephthalic acid to prepare drug A;

步骤二、向步骤一中所得药品A中加入DMF、甲醇和去离子水,制得混合溶液A;Step 2, adding DMF, methanol and deionized water to the drug A obtained in step 1 to prepare a mixed solution A;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到反应釜中,然后放入恒温干燥箱中,在110~140℃条件下水热反应22~30h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to the reactor, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 110-140° C. for 22-30 hours. After the reactor is cooled to room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥后,将样品至于烧杯中在室温条件下用甲醇浸泡2~5天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在80~100℃的真空干燥箱中干燥6~12h,得到最终产物M(I)x(nM)y-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven to dry, put the sample in a beaker and soak it in methanol at room temperature for 2 to 5 days, during which the methanol is constantly replaced to remove DMF and unreacted reactants, and dry the final product in a vacuum oven at 80-100° C. for 6-12 hours to obtain the final product M(I)x(nM)y-MOF-74 material.

所述步骤一中I价金属盐的种类为碱金属盐,II价、III价金属盐为硝酸盐、氯化盐或乙酸盐中的一种。The type of the I-valent metal salt in the step 1 is an alkali metal salt, and the II-valent and III-valent metal salt is one of nitrate, chloride or acetate.

所述步骤一中金属盐的总量与2,5-二羟基对苯二甲酸的摩尔比为2~3:0.78。。In the first step, the molar ratio of the total amount of metal salt to 2,5-dihydroxyterephthalic acid is 2-3:0.78. .

所述步骤二中所加入的DMF、甲醇和去离子水体积比为V:V:V=(10~15):1:1。The volume ratio of DMF, methanol and deionized water added in the second step is V:V:V=(10-15):1:1.

所述步骤二中金属元素的物质的量与DMF的体积比为2.5mmol:61.5mL。The volume ratio of the amount of metal element to DMF in the step 2 is 2.5mmol:61.5mL.

所述步骤三采用的反应釜为内衬为聚四氟乙烯材质得不锈钢水热反应釜。The reactor used in the step 3 is a stainless steel hydrothermal reactor lined with polytetrafluoroethylene.

所述步骤三中磁力搅拌处理过程中的溶液温度不超过40℃,步骤五中真空干燥箱中干燥时间为4~6h,步骤五中甲醇浸泡样品过程中,使用保鲜膜密封烧杯,步骤五中甲醇置换的次数为3次。The temperature of the solution in the magnetic stirring process in the step 3 does not exceed 40°C, the drying time in the vacuum drying oven in the step 5 is 4 to 6 hours, and in the process of soaking the sample in methanol in the step 5, use a plastic wrap to seal the beaker, and in the step 5 The number of methanol substitutions was 3 times.

一种新型多金属MOF材料在CO2吸附方面的应用。Application of a novel polymetallic MOF material in CO2 adsorption.

本发明的有益效果为:The beneficial effects of the present invention are:

1、本发明一种新型多金属MOF材料引入硝酸锂,硝酸钠,硝酸钾作为I价金属源,分别和II价III价金属盐为硝酸镁,硝酸镍,硝酸锌,硝酸钴,硝酸铜,乙酸锌,硝酸嫁等成功的制备了M(I)x(nM)y-MOF-74晶体材料,并对其进行CO2吸附性能实验测试和部分表征,通过实验结果可得,本发明所制备的多金属MOF材料都具有良好的CO2吸附性能,在298K,1bar的实验条件下,Mg0.5Na0.5-MOF-74的CO2吸附容量最高,为8.5mmol/g,是商业活性炭(0.89mmol/g)的近10倍,并且循环性能稳定。1. A novel polymetallic MOF material of the present invention introduces lithium nitrate, sodium nitrate, and potassium nitrate as I-valent metal sources, respectively, and II- and III-valent metal salts are magnesium nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, and copper nitrate. M(I)x(nM)y-MOF-74 crystalline material has been successfully prepared by zinc acetate, nitrate etc., and it is carried out CO2 adsorption performance experimental test and partial characterization, the experimental results can be obtained, the prepared by the present invention All multimetallic MOF materials have good CO 2 adsorption properties. Under the experimental conditions of 298K, 1bar, the CO 2 adsorption capacity of Mg 0.5 Na 0.5 -MOF-74 is the highest, 8.5mmol/g, which is the highest among commercial activated carbons (0.89mmol /g) nearly 10 times, and the cycle performance is stable.

2、本发明一种新型多金属MOF材料加入I价金属作为次级金属位点,不仅能调节MOF材料的孔径结构,增加其比表面积;同时材料的组成部分会因路易斯酸和金属离子的静电效应,具有结构的多样性;使用I价碱金属作为次级金属位点而形成的异价态多金属MOF材料,在对材料的酸碱性和静电效应上效果更佳的优异;因此二氧化碳吸附性能也更强,在动态吸附条件下,其最佳的CO2吸附性能高达8.5mmol/g,在目前吸附效果最佳的MOF材料Mg-MOF-74的基础上,提高了接近15%,是商业活性炭的近10倍,与II价金属作为次级金属位点的双金属MOF材料相比,性能也更加优异,背景技术中安晓银等采用II金属Co和Ni所合成的双金属MOF材料为Ni25Co-MOF-74,在常温常压下CO2吸附性能为4.77mmol/g,吸附性能仅为本申请中Mg0.5Na0.5-MOF-74的56%。2. A new multi-metal MOF material of the present invention adds I-valent metals as secondary metal sites, which can not only adjust the pore structure of the MOF material, but also increase its specific surface area; at the same time, the components of the material will be affected by the static electricity of Lewis acids and metal ions. Effect, has the diversity of structure; the heterovalent polymetallic MOF material formed by using I-valent alkali metal as the secondary metal site has better effect on the acidity, alkalinity and electrostatic effect on the material; therefore carbon dioxide adsorption The performance is also stronger. Under dynamic adsorption conditions, its best CO2 adsorption performance is as high as 8.5mmol/g. On the basis of the current MOF material Mg-MOF-74 with the best adsorption effect, it has increased by nearly 15%. It is a commercial Nearly 10 times that of activated carbon, compared with the bimetallic MOF material with II metal as the secondary metal site, the performance is also more excellent. In the background technology, the bimetallic MOF material synthesized by II metal Co and Ni by An Xiaoyin and others is Ni25Co -MOF-74, the CO2 adsorption performance at normal temperature and pressure is 4.77mmol/g, and the adsorption performance is only 56% of that of Mg0.5Na0.5-MOF-74 in this application.

附图说明Description of drawings

图1为M(I)x(nM)y-MOF-74材料的CO2吸附穿透曲线图。Figure 1 is the CO2 adsorption breakthrough curve of M(I)x(nM)y-MOF-74 material.

图2为M(I)x(nM)y-MOF-74材料的XRD图。Figure 2 is the XRD pattern of M(I)x(nM)y-MOF-74 material.

图3为M(I)x(nM)y-MOF-74的CO2吸附实验循环稳定性性能图。Figure 3 is a graph of the cycle stability performance of the CO2 adsorption experiment of M(I)x(nM)y-MOF-74.

具体实施方式Detailed ways

下面结合图1-3对本发明进一步说明,但本发明保护范围不局限所述内容。The present invention will be further described below in conjunction with FIGS. 1-3 , but the protection scope of the present invention is not limited to the content described above.

为了清楚,不描述实际实施例的全部特征,在下列描述中,不详细描述公知的功能和结构,因为它们会使本发明由于不必要的细节而混乱,应当认为在任何实际实施例的开发中,必须做出大量实施细节以实现开发者的特定目标,例如按照有关系统或有关商业的限制,由一个实施例改变为另一个实施例,另外,应当认为这种开发工作可能是复杂和耗费时间的,但是对于本领域技术人员来说仅仅是常规工作。For the sake of clarity, not all features of an actual embodiment are described. In the following description, well-known functions and constructions are not described in detail since they would obscure the invention with unnecessary detail and should be considered in the development of any actual embodiment. , a great deal of implementation detail must be worked out to achieve the developer's specific goals, such as changing from one embodiment to another in accordance with system-related or business-related constraints, and it should also be recognized that such development work may be complex and time-consuming Yes, but just routine work for those skilled in the art.

实施例1:Example 1:

本实施例为对比例,一种合成金属有机框架材料Mg-MOF-74的方法,通过以下步骤进行的:This example is a comparative example, a method for synthesizing metal organic framework material Mg-MOF-74, which is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁10mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Weighing quantitative magnesium nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to obtain drug A; wherein, 10 mmol of magnesium nitrate and 3.12 mmol of 2,5-dihydroxy terephthalic acid;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product and obtain the Mg-MOF-74 material.

实施例2:Example 2:

本实施例的一种合成金属有机框架材料Mg0.5Na0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Na 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁5mmol,硝酸钠5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative magnesium nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, 5 mmol of magnesium nitrate, 5 mmol of sodium nitrate, and 2,5-dihydroxy terephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=10:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=10:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is a Mg 0.5 Na 0.5 -MOF-74 material.

实施例3:Example 3:

本实施例的一种合成金属有机框架材料Mg0.5Na0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Na 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁5mmol,硝酸钠5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative magnesium nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, 5 mmol of magnesium nitrate, 5 mmol of sodium nitrate, and 2,5-dihydroxy terephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=13:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=13:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is a Mg 0.5 Na 0.5 -MOF-74 material.

实施例4:Example 4:

本实施例的一种合成金属有机框架材料Mg0.5Na0.5-MOF-74的方法,它是通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Na 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁5mmol,硝酸钠5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative magnesium nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, 5 mmol of magnesium nitrate, 5 mmol of sodium nitrate, and 2,5-dihydroxy terephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is a Mg 0.5 Na 0.5 -MOF-74 material.

实施例5:Example 5:

本实施例的一种合成金属有机框架材料Mg0.5Li0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Li 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸锂和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁0.5mmol,硝酸锂0.5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative magnesium nitrate, lithium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, magnesium nitrate 0.5mmol, lithium nitrate 0.5mmol, 2,5-dihydroxyterephthalic acid Diformic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Li0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100°C for 12 hours to obtain the final product, which is a Mg 0.5 Li 0.5 -MOF-74 material.

实施例6:Embodiment 6:

本实施例的一种合成金属有机框架材料Mg0.9K0.1-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.9 K 0.1 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镁、硝酸钾和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁9mmol,硝酸钾1mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative magnesium nitrate, potassium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, 9 mmol of magnesium nitrate, 1 mmol of potassium nitrate, 2,5-dihydroxy terephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.9K0.1-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100°C for 12 hours to obtain the final product, and obtain the Mg 0.9 K 0.1 -MOF-74 material.

实施例7:Embodiment 7:

本实施例的一种合成金属有机框架材料Ni0.5Na0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing the metal organic framework material Ni 0.5 Na 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镍、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镍0.5mmol,硝酸钠5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative nickel nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, nickel nitrate 0.5mmol, sodium nitrate 5mmol, 2,5-dihydroxyterephthalic acid Formic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Ni0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is Ni 0.5 Na 0.5 -MOF-74 material.

实施例8:Embodiment 8:

本实施方式的一种合成金属有机框架材料Zn0.5Na0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Zn 0.5 Na 0.5 -MOF-74 according to this embodiment is carried out through the following steps:

步骤一、分别称取定量的乙酸锌、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,乙酸锌5mmol,硝酸钠0.5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Weigh quantitative zinc acetate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare medicine A; wherein, 5 mmol of zinc acetate, 0.5 mmol of sodium nitrate, 2,5-dihydroxyterephthalic acid Formic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Zn0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is a Zn 0.5 Na0.5-MOF-74 material.

实施例9:Embodiment 9:

本实施方式的一种合成金属有机框架材料Ga0.5Na0.5-MOF-74的方法,通过以下步骤进行的:A method for synthesizing a metal organic framework material Ga 0.5 Na 0.5 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的硝酸镓、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸嫁5mmol,硝酸钠0.5mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative gallium nitrate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, 5 mmol of nitric acid, 0.5 mmol of sodium nitrate, 2,5-dihydroxyterephthalic acid Formic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Ga0.5Na0.5-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100° C. for 12 hours to obtain the final product, which is a Ga 0.5 Na0.5-MOF-74 material.

实施例10:Example 10:

本实施方式的一种合成金属有机框架材料Mg0.5Ni0.4Nao.1-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Ni 0.4 Na o.1 -MOF-74 according to this embodiment is carried out through the following steps:

步骤一、分别称取定量的乙酸锌、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁5mmol,硝酸镍0.4mmol,硝酸钠0.1mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative zinc acetate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, magnesium nitrate 5mmol, nickel nitrate 0.4mmol, sodium nitrate 0.1mmol, 2,5- Dihydroxyterephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Ni0.4Nao.1-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and unreacted reactants, the final product was dried in a vacuum oven at 100°C for 12 hours to obtain the final product, and Mg 0.5 Ni 0.4 Na o.1 -MOF-74 material was obtained.

实施例11:Example 11:

本实施例的一种合成金属有机框架材料Mg0.5Na0.4Ko.1-MOF-74的方法,通过以下步骤进行的:A method for synthesizing metal organic framework material Mg 0.5 Na 0.4 K o.1 -MOF-74 in this embodiment is carried out through the following steps:

步骤一、分别称取定量的乙酸锌、硝酸钠和2,5-二羟基对苯二甲酸,制得药品A;其中,硝酸镁5mmol,硝酸钠0.4mmol,硝酸钾0.1mmol,2,5-二羟基对苯二甲酸3.12mmol;Step 1. Take quantitative zinc acetate, sodium nitrate and 2,5-dihydroxyterephthalic acid respectively to prepare drug A; wherein, magnesium nitrate 5mmol, sodium nitrate 0.4mmol, potassium nitrate 0.1mmol, 2,5- Dihydroxyterephthalic acid 3.12mmol;

步骤二、向步骤一中所得药品A中加入体积比为V:V:V=15:1:1的DMF、甲醇和去离子水,制得混合溶液A;其中,所加入的DMF、甲醇和去离子水分别为246ml,16.4ml,16.4ml;Step 2, adding DMF, methanol and deionized water with a volume ratio of V:V:V=15:1:1 to the drug A obtained in step 1, to prepare a mixed solution A; wherein, the added DMF, methanol and Deionized water is 246ml, 16.4ml, 16.4ml respectively;

步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B;

步骤四、将步骤三中所得混合溶液B转移到内衬为聚四氟乙烯材质得不锈钢水热反应釜中,然后放入恒温干燥箱中,在125℃条件下水热反应24h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to a stainless steel hydrothermal reaction kettle lined with polytetrafluoroethylene, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 125°C for 24 hours, and wait for the reaction kettle to cool. After reaching room temperature, take out the reactor;

步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥数小时后,将样品至于烧杯中在室温条件下用甲醇浸泡3天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在100℃的真空干燥箱中干燥12h,得到最终产物,制得Mg0.5Na0.4Ko.1-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven and dry it for several hours, then place the sample in a beaker and soak it in methanol for 3 days at room temperature, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 100°C for 12 hours to obtain the final product, and obtain the Mg 0.5 Na 0.4 K o.1 -MOF-74 material.

将实例2-4所制得的Mg0.5Na0.5-MOF-74材料进行CO2动态吸附性能测试,结果发现,步骤二中加入体积比为V:V:V=(10-15):1:1的DMF、甲醇和去离子水,都可以成功合成MOF-74材料,CO2吸附性能接近,其中体积比为15:1:1的DMF、甲醇和去离子水,所合成材料CO2吸附性能最佳,但耗费溶剂相对较多,性价比略低,具体比例可由实际情况确定。The CO 2 dynamic adsorption performance test was carried out on the Mg 0.5 Na 0.5 -MOF-74 material prepared in Example 2-4. It was found that the volume ratio added in step 2 was V:V:V=(10-15):1: 1 of DMF, methanol and deionized water can successfully synthesize MOF-74 material, and the CO2 adsorption performance is close. Among them, the volume ratio of DMF, methanol and deionized water is 15:1:1, and the CO2 adsorption performance of the synthesized material is the best. Good, but relatively more solvent is consumed, and the cost performance is slightly lower. The specific ratio can be determined by the actual situation.

将实例4-11所制得的多金属MOF材料进行CO2动态吸附性能测试,结果可见表1,其中Mg0.5Na0.5-MOF-74吸附性能最高,为8.5mmol/g,比目前CO2吸附性能最佳的单金属MOF材料(Mg-MOF-74,7.34mmol/g)提高了接近15%,其次为Mg0.9K0.1-MOF-74>Mg0.5Li0.5-MOF-74>Ni0.9Na0.1-MOF-74。这是由于在Mg-MOF-74中加入I价金属Li,Na,K作为次级金属位点,可以形成丰富的三维蜂窝状结构,调节MOF材料的孔结构,增加微孔数量,从而使其CO2吸附性能显著增强。由循环稳定性实验可知,加入I价金属作为次级金属位点,材料的稳定性也有显著提升。The polymetallic MOF materials prepared in Examples 4-11 were tested for dynamic adsorption performance of CO 2 , the results are shown in Table 1, wherein Mg 0.5 Na 0.5 -MOF-74 has the highest adsorption performance of 8.5 mmol/g, which is higher than the current CO 2 adsorption The single metal MOF material with the best performance (Mg-MOF-74, 7.34mmol/g) improved by nearly 15%, followed by Mg 0.9 K 0.1 -MOF-74>Mg 0.5 Li 0.5 -MOF-74>Ni 0.9 Na 0.1 -MOF-74. This is due to the addition of I-valent metals Li, Na, and K as secondary metal sites in Mg-MOF-74, which can form a rich three-dimensional honeycomb structure, adjust the pore structure of the MOF material, and increase the number of micropores, thereby making it The CO2 adsorption performance is significantly enhanced. From the cycle stability experiments, it can be seen that the stability of the material is also significantly improved by adding I-valent metals as secondary metal sites.

表1合成后Mg-MOF-74与多金属MOF CO2吸附性能总结Table 1 Summary of CO2 adsorption performance of Mg-MOF-74 and multimetallic MOF after synthesis

尽管已经对本发明的技术方案做了较为详细的阐述和列举,应当理解,对于本领域技术人员来说,对上述实施例做出修改或者采用等同的替代方案,这对本领域的技术人员而言是显而易见,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。Although the technical solutions of the present invention have been elaborated and listed in detail, it should be understood that for those skilled in the art, it is necessary for those skilled in the art to make modifications to the above-mentioned embodiments or adopt equivalent alternatives. Obviously, the modifications or improvements made on the basis of not departing from the spirit of the present invention all belong to the protection scope of the present invention.

Claims (10)

1.一种新型多金属MOF材料,其特征在于:其成分为M(I)x(nM)y-MOF-74,其中,M(I)为I价碱金属,M为I价或者II价或者III价的碱金属,n表示M金属的种类。1. A novel polymetallic MOF material is characterized in that: its composition is M (I) x (nM) y-MOF-74, wherein, M (I) is I valence alkali metal, and M is I valence or II valence Or a III-valent alkali metal, n represents the type of M metal. 2.根据权利要求1所述的一种新型多金属MOF材料,其特征在于:x+y=1,x>0,y>0,n≥1。2. A novel polymetallic MOF material according to claim 1, characterized in that: x+y=1, x>0, y>0, n≥1. 3.一种新型多金属MOF材料的制备方法,其特征在于:其按照以下步骤进行:3. A preparation method for a novel polymetallic MOF material, characterized in that: it proceeds according to the following steps: 步骤一、分别定量称取一种I价碱金属盐和一种或多种I价、II价或III价金属盐和2,5-二羟基对苯二甲酸,制得药品A;Step 1. Quantitatively weighing one I-valent alkali metal salt, one or more I-valent, II-valent or III-valent metal salts and 2,5-dihydroxyterephthalic acid to prepare drug A; 步骤二、向步骤一中所得药品A中加入DMF、甲醇和去离子水,制得混合溶液A;Step 2, adding DMF, methanol and deionized water to the drug A obtained in step 1 to prepare a mixed solution A; 步骤三、将步骤二中所得混合溶液A置于磁力搅拌器上搅拌数小时,至药品完全溶解,得到混合溶液B;Step 3, the mixed solution A obtained in step 2 is placed on a magnetic stirrer and stirred for several hours until the medicine is completely dissolved to obtain the mixed solution B; 步骤四、将步骤三中所得混合溶液B转移到反应釜中,然后放入恒温干燥箱中,在110~140℃条件下水热反应22~30h,待反应釜冷却到室温后,取出反应釜;Step 4. Transfer the mixed solution B obtained in step 3 to the reactor, then put it into a constant temperature drying oven, and conduct a hydrothermal reaction at 110-140° C. for 22-30 hours. After the reactor is cooled to room temperature, take out the reactor; 步骤五、通过抽滤去除反应釜中溶液,将获得的产物放入真空干燥箱中干燥后,将样品至于烧杯中在室温条件下用甲醇浸泡2~5天,期间不断更换甲醇用于去除DMF和未反应掉的反应物,将最后得到的产物在80~100℃的真空干燥箱中干燥6~12h,得到最终产物M(I)x(nM)y-MOF-74材料。Step 5. Remove the solution in the reaction kettle by suction filtration, put the obtained product in a vacuum drying oven to dry, put the sample in a beaker and soak it in methanol at room temperature for 2 to 5 days, during which the methanol is constantly replaced to remove DMF and the unreacted reactants, and dry the final product in a vacuum oven at 80-100° C. for 6-12 hours to obtain the final product M(I)x(nM)y-MOF-74 material. 4.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤一中I价金属盐的种类为碱金属盐,II价、III价金属盐为硝酸盐、氯化盐或乙酸盐中的一种。4. the preparation method of a kind of novel polymetallic MOF material according to claim 1, is characterized in that: the kind of I-valence metal salt is alkali metal salt in described step 1, and II-valence, III-valence metal salt are nitrates , chloride or acetate. 5.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤一中金属盐的总量与2,5-二羟基对苯二甲酸的摩尔比为2~3:0.78。5. the preparation method of a kind of novel polymetallic MOF material according to claim 1, is characterized in that: the total amount of metal salt and 2 in described step 1, the mol ratio of 5-dihydroxyterephthalic acid is 2 ~3:0.78. 6.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤二中所加入的DMF、甲醇和去离子水体积比为V:V:V=(10~15):1:1。6. the preparation method of a kind of novel polymetallic MOF material according to claim 1 is characterized in that: the DMF added in the described step 2, methyl alcohol and deionized water volume ratio are V:V:V=(10 ~15): 1:1. 7.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤二中金属元素的物质的量与DMF的体积比为2.5mmol:61.5mL。7. The preparation method of a novel polymetallic MOF material according to claim 1, characterized in that: the volume ratio of the amount of metal elements to DMF in the step 2 is 2.5mmol:61.5mL. 8.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤三采用的反应釜为内衬为聚四氟乙烯材质得不锈钢水热反应釜。8. The preparation method of a novel polymetallic MOF material according to claim 1, characterized in that: the reactor used in the third step is a stainless steel hydrothermal reactor lined with polytetrafluoroethylene. 9.根据权利要求1所述的一种新型多金属MOF材料的制备方法,其特征在于:所述步骤三中磁力搅拌处理过程中的溶液温度不超过40℃,步骤五中真空干燥箱中干燥时间为4~6h,步骤五中甲醇浸泡样品过程中,使用保鲜膜密封烧杯,步骤五中甲醇置换的次数为3次。9. The preparation method of a novel polymetallic MOF material according to claim 1, characterized in that: the temperature of the solution in the magnetic stirring process in the step 3 does not exceed 40°C, and the step 5 is dried in a vacuum oven The time is 4-6 hours. During the process of immersing the sample in methanol in step 5, use a plastic wrap to seal the beaker, and the number of methanol replacements in step 5 is 3 times. 10.一种新型多金属MOF材料在CO2吸附方面的应用。10. The application of a novel polymetallic MOF material in CO2 adsorption.
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