CO2在氨基改性MIL-101(Cr)中吸附的分子模拟

采用实验与分子模拟结合的方法研究298 K下CO₂在氨基改性得到的MIL-101（Cr）-NH₂和MIL-101（Cr）-ED（ED：乙二胺）上的吸附性能。比较MIL-101（Cr）、MIL-101（Cr）-NH₂和MIL-101（Cr）-ED的吸附等温线与吸附热的结果,表明采用直接合成改性法得到的MIL-101（Cr）-NH₂比采用合成后再改性得到的MIL-101（Cr）-ED有更高的CO₂吸附容量。进一步比较密度分布图和径向密度分布曲线,分析CO₂在氨基改性MIL-101（Cr）中的吸附位,表明在低压下CO₂首先吸附在MIL-101（Cr）微孔的超级四面体中,随着吸附压力的增大逐渐填充到更大的孔中。氨基的存在增加了CO₂的吸附位点,使MIL-101（Cr）-NH₂具有较高CO₂吸附容量;同时MIL-101（Cr）-ED中的ED分子的存在增加了CO₂的吸附位点,使MIL-101（Cr）-ED也具有较高CO₂吸附容量;但是MIL-101（Cr）-ED中的ED分子占据了MIL-101（Cr）中Cr的吸附位点,使Cr对CO₂的吸附强度减弱,同时可吸附位点少于MIL-101（Cr）-NH₂,导致其对CO₂的吸附容量少于MIL-101（Cr）-NH₂。     

五乙烯六胺改性金属有机骨架材料MIL-101(Cr)对CO_2的吸附性能

采用溶剂热法合成金属有机骨架材料MIL-101(Cr),用回流法将五乙烯六胺(PEHA)负载到MIL-101(Cr)孔道中的不饱和金属位点上,使用扫描电镜、粉末X射线衍射、氮气物理吸附、元素分析和傅里叶变换红外光谱等表征手段考察材料的结构和形貌,测试氨基改性前后的MIL-101(Cr)在25℃、不同压力下对CO_2的吸附效果。结果表明,负载0.24 m L五乙烯六胺后的MIL-101(Cr)对CO_2的吸附效果最好,在25℃、常压下对CO_2的饱和吸附量可达58.944 mg/g,相比未负载五乙烯六胺的MIL-101(Cr)吸附量(CO_2饱和吸附量为44.208 mg/g)增加了33%。随着吸附压力的增加,MIL-101(Cr)和0.24PEHAM IL-101(Cr)对CO_2的饱和吸附量逐渐增加,当吸附压力为1.1 MPa时,两者的吸附量分别为1 147.59和1 256.74 mg/g,表明该类材料在高压下对CO_2有着良好的吸附效果。     

乙二胺改性轻金属铝-金属有机骨架材料用于CO_2/CH_4分离

胺类分子在CO_2的捕获中可以起到选择性提升的作用,本文选择小尺寸的乙二胺分子对具有不饱和金属位点的轻金属铝基金属有机骨架(Al-MOFs)材料MIL-100Al进行改性,利用XRD、N2吸附和FT-IR等对改性材料的结构进行表征,测试了不同浓度的乙二胺改性的MIL-100Al对CO_2和CH4吸附性能。结果表明,与原始的MIL-100Al材料相比,改性后的材料对CO_2吸附量有明显提高,CH4的吸附量却降低,从而进一步提高了材料的CO_2/CH4吸附选择性,提升了吸附分离的效果。     

氨基功能化的金属有机框架与模型燃油中含氮化合物的结合作用

合成了金属有机骨架MIL-53(Al)和MIL-53(Al)-NH_2,并且将其作为吸附剂去除油品中的含氮化合物(喹啉和吡咯)。采用X射线衍射(XRD)、扫描电镜(SEM)、FT-IR光谱以及热重分析等对两种吸附剂进行了表征。结果表明,MIL-53(Al)-NH_2能够快速地吸附油品中的喹啉/吡咯并且显示了较高的吸附容量,但MIL-53(Al)对喹啉/吡咯的吸附容量较低,原因是MIL-53(Al)-NH_2和喹啉之间存在有利的氢键结合,但MIL-53(Al)-NH_2与吡咯的氢键作用相对较低。研究了影响吸附容量的因素,包括吸附时间和温度。采用准一级和准二级动力学模型拟合了喹啉和吡咯的吸附数据,研究了MIL-53(Al)-NH_2对喹啉和吡咯的吸附等温线和吸附热力学。通过简单的溶剂洗涤使得MIL-53(Al)-NH_2再生,并重新用于吸附过程。     

MIL-101(Cr)-NH_2负载Pd低温催化糠醛高选择性加氢生成四氢糠醇（英文）

随着资源枯竭和环境污染严重问题的凸显,生物质转化的研究越来越多,特别是生物质催化裂解制备生物燃料及高附加值的化学品.糠醛是一种半纤维素酸解的产物,也是生产糠醇、四氢糠醇、2-甲基呋喃、环戊酮等的重要原料.其中四氢糠醇既可以用于生产其他高附加值化学品,也可以用作生物燃料或者燃料添加剂.虽然Pd/MFI,Ni/SiO_2,Pd-Ir/SiO_2等催化剂均可用于糠醛选择加氢制备四氢糠醇,但是反应通常在高温高压条件下进行.为此我们希望找到一种在温和条件下使用的高效催化剂.MOF多孔材料具有丰富的孔道结构、极高的比表面积、表面可修饰的特点,还可与其他客体发生相互作用,进而影响催化性能.因此本课题组合成了一种含有氨基的MOF材料MIL-101(Cr)-NH_2,进一步利用表面氨基吸附Pd的氯酸盐前体,经还原直接制得负载型催化剂Pd@MIL-101(Cr)-NH_2,并用于糠醛选择加氢反应.本文采用X射线粉末衍射(PXRD)、热重分析(TG)、N2物理吸附-脱附、透射电镜(TEM)等手段表征了所制的MOFs和催化剂.通过将MIL-101(Cr)-NH_2和不同Pd@MIL-101(Cr)-NH_2的XRD谱与标准谱图对比,发现MIL-101(Cr)-NH_2已成功合成,并在催化剂制备过程中和反应之后仍然保持稳定.TG结果表明,所制备MIL-101(Cr)-NH_2在低于350°C时结构不会被破环.MIL-101(Cr)-NH_2的比表面积可达到1669 m~2 g~(-1),孔容达1.35 cm~3 g~(-1),从而为Pd纳米粒子均匀分散在载体上提供了可能性.各Pd@MIL-101(Cr)-NH_2样品的TEM照片我们看出,Pd纳米粒子可均匀分散在MIL-101(Cr)-NH_2上,粒径为3-4 nm.对比实验表明,氨基与金属的相互作用有利于Pd纳米粒子分散均匀.将Pd@MIL-101(Cr)-NH_2用于糠醛选择加氢反应时,在40℃,2 MPaH_2的温和条件下,反应6 h后糠醛完全转化为四氢糠醇其选择性接近100%.表现出比文献报导的更加优异的催化性能.这得益于高度均匀分散的Pd纳米粒子,以及催化剂载体与Pd纳米粒子的配位作用和π-π相互作用.结果还表明当高于80℃反应时,即有副产物生成,进一步提高反应温度会促进环戊酮的生成.可见,Pd@MIL-101(Cr)-NH_2所表现的低温高加氢活性对提高四氢糠醇选择性至关重要.     

铬-对苯二甲酸MOF的框架异构：MIL-88B(Cr)和MIL-101(Cr)

可以通过简单地控制乙酸浓度的方法,在相似的水热合成条件下合成2种同一家族的金属有机框架材料(MOFs):MIL-88B(Cr)和MIL-101(Cr)。在相对较低的乙酸浓度下,可以得到平均粒径为100 nm的MIL-101(Cr),并拥有很高的BET比表面积(3543 m^2·g^-1)。而在相对较高的乙酸浓度下,则可得到另一种具有“呼吸”特性结构的MOF——MIL-88B(Cr)。利用粉末X射线衍射、扫描电镜、N2吸附-脱附分析、热重分析等对它们的结构、形貌、孔隙率等性质做了详细的分析。     

磺酸功能化金属-有机骨架吸附脱氮性能

以硝基甲烷为溶剂,采用三氟甲磺酸酐(Tf2O)和浓硫酸对金属有机骨架材料MIL-101(Cr){Cr3F(H2O)2O[(O2C)-C6H4-(CO2)]3nH2O(n~25)}进行磺酸功能化修饰,使其孔壁配体上形成磺酸基团.通过改变MIL-101(Cr)、Tf2O和浓硫酸的摩尔配比,得到含有不同磺酸基团数量的S-MIL-101(Cr),对磺化后的材料进行了X射线衍射(XRD)、傅里叶变换红外(FTIR)、氮气物理吸附、酸碱电位滴定以及热重分析(TGA)表征.结果表明,磺酸功能化后MIL-101(Cr)的孔道结构仍然保持,比表面积和孔径有所下降,表面磺酸基团的数量根据磺化程度的不同从0.21到0.42 mmol g-1不等.将磺酸功能化后的MIL-101(Cr)用于液体燃料的吸附脱氮,发现磺酸功能化能够增强MIL-101(Cr)与含氮化合物的相互作用,有利于其对碱性氮化物的吸附脱除.相对于未经磺化的样品,按照摩尔配比n(MIL-101(Cr)):n(H2SO4):n(Tf2O)=1:3:4.5反应得到的磺酸功能化MIL-101(Cr)对喹啉和吲哚的吸附量提高较大,其对喹啉和吲哚的Langmuir最大吸附量分别提高了12.2%和6.3%.通过乙醇洗涤,吸附剂可再生,经过三次再生之后的吸附剂对模拟燃料中含氮化合物的吸附量没有明显的降低.     

基于金属有机骨架材料分散固相萃取-高效液相色谱法检测环境水体中两种磺胺类药物

比较了3种金属有机骨架材料(MIL-101(Cr)、MIL-101(Cr)-SO_3H和MIL-101(Cr)-NH_2)在不同pH的环境水体中对两种磺胺类药物(磺胺对甲氧嘧啶和磺胺氯哒嗪)的吸附性能,从而选择出最佳吸附剂及pH条件。研究发现pH为9时MIL-101(Cr)吸附性能最佳,进而对影响吸附及解析效率的主要因素,如吸附剂使用量、吸附时间和解析溶剂及其用量、解析时间等进行优化。优化后的最佳实验条件为:每10.0 mL样品溶液(pH=9)中加入6.0 mg的MIL-101(Cr)吸附剂,吸附4.0 min,离心去掉上清液,然后用1.5 mL的甲酸-甲醇溶液解析-10.0 min后离心。结果表明:2种磺胺类药物在5.0～8000μg/L范围内线性良好且相关系数均大于0.9990,方法检出限以信噪比(S/N=3)计磺胺对甲氧嘧啶和磺胺氯哒嗪分别为0.08μg/L、0.05μg/L,3种浓度加标回收率为71.2%～91.9%,相对标准偏差为3.1%～8.5%。     

金属有机框架@介孔分子筛复合材料的构建和性质

通过蒸汽诱导内部水解法(VIH)在介孔分子筛SBA-15孔壁上引入Al_2O_3,合成得到Al_2O_3@SBA-15复合物,随后与对二苯甲酸配体反应,从而制备得到金属有机框架化合物(MIL-53)与介孔分子筛(SBA-15)复合材料(MIL-53@SBA-15)。采用粉末X射线衍射(PXRD)、N_2吸附-脱附测试、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术证明成功合成了MIL-53@SBA-15复合材料。染料吸附实验结果表明,MIL-53@SBA-15复合材料相比于SBA-15、MIL-53及其物理混合样品,表现出对丁基罗丹明染料更高效吸附特性。     

乙二胺改性轻金属铝-金属有机骨架材料用于CO2/CH4分离

胺类分子在CO₂的捕获中可以起到选择性提升的作用,本文选择小尺寸的乙二胺分子对具有不饱和金属位点的轻金属铝基金属有机骨架（Al-MOFs）材料MIL-100Al进行改性,利用XRD、N₂吸附和FT-IR等对改性材料的结构进行表征,测试了不同浓度的乙二胺改性的MIL-100Al对CO₂和CH₄吸附性能。结果表明,与原始的MIL-100Al材料相比,改性后的材料对CO₂吸附量有明显提高,CH₄的吸附量却降低,从而进一步提高了材料的CO₂/CH₄吸附选择性,提升了吸附分离的效果。     

苯部分加氢制环己烯新型Ru-B/MOF催化剂

制备了多种金属-有机骨架(MOF)材料,采用浸渍-化学还原法制备了非晶态Ru-B/MOF催化剂,考察了它们在苯部分加氢反应中的催化性能.催化性能评价结果表明,这些催化剂的初始反应速率(r0)顺序为Ru-B/MIL-53(Al)Ru-B/MIL-53(Al)-NH2Ru-B/UIO-66(Zr)Ru-B/UIO-66(Zr)-NH2Ru-B/MIL-53(Cr)Ru-B/MIL-101(Cr)Ru-B/MIL-100(Fe),环己烯初始选择性(S0)顺序为Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)Ru-B/UIO-66(Zr)-NH2Ru-B/MIL-101(Cr)Ru-B/MIL-53(Al)-NH2Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe).催化性能最好的Ru-B/MIL-53(Al)催化剂上的r0和S0分别为23 mmol·min-1·g-1和72%.采用多种手段,对催化性能差异最为显著的Ru-B/MIL-53(Al)和Ru-B/MIL-100(Fe)催化剂的物理化学性质进行了表征.发现MIL-53(Al)载体能够更好地分散Ru-B纳米粒子,粒子的平均尺寸为3.2 nm,而MIL-100(Fe)载体上Ru-B纳米粒子团聚严重,粒径达46.6 nm.更小的粒径不仅能够提供更多的活性位,而且也有利于环己烯选择性的提高.对Ru-B/MIL-53(Al)催化剂的反应条件进行了优化,在180°C和5 MPa的H2压力下,环己烯得率可达24%,展示了MOF材料用作苯部分加氢催化剂载体的良好前景.     

Adsorption separation of CO2 and N2 on MIL-101 metal-organic framework and activated carbon

In this work, the CO₂ and N₂ adsorption properties of MIL-101 metal-organic framework (MOF) and activated carbon (AC) were investigated using a standard gravimetric method within the pressure range of 0–30 bar and at four different temperatures (298, 308, 318 and 328 K). The dual-site Langmuir–Freundlich (DSLF) model was used to describe the CO₂ adsorption behaviors on these two adsorbents. The diffusion coefficients and activation energy E _a for diffusion of CO₂ in the MIL-101 and AC samples were estimated separately. Results showed that the isosteric heat of CO₂ adsorption on the MIL-101 at zero loading was much higher than that on the AC due to a much stronger interaction between CO₂ molecule and the unsaturated metal sites Cr³⁺ on MIL-101. Meanwhile, the dramatically decreased isosteric heats of CO₂ adsorption on MIL-101 indicated a more heterogeneous surface of MIL-101. Furthermore, the adsorption kinetic behaviors of CO₂ on the two samples can be well described by the micropore diffusion model. With the increase of temperature, the diffusion coefficients of CO₂ in the two samples both increased. The activation energy E _a for diffusion of CO₂ in MIL-101 was slightly lower than that in AC, suggesting that MIL-101 was much favorable for the CO₂ adsorption. The CO₂/N₂ selectivities on MIL-101 and AC were separately estimated to be 13.7 and 9.2 using Henry law constant, which were much higher than those on other MOFs.     

Adsorption of antimony using amino-functionalized magnetic MIL-101(Cr): Optimization by response surface methodology

Amino-functionalized magnetic MIL-101(Cr) was prepared via a one-step solvothermal method, characterized, and applied in adsorptive Sb(III) removal. The effects of solution pH, adsorbent dosage, and coexisting substances on the adsorption of Sb(III) by MIL-101(Cr)–NH₂/MnFe₂O₄ were studied. The adsorption kinetics were analyzed using pseudo-first order, pseudo-second order, intraparticle diffusion, and Elovich models, while Freundlich and Langmuir isotherm models were used to fit the experimental data. The pseudo-second-order kinetic model provided the best fit for the kinetic data. The maximum adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) was 91.07 ​mg/g, as calculated using the Langmuir adsorption isotherm model. Thermodynamic analysis revealed that the adsorption of antimony onto MIL-101(Cr)–NH₂/MnFe₂O₄ is spontaneous and endothermic, while response surface optimization revealed that the optimal conditions for Sb(III) adsorption by MIL-101(Cr)–NH₂/MnFe₂O₄ are an adsorbent loading of 222.55 ​mg/L, a pH of 4.5, and a temperature of 294.59 ​K. The predicted adsorption capacity of MIL-101(Cr)–NH₂/MnFe₂O₄ for Sb(III) is only a 1.8% deviation from the actual value. Furthermore, MIL-101(Cr)–NH₂/MnFe₂O₄ exhibits strong magnetism, allowing it to be separated from wastewater using a magnet. Finally, a preliminary economic analysis showed that the cost of treating a ton wastewater containing 25 ​mg/L antimony using this composite would be 26.24 USD. Thus, MIL-101(Cr)–NH₂/MnFe₂O₄ is promising for treatment of Sb(III)-containing wastewater.     

The Significance of Metal Coordination in Imidazole-Functionalized Metal–Organic Frameworks for Carbon Dioxide Utilization

The grafting of imidazole species onto coordinatively unsaturated sites within metal–organic framework MIL-101(Cr) enables enhanced CO₂ capture in close proximity to catalytic sites. The subsequent combination of CO₂ and epoxide binding sites, as shown through theoretical findings, significantly improves the rate of cyclic carbonate formation, producing a highly active CO₂ utilization catalyst. An array of spectroscopic investigations, in combination with theoretical calculations reveal the nature of the active sites and associated catalytic mechanism which validates the careful design of the hybrid MIL-101(Cr).     

Experimental and molecular simulation studies of CO2 adsorption on zeolitic imidazolate frameworks: ZIF-8 and amine-modified ZIF-8

ZIF-8 has been rapidly developed as a potential candidate for CO₂ capture due to its low density, high surface area, and robust structure. Considering the electron-donating effect of amino functional groups, amino-modification is expected to be an efficient way to improve CO₂ adsorption of ZIF-8. In this work, grand canonical Monte Carlo (GCMC) simulation was performed to study the CO₂ adsorption isotherm based on ZIF-8, ZIF-8-NH₂, and ZIF-8-(NH₂)₂. ZIF-8 was synthesized and CO₂ adsorption isotherms based on ZIF-8 was measured. The experimental surface area, pore volume, and CO₂ adsorption isotherm were used to validate the force field. Adsorptive capacity of ZIF-8-NH₂, and ZIF-8-(NH₂)₂ were first estimated. The GCMC simulation results indicated that the order of increasing CO₂ capacity of the ZIF-8 in the lower pressure regime is: ZIF-8 < ZIF-8-NH₂ < ZIF-8-(NH₂)₂, and in the high pressure is: ZIF-8 < ZIF-8-(NH₂)₂ < ZIF-8-NH₂. New adsorption sites can be generated with the existence of-NH₂ groups. In addition, for non-modified and amino-modified ZIF-8, it was the first time to use density functional theory (DFT) calculations to investigate their CO₂ adsorption sites and CO₂ binding energies. The present work indicates that appropriate amine-functionalized can directly enhanced CO₂ capacity of ZIF-8.