乙二胺改性金属有机骨架材料MIL-101(Cr)常压下吸附CO

采用溶剂热法将乙二胺接枝到金属有机骨架材料MIL-101(Cr)上,用于常压下CO_2的吸附,研究了乙二胺接枝量及温度对材料结构、形貌和CO_2吸附性能的影响.结果表明,乙二胺改性的MIL-101材料在常温常压下对CO_2的吸附量可达2.43 mmol/g,比改性前提高14.6%,CO_2/N_2的吸附分离系数从11提高至17,比改性前提高55.6%.改性后材料经80℃真空加热可完全脱附再生,具有很好的再生稳定性.     

Cu/MIL-101(Cr)吸附剂的制备及其CO吸附性能

采用浸渍法将甲酸铜与氯化铜前驱体负载到金属有机骨架材料MIL-101载体上,通过改变活化温度和铜盐负载量,制备Cu/MIL-101吸附剂。用XRD、FT-IR、TG、N_2吸附和脱附等表征手段考察材料的结构和性能,测试Cu/MIL-101吸附剂在101.3k Pa、25℃的CO、N_2吸附量。结果表明,制备该吸附剂的最佳活化温度为220℃,最佳铜盐负载量为4mmol·(gMIL-101)~(-1)。铜基改性后的吸附剂CO的吸附量由23.93cm~3·g~(-1)提高到53.55cm~3·g~(-1),N_2的吸附量由5.81cm~3·g~(-1)下降到3.29cm~3·g~(-1),用理想吸附溶液理论IAST模型预测CO/N_2吸附选择性由26提高到2194。吸附剂可在200℃、真空下再生。     

油气/水蒸气在乙二胺改性MIL-101(Cr)-NDC材料上的吸附性能研究

以乙二胺(ED)为改性剂对MIL-101(Cr)-NDC进行表面改性,以改变材料的亲油疏水性能。经XRD、FT-IR、N2吸附和脱附等表征表明,ED分子成功连接入材料中。采用C_5~C_7正构烷烃模拟油气组份测定材料的油气吸附性能,并考察了相对湿度对改性前后材料油气吸附性能的影响。结果表明,25℃下,C_5~C_7正构烷烃和水蒸气在ED-MIL-101(Cr)-NDC上静态吸附量分别为0.558、0.695、0.613 g/g和0.254 g/g,与改性前材料相比,ED-MIL-101(Cr)-NDC的C_5~C_7正构烷烃静态吸附量较高,水蒸气静态吸附量较低;ED-MIL-101(Cr)-NDC在97%相对湿度下的C_5~C_7正构烷动态吸附量为0%相对湿度下C_5~C_7正构烷动态吸附量的65%左右。改性后材料的油气静态吸附性能提升明显,且水蒸气对ED-MIL-101(Cr)-NDC油气吸附影响较小。     

金属有机骨架材料MIL-101（Cr）-NH2的合成及其气体吸附性能

采用碱辅助的原位水热合成法制备了纳米金属有机骨架材料MIL-101(Cr)NH2,研究了合成液中NaOH加入量对其晶体结构、形貌和孔结构的影响,测定了273.4,298和333K下CO2和N2在MIL-101(Cr)NH2上的等温吸附曲线,并对其性质进行了表征.结果表明,加入适量碱(NaOH:NH2BDC=4:2,摩尔比)可得到粒径约40nm的MIL-101(Cr)NH2纳米颗粒,其BET比表面积可达2594m2/g,孔容为2.11cm3/g,273.4K时CO2的吸附量可达25.9mmol/g,CO2与N2的理想分离系数为19.4.     

银、铈改性MIL-101脱硫吸附剂的制备与优化

利用银、铈双金属改性金属有机骨架MIL-101制备Ag-Ce/MIL-101吸附剂，并对Ag-Ce/MIL-101进行XRD、SEM、BET和ICP表征。考察了制备条件对Ag-Ce/MIL-101吸附苯并噻吩(BT)性能的影响。结果表明，Ag-Ce/MIL-101未破坏MIL-101的原始晶格结构，比表面积和孔容有所降低。适宜Ag-Ce/MIL-101的制备条件为：负载顺序为先银后铈，金属负载浓度均为40 mmol/L,金属溶液用量均为2 mL,负载温度为150℃,负载时间为9 h。在吸附剂质量为0.1 g、模拟油用量为20 mL、吸附温度为30℃、吸附时间为12 h时，Ag-Ce/MIL-101对BT的吸附量达到33.9 mg/g。     

D301树脂的胺基化改性及其对AuCl4-的吸附性能

以D301树脂表面的胺基与过硫酸铵构成氧化-还原引发体系,将单体甲基丙烯酸缩水甘油酯(GMA)接枝聚合到D301树脂表面,制得接枝材料D301-g-PGMA;通过聚甲基丙烯酸缩水甘油酯(PGMA)分子链上的环氧基团与乙二胺中胺基的开环反应,实现接枝材料的胺基化改性,制得吸附材料D301-g-APGMA,考察了接枝聚合条件对接枝率的影响及胺基化反应条件对胺基含量的影响,对材料的结构进行了表征,研究了其对AuCl4-的吸附性能. 结果表明,在GMA用量10 mL、过硫酸铵为单体质量的1.5%及40℃条件下反应18 h, PGMA接枝率达41.15%. 胺基化改性时,在90℃下反应8 h,D301-g-PGMA上环氧键的开环率达91.67%. 改性后D301-g-APGMA对AuCl4-的吸附能力比D301树脂有较大提升,吸附容量达276.74 mg/g. D301-g-APGMA具有良好的再生与重复使用性能.     

乙醇在MIL-101上的吸附相平衡及其吸附机理

主要研究了MIL-101材料对乙醇的吸附性能和吸附机理。采用水热合成法制备了MIL-101(Cr),并分别应用N₂静态吸附、X射线粉末衍射(PXRD)、傅里叶红外光谱(FTIR)等分析手段对MIL-101晶形结构、孔隙结构参数进行分析表征。应用静态吸附法测定乙醇和水蒸气在不同温度下的吸附等温线,并讨论乙醇吸附在MIL-101(Cr) 4种吸附位的机理,根据吸附等温线估算出乙醇和水蒸气在MIL-101上的等量吸附热,并测试了乙醇在MIL-101上的吸附循环性能。研究表明,在298 K下,MIL-101的乙醇吸附容量为20.3 mmol·g^-1,远高于传统吸附材料。在低压下MIL-101对乙醇的吸附量高于水蒸气的吸附量,这是由于乙醇的偶极矩和分子动力学直径均比水大,使得乙醇分子在孔道中受到更大吸附力场作用;在低吸附量范围,乙醇在MIL-101上的等量吸附热要高于水蒸气的等量吸附热。在较高吸附压力条件下,主要发生多层吸附或孔填充,受吸附剂的孔容限制效应,尺寸越大的分子被吸附的物质的量会越少,由于乙醇的动力学直径(0.45 nm)大于水分子的动力学直径(0.268 nm),所以在较高吸附压力下乙醇在MIL-101上吸附量要小于水蒸气的吸附量。多次吸附脱附等温线测试显示MIL-101具有良好的乙醇吸附循环性能。     

MIL-101(Cr)开式吸附性能实验

采用水热合成法制备水热稳定金属有机骨架MIL-101(Cr),基于太阳能吸附式空气取水选取不同的实验工况,将MIL-101(Cr)、细孔硅胶作为研究对象,相对湿度控制在50%、温度范围5～45℃条件下,测试并对比了MIL-101(Cr)与细孔硅胶的吸附性能。实验表明,35℃、50%RH条件下,吸附过程进行1000min,MIL-101(Cr)水吸附量为22.05g/100g,其吸附量相比细孔硅胶提高93%左右;当系统平衡时,MIL-101(Cr)有效平均吸附速率相比细孔硅胶提高120%左右。此外,在相对湿度（RH）50%、温度范围5～45℃条件下,MIL-101(Cr)的平衡吸附量在11.40～23.47g/100g之间。在所控温度下,MIL-101(Cr)在25℃时平衡吸附量最大,在5℃时平衡吸附量最小,25℃时MIL-101(Cr)的平衡吸附量相比5℃时提高106%左右。该实验可以为四季工况不同温度下MIL-101(Cr)用于太阳能吸附式空气取水提供基础数据。     

油气/水蒸气在TMCS改性MIL-101(Cr)上的吸附性能研究

采用三甲基氯硅烷(TMCS)对MIL-101(Cr)进行表面改性处理以改变材料的疏水亲油性能,经XRD、FT-IR、N2吸附和脱附、表面羟基滴定等表征证明TMCS分子通过与MIL-101(Cr)表面羟基缩合进入骨架。采用C5~C7正构烷烃模拟油气组份,测试了MIL-101(Cr)和TMCS-MIL-101(Cr)的油气和水蒸气的静态吸附性能,并考察了相对湿度对油气动态吸附性能的影响。结果表明,25℃下C5~C7正构烷烃以及水蒸气在TMCS-MIL-101(Cr)上静态吸附量分别为0.433、0.510、0.464和0.233 g?g?1,与MIL-101(Cr)相比TMCS-MIL-101(Cr)的C5~C7正构烷烃静态吸附量较高,水蒸气静态吸附量较低;根据穿透曲线计算,在相对湿度97%时TMCS-MIL-101(Cr)对C5~C7正构烷烃的动态吸附量为相对湿度0%时的80%以上。改性后材料的油气静态吸附性能提升明显,且水蒸气对TMCS-MIL-101(Cr)油气吸附影响较小。     

金属有机骨架结构MIL-101的合成及其吸附脱硫的工艺研究

采用水热合成方法合成金属有机骨架化合物MIL-101,利用X射线粉末衍射(XRD),对其产品表征,并研究提高合成产率的影响因素;以MIL-101做为吸附剂,研究吸附脱除汽油模型油中噻吩的最佳工艺条件。实验结果表明,晶化时间提高到10h,pH值为1.5时,MIL-101的合成产率达到60%,产率比文献值提高10%;在空速150h-1,MIL-101质量为0.075g,噻吩质量分数为1×10-3时,噻吩在正辛烷中的穿透容量为0.69%,饱和吸附量为4.62%;MIL-101和4A分子筛分层装柱,并利用N2在100℃对床层进行活化处理,消除了溶解水对吸附脱硫过程的影响;以甲苯为脱附剂,在100℃,空速为100h-1对吸附剂进行再生处理,再生率为96.38%。     

胺功能化MIL-101(Cr)@SiO_2@Fe_3O_4催化剂及其Knoevenagel反应性能

采用溶剂热法在纳米SiO_2@Fe_3O_4磁性颗粒表面原位合成MIL-101(Cr),制备磁性MIL-101(Cr)@SiO_2@Fe_3O_4催化剂。采用甲胺、乙二胺和丁二胺对制备的磁性催化剂进行功能化,得到胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂。利用XRD、FT-IR、BET、SEM、TEM和VSM等对催化剂结构进行表征,评价胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂对糠醛和氰乙酸乙酯Knoevenagel缩合反应性能和重复使用性能,考察反应条件与催化性能的关系。结果表明,制备的新型胺功能化NH2-MIL-101(Cr)@SiO_2@Fe_3O_4催化剂具有MIL-101(Cr)的结构特征和良好的超顺磁性能,对糠醛和氰乙酸乙酯Knoevenagel缩合反应表现出很好的催化性能,其中,乙二胺功能化30%MIL-101(Cr)@SiO_2@Fe_3O_4催化剂对Knoevenagel缩合反应的性能最佳,在反应温度40℃和反应时间1 h条件下,氰乙酸乙酯转化率为97. 0%,产物选择性接近100%。反应后磁性催化剂可以通过外磁场容易进行分离,重复使用5次,氰乙酸乙酯转化率仍大于93%。     

多种因素对MIL-101(Cr)选择性吸附水溶液中染料的影响

在多种条件下研究了金属有机框架MIL-101(Cr)对阳离子型染料(亚甲基蓝、罗丹明B)和阴离子型染料(甲基橙、酸性铬蓝K)的吸附性质,主要研究了MIL-101(Cr)对亚甲基蓝和甲基橙的选择性吸附作用。结果表明,中性环境下无论在单组分还是双组分体系中MIL-101(Cr)对阴离子型染料的吸附能力均大于对阳离子型的吸附能力。在pH=3,T=300 K的条件下,选择性系数β可达5.9,但随着pH的增加,选择性系数逐渐降低。相比之下,温度对吸附的选择性影响不大。选择性吸附的机理可以解释为:由于表面带正电荷,MIL-101(Cr)对阴离子型染料产生静电吸引作用;相反,对阳离子型染料的排斥作用而降低了其吸附能力。另外,乙二胺改性提高了MIL-101(Cr)对阴离子型染料的选择吸附性能,而草酸改性降低了选择吸附性。     

Rapid synthesis of CNTs@MIL-101(Cr) using multi-walled carbon nanotubes (MWCNTs) as crystal growth accelerator☆

In this work,hybrid material CNTs@MIL-101(Cr) was synthesized in 2 h using multi-walled carbon nanotubes(MWCNTs) as the crystal growth accelerator with hydrothermal method.The characteristic differences between the crystals of CNTs@MIL-101(Cr) and MIL-101 were investigated by N_2 adsorption–desorption isotherms,X-ray diffraction(XRD),scanning electron microscope(SEM) and thermogravimetric analyzer(TGA).The results showed that MWCNTs embedding in the hybrid material provide more mesoporous volumes than that of MIL-101.Moreover,the fast synthesized crystals of CNTs@MIL-101(Cr) still preserve the octahedral shape like MIL-101 and have a larger size ranging from 1.5 to 2.0 μm which were approximately three times larger than that of MIL-101.In the proposed mechanism,the roles of MWCNTs played in the crystallization were discussed where MWCNTs can be seen as coaxial cylindrical tubes composed of multi-layer graphenes and the place where nucleation and crystal growth processes occur at the tubes' out surface.Then,a crystal seeding layer bonding with the MWCNTs may be easily formed which accelerates the growth rate of MIL-101 crystals.Thus,larger crystals of CNTs@MIL-101(Cr) were formed due to the faster crystal growth rate of MIL-101.     

Hierarchically structural polyacrylonitrile/MIL-101(Cr) nanofibrous membranes with super adsorption performance for indoxyl sulfate

Excess protein-bound uremic toxins (such as indoxyl sulfate [IS]) in the blood could aggravate chronic kidney disease and also predispose to serious cardiovascular disease. In this study, we constructed a novel IS adsorbent polyacrylonitrile/MIL-101(Cr) (PAN-M) nanofibrous membrane with high adsorption capacity and ultra-fast sorption rate for IS. The porous metal–organic framework MIL-101(Cr) were embedded in PAN nanofibers by electrospinning as an adsorbent for easy recovery. It was found that MIL-101(Cr) had a strong electrostatic effect on the SO₃⁻ of IS and could reach the adsorption equilibrium within 5 min. Notably, MIL-101(Cr) showed an extremely high adsorption capacity (~170 mg/g) for IS. The MIL-101(Cr) loading of prepared PAN-M nanofibrous membrane was optimized at 60 wt% and the optimal PAN-M60 exhibited an appreciable IS adsorption capacity (103 mg/g). The removal of IS was enhanced from 35.4% to 62.5% during hemodialysis by using PAN-M60 as adsorbent immersed in dialysate. This efficient adsorption performance can greatly reduce the consumption of dialysate and may shorten the hemodialysis time. This work would provide a fresh perspective on the development of MOF-based adsorbents to improve hemodialysis therapies.     

MIL-101Cr-F/Cl用于N2O的捕集研究

氧化亚氮（N₂O）是仅次于CO₂和CH₄的第三大温室气体,对其捕集具有资源回收和减排温室气体的双重价值。本文通过添加氢氟酸和盐酸合成了末端具有不同阴离子的MIL-101Cr材料：MIL-101（Cr）-F和MIL-101（Cr）-Cl,通过XRD、BET、SEM等对样品进行了表征,测试并分析了两种样品对N₂O和N₂的吸附性能,进行了选择性和吸附热的计算以及混合气体的穿透模拟。研究结果表明,MIL-101（Cr）-Cl拥有目前最高的N₂O吸附容量（6.43 mmol/g,298 K）和N₂O/N₂选择性（267）,混合气体（N₂O/N₂=0.1%/99.9%）穿透模拟结果显示MIL-101（Cr）-Cl具有更加优异的微量N₂O捕获能力。     

Conversion of CO into CO2 by high active and stable PdNi nanoparticles supported on a metal-organic framework

The solubility of Pd(NO₃)₂ in water is moderate whereas it is completely soluble in diluted HNO₃ solution. Pd/MIL-101(Cr) and Pd/MIL-101-NH₂(Cr) were synthesized by aqueous solution of Pd(NO₃)₂ and Pd(NO₃)₂ solution in dilute HNO₃ and used for CO oxidation reaction. The catalysts synthesized with Pd(NO₃)₂ solution in dilute HNO₃ showed lower activity. The aqueous solution of Pd(NO₃)₂ was used for synthesis of mono-metal Ni, Pd and bimetallic PdNi nanoparticles with various molar ratios supported on MOF. Pd₇₀Ni₃₀/MIL-101(Cr) catalyst showed higher activity than monometallic counterparts and Pd+ Ni physical mixture due to the strong synergistic effect of PdNi nanoparticles, high distribution of PdNi nanoparticles, and lower dissociation and desorption barriers. Comparison of the catalysts synthesized by MIL-101(Cr) and MIL-101-NH₂(Cr) as the supports of metals showed that Pd/MIL-101-NH₂(Cr) outperforms Pd/MIL-101-(Cr) because of the higher electron density of Pd resulting from the electron donor ability of the NH₂ functional group. However, the same activities were observed for Pd₇₀Ni₃₀/MIL-101(Cr) and Pd₇₀Ni₃₀/MIL-101-NH₂(Cr), which is due to a less uniform distribution of Pd nanoparticles in Pd₇₀Ni₃₀/MIL-101-NH₂(Cr) originated from amorphization of MIL-101-NH₂(Cr) structure during the reduction process. In contrast, Pd₇₀Ni₃₀/MIL-101(Cr) revealed the stable structure and activity during reduction and CO oxidation for a long time.     

Adsorption Refrigeration Performance of Shaped MIL-101-Water Working Pair

A new metal-organic framework of MIL-101 was synthesized by hydrothermal method and the powder prepared was pressed into a desired shape. The effects of molding on specific surface area and pore structure were investigated using a nitrogen adsorption method. The water adsorption isotherms were obtained by high vacuum gravimetric method, the desorption temperature of water on shaped MIL-101 was measured by thermo gravimetric analyzer, and the adsorption refrigeration performance of shaped MIL-101-water working pair was studied on the simulation device of adsorption refrigeration cycle system. The results indicate that an apparent hysteresis loop ap-pears in the nitrogen adsorption/desorption isotherms when the forming pressure is 10 MPa. The equilibrium ad-sorption capacity of water is up to 0.95 kg·kg^-1 at the forming pressure of 3 MPa （MIL-101-3）. The desorption peak temperature of water on MIL-101-3 is 82℃, which is 7 ℃ lower than that of silica gel, and the desorption temperature is no more than 100 ℃. At the evaporation temperature of 10 ℃, the refrigeration capacity of MIL-101-3-water is 1059 kJ·kg^-1, which is 2.24 times higher than that of silica gel-water working pair. Thus MIL-101-water working pair presents an excellent adsorption refrigeration performance.     

Heterogeneity of Adsorption Sites and Adsorption Kinetics of n-Hexane on Metal-Organic Framework MIL-101(Cr)

abstract The heterogeneity of adsorption sites and adsorption kinetics of n-hexane on a chromium terephthalate-based metal-organic framework MIL-101(Cr) were studied by gravimetric method and temperatu...