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。     

FeCo2(CO)9(μ3-S)簇合物羰基取代衍生物的合成与表征

Mono-、 di- and tri-substituted derivatives of FeCo₂(CO)₉(μ₃-S) with P(OR)₃ were synthesized. They have the following formular, FeCo₂(CO)_9-n(μ₃-S)［P(OR)₃］_n ［n=1, R=CH₂CH₂CH₃(a); n=1,2,3, R=CH₂CH₂CH₂CH₃(b); n=1,2,R=CH(CH₃)(CH₂)₂CH₃(c)］. The six new compounds were characterized by elemental analysis, IR, ¹H NMR and MS spectra and their molecular structures were deduced.     

纳米固体超强酸SO42-/Fe2O3的制备及其催化合成乙酸乙酯

将Fe₂O₃纳米粉体经一定浓度的H₂SO₄浸泡活化后制成纳米固体超强酸SO₄^2-/Fe₂O₃,将其用于催化合成乙酸乙酯以考察其活性。利用均匀设计分析了超强酸制备过程及酯化反应过程中各因素的影响,研究结果表明较好的制备条件是:H₂SO₄浓度:2.5mol·L^-1;浸泡时间:1h;活化温度:167℃;活化时间:1h,此时获得的固体超强酸SO₄^2-/Fe₂O₃的粒径小于50nm。当催化剂用量为冰乙酸质量的5%,n(乙醇)∶n(冰乙酸)为3∶1,反应3.5h后乙酸的转化率高于80%。该催化剂经H₂SO₄溶液浸泡、活化再生后可重新使用,推断出其酸强度H₀<-14.5。     

锂参与合成MOF-5用于CO2/CH4混合气体分离

利用溶剂热法合成了不同锂含量的MOF-5(xLi-MOF-5, x=0, 1, 3, 5).在MOF-5结晶过程中,锂离子被合并入其骨架结构中.实验表明,合并入骨架的锂能够改变MOF-5的结构和表面化学性质.不同的xLi-MOF-5能够不同程度降低骨架相互穿插的程度从而导致其吸附分离能力的大幅改变.其中,3Li-MOF-5具有最高的二氧化碳捕获能力(5.47 mmol·g^-1),对40% CO₂/60% CH₄混合气体具有最优吸附选择性.     

双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=5,6)的合成、结构、热稳定性及生物活性

氧化双[三(2-甲基-2-苯基)丙基]锡分别与庚二酸和辛二酸反应, 合成了2个双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂[(n=5 (1), 6 (2)], 经IR、¹H和¹³C NMR、元素分析和X射线单晶衍射对化合物进行了表征。化合物属单斜晶系, 空间群为P2₁/c。锡原子均为畸型四面体构型, 化合物1以氢键作用形成一维链状结构, 化合物2以氢键和C-H…π作用形成二维网状结构。化合物1和2在340 ℃以下具有良好的热稳定性, 对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有较好的体外抑制活性, 且具有一定的抑菌活性。     

双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=5, 6)的合成、结构、热稳定性及生物活性

氧化双[三(2-甲基-2-苯基)丙基]锡分别与庚二酸和辛二酸反应, 合成了2个双[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂[(n=5 (1), 6 (2)], 经IR、¹H和¹³C NMR、元素分析和X射线单晶衍射对化合物进行了表征。化合物属单斜晶系, 空间群为P2₁/c。锡原子均为畸型四面体构型, 化合物1以氢键作用形成一维链状结构, 化合物2以氢键和C-H…π作用形成二维网状结构。化合物1和2在340 ℃以下具有良好的热稳定性, 对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有较好的体外抑制活性, 且具有一定的抑菌活性。     

一个微孔钴基金属有机骨架的合成及其选择性气体吸附

利用硝酸钴与配体5,5''-di(1H-1,2,4-triazol-1-yl)-(1,1''-biphenyl)-2,2''-dicarboxylic acid (H₂DTBDA)进行溶剂热反应,制备了一个结构新颖的金属有机骨架{[Co(DTBDA)]₂·DMF·MeOH}_n (FJI-H37)。FJI-H37不仅具有适合气体分子吸附的0.69 nm的微孔,还具有良好的热稳定性及有机溶剂容忍性。气体吸附测试表明FJI-H37不仅能从C₂H₂/CO₂(体积比50:50)混合气中选择性吸附C₂H₂,还可以从CO₂/N₂(体积比15:85)和CO₂/CH₄(体积比50:50)混合气中选择性捕获CO₂;固定床突破实验进一步证实了其高效的气体分离能力。     

ZrCdOx/SAPO-18双功能催化剂催化CO2加氢合成低碳烯烃性能

采用并流共沉淀法制备了不同Zr/Cd原子比（n_Zr/n_Cd）的ZrCdO_x金属氧化物，并与水热法制备的不同硅铝比（n_SiO2/n_{Al2O3）的片状SAPO-18分子筛物理混合制得ZrCdOx/SAPO-18双功能催化剂，研究了其催化CO2加氢直接合成低碳烯烃性能。采用透射电子显微镜（TEM）、X射线衍射（XRD）、N2吸附-脱附、CO2程序升温脱附（CO2-TPD）、NH3程序升温脱附（NH3-TPD）和X射线光电子能谱（XPS）对催化剂进行了分析。与单一ZrO2相比，引入CdO使得ZrCdOx比表面积下降，当nZr/nCd=8时制备的Zr8Cd1氧化物呈现出无定形小颗粒状，Zr与Cd之间较强的协同作用使得ZrCdOx氧化物产生了更多的氧空位，有利于CO2的吸附活化。通过对Zr8Cd1金属氧化物与SAPO-18（硅铝比0.1）的质量比、工艺反应温度、压力和空速对催化性能影响的考察，获得了最佳反应条件。研究还发现，当SAPO-18的硅铝比从0.1降为0.01时，Brø；nsted酸含量降低，产物中烯烃/烷烃物质的量之比从18.6提高至37.2，但副产物CO含量迅速增加，低碳烯烃时空收率明显下降。}     

二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=2,3,4)的合成、结构及体外抗癌活性

丁二酸、戊二酸和己二酸分别与μ-氧-双[三(2-甲基-2-苯基)丙基]锡反应,合成了3个二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂(n=2(1),3(2),4(3))。对化合物1~3进行了元素分析、红外光谱及核磁共振(¹H,¹³C)表征,并通过X-射线晶体衍射分析测定晶体结构。化合物中锡与配基原子构成畸型四面体构型。试验表明,化合物2和3均对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460的增殖具有较强的抑制作用。     

二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH2)n[CO2Sn(CH2CMe2Ph)3]2(n=2, 3, 4)的合成、结构及体外抗癌活性

丁二酸、戊二酸和己二酸分别与μ-氧-双[三(2-甲基-2-苯基)丙基]锡反应, 合成了3个二[三(2-甲基-2-苯基)丙基锡]二元酸酯(CH₂)_n[CO₂Sn(CH₂CMe₂Ph)₃]₂(n=2 (1), 3 (2), 4 (3))。对化合物1~3进行了元素分析、红外光谱及核磁共振(¹H, ¹³C)表征, 并通过X-射线晶体衍射分析测定晶体结构。化合物中锡与配基原子构成畸型四面体构型。试验表明, 化合物2和3均对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460的增殖具有较强的抑制作用。     

Preparation of activated carbons and their adsorption properties for greenhouse gases: CH4 and CO2

Three kinds of activated carbons were prepared using coconut-shells as carbon precursors and characterized by XRD, FT-IR and texture property test. The results indicate that the prepared activated carbons were mainly amorphous and only a few impurity groups were adsorbed on their surfaces. The texture property test reveals that the activated carbons displayed different texture properties, especially the micropore size distribution. The adsorption capacities of the activated carbons were investigated by adsorbing CH4, CO2, N2 and O2 at 25 ?C in the pressure range of 0-200 kPa. The results reveal that all the activated carbons had high CO2 adsorption capacity, one of which had the highest CO2 adsorption value of 2.55 mmol/g at 200 kPa. And the highest adsorption capacity for CH4 of the activated carbons can reach 1.93 mmol/g at 200 kPa. In the pressure range of 0-200 kPa, the adsorption capacities for N2 and O2 were increased linearly with the change of pressure and K-AC is an excellent adsorbent towards the adsorption separation of greenhouse gases.     

树脂基球状活性炭的制备及对二氧化碳吸附性能的研究

以四种离子交换树脂（两种强碱性树脂D201和D280、两种弱碱性树脂D301G和D301R）为原料,经过磺化、炭化、活化处理制备了树脂基球状活性炭。采用TG、SEM、N₂吸附等对球状活性炭的收率、表面形貌、比表面积进行了表征,研究了所制球状活性炭对CO₂的吸附性能。结果表明,磺化处理有助提高树脂球的炭化收率;得到的四种球状活性炭对CO₂吸附性能良好,强碱性树脂球原料比弱碱性树脂球更具有优势,其中,由强碱性树脂球D201制得的树脂球状活性炭在30 ℃下对CO₂的吸附量可达2.57 mmol/g;十次循环吸附之后,树脂球仍能保持很好的CO₂吸附性能。     

Pilot production of activated carbon from cotton stalks using H3PO4

Cotton stalks, an agricultural waste, were chemically activated in a batch process using H₃PO₄ in a locally designed carbonizer at 420 °C in the absence of any purging gases. Mechanically cut short sticks were soaked in diluted H₃PO₄ for a short duration (Batch 1) and an extended period (Batch 2) prior to thermal treatment. The derived carbons contained both coarse and fine grains with acidic effect. Porosity was characterized by N₂ adsorption at −196 °C and the isotherms analyzed by the α-method to estimate total and microporous surface areas in addition to total and microporous volumes. The produced carbons exhibited well-developed porosity that was essentially microporous in composition. Several key performance parameters were altered considerably as a result of impregnation with H₃PO₄ and the extended chemical activation period (Batch 2). Most of the internal porosity of both carbons was accessible to adsorption of iodine, whereas the uptake of methylene blue dye was proportional to the average size of micropores which were larger for the batch with a longer acid soaking time. SEM and FTIR investigations revealed the presence of a developed honeycomb structure and different oxygen functionalities on surfaces of the activated products which are advantageous in liquid-phase applications. Preliminary laboratory-scale experiments with Pb(II) indicate that adsorption capacity of target heavy metals compares favorably with commercially available activated carbons. The raw material, pre-processing, and activation process prove feasible for the production of activated carbon on a large scale, thereby providing a sustainable strategy for treatment of toxic waste streams.     

ZrO4/SiO2-Al2O3催化肉桂醛MPV转移加氢性能

以九水合硝酸铝（Al（NO₃）₃·9H₂O）与正硅酸乙酯（TEOS）为前驱盐,采用溶胶-凝胶法制备一系列不同Al₂O₃含量的SiO₂-Al₂O₃复合氧化物,并通过浸渍硝酸氧锆引入ZrO₂,制备ZrO₂/SiO₂-Al₂O₃复合氧化物催化剂,考察催化剂在肉桂醛（CAL）MPV转移加氢中的催化性能,并结合N₂物理吸附、X射线粉末衍射（XRD）、傅里叶变换红外光谱（FTIR）、NH₃-程度升温脱附（NH₃-TPD）、Py-原位红外（Py-IR）等技术,研究催化剂结构、织构以及表面性质与其催化性能间的构效关系.研究表明,所制备的催化剂均以L酸为主,并含有少量B酸中心,这使得加氢产物以肉桂醇（COL）为主,并含有少量1-苯丙烯-2-丙基醚（CPE）.Al₂O₃含量不仅影响催化剂表面的酸中心数量,而且对催化剂的织构参数有较大影响.随Al₂O₃含量的增加,催化剂表面L酸与B酸中心均有所增加,而孔径则持续变小,这使得催化反应呈现CAL转化率先增加后减少、目标产物COL选择性先稍有减小后有所增加的趋势.在Si/Al比为2时,催化剂具有最优的催化性能,优化反应条件下,CAL转化率达96%,目标产物COL选择性达90%.     

Eu0.5RE0.5Fe0.5Mn0.5O3的57Fe Msosbauer谱研究

利用固相反应合成了Eu0.5RE0.5Fe0.5Mn0.5O3(RE=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Y)等化合物。测量了其XRD谱及57FeMssbauer谱。实验发现,随着RE原子序数的增加,样品的晶胞体积减小,Fe在化合物中处于Fe3+的高自旋状态,57Fe的四极裂矩与样品的畸变参数D成线性关系。     

Selective fast pyrolysis of biomass impregnated with ZnCl2: Furfural production together with acetic acid and activated carbon as by-products

Fast pyrolysis of biomass materials impregnated with ZnCl₂ offered a promising way to obtain a liquid product rich in furfural (FF) and acetic acid (AA), and the pyrolytic solids could be used as the precursors to prepare activated carbons (ACs). In this study, a lab-scale fast pyrolysis set was designed and used for the quantitative production of the three chemicals. The maximum FF was produced from the corncob impregnated with at least 15 wt% ZnCl₂ and at the pyrolysis temperature around 340 °C, with the yield of more than 8 wt% compared with only 0.49 wt% from the raw corncob. Meanwhile, AA of around 4 wt% could be obtained. The content of the FF and AA was over 50 wt% and 25 wt% on the water-free basis of the pyrolytic liquids. In addition, ACs were prepared from the pyrolytic solids, and they exhibited similar properties as those prepared from direct activation of ZnCl₂-impregnated biomass materials.     

Y掺杂Ba0.90Sr0.08Ca0.02TiO3固溶体纳米晶粒尺寸 对其晶体结构的影响

The title nanocrystalline powders were prepared by sol-gel method, the influences of grain size on crystal structure were investigated by XRD and DSC techniques.The experiment results show that the tetragonal ferroelectric phase content of the powders and the Curie temperature Tc are increased with the increase of grain size.When the grain size is less than 34.7nm, crystal structure of the particle changes into cubic paraelectric phase and the transition of ferro-paraelectric phase disappears as well.     

SnO_2改性TiO_2对V_2O_5-WO_3/TiO_2催化剂结构和SCR性能影响

采用共沉淀法将SnO_2组分掺入到V_2O_5-WO_3/TiO_2催化剂载体TiO_2中,并通过多种物理化学手段,考察了不同SnO_2掺入量时对催化剂结构,表面分散物种和SCR性能影响.结果表明,SnO_2掺入到TiO_2中,元素Sn与Ti以Sn—O—Ti键形式相互作用,促进锐钛矿型TiO_2向金红石型TiO_2转变.在特定条件下,VO_x与WO_x物种和SnTi氧化物之间以V—O—Ti(Sn)和W—O—Ti(Sn)键形式相互作用,提高了VO_x物种可还原能力、促进了具有更多B酸酸量四面体WOx物种和V~(5+)物种生成.VW/SnTi催化剂表面VO_x物种与WO_x物种之间的相互作用更强.因此,VW/SnTi催化剂具有更好的SCR活性.     

一维纳米Co_3O_4,Ag/Co_3O_4及CuO/Co_3O_4的合成与电催化性能(英文)

采用水热合成法制备了Co3O4及复合Ag/Co3O4、CuO/Co3O4一维纳米产品。用XRD,FE-SEM和TEM手段对产品进行了表征。采用循环伏安法研究了合成产品修饰的玻碳电极在碱性溶液中对对硝基苯酚的电催化还原性能。与裸玻碳电极相比,1mmol·L-1的对硝基苯酚在用Co3O4、特别是CuO/Co3O4修饰的玻碳电极上还原的峰电流明显增大,用Ag/Co3O4(Ag/Co原子比分别为1∶5和2∶5)修饰的玻碳电极催化还原对硝基苯酚时,尽管还原峰电流增大不是太大,但其峰电位明显降低(分别降低0.265和0.371V)。     

复合多铁材料NiFe2O4/BaTiO3的制备及性能

采用溶胶-凝胶与固相反应相结合的方法制备了xNiFe2O4/(1-x)BaTiO3(x=0.1,0.2,0.3,0.4,0.5,0.6)系列复合多铁材料.X射线衍射(XRD)结果表明,复合材料中只含有钙钛矿结构的BaTiO3和尖晶石结构的NiFe2O4,说明共烧过程中两者未发生明显的化学反应,铁电相与铁磁相共存.扫描电子显微镜(SEM)观测结果表明材料内部是异质结构的,高分辨透射电子显微镜(HRTEM)观测结果进一步说明了NiFe2 O4和BaTiO3共存,并且在两种物质的接触处能够看到清晰的界面.这种由BaTiO3和NiFe2 O4组成的复合材料对外同时表现出铁电性和铁磁性.电滞回线结果表明,该复合材料具有铁电性,但存在着一定的漏电.介电频谱表明材料的介电常数随着频率的升高而下降,在低频下达到定值,并且铁磁相的含量对材料的介电性有影响.磁性能测试结果表明材料的磁性源于NiFe2O4,并且磁性随着NiFe2O4含量的增加而增强.