Cu-MCM-41介孔分子筛中不同价态铜上的吸附性能研究

合成了不同铜含量的Cu-MCM-41，高温还原后仍具有良好的介孔结构。孔壁中的铜容易被H₂还原为Cu(0)。通过在氦气流中加热，可以导致孔壁中的Cu(II)还原为Cu(I)。MCM-41中不同价态的铜具有不同的吸附性能：Cu(0)强烈吸附O₂，吸附热高达427 kJ·mol^-1；Cu(I)在室温下几乎不吸附O₂，表明Cu(I)在室温下较稳定；而Cu(I)在对CO与C₂H₄的吸附中，除了CO的吸附热与Cu(0)的相近外，所生成的吸附热与吸附量均较高。红外光谱也表明，Cu(I)比Cu(0)更容易吸附CO与C₂H₄。C₂H₄仅仅以π-键键合在Cu(0)表面，而在Cu(I)表面上却是以di-σ和π-键键合，由于di-σ键较强，使得C₂H₄在Cu(I)上具有较高的吸附热。     

Effect of Phosphorylation of Si-MCM-41 and Ti-Si-MCM-41 Mesoporous Molecular Sieves on Their Structure-Adsorption and Acid Properties

Transmission electron microscopy, X-ray diffraction, nitrogen and argon adsorption, thermal analysis, thermoprogrammed ammonia desorption, and ¹H MAS NMR spectroscopy were used to show that phosphorylation by POCl₃ yields MCM-41 silica gel and Ti-MCM-41 titanium-silica gel mesoporous molecular sieves with about 1.1 mmol/g acid sites consisting largely of hydroxyl group protons of supported phosphoric acid. These materials display catalytic activity in the esterification of acetic acid by ethanol.     

吸附量热技术和金属氧化物催化剂的表面酸碱性

 探讨了吸附量热技术及其在测定固体表面酸碱性中的应用．使用NH3和CO2为探针分子,吸附量热技术能够定量地描述固体表面酸碱中心的数目和强度分布．结合原位红外光谱,还能够详细地了解表面酸碱中心的性质：金属氧化物表面的Lewis酸中心和碱中心分别是表面配位不饱和的金属离子和氧负离子,Brnsted酸中心和碱中心则是金属氧化物表面的羟基．通过测量吸附热,金属氧化物的表面酸碱性强度可与Sanderson电负性关联起来,也可以考虑使用Drago参数来描述固体表面的酸碱性．根据酸碱性与电负性的关系以及对表面配位不饱和离子的要求,有可能通过选择合适的复合金属氧化物组成,获得具有一定酸（碱）量和酸（碱）强度的固体酸（碱）．     

Acid Properties of SiMCM-41 Mesoporous Molecular Sieve

The SiMCM-41 mesoporous molecular sieve was synthesised by the hydrothermal method. The physicochemical characterisation by infrared spectroscopy, X-ray diffraction and thermogravimetry, showed that the material presents a well-defined structure. In this study, the determination of the total acidity and relative strength of the acid sites of the SiMCM-41,was performed by desorption of adsorbed n-butylamine combined with thermogravimetric measurements. The total acidity, determined by means of the amount of amine desorbed normalised by mass of solid, was equivalent to 0.927 mmol g^–1, in the temperature range from 96 to 235°C. By using the Flynn and Wall integral kinetic model, at 5, 10 and 20°C min^–1 heating rates, it was determined that the activation energy to desorb n-butylamine was 90.7 kJ mol^–1, in the same temperature range, evidencing that SiMCM-41 presents only weak acid sites on its surface. This revised version was published online in July 2006 with corrections to the Cover Date.     

NH3在选择性催化还原NO过程中的吸附与活化

 通过大量文献并结合自己的工作,以NH3在催化剂表面的阶段氧化脱氢为主线,分析归纳了选择性催化还原(SCR)反应机理和该体系中可能发生的NH3氧化副反应机理的联系和共性. 对于V2O5/TiO2催化剂,大部分学者认为SCR反应与Brnsted酸性位上的NH+4有关,中间体为NH+3(ads); 而少数学者认为SCR反应与Lewis酸性位上的NH3有关,中间体为NH2(ads). 对于其它SCR催化剂,普遍认可L酸性位上NH3活化脱氢形成的NH2(ads)既是SCR反应中间体,也是NH3氧化生成N2的中间体; NH3氧化生成N2O和NO的反应源于NH2(ads)的进一步脱氢. 尽管有关SCR反应中NH3的吸附位存在分歧,但从NH3吸附后活化的角度看, NH3无论吸附在L酸性位还是B酸性位,都先经过阶段氧化脱氢,然后再参与SCR反应. 由于反应中生成的H2O可能导致L酸向B酸转化,且该转化受反应温度影响,因此不同酸性位机理可能没有本质区别, SCR反应关键是NH3吸附位的氧化性. SCR活性取决于NH3在催化剂表面的吸附量和阶段氧化程度. 催化剂应能吸附足够的NH3, 这与其表面酸碱性有关; 吸附的NH3要能被活化脱氢且程度不宜太高,这与表面氧化还原性有关. 反应温度也会影响NH3的吸附量和活化程度,因此开发高效SCR脱硝催化剂的关键是根据反应温度调控其表面酸性和吸附位的氧化性.     

改性Y分子筛的酸碱性能及吸附性能的研究

吡啶、吡咯、苯、甲苯、乙苯作为探针分子，在Li＋, Na＋, K＋, Cs＋改性的Y型分子筛上进行吸附，用TPD及IR方法系统地研究了不同碱金属离子改性的Y型分子筛的酸碱性能和吸附性能的变化. 结果表明，按Li、Na、K、Cs的顺序, 随着碱金属离子半径的增大, 其L酸酸强度依次减弱，L碱的强度逐渐增强.由于改性Y型分子筛所含碱金属离子的不同，其对芳烃的吸附的强弱及吸附量的大小亦不同.随着骨架外的阳离子的半径逐渐增大，碱的强度逐渐增强，与芳烃的作用愈强烈，导致TPD脱附峰温增高及芳烃和侧链上的C－H伸缩振动谱带向低波数位移愈多.由于位阻的原因，对含同一种碱金属离子的分子筛来说，随着芳烃侧链C数的增加，芳烃的吸附量逐渐减小.     

Synthesis and Characterization of Mesoporous Titanosilicate as an Adsorbent for Toxic Metal Ions

Hexagonal mesoporous titanosilicates (Ti‐MCM‐41) have been prepared using cetyltrimethylammonium bromide (CTAB) as the structure directing agent under the mild alkaline conditions. Powder X‐ray diffraction, nitrogen gas sorption, FTIR spectroscopy and thermogravimetry analysis of samples have confirmed that well ordered MCM‐41 type mesoporous materials were prepared. The potential of removing toxic metal ions from waste waters using mesoporous titanosilicates was evaluated. Separation of Co^II‐U^VI, Cs^I‐U^VI and Sm^III‐U^VI has been developed on columns of this adsorbent.     

用PASCA及NH3-TPD法表征Al2O3载体表面酸度

采用PASCA（化学分析正电子湮没谱）及NH3-TPD法表征加氢处理催化剂Al2O3载体表面酸度及焙烧条件对Al2O3载体表面酸度的影响。实验结果对比表明：采用两种方法所测定的各类酸中心数结果非常接近，在焙烧温度为750℃时，Al2O3表面的强酸中心已全部丧失，只保留少量中强酸中心和相当数量的弱酸中心。     

介孔材料Co-MCM-41的合成及其吸附脱除各种碱性氮化物

采用水热法合成了MCM-41和不同Co/Si物质的量比的Co-MCM-41介孔材料,并采用XRD、FT-IR和低温氮气吸附-脱附方法对样品进行了表征。FT-IR及XRD表征结果说明,Co原子已经进入了介孔材料的孔壁。合成的MCM-41及Co/Si(物质的量比)为0.18以下的Co-M CM-41都具有六方有序排列的介孔结构。当加入的Co/Si(物质的量比)为0.22时,样品的(100)峰完全消失,不具备六方有序排列的介孔结构,说明以硝酸钴为钴源合成Co-MCM-41的最大Co加入量为Co/Si(物质的量比)为0.18左右。与MCM-41相比,各Co-MCM-41样品的XRD(100)峰随着Co加入量的增加逐渐变宽变弱,比表面积和孔容变小,平均孔径增大。当加入的Co/Si物质的量比大于0.06时,Co-MCM-41的介孔孔道中存在少量聚集态的Co3O4。利用合成的Co-MCM-41吸附脱除氮含量为1737.35μg/g模拟燃料中的碱性氮化物喹啉、苯胺或吡啶,结果表明,所有样品的吸附脱氮效果顺序为苯胺吡啶喹啉。Co-MCM-41(0.06)的吸附容量和氮脱除率明显要高于其他样品,对苯胺、吡啶和喹啉的吸附容量分别为42.17、35.66和29.18 mg(N)/g,去除率分别为82.38%、73.53%和61.11%。添加到模拟燃料中的芳烃化合物萘、苯或甲苯对其吸附脱氮没有影响,表明介孔材料Co-MCM-41对各种含氮化合物的吸附主要是N原子与Co的配位络合吸附,而不是π-π络合作用。采用焙烧或乙醇溶剂洗涤再生后的Co-MCM-41(0.06)恢复了吸附脱氮能力,说明其具有较好的再生性能。     

氨基改性介孔二氧化硅的制备及其吸附性能研究

合成了一种具有较大孔径的氨基改性介孔二氧化硅材料(m-MCF)。通过XRD、TEM、低温氮吸附、TGA、FTIR以及原子吸收光谱(AAS)等表征方法对产物的结构和性能进行的分析表明:利用三甲基苯为扩孔剂制备得到的介孔材料具有较大的孔径，有利于功能基团对孔内表面的改性。当氨基改性介孔材料后，该材料仍然保留较大的孔径(22 nm)和较高的比表面积(444 m²·g^-1)。研究发现:与改性而未扩孔的介孔二氧化硅SBA-15相比，该材料对铜离子的吸附能力提高了2倍。     

Tg/dta,Xrd and NH3-TPD Characterization of Layered VOPO4·2H2O and its Fe3+-Substituted Compound

Iron(III)-substituted vanadyl phosphate, [Fe(H2O)]0.20VO0.80PO4·2.25H2O (FeVOP), has been prepared and characterized by XRD and TG/DTA analyses. The new compound is isomorphous with layered tetragonal VOPO4·2H2O (VOP), but it possesses a lower interlayer distance. Information on the reactivity and surface acidity of both VOP and FeVOP has been obtained by NH3-TPD experiments. The hydrated materials adsorb high amounts of NH3 (up to 2 mmol g-1). Different ammonia-containing phases are formed, characterized by lower interlayer distances in comparison with the NH3-free parent compounds. NH3 is intercalated between the layers without displacement of water. The materials dehydrated by heat treatment at 450°C retain the layered structure but adsorb NH3 only on the external surface. A wide variety of acid sites, from weak to strong, was observed. A mechanism is proposed for the NH3- acid sites interaction. SEM micrographs of VOP and FeVOP are shown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of adsorption properties of synthesized mesoporous silica doped with dysprosium and modified with nickel

Mesoporous silica (MPS) modified with nickel and MPS doped with dysprosium and modified with nickel have been synthesized by the template method. The adsorbents are characterized by various techniques such as transmission electron microscopy, scanning electron microscopy, X-ray diffraction, inductively coupled plasma spectroscopy, and X-ray fluorescence analyses. The adsorption properties of the synthesized samples have been investigated by inverse gas chromatography. Furthermore, thermodynamic characteristics of the adsorption of test compound belonging to different classes of organic compounds were obtained. In addition, the contributions of the energy of specific interactions to the total adsorption energy were calculated. It is also shown that entropy plays the determining role in the adsorption of test compounds on synthesized mesoporous materials.     

Sulfonic and Phosphonic Acid and Bifunctional Organic–Inorganic Hybrid Membranes and Their Proton Conduction Properties

Hybrid organic–inorganic approaches are used for the synthesis of bifunctional proton exchange membrane fuel cell (PEMFC) membranes owing to their ability to combine the properties of a functionalized inorganic network and an organic thermostable polymer. We report the synthesis of both sulfonic and phosphonic acid functionalized mesostructured silica networks into a poly(vinylidenefluoride‐co‐hexafluoropropylene) (poly(VDF‐co‐HFP) copolymer. These membranes, containing different amounts of phosphonic acid and sulfonic acid groups, have been characterized using FTIR and NMR spectroscopy, SA‐XRD, SAXS, and electrochemical techniques. The proton conductivity of the bifunctional hybrid membranes depends strongly on hydration, increasing by two orders of magnitude over the relative humidity (RH) range of 20 to 100 %, up to a maximum of 0.031 S cm⁻¹ at 60 °C and 100 % RH. This value is interesting as only half of the membrane conducts protons. This approach allows the synthesis of a porous SiO₂ network with two different functions, having  SO₃H and  PO₃H₂ embedded in a thermostable polymer matrix.     

Aluminum Redistribution during the Preparation of Hierarchical Zeolites by Desilication

A literature survey reveals a prominent reduction in the concentration of Brønsted acid sites in hierarchically organized zeolites with increasing mesoporous or external surface area independent of the framework type or synthesis route; this suggests a common fundamental explanation. To determine the cause, nature, and impact of the underlying changes in aluminum speciation, this study combines a multitechnique analysis that integrates basic characterization, a detailed synchrotron XRD and multiple‐quantum NMR spectroscopy assessment, and catalytic tests to correlate evolution of the properties with performance during successive steps in the preparation of hierarchical MFI‐type zeolites by desilication. The findings, subsequently generalized to FAU‐ and BEA‐type materials, identify the crucial impact of calcination on the protonic form, which is an integral step in the synthesis and regeneration of zeolite catalysts; on aluminum coordination; and the associated acidity trends.     

Synthesis and characterization of nanocast silica NCS-1 with CMK-3 as a template

Nanocast silica (NCS-1) was synthesized by a casting process by employing the mesoporous carbon CMK-3 (the replica of SBA-15) as a template, tetraethoxysilane (TEOS) as the silica source, and hydrochloric acid (HCl) as the catalyst. The ordered carbon template was removed by employing different methods, such as calcination, thermal treatment followed by calcination, and controlled combustion. According to XRD and TEM characterization, NCS-1 exhibits an ordered structure with hexagonal symmetry and retains the morphology of the original SBA-15 used for the synthesis of CMK-3 over two replication steps on the nanometer scale. This demonstrates the well-connected porosity in CMK-3 type carbon, which can be used as a mold to synthesize mesostructured materials. The nitrogen adsorption isotherms generally show type IV shape, indicating mesoporous characteristics. The structure of NCS-1 is strongly influenced by variables of the nanocasting process, such as the loading amount of silica, hydrolysis temperature, and carbon removal methods. The surface area, pore size, and pore volume of NCS-1 can be tuned to a certain range by varying these parameters.     

Studies on the State of Fe and La in MCM-41 Mesoporous Molecular Sieve Materials by TG Analysis and Other Techniques

Siliceous MCM-41 mesoporous materials and those possessing Fe, La, Al,respectively, were synthesized using water glass as silica source. Results from thermogravimetric analysis and other techniques showed us that Fe(III) or La(III) species was incorporated into framework. Owing to Fe–O or La–O bond longer than Si–O bond, Fe(III) or La(III) species was limited to insert into framework and transformed from tetrahedrally coordinated state to octahedrally coordinated state upon calcination to remove template. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mesoporous Silicoaluminum Pillared Clays with High Thermal Stability and Br?nsted /Lewis Acidity by One-pot Synthesis

The intercalation of polynuclear hydroxy metal cations in smectites affords porouspillared clays which show great potential applications involving separations,adsorptionand catalysis.Though the range of pillared agents has been considerably enlarged1since its invention,aluminum Keggion ions[Al13O4(OH)]7+24and silicon cations arestill often used as pillaring species.Pinnavaia reported that introduction of silica intointerlayers by ion exchange of swollen clays with silicon acetylacetonate cat…     

Ultralight Mesoporous Magnetic Frameworks by Interfacial Assembly of Prussian Blue Nanocubes

A facile approach for the synthesis of ultralight iron oxide hierarchical structures with tailorable macro‐ and mesoporosity is reported. This method entails the growth of porous Prussian blue (PB) single crystals on the surface of a polyurethane sponge, followed by in situ thermal conversion of PB crystals into three‐dimensional mesoporous iron oxide (3DMI) architectures. Compared to previously reported ultralight materials, the 3DMI architectures possess hierarchical macro‐ and mesoporous frameworks with multiple advantageous features, including high surface area (ca. 117 m² g^?1) and ultralow density (6–11 mg cm^?3). Furthermore, they can be synthesized on a kilogram scale. More importantly, these 3DMI structures exhibit superparamagnetism and tunable hydrophilicity/hydrophobicity, thus allowing for efficient multiphase interfacial adsorption and fast multiphase catalysis.     

分子筛基NH3吸附材料的制备与性能研究

通过对分子筛原粉添加黏结剂,制备出了适宜作为吸附材料的成型分子筛颗粒.随后对成型分子筛颗粒进行活性组分的负载,并采用氮气吸附等温线对不同样品的比表面积和孔径分布进行了分析表征.通过考察样品对氨气的动态吸附能力,对活性组分的种类和含量进行筛选和优化,最终确定以质量分数为8%的H_2SO_4作为分子筛基氨气吸附材料的配比组成.通过与活性炭吸附材料的对比发现,在低湿度和高湿度2种条件下,分子筛基防护材料对NH3的防护性能均优于活性炭.     

Evidence for Lewis and Brønsted Acid Sites on MgO Obtained by Sol-Gel

Traditionally, magnesium oxide has been considered a typical basic catalyst, catalyst carrier and/or adsorbent. In this study MgO was prepared using Mg-ethoxide dissolved in ethanol and hydrolyzed with various aqueous inorganic acids and bases. We have found that it is possible to induce Brønsted and Lewis acid sites depending on the method of preparation and, more specifically, on the type of inorganic acids used in the hydrolysis stage. In the FTIR spectra of adsorbed pyridine on MgO obtained using aqueous HCl (pH = 3), the bands corresponding to Lewis (1603, 1496 and 1444 cm–1) and Brønsted (1550 cm–1) acid sites are observed. The fact that upon vacuum and high temperature treatment, i.e., at 773 K, the above mentioned bands are clearly distinguishable indicated that the acid sites are very strong. On the other hand, the MgO materials obtained using aqueous acetic acid as a hydrolysis catalyst (pH = 5), and that without any catalyst (pH = 7) showed only Lewis acid sites which decreased markedly upon higher temperature treatment. When aqueous NH4OH (pH = 9) was used as the hydrolysis catalyst, the MgO obtained showed only Lewis acid sites. In all cases the number of Lewis acid sites was greater than that of Brønsted sites.