非碱性介质中分子筛的合成

分子筛的合成通常是采用含碱金属离子的强碱性体系,通过水热晶化法实现~[1,2]的.得到的分子筛原粉不但必须通过铵离子交换和焙烧才能转变为氢型催化剂,而且在该体系中晶体的粒度也较小.Guth等人~[3]首次报道了在非碱性介质F-离子存在下直接合成铵型ZSM-5的工作.除用四丙基溴化铵合成ZSM-5及其杂原子分子筛外~[4],尚未见到在非碱性介质中合     

Ti-ZSM-5和B-ZSM-5分子筛大单晶的合成

具有ZSM-5结构的含钛和含硼分子筛是催化性能良好的新型杂原子分子筛,可分别作为碳氢化合物的氧化反应^[1]和制备高纯异丁烯的催化剂^[2]。近年来,有关这2种分子筛的合成已见报道^[1~4]。但其合成均采用碱性介质,成核和晶化都比较快,因此未能得到生长完美的杂原子ZSM-5型分子筛大单晶。     

无胺合成[Fe]ZSM-5分子筛的结构鉴定及其催化性能的研究

不用有机胺为模板剂,在碱性介质中采用水热合成法成功地合成了[Fe]ZSM-5分子筛.用X射线衍射、透射电镜、红外光谱、顺磁共振谱、X射线光电子能谱和穆斯堡尔谱等对其结构进行了表征,结果表明,Fe原子进入了分子筛骨架,并处于四面体的配位环境.在由甲醇转化为汽油的过程中,以本文合成的[Fe]ZSM-5与用有机胺为模板剂合成的[Fe]ZSM-5分子筛为催化剂相比,其活性和选择性几乎相同,且都比通常的H[Al]ZSM-5好,C₅组分以上的选择性大于80%,且芳烃(包括脂环烃)和异构烃的含量达75%以上.     

弱酸性介质中Ga-ZSM-5型分子筛的合成与鉴定

本文报道在弱酸性介质中, NH4F存在下, Ga-ZSM-5型分子筛的合成, 这种新的合成途径, 克服了在碱性介质中合成的缺点, 用多种手段研究了Ga-ZSM-5型分子筛结构与性能的关系, 为Ga对ZSM-5沸石骨架的同晶取代提供了充分的证据.     

Ti-ZSM-11的红外光谱研究

随着杂原子分子筛研究领域的开拓与发展，近年来，对钛硅沸石的研究逐渐增多．Ti－ZSM－11（TS－2）型分子筛是由Reddy，Ratanasarny等[1]首先合成的．钛硅沸石的表征与其它杂原子分子筛相比较为复杂，对杂原子Ti是否进入了骨架还没有一个直接的证据，且争议较多．在红外光谱的研究中，对960cm－1－980cm－1区间的特征吸收的归属也存在着很大的分歧[2－4]．钛硅沸石在H2O2对有机化合物的选择氧化领域有极其优良的催化性能[1]，因此，对它的开发有广泛的应用前景．本文以动态和静态相结合的水热晶化法合成了Ti－ZSM－11型分子筛．IR光…     

非碱性介质中合成ZSM-39型分子筛

自1981年Brace报导ZSM-39分子筛合成工作之后,人们在用不同有机胺模板剂合成ZSM-39分子筛方面做了很多工作.并在甲胺存在下,加晶种的方法得到了全硅ZSM-39单晶.目前合成ZSM-39的报道都是在碱性体系进行,Guth等报道了在非碱性介质中合成ZSM-5的新途径,认为全硅ZSM-5孔道内模板剂是以TPAF形式存在.本工作在非碱性介质中,F离子存在下,合成出ZSM-39分子筛,得到了全硅ZSM-39大单晶,并对其结构进行了测定.     

Cr-ZSM-48和V-ZSM-48型分子筛的合成与结构

合成了新的Cr-ZSM-48型和V-ZSM-48型杂原子分子筛,并进行了结构表征,结果表明,Cr-ZSM-48、V-ZSM-48与全硅ZSM-48结构相同,Cr和V分别以+3和+4价态存在;杂原子以畸变四面体配位方式进入分子筛骨架。     

弱酸性介质中合成B-ZSM-5型分子筛

在弱酸性介质中,用四丙基溴化铵、氟化铵合成了B-ZSM-5型分子筛。由于晶化过程中无碱金属氢氧化物等强碱参与,B-ZSM-5型分子筛原粉为铵型,灼烧除掉NH₃及有机模板剂后,直接转化为氢型,吸附吡啶后IR谱中有B酸和L酸中心存在。扫描电镜分析表明,B-ZSM-5分子筛晶体生长完美,晶体形貌随硼含量不同呈规律性变化。X射线衍射、红外光谱、X射线光电子能谱、差热分析等结果表明,硼原子位于ZSM-5分子筛骨架中。     

杂原子ZSM-48型分子筛研究 I. B-ZSM-48和Ge-ZSM-48的合成与表征

在Na2O HMDA MOn/2SiO2-H2O体系中及160℃下合成了杂原子M-ZSM-48型分子筛(M=B.Go), 结构研究表明, 杂原子进入了分子筛骨架, 杂原子B以四配位方式存在。     

杂原子ZSM-48型分子筛研究 I. B-ZSM-48和Ge-ZSM-48的合成与表征

在Na2O HMDA MOn/2SiO2-H2O体系中及160℃下合成了杂原子M-ZSM-48型分子筛(M=B.Go), 结构研究表明, 杂原子进入了分子筛骨架, 杂原子B以四配位方式存在。     

Cu－ZSM－5分子筛中铜的精细结构和NO催化分解

用ＥＸＡＦＳ技术研究了不同交换度的和还原、再氧化处理的Ｃｕ－ＺＳＭ－５分子筛中铜离子的精细结构．在ＺＳＭ－５分子筛中，存在两种铜可占据的位置：一种具有饱和的氧配位和较短的铜氧距离，另一种钢氧配位不饱和且铜氧距离较远．离子交换时，铜离子可能优先占据前者，其量低于３０％．这两类铜的催化能力差别甚大，前者几乎无催化分解ＮＯ的活性．     

Rh, Co, Ru and Pd complex catalyzed hydroformylation of ethylene using triphenylphosphine, triphenylarsine and triphenylstibine as ligands

Summary Zn-promoted Cu-ZSM-5 catalysts are active and selective for CO oxidation in the presence of H₂. This high activity was attributed to the improved reducibility of copper species in exchanged samples.</o:p>     

BaFeO_(3-x)与Cu-ZSM-5耦合催化剂的NO_x储存还原性能

为替代传统的贵金属基NOx储存还原(NSR)催化剂,本文设计并制备了不含贵金属的BaFeO3-x+CuZSM-5耦合催化剂,用于催化消除稀燃发动机尾气中的NOx.在稀燃阶段,NO在BaFeO3-x催化剂上发生了氧化和储存反应;在富燃阶段,从BaFeO3-x催化剂中脱附出来未能消除的NOx被置于其后的Cu-ZSM-5催化剂进一步催化消除.实验结果表明,BaFeO3-x+Cu-ZSM-5耦合催化剂的工作温度窗口被拓宽到250-400°C,同时NOx消除性能得到了显著提高:NOx转化率最高可达98%,N2选择性接近100%.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Correlation between the Cu/Al Value and Activity of Cu-ZSM-5 Catalysts and the Chemical Nature of the Starting Copper Salt

Cu-ZSM-5 catalysts for the selective reduction of NO with propane were obtained by ion exchange between H-ZSM-5 zeolite and an aqueous or aqueous ammonia solution of a copper salt (acetate or nitrate). Their Cu/Al values (%) defined as 2 × 100 (Cu : Al), where Cu : Al is the copper-to-aluminum atomic ratio, were determined as a function of ion exchange pH, which was varied by changing the copper salt and solution concentration. Cu/Al is primarily determined by the chemical nature of the starting copper salt. For a given salt, it is governed by the salt concentration in the solution. At a fixed salt concentration, Cu/Al is always larger for copper acetate than for copper nitrate. It can be raised to ≫100% by using an aqueous ammonia solution of a copper salt. Furthermore, it increases with increasing Si/Al in the starting zeolite if the other ion exchange conditions are equal. Irrespective of preparation conditions, the catalytic activity of Cu-ZSM-5 grows in proportion to Cu/Al. It peaks at Cu/Al ∼ 100% and then remains constant up to Cu/Al ∼ 400%. In order to achieve Cu/Al ∼ 100%, it is most appropriate to use a copper acetate solution.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 652–656.Original Russian Text Copyright © 2005 by Tsikoza, Matus, Ismagilov, Sazonov, Kuznetsov.     

Pulsed ENDOR study of Cu(I)-NO adsorption complexes in Cu-L zeolite

The local environments of Cu(I)-NO adsorption complexes formed in zeolites Cu-L and Cu-ZSM-5 were studied by electron spin resonance (ESR), pulsed electron nuclear double resonance (ENDOR), and hyperfine sublevel correlation spectroscopy (HYSCORE). Cu(I)-NO complexes have attracted special interest because they are important intermediates in the catalytic decomposition of nitric oxide over copper exchanged zeolites. Recently, detailed structures of the complexes in Cu-ZSM-5 zeolites, O2-Al-O2-Cu(I)-NO, have been proposed on the basis of quantum chemical calculations (Pietrzyk, et al. J. Phys. Chem. B 2003, 107, 6105. Dedecek, et al. Phys. Chem. Chem. Phys. 2002, 4, 5406). 27Al pulsed ENDOR and HYSCORE experiments allowed the hyperfine coupling parameters of an aluminum nuclei found in the vicinity of the Cu(I)-NO complex formed in zeolite Cu-L to be estimated. The data indicate that the aluminum atom is located in the third coordination sphere of the adsorbed NO molecule in agreement with the suggested geometry of the adsorption sites. Broad distributions of aluminum nuclear quadrupole and hyperfine coupling parameters and short electron spin relaxation times of the Cu(I)-NO species prevented the determination of the 27Al hyperfine couplings for zeolite Cu-ZSM-5.     

BaFeO3-x与Cu-ZSM-5耦合催化剂的NOx储存还原性能

为替代传统的贵金属基NO_x储存还原（NSR）催化剂,本文设计并制备了不含贵金属的BaFeO_3-x+Cu-ZSM-5 耦合催化剂,用于催化消除稀燃发动机尾气中的NO_x. 在稀燃阶段,NO在BaFeO_3-x催化剂上发生了氧化和储存反应;在富燃阶段,从BaFeO_3-x催化剂中脱附出来未能消除的NO_x被置于其后的Cu-ZSM-5催化剂进一步催化消除. 实验结果表明,BaFeO_3-x+Cu-ZSM-5 耦合催化剂的工作温度窗口被拓宽到250-400 ℃,同时NO_x消除性能得到了显著提高：NO_x转化率最高可达98%,N₂选择性接近100%.     

整体式 Cu-ZSM-5 催化剂上 NH3 选择性催化还原 NO 活性

 采用浸渍法制备了一系列不同 Cu 含量的 Cu-ZSM-5 催化剂, 并用于 NH₃ 选择性催化还原 (SCR)NO 反应. 结果表明, 当 Cu 含量为 8%时, Cu-ZSM-5 催化剂的活性最高; 当空速为 30 000 h^–1. , 在 198~440 ^oC 反应时 NO 转化率均高于 80%, 最高可达 97%, 且空速的影响较小. 经快速水热老化后, 该催化剂活性明显优于商用 V 基催化剂. H₂O 和 SO₂ 对 Cu-ZSM-5 催化剂的 SCR 活性有所影响, 但可明显恢复. X 射线衍射和 NH3 程序升温脱附结果表明, 当 Cu-ZSM-5 中 Cu 含量为 8% 时, 进入 ZSM-5 中阳离子位的 Cu 较多, 催化剂的活性较高, 且其表面具有较多的酸中心和酸量, 从而有利于 SCR 反应.     

Bis(mu-oxo)dicopper in Cu-ZSM-5 and its role in the decomposition of NO: a combined in situ XAFS,UV-vis-near-IR,and kinetic study

In situ XAFS combined with UV-vis-near-IR spectroscopy are used to identify the active site in copper-loaded ZSM-5 responsible for the catalytic decomposition of NO. Cu-ZSM-5 was probed with in situ XAFS (i) after O(2) activation and (ii) while catalyzing the direct decomposition of NO into N(2) and O(2). A careful R-space fitting of the Cu K-edge EXAFS data is presented, including the use of different k-weightings and the analysis of the individual coordination shells. For the O(2)-activated overexchanged Cu-ZSM-5 sample a Cu.Cu contribution at 2.87 A with a coordination number of 1 is found. The corresponding UV-vis-near-IR spectrum is characterized by an intense absorption band at 22 700 cm(-1) and a relatively weaker band at 30 000 cm(-1), while no corresponding EPR signal is detected. Comparison of these data with the large databank of well-characterized copper centers in enzymes and synthetic model complexes leads to the identification of the bis(mu-oxo)dicopper core, i.e. [Cu(2)(mu-O)(2)](2+). After dehydration in He, Cu-ZSM-5 shows stable NO decomposition activity and the in situ XAFS data indicate the formation of a large fraction of the bis(mu-oxo)dicopper core during reaction. When the Cu/Al ratio of Cu-ZSM-5 exceeds 0.2, both the bis(mu-oxo)dicopper core is formed and the NO decomposition activity increases sharply. On the basis of the in situ measurements, a reaction cycle is proposed in which the bis(mu-oxo)dicopper core forms the product O(2) on a single active site and realizes the continuous O(2) release and concomitant self-reduction.     

SYNERGISTIC EFFECT OF Cu-ZSM-5 ZEOLITE ON FLAME RETARDED PP BY MELAMINE SALT OF DIPENTAERYTHRIOL PHOSPHATE

A novel intumnescent flame melamine salt of dipentaerythriol phosphate (MDP),was prepared from dipentaerythritol (DPE) polyphosphoric acid,and melamine.The flammability,combustion behavior,and thermal degradation and stability of PP-MDP were characterized.When MDP loading was 20 wt%,LOI values of the composites reached up to 27%,and UL94 rating,V-2.PP-MDP containing 1 wt% Cu-ZSM-5 presented the highest LOI value of 30.5% and UL94 rating,V-0,and released lest heat during cone test.TG data showed that the ...