m.634226.c.html,Xu-2011-Catalytic applicatio

MgAl-LDH is a weak base,and can be made stronger by intercalating OBu ?anion,as reported by Choudary et al.(2004).They found that MgAl-OBu-LDH (Mg/Al=3)showed an activity similar or superior to KOBu and NaOH for N-oxidation of N-methylmorpholine and dibutylamine using H 2O 2as the oxidant in benzonitrile-methanol at 65–75°C.Several secondary and tertiary amines were readily N-oxidized with a high yield (72–98%).It seems that N-oxidation of tertiary amines is much faster than secondary amines as the tertiary amines are almost quantitatively N-oxidized with H 2O 2over MgAl-WO 4-LDH under similar conditions (95%yield)(Choudary et al.,2001a ).These LDH-based catalysts are all recyclable,without any obvious loss of activity.

2.5.Formation of S \O bond:Oxidation of organic sul ?de

In general,organic sul ?des can be oxidized with various polyoxometalates (POMs),which normally occur in two steps to form sulfoxide and sulfone,respectively,as schematically shown below (Scheme 11):

R 2

S R 1

R 2

S

R 1

O R 2

S

R 1

O O Cat

Cat

Sulfide Sulfoxide

Sulfone

Scheme 11

where R 1and R 2can be aromatic and/or alkyl groups.For this oxidation,LDH is designed as a support to host POM in the interlayer.It is extremely interesting that POM intercalation into the LDH interlayer results in a fast reaction,a high yield,a high selectivity and an asymmetric oxidation (Choudary et al.,2003;Kantam et al.,2005).Choudary et al.(2003)intercalated osmate (OsO 42?)into the MgAl-LDH interlayer and used it to oxidize various organic sul ?des directly to sulfone,with a yield of 95–99%and without formation of intermediate sulfoxide in the t-butanol phosphate buffer at 55°C for 5–24h.They attributed this to the 3+1cycloaddition catalytic process.Very surprisingly,LDH-OsO 4was found to selectively and asymmetrically catalyze organic sul ?des to sulfoxides in t-butanol with the presence of a chiral ligand (Kantam et al.,2005).When MgAl-OsO 4-LDH (Mg/Al=3)was used in the oxidation of methyl phenyl sul ?de at 0–25°C for 3h in t-butanol with hydroquinidine 1,4-phthalazinediyl diether as the chiral ligand,75–80%of methyl phenyl sul ?de was selectively oxidized to sulfoxide with N-methyl morpholine N-oxide as the co-oxidant,in which there was up to 50%enantiomeric excess.Some other organic sul ?des were also found to be selectively oxidized to sulfoxides with a yield of about 80%and a moderate enantiomeric excess (10–30%)(Kantam et al.,2005).

Recently,V-,Mo-and W-containing LDHs were investigated for oxidation of various sul ?des by Hulea and co-workers using H 2O 2as the oxidant at 25–50°C (Hulea et al.,2006,2009;Maciuca et al.,2008a,2008b ).Their results indicate that (1)W-LDH is the most active catalyst for oxidation of methyl phenyl sul ?de,benzyl phenyl sul ?de,di-phenyl sul ?de,benzothiophene,dibenzothiophene,tetra-hydrothiophene,dimethyl sul ?de;(2)sulfoxide is detected in the early stage of reaction (normally within the ?rst 30min)and then gradually transferred to sulfone;(3)sulfone is the predominant product after 1-hr reaction;and (4)the conversion can be up to 100%in most cases under the suitable http://www.doczj.com/doc/bcc3cae1551810a6f52486dc.htmlT formation

Carbon nanotubes (CNTs)have received much attention for various potential applications such as transistors,?eld-emission

tips,sensors,supercapacitors and biomedical agents because of their superior mechanical,thermal and electrical properties,and can be prepared in many methods,such as arc-discharge,laser ablation,catalytic chemical vapor deposition (CCVD),and hydrocarbon pyrolysis (Baughman et al.,2002;Kitiyanan et al.,2000;Thess et al.,1996).However,CCVD appears the most promising one for large-scale production at a lower energy cost.In this method,CNTs are normally formed through catalytic decomposition of a hydrocarbon gas and subsequent carbon deposition on catalytic nanosized transition metal particles supported on metal oxides,silica or zeolites.As transition metal cation(s)can be readily incorporated and well dispersed in the brucite-like layers,so the physicochemical properties of such metal nanoparticles (such as size,surface reactivity,and chemical composition)can be ?nely tuned through careful selection of the metal cation combination,controllable calcination of LDH precursors and manageable reduction of transition metal cation(s).The ?nely-tuned metal particles can be used to control the growth of nanotubes,as demonstrated by various research efforts in recent years.

Li et al.(2005)for the ?rst time synthesized multi-walled CNTs at 700°C in this method by decomposing/depositing acetylene over reduced Co 1.7Al-LDO catalyst.As-prepared CNTs showed a uniform size with the diameter ranging from 20to 30nm.Benito et al.(2009)utilized microwave to enhance Co dispersion in CoZnAl-LDH precursor and then used the calcined/reduced LDO as the catalyst to produce multi-walled CNTs (diameter=~20–30nm)via CCVD of methane.In contrast,the ‘similar ’catalyst derived from the normally co-precipitated LDH precursor just gave rise to herringbone carbon nano ?bers (diameter =~14nm).Ni-and Fe-containing reduced MgAl-LDOs were also able to produce CNTs,where NiMgAl-LDO shows the higher activity (Zhao et al.,2005).Li and colleagues further investigated the composition effect of NiMgAl-LDHs with (Ni 2++Mg 2+)/Al 3+=2.0but varying Mg 2+/Ni 2+from 0,0.5,1to 2.They noted that the carbon yield was enhanced with more Mg,which could be attributed to the good dispersion of active Ni particles with small sizes that mainly resulted from the inhibition effect of spinel phases (Ni 1–x Mg x Al 2O 4)formed in calcined LDHs (Zhang et al.,2009).In addition,Zhao et al.(2007)noted that Fe 0.1Mg 2Al 0.9-LDO was able to produce single-walled CNTs.In a more detailed study,Zhao et al.(2010)prepared the single/double-walled CNTs over FeMgAl-LDO in a controllable way that were interlinked between LDO ?akes.Such a composite (LDO-CNT)shows a much greater enhancement in the tensile strength and the Young's modulus in comparison with pure CNTs at the similar loading in the polyimide matrix.

A few LDOs with multiple transition metals were used to produce CNTs or carbon nano ?bers (CNFs).Dussault et al.(2006)found that NiCuMgAl-LDOs produced quality CNFs,and that LDO with 3.8wt.%Cu resulted in a narrow size distribution of CNFs.CoFeAl-LDOs can also catalyze the formation of CNTs via a similar process where Co content in LDHs precursors is critical to CNT yield and structure,because Co readily forms spinel-like oxides (e.g.CoAl 2O 4,CoFe 2O 4and Co 3O 4),e.g.the active cobalt clusters are well stabilized and dispersed in the oxide matrix (Xiang et al.,2009).

Very interestingly,N-doped carbon nanotubes (NCNTs)can also be prepared over LDH derived catalysts.Cao et al.(2009)synthesized NCNTs by pyrolyzing ethylenediamine over NiMgAl-LDO at 650°C.The N content and the morphology of as-formed NCNTs were related to the Ni II content in LDH precursors.The higher Ni II content in the catalyst resulted in NCNTs with a higher N content (up to 8.8wt.%N)and a more graphitic-like structure.Xue et al.(2010)used Co-based catalyst derived from Co 2Al-LDHs to ef ?ciently produce large-scale NCNTs from methane and acetoni-trile.The typical NCNTs obtained have bamboo-like structures with a varying N content that depends on the gas ?ow rate and the methane/acetonitrile ratio.

144Z.P.Xu et al./Applied Clay Science 53(2011)139–150