Catalysis Communications, Volume 10, Issue 14, 25 August 2009, Pages 1875-1880
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Practical synthesis of aromatic amines by photocatalytic reduction of aromatic nitro compounds on nanoparticles N-doped TiO 2Huqun Wang a ,Junping Yan a ,Wenfu Chang b ,Zhimin Zhang a,*a School of Chemistry and Chemical Engineering,Shanxi University,Wucheng Road,Taiyuan 030006,PR China bInstitute of Molecular Science,Shanxi University Taiyuan 030006,PR Chinaa r t i c l e i n f o Article history:Received 9September 2008Received in revised form 15December 2008Accepted 17December 2008Available online 25December 2008Keywords:ReductionAromatic amines N-doped TiO 2Potassium iodidea b s t r a c tA novel efficient method for the catalytic reduction of aromatic nitro compounds to the corresponding amines was reported.Aromatic nitro compounds were chemoselectively reduced to the corresponding amines by using N-doped TiO 2and potassium iodide as photocatalysts in the presence of methanol.The novel method is highly efficient with very short reaction time (<20min),excellent yields (>90%)and wide functional group tolerance such as carbonyl,halogen,amino,hydroxyl and carboxylic acid groups.And N-doped TiO 2was prepared by a modified sol-gel method using urea as nitrogen source and had higher photocatalytic activity comparing with pure TiO 2.The catalysts were characterized by XRD,XPS,TEM and UV–Vis DRS.Ó2009Published by Elsevier B.V.1.IntroductionAromatic amines are widely used key intermediates in the industrial synthesis of dyes,pharmaceuticals and agrochemicals [1].A variety of methods for the direct reduction of aromatic nitro compounds to the corresponding amines has been well docu-mented [2–4].However,development of new methodology espe-cially the environmentally benign process still attracts the great interests in the chemistry community [5–8].In comparison to the commonly used methods which involve hydrogenation,elec-tron transfer and hydride reduction,photocatalytic reduction emerges as cost-effective,highly selective,rapid and environmen-tally friendly.Li and co-workers first reported a photoinduced reduction of nitro compounds to the corresponding amines using TiO 2semiconductor as a catalyst [9].Ferry and co-workers further investigated the mechanism of photocatalytic reduction of nitro aromatics at the surface of titanium dioxide slurries in the pres-ence of the sacrificial electron donor methanol or isopropanol [10].Heterogeneous photocatalysis has been rapidly becoming an exciting and growing area of research due to its direct application for synthetic chemistry,such as Photo–Kolbe oxidation [11],reduc-tion [12],amino acid [13],Diels–Alder [14]and Friedel–Crafts alkylation [15]reactions.However,so far these reactions are still hardly applied to the industrial field.Research in our laboratory has focused in the late few years on new active-TiO 2based reduc-ing systems.The reaction for synthesis of amines from nitro com-pounds was catalyzed by irradiating N-doped TiO 2(N-TiO 2)and potassium iodide in solution of methanol (Scheme 1).The proce-dure of synthesis of aromatic amines was much simpler and more efficient than those in any other literature.In addition,the photo-catalyst could be reused and remained sufficient catalytic activity.2.Experimental2.1.Catalyst preparation and characterizationAll reagents were analytical reagent grade and were used with-out any further purification.A solution of tetrabutyltitanate (8.5mL)in absolute ethanol (30mL)was mixed with glacial acetic acid (1.5mL)as constraining reagent to prevent the precipitation of oxides and stabilize the solution and an ethanol solution of dis-tilled water and urea (EtOH:H 2O:CH 4ON 2=3:48:1)was added to above solution under vigorous stirring.The pH of solution was ad-justed about three by nitric acid.After 3h,the gel so obtained had been left ageing overnight at room temperature to ensure the com-pletion of the hydrolysis,subsequently evaporation of the solvent,drying at 100°C for 8h and finally calcination at 450°C for 4h.The anatase crystal phase was determined from the X-ray diffraction (XRD)patterns obtained by using an X-ray diffractometer (Model D/Max 2550V)with a Cu target Ka-ray (k =1.544178Å).The mor-phology of the N-TiO 2powders was examined by using a Hitachi-600-2transmission electron microscope (TEM)and UV–Vis diffuse reflectance spectrophotometer (Cary 300,Varian,US)was employed to determine the optical properties of N-TiO 2and pure1566-7367/$-see front matter Ó2009Published by Elsevier B.V.doi:10.1016/j.catcom.2008.12.045*Corresponding author.Tel.:+863517010588;fax:+863517011688.E-mail address:mqz1003@ (Z.Zhang).Catalysis Communications 10(2009)989–994Contents lists available at ScienceDirectCatalysis Communicationsjournal homepage:www.elsev i e r.c o m /l o c a t e /c a t c omTiO 2.The surface composition and bonding configuration were measured by XPS in a VG ESCALAB250system.2.2.Photocatalytic synthesis of aromatic aminesPhotocatalytic reactions were carried out in a cylindrical round bottomed quartz photo-reactor and irradiated using 500W high-pressure mercury lamp and solar light under magnetic stirring at room temperature.The reduction of aromatic nitro compounds (1mmol)was carried out in the present of N-TiO 2(10g/L)and potassium iodide (0.3mmol)in methanol (30mL),which was irra-diated for 6–20min.Then while stirring,the reaction mixture be-came heterogeneous as the reaction progressed.The light yellow N-TiO 2was filtered and the filtrate was concentrated to dryness.The crude product was further purified by silica-gel column chro-matography to give the product amines.All products gave HPLC spectra consistent with the spectra of standard.3.Results and discussion3.1.TEM observations and optical properties of N-TiO 2powders Fig.1a shows typical TEM images of anatase N-TiO 2particles.The characterization of catalyst by TEM studies showed that the nanoparticles were well-distributed.The average size of nitrogen doped TiO 2nanoparticles was between 5.20and 13.5nm which were essentially consistent with the XRD result.The size distribu-tion graphic was depicted in Fig.1b.The UV–Vis DRS absorption spectra of N-TiO 2and TiO 2were shown in Fig.2.N-TiO 2sample absorbed more visible light in the range of 400–550nm comparing with pure TiO 2,and the method was effective to shift the optical absorption of N-TiO 2particles to-ward the visible regions.The band gap of sample is determined by the equation E g =1239.8/k [16],where E g (eV)is band gap and k (nm)is the wavelength of the absorption edge in the spectrum.The band gaps obtained optically were approximately 2.85and3.02eV for N-doped TiO 2and TiO 2,respectively,revealing that the band gap of TiO 2was narrowed by N doping.The absorption edge of N-TiO 2was moved to 550nm,resulting in extending the activating spectrum from UV to the visible range.The absorption edge was shifted to the lower-energy region in the spectrum of N-TiO 2.The band gap narrowing in our research may be caused by introduction of nitrogen from urea into the lattice of titanium.Thus,the sample of N-TiO 2showed the excellent visible light absorption,indicating the increase of photocatalytic activity in vis-ible region.3.2.XRD observations and XPS analysisShown in Fig.3were X-ray powder diffraction patterns of TiO 2and N-TiO 2powder samples prepared.From the intensity ratios be-tween the diffraction appearing at 2h =25.5(anatase 101)may conclude that the TiO 2deposited at 450°C consists almost com-pletely of the anatase phase and no other crystal phase can be de-tected.The average crystalline size of N-TiO 2was calculated using the Scherrer equation.Pure TiO 2had a particle size of 10.4nm;doped TiO 2,about 6.80nm.N-doped TiO 2powers showed smaller size than undoped-TiO 2prepared at the same calcinationtemperature.Fig.1.(a)TEM micrograph of N-TiO 2nanoparticles.(b)Size distribution of N-TiO 2nanoparticles determined by TEM.The sizes were determined for 100nanoparticles selected at random.990H.Wang et al./Catalysis Communications 10(2009)989–994Shown in Fig.4were XPS spectra of the as-synthesized N-TiO2 samples.The N1s and Ti2p were found from the XPS patterns of N-TiO2.It could be seen from Fig.4a that the broad N1s peak was found at399.8eV,showing that nitrogen was incorporated into the TiO2.The N feature at a binding energy of396.6eV was mostly assigned as the substitutional incorporation of nitrogen into the TiO2lattice,and the peak at399.8eV was assigned as N A O and N A N bonding,or the nitrogen chemically bound to hydrogen when introduced by N dopants.Chen and Burda[17]ob-served a broad XPS peak centered at401.3eV for their N-doped TiO2nanoparticles and they attributed it to the substitutional O–Ti–N sites in the TiO2lattice.However,the nitrogen state in the doped TiO2may vary form case to case and variations in the XPS results may be associated with the different surface structures. So we could conclude the Ti–O–N bonds had been formed.In the Ti2p region,both the Ti2p2/3and Ti2p1/2were found at461.9 and467.6eV,respectively.According to the XPS standard spec-trum[18],the Ti2p2/3peak of TiO2should be at458.8eV,but from Fig.4b the Ti2p2/3was found at461.9eV,and so,it was confirmed that Ti in N-TiO2did not exist in the form of TiO2only.Miao et al.[19]also assigned these shifted peaks to TiO2Àx N x.Based on the above XPS analysis,the broad N1s feature and the shift of Ti2p peaks in this work provide strong evidence for the substitutional incorporation of nitrogen into the TiO2and the TiO2Àx N x structure was well formed.3.3.Photocatalytic activityThe photocatalytic activity of doped and undoped nanoparticles was investigated by the photocatalytic reduction of o-nitrophenol as a model of reaction.The P25,pure TiO2and N-TiO2were irradi-ated by UV light.Results were shown in Fig.5.Under UV irradia-tion,the yield of photocatalytic synthesis of o-aminophenol was about10%with P25.This was anticipated because the activity of P25had been proved to be very low.However,the yield with N-TiO2was very high(99.27%)after reaction for7.5min,compar-ing with pure TiO2(40.05%).Similarly,we also investigated the photocatalytic activity under solar light and the results were shown in Fig.5.As shown in Fig.5,no reducing products were ob-tained with P25under solar light after300min,while the yield was also very small(3.24%)with pure TiO2in the same time. According to the previous report,pure TiO2had no photocatalytic activity under visible light.So this may be attributed to the pres-ence of ultraviolet in solar light.Then we made the supplement experiment under solar light through UV-cutfilter sheet and the result showed no products were detected on pure TiO2after 300min.The N-TiO2still showed the best catalytic activity among the catalysts under solar light.As a comparison,we also measured the photocatalytic performance of potassium iodide under the same experimental conditions.Nevertheless,no photo-reduction products were obtained with KI alone under UV irradiation.Fur-ther experiments were carried out to confirm whether the reaction was photocatalytic or not and it was observed that no products were formed in the absence of N-TiO2catalyst.It was therefore be-lieved that the interactions between N-TiO2and KI contributed toH.Wang et al./Catalysis Communications10(2009)989–994991992H.Wang et al./Catalysis Communications10(2009)989–994 Table1the superior activity for the reduction of nitroarenes.Based on the experiments above,it was obvious that N-TiO2had higher photo-catalytic activity comparing with pure TiO2and P25,which was as-cribed to the N dopant.This was consistent with the analytical results.According to the XRD analysis,the N dopant of TiO2de-creased the crystalline size of TiO2which resulted in the enhance-ment of photocatalytic activity.According to XPS analysis,the entry of N into the TiO2lattices suppressed the particle growth and consequently caused a decrease of oxygen vacancies,whichminimized the electron-hole recombination during the photocata-lytic synthesis of aromatic amines.3.4.Photocatalytic synthesis of aromatic aminesThe reduction for aromatic nitro compounds has been carried out using the procedure under UV irradiation because of the long reaction time under solar light.Quantitative analysis of the yield for the reaction was performed in triplicate and the standard devi-ation was calculated.The results were listed in Table1.The data presented clearly showed the efficiency of potassium iodide and N-TiO2in the reduction of several nitro compounds.Moreover, the reaction time was much shorter than those reported in any other literature.It could be seen that the reduction of nitroarenes gave corre-sponding amines in excellent yield(above90%).The catalytic sys-tem was efficient in the reduction of aromatic nitro compounds bearing additional substituents in aromatic ring.With regard to the reactivity of the different nitroarenes tested,it was worth not-ing that the electronic properties of substituents attached to the aromatic ring have any effect on the reduction of nitro groups. Moreover,nitro compounds bearing electron-withdrawing groups, which have been reported as more reactive or active when reacted, gave the corresponding amines in better yields and in shorter reac-tion time comparing with that of the aromatic nitro compounds substituted with strong-electron releasing groups.Concerning the steric hindrance effect of nitro groups with substituent at their ortho position,we have observed no adverse affect for the reduc-tive process in the case of ortho substituent that were expected less reactivity such as hydroxyl,methyl and amino at this position and this was inconsistent with the conventional principle.How-ever,as shown in Table1,the meta position required a longer irra-diation time compared with the ortho position and this was also different from what would be expected.The effect of the additives by reduction of o-nitrophenol as a model reaction has been checked out by comparing preliminary yields with additives and without additives.Potassium iodide and sodium iodide were found to be the most effective additives (Table2).Indeed,using an additive could improve the yield of reac-tion.The probable reaction mechanism was shown in Scheme2. With UV or high energy visible light,an excited state iodide ion would be probably produced.This together with the solvent led to the electron cage complex which,in turn,reacts either with an oxidizing agent or a proton donor.In the process of reaction,meth-anol provided the proton and produced the hydrogen radicals, while TiO2produced pairs of electron-holes(eÀ,h+)under irradia-tion,and the iodide anion was oxidized into the iodine by parts of holes.Accordingly,iodide ion was a scavenger that reacts with po-sitive holes,decreasing the number of oxidizing species available on the catalyst surface.However,with the increase of the KI con-centration,iodide anion competed for the adsorptive sites on the N-TiO2surface with o-nitrophenol,resulting in the decrease of yield.With KI alone the reduction reaction didn’t occur and it may be interpreted that the iodide ion was not oxidized into the molecular iodine without conventional oxidant,because the ex-cited state iodide ion would be prone to return the base state.That is,it will be not completely effectively carried out for the reduction of molecular iodine by organic matter,and hence molecular iodine should not appear.4.ConclusionsIn conclusion,we have described herein a new methodology which can efficiently convert aromatic nitro compounds in metha-nol using N-TiO2and potassium iodide,under more facile and inex-pensive conditions than those described in a previous work.The reagent system described here has been proved to be a good alter-native to well known methods of reduction of aromatic nitro com-pounds.Most interestingly the N-TiO2photocatalyst is stable and reusable under photo-irradiation in the repeated experiments.No meaningful difference in reaction yields is observed in the three re-peated photo-reduction experiments.New applications of this reducing process are being developed.HPLC yield.b SD,standard deviation.Table2Reduction of o-nitrophenol with N-TiO2in the presence of additives(n=3).Entry Additive Reaction time(min)Yield a(mean±SD b)(%)17Without additive1095.47±0.3518KI7.599.27±0.2119KBr1194.90±0.2620NaI7.599.30±0.3621NaBr1093.70±0.8222Na2SO41095.07±0.1223C6H7SO3Na1294.73±0.25a HPLC yield.b SD,standard deviation.H.Wang et al./Catalysis Communications10(2009)989–994993AcknowledgementsWe thank the Science and Technology of Shanxi Province,China (Project No.2006031141)forfinancial assistance and nature sci-ence fund of Shanxi University.References[1]J.S.D.Kumar,M.H.ManKit,T.Toyokuni,Tetrahedron Lett.42(2001)5601.[2]C.Kazmierski,J.M.P.Gosmini,J.Périchon,Tetrahedron Lett.44(2003)6417.[3]Y.Moglie,C.Vitale,G.Radivoy,Tetrahedron Lett.49(2008)1828.[4]U.Stéphane,A.Falguières,A.Guy,C.Ferroud,Tetrahedron Lett.46(2005)5913–5917.[5]A.R.Gandhe,J.B.Fernandes,Bull.Catal.Soc.India4(2005)31.[6]T.C.Jagadale,S.P.Takale,R.S.Sonawane,et al.,J.Phys.Chem.C112(2008)14595.[7]M.Sathish,B.Viswanathan,R.P.Viswanath,Appl.Catal.B:Environ.74(2007)307.[8]K.Abiraj,G.R.Srinivasa,D.C.Gowda,Aust.J.Chem.58(2005)149.[9]F.Mahdavi,T.C.Bruton,Y.Z.Li,.Chem.58(1993)744.[10]L.John,H.G.FerryWilliam,Langmuir14(1998)3551.[11]B.Kraeutler,A.J.Bard,J.Am.Chem.Soc.100(1978)2239.[12](a)L.Lin,R.R.Kuntz,Langmuir8(1992)870.[13](a)W.W.Dunn,Y.Aikawa, A.J.Bard,J.Am.Chem.Soc.103(1981)6893.[14]W.Zhang,X.D.Jia,L.Yang,Z.L.Liu,Tetrahedron Lett.43(2002)9433.[15]M.L.Kantam,ha,J.Yadav, B.Sreedhar,Tetrahedron Lett.47(2006)6213.[16]K.S.Rane,R.Mhalsiker,S.Yin,T.Sato,K.Cho,E.Dunbar,P.Biswas,J.Solid StateChem.179(2006)3033.[17]X.Chen,C.Burda,J.Phys.Chem.B108(2004)15446.[18]Y.Liu,D.Z.Sun,Appl.Catal.B:Environ.72(2007)205.[19]L.Miao,S.Tanemura,H.Watanabe,Y.Mori,K.Kaneko,S.Toh,J.Cryst.Growth260(2004)118.994H.Wang et al./Catalysis Communications10(2009)989–994。
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Chemical Society Of Et化学综合Afinidad Afinidad化学综合J Autom Method Manag Journal Of Automated Methods & Man分析化学J Autom Method Manag Journal Of Automated Methods & Man仪器仪表Kobunshi Ronbunshu Kobunshi Ronbunshu高分子科学J Chem Soc Pakistan Journal Of The Chemical Society Of Pa化学综合J Chem Res-S Journal Of Chemical Research-S化学综合Actual Chimique Actualite Chimique化学综合Russ J Phys Chem B+Russian Journal Of Physical Chemistry物理:原子、分子和化学物理Chem Phys Carbon Chemistry And Physics Of Carbon物理化学Chem Phys Carbon Chemistry And Physics Of Carbon能源与燃料Chem Phys Carbon Chemistry And Physics Of Carbon工程:化工J Appl Crystallogr Journal Of Applied Crystallography晶体学Acta Crystallogr B Acta Crystallographica Section B-Struc晶体学Acta Crystallogr A Acta Crystallographica Section A晶体学J Cryst Growth Journal Of Crystal Growth晶体学Liq Cryst Liquid Crystals晶体学Cryst Res Technol Crystal Research And Technology晶体学Acta Crystallogr C Acta Crystallographica Section C-Cryst晶体学Mol Cryst Liq Cryst Molecular Crystals And Liquid Crystals晶体学Acta Crystallogr E Acta Crystallographica Section E-Struc晶体学Crystallogr Rep+Crystallography Reports晶体学Z Krist-New Cryst St Zeitschrift Fur Kristallographie-New Cr晶体学小类名称(英文)小类分区大类分区2008年影响因子2007年影响因子2006年影响因子2008年平均影响因子Chemistry, Multidisciplinary 1123.59222.75726.05424.13433Chemistry, Multidisciplinary 1112.17616.21417.11315.16767Polymer Science 1116.81912.80914.81814.81533Chemistry, Multidisciplinary 1117.41913.08213.6914.73033Chemistry, Organic 1116.73311.92910.69213.118Chemistry, Physical 1114.6889.43911.2511.79233Chemistry, Physical 1112.80811.9239.30411.345Physics, Condensed Matter 1112.80811.9239.30411.345Chemistry, Multidisciplinary 1110.87910.03110.23210.38067Chemistry, Inorganic & Nuclear 1110.5668.5688.8159.316333Chemistry, Medicinal 117.457.6678.8898.002Chemistry, Organic 117.457.6678.8898.002Biochemistry & Molecular Biolo 217.457.6678.8898.002Chemistry, Physical 11 4.8127.66711.257.909667Chemistry, Multidisciplinary 218.0917.8857.6967.890667Chemistry, Physical 11 5.625 6.3339.2227.06Chemistry, Physical 21 6.8928.121 6.0367.016333Chemistry, Physical 21 5.36 5.7317.32 6.137Polymer Science 12 6.802 5.93 4.284 5.672Chemistry, Analytical 12 5.712 5.287 5.646 5.548333Chemistry, Multidisciplinary 22 5.27 6.394 4.789 5.484333Chemistry, Analytical 12 5.485 5.827 5.068 5.46Chemistry, Multidisciplinary 22 5.454 5.33 5.015 5.266333Chemistry, Applied 12 5.619 4.977 4.762 5.119333Chemistry, Organic 12 5.619 4.977 4.762 5.119333Chemistry, Multidisciplinary 22 5.34 5.141 4.521 5.000667Chemistry, Inorganic & Nuclear 12 3.571 4.176 6.85 4.865667Chemistry, Organic 22 3.571 4.176 6.85 4.865667Chemistry, Organic 22 5.128 4.802 4.659 4.863Chemistry, Physical 22 5.493 4.354 4.63 4.825667Chemistry, Physical 22 4.6045 4.731 4.778333Chemistry, Multidisciplinary 22 4.542 4.836 4.192 4.523333Chemistry, Physical 22 6.511 4.041 2.893 4.481667Chemistry, Inorganic & Nuclear 22 6.511 4.041 2.893 4.481667Chemistry, Inorganic & Nuclear 22 4.214 4.6 3.792 4.202Crystallography 12 4.215 4.046 4.339 4.2Materials Science, Multidisciplin22 4.215 4.046 4.339 4.2Chemistry, Multidisciplinary 22 4.215 4.046 4.339 4.2Chemistry, Multidisciplinary 22 4.19700 4.197Chemistry, Multidisciplinary 32 3.39 4.297 4.893 4.193333Chemistry, Physical 22 4.189 4.086 4.115 4.13Chemistry, Multidisciplinary 32 4.274 4.308 3.627 4.069667Chemistry, Physical32 5.333 3.074 3.79 4.065667 Chemistry, Inorganic & Nuclear22 4.147 4.123 3.911 4.060333 Chemistry, Physical32 4.097 4.009 3.902 4.002667 Polymer Science22 4.146 4.169 3.664 3.993 Chemistry, Organic22 4.146 4.169 3.664 3.993 Biochemistry & Molecular Biolo32 4.146 4.169 3.664 3.993 Chemistry, Organic22 3.952 3.959 3.79 3.900333 Chemistry, Inorganic & Nuclear22 3.815 3.833 3.632 3.76 Chemistry, Organic22 3.815 3.833 3.632 3.76 Chemistry, Analytical22 3.756 3.641 3.554 3.650333 Biochemical Research Methods22 3.756 3.641 3.554 3.650333 Chemistry, Analytical22 4.028 3.269 3.63 3.642333 Spectroscopy22 4.028 3.269 3.63 3.642333 Polymer Science22 3.821 3.529 3.405 3.585 Crystallography22 3.535 3.468 3.729 3.577333 Chemistry, Multidisciplinary32 3.535 3.468 3.729 3.577333 Physics, Atomic, Molecular & C12 3.636 3.502 3.449 3.529 Chemistry, Physical32 3.636 3.502 3.449 3.529 Chemistry, Analytical22 3.761 3.553 3.198 3.504 Chemistry, Organic22 3.184 3.961 3.232 3.459 Physics, Atomic, Molecular & C22 4.064 3.343 2.892 3.433 Chemistry, Physical32 4.064 3.343 2.892 3.433 Chemistry, Inorganic & Nuclear22 3.6 3.325 3.303 3.409333 Biochemistry & Molecular Biolo32 3.6 3.325 3.303 3.409333 Materials Science, Multidisciplin22 3.39600 3.396 Chemistry, Physical32 3.39600 3.396 Nanoscience & Nanotechnology32 3.39600 3.396 Chemistry, Analytical22 3.181 3.664 3.307 3.384 Spectroscopy22 3.181 3.664 3.307 3.384 Chemistry, Physical32 3.181 3.664 3.307 3.384 Computer Science, Information 12 3.643 2.986 3.423 3.350667 Computer Science, Interdisciplin22 3.643 2.986 3.423 3.350667 Chemistry, Multidisciplinary32 3.643 2.986 3.423 3.350667 Chemistry, Inorganic & Nuclear22 3.58 3.212 3.012 3.268 Chemistry, Multidisciplinary33 3.477 2.641 3.583 3.233667 Chemistry, Organic23 3.55 3.167 2.874 3.197 Chemistry, Analytical23 3.206 3.374 2.81 3.13 Chemistry, Applied13 3.011 3.154 3.153 3.106 Chemistry, Multidisciplinary33 3.011 3.154 3.153 3.106 Chemistry, Medicinal33 3.011 3.154 3.153 3.106 Chemistry, Analytical23 3.146 3.186 2.894 3.075333 Polymer Science23 3.331 3.065 2.773 3.056333 Environmental Sciences23 3.19 3.166 2.63 2.995333Chemistry, Physical33 3.19 3.166 2.63 2.995333 Spectroscopy23 2.94 3.062 2.945 2.982333 Biophysics33 2.94 3.062 2.945 2.982333 Chemistry, Organic33 2.94 3.062 2.945 2.982333 Chemistry, Physical33 2.424 3.333 3.083 2.946667 Chemistry, Multidisciplinary33 2.424 3.333 3.083 2.946667 Physics, Multidisciplinary33 2.424 3.333 3.083 2.946667 Physics, Atomic, Molecular & C23 2.871 2.918 3.047 2.945333 Chemistry, Physical33 2.871 2.918 3.047 2.945333 Chemistry, Analytical23 3.328 2.867 2.591 2.928667 Biochemical Research Methods33 3.328 2.867 2.591 2.928667 Oceanography23 2.977 3.085 2.663 2.908333 Chemistry, Multidisciplinary33 2.977 3.085 2.663 2.908333 Chemistry, Organic33 3.016 2.914 2.769 2.899667 Chemistry, Organic33 2.897 2.869 2.817 2.861 Chemistry, Organic33 2.61 2.8443 2.818 Chemistry, Analytical23 2.772 2.971 2.68 2.807667 Spectroscopy33 2.772 2.971 2.68 2.807667 Chemistry, Analytical23 2.901 2.949 2.444 2.764667 Electrochemistry33 2.901 2.949 2.444 2.764667 Chemistry, Organic33 2.659 2.763 2.838 2.753333 Chemistry, Multidisciplinary33 2.942 2.651 2.647 2.746667 Chemistry, Analytical33 3.5 2.973 1.656 2.709667 Chemistry, Inorganic & Nuclear332 2.1184 2.706 Mathematics, Interdisciplinary A13 3.5 2.582 2.693333 Computer Science, Interdisciplin23 3.5 2.582 2.693333 Chemistry, Multidisciplinary33 3.5 2.582 2.693333 Chemistry, Physical33 2.814 2.707 2.511 2.677333 Chemistry, Inorganic & Nuclear33 2.694 2.597 2.704 2.665 Engineering, Chemical13 3.004 2.764 2.148 2.638667 Chemistry, Applied23 3.004 2.764 2.148 2.638667 Chemistry, Physical33 3.004 2.764 2.148 2.638667 Chemistry, Analytical33 2.746 2.632 2.535 2.637667 Chemistry, Physical33 2.796 2.634 2.468 2.632667 Chemistry, Inorganic & Nuclear33 2.796 2.634 2.468 2.632667 Chemistry, Organic33 2.796 2.634 2.468 2.632667 Chemistry, Organic33 2.538 2.615 2.509 2.554 Materials Science, Multidisciplin23 2.555 2.21 2.796 2.520333 Chemistry, Applied23 2.555 2.21 2.796 2.520333 Chemistry, Physical33 2.555 2.21 2.796 2.520333 Nanoscience & Nanotechnology33 2.555 2.21 2.796 2.520333 Chemistry, Physical33 1.833 2.6673 2.5 Chemistry, Organic33 1.833 2.6673 2.5。
ScienceDirect (SD)网址:/(1) Catalysis Communications (催化通讯)(2) Journal of Molecular Catalysis A: Chemical (分子催化A:化学)(3) Tetrahedron (T) (四面体)(4) Tetrahedron: Asymmetry (TA) (四面体:不对称)(5) Tetrahedron Letters (TL) (四面体快报)(6) Applied Catalysis A: General (应用催化A)2. EBSCOhost数据库网址:/(1) Synthetic Communcations (合成通讯)(2) Letters in Organic Chemistry (LOC)(3) Current Organic Synthesis(4) Current Organic Chemistry3. Springer数据库网址:http:// /(1) Molecules (分子)(2) Monatshefte für Chemie / Chemical Monthly (化学月报)(3) Science in China Series B: Chemistry (中国科学B)(4) Catalysis Letts (催化快报)4. ACS Publications (美国化学会)网址:/(1) Journal of the American Chemical Society (JACS) (美国化学会志)(2) Organic Letters (OL) (有机快报)(3) The Journal of Organic Chemistry (JOC) (美国有机化学)(4) Journal of Medicinal Chemistry (JMC) (美国药物化学)(5) Chemical Reiew (化学评论)5. Royal Society of Chemistry (RSC) (英国皇家化学会)网址:/Publishing/Journals/Index.asp(1) Green Chemistry (绿色化学)(2) Chemical Communications (CC) (化学通讯)(3) Chemical Society Reviews (化学会评论)(4) Journal of the Chemical Society (化学会志)Journal of the Chemical Society, Perkin Transactions 1 (1972-2002) Journal of the Chemical Society, Perkin Transactions 2 (1972-2002) Journal of the Chemical Society B: Physical Organic (1966-1971)Journal of the Chemical Society C: Organic (1966-1971)(5) Organic & Biomolecular Chemistry (OBC) (有机生物化学)/publishing/jo ... p?type=CurrentIssue6. Wiley网址:/(1) Advanced Synthesis & Catalysis (ASC) (先进合成催化)(2) Angewandte Chemie International Edition (德国应用化学)(3) Chemistry - A European Journal (欧洲化学)(4) Chinese Journal of Chemistry (中国化学)(5) European Journal of Organic Chemistry (欧洲有机化学)(6) Helvetica Chimica Acta (瑞士化学)(7) Heteroatom Chemistry (杂原子化学)7. Ingent网址:/(1) Journal of Chemical Research (JCR) (化学研究杂志)(2) Canadian Journal of Chemistry (加拿大化学)(3) Current Organic Chemistry(4) Mini-Reviews in Organic Chemistry(5) Phosphorus, Sulfur, and Silicon and the Related Elements (磷、硫、硅和相关元素)(6) Letters in Organic Chemistry8. Taylor & Francis数据库网址:http://www.journalsonline.tandf. ... sp?referrer=default(1) Synthetic Communications(2) Journal of Sulfur Chemistry(硫化学杂志)(3) Phosphorus, Sulfur, and Silicon and the Related Elements9. Thieme数据库网址:/(1) Synlett (合成快报)(2) Synthesis (合成)10. 日本化学会网址:(1) Chem. Lett. (CL) (化学快报)http://www.jstage.jst.go.jp/browse/cl/_vols(2) Bull. Chem. Soc. Jpn. http://www.csj.jp/journals/bcsj/index.html11. 澳大利亚化学会(Australian Journal of Chemistry)http://www.publish.csiro.au/nid/52.htm12.巴西化学会.br/13.Molecules/molecules/14.韩国化学会http://journal.kcsnet.or.kr/15.印度化学会http://www.niscair.res.in/Scienc ... hin.htm&d=test816.国际有机制备和程序(Organic Preparations and Procedures International,OPPI)/17.有机化学/index.htm有机合成:Organic Syntheses(有机合成手册), John Wiley & Sons (免费)/Named Organic Reactions Collection from the University ofOxford (有机合成中的命名反应库) (免费)/thirdyearcomputing/NamedOrganicReac...有机化学资源导航Organic Chemistry Resources Worldwide/有机合成文献综述数据库Synthesis Reviews (免费)/srev/srev.htmCAMEO (预测有机化学反应产物的软件)/products/cameo/index.shtmlCarbohydrate Letters (免费,摘要)/Carbohydrate_Letters/Carbohydrate Research (免费,摘要)/locate/carresCurrent Organic Chemistry (免费,摘要)/coc/index.htmlElectronic Encyclopedia of Reagents for Organic Synthesis (有机合成试剂百科全书e-EROS) /eros/European Journal of Organic Chemistry (免费,摘要)/jpages/1434-193X/Methods in Organic Synthesis (MOS,有机合成方法)/is/database/mosabou.htmOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlRussian Journal of Bioorganic Chemistry (Bioorganicheskaya Khimiya) (免费,摘要)http://www.wkap.nl/journalhome.htm/1068-1620Russian Journal of Organic Chemistry (Zhurnal Organicheskoi Khimii) (免费,摘要)http://www.maik.rssi.ru/journals/orgchem.htmScience of Synthesis: Houben-Weyl Methods of Molecular Transformation/Solid-Phase Synthesis database (固相有机合成)/chem_db/sps.htmlSynthetic Communications (免费,摘要)/servlet/product/productid/SCCSyntheticPages (合成化学数据库) (免费)/The Complex Carbohydrate Research Center (复杂碳水化合物研究中心)/合成材料老化与应用 (免费,目录)/default.html金属卡宾络合物催化的烯烃复分解反应 (免费)/html/books/O61BG/b1/2002/2.6%20.htm上海化学试剂研究所/英国化学数据服务中心CDS (Chemical Database Service)/cds/cds.html英国皇家化学会碳水化合物研究组织 (Carbohydrate Group of the Royal Society of Chemistry) /lap/rsccom/dab/perk002.htm有机反应催化学会 (ORCS, Organic Reaction Catalysis Society)/有机合成练习 (免费)/中国科学院成都有机化学研究所:催化与环境工程研究发展中心/MainIndex.htm金属有机及元素有机化学:CASREACT - Chemical Reactions Database(CAS的化学反应数据库)/CASFILES/casreact.html日本丰桥大学 Jinno实验室的研究数据库(液相色谱、多环芳烃/药物/杀虫剂的紫外谱、物性) (免费) http://chrom.tutms.tut.ac.jp/JINNO/ENGLISH/RESEARCH/research...A New Framework for Porous Chemistry (金属有机骨架) (免费)/alchem/articles/1056983432324.htmlActa Crystallographica Section B (免费,摘要)/b/journalhomepage.htmlActa Crystallographica Section E (免费,摘要)/e/journalhomepage.htmlBibliographic Notebooks for Organometallic Chemistryhttp://www.ensc-lille.fr/recherche/cbco/bnoc.htmlBiological Trace Element Research (生物痕量元素研究杂志) (免费,摘要)/JournalDetail.pasp?issn=0163-4984...Journal of Organometallic Chemistry (免费,摘要)/locate/jnlabr/jomOrganic Letters (免费,目录)/journals/orlef7/index.htmlOrganometallics (免费,目录)/journals/orgnd7/index.htmlSyntheticPages (合成化学数据库) (免费)/金属卡宾络合物催化的烯烃复分解反应 (免费)/html/books/O61BG/b1/2002/2.6%20.htm金属有机参考读物:The Organometallic HyperTextBook by Rob Toreki/organomet/index.html金属有机化学国家重点实验室,中国科学院上海有机所/元素有机化学国家重点实验室(南开大学)/在线网络课程:有机金属反应和均相催化机理 (Dermot O'Hare 主讲)/icl/dermot/organomet/药物化学:Fisher Scientific/PubMed: MEDLINE和PREMEDLINE (免费)/PubMed/生物医药:BioMedNet: The World Wide Club for the Biological and Medical Community/AIDSDRUGS (艾滋病药物) (免费)/pubs/factsheets/aidsinfs.htmlautodock (分子对接软件) (免费)/pub/olson-web/doc/autodock/DIRLINE (卫生与生物医药信息源库) (免费)/HISTLINE (医药史库) (免费)/TOXNET (化合物毒性相关数据库系列) (免费)/日本药典,第14版 (免费)http://jpdb.nihs.go.jp/jp14e/index.html小分子生物活性数据库ChemBank (免费)/Ashley Abstracts Database (药物研发、市场文献摘要) (免费)/databases/ashley/search.aspBIOSIS/BIOSIS/ONLINE/DBSS/biosisss.html从检索药物交易信息库PharmaDeals (部分免费)/从ChemWeb检索有机药物用途及别名库Negwer: organic-chemical drugs and their synonyms (部分免费) /negwer/negwersearch.html美国常用药品索引库RxList (免费)/美国国家医学图书馆NLM的免费在线数据库 (免费)/hotartcl/chemtech/99/tour/internet.html制药公司目录(Pharmaceutical Companies on Virtual Library: Pharmacy Page)/company.html37℃医学网/AAPS PharmSci (免费,全文)/Abcam Ltd.有关抗体、试剂的销售,抗体的搜索)/Acta Pharmaceutica (免费,摘要)http://public.srce.hr/acphee/Advanced Drug Delivery Reviews (免费,摘要)http://www.elsevier.nl/locate/drugdelivAmerican Journal of Drug and Alcohol Abuse (免费,摘要)/servlet/product/productid/ADAAmerican Journal of Pharmaceutical Education (AJPE) (免费,全文)/Amgen Inc. (医药)/Anita's web picks (药学与药物化学信息导航)http://wwwcmc.pharm.uu.nl/oyen/webpicks.htmlAnnals of Clinical Microbiology and Antimicrobials (免费,全文)/Annual Review of Pharmacology and Toxicology (免费,摘要)/Anti-Cancer Drug Design (免费,摘要)/antcan/生物有机化学:ScienceDirect: 在线访问Elsevier的1100种期刊全文 (免费目录) (免费)/生命、环境科学综合性资源TheScientificWorld (sciBASE)/生物医药:BioMedNet: The World Wide Club for the Biological and Medical Community /BIOETHICSLINE (BIOETHICS onLINE) (免费)/BIOME (生命科学资源导航)/browse/Directory of P450-containing Systems(P450酶系目录)http://p450.abc.hu/DIRLINE (卫生与生物医药信息源库) (免费)/百名最佳生物技术网站列表 (Top 100 Biotechnology WWW Sites)/top100.asp从ChemWeb检索《化学工程与生物技术文摘》库CEABA (部分免费)/课程材料:MIT生物学超文本教材http://esg-[url]:8001/esgbio/7001main.html[/url]生物材料网 (Biomaterials Network)/生物信息学资源导航,上海生物化学所/bio/index.htm小分子生物活性数据库ChemBank (免费)/英国剑桥医学研究委员会:分子生物学实验室LMB/biology site of the network./生物有机化学:ScienceDirect: 在线访问Elsevier的1100种期刊全文 (免费目录) (免费)/生命、环境科学综合性资源TheScientificWorld (sciBASE)/生物医药:BioMedNet: The World Wide Club for the Biological and Medical Community /BIOETHICSLINE (BIOETHICS onLINE) (免费)/BIOME (生命科学资源导航)/browse/Directory of P450-containing Systems(P450酶系目录)http://p450.abc.hu/DIRLINE (卫生与生物医药信息源库) (免费)/百名最佳生物技术网站列表 (Top 100 Biotechnology WWW Sites)/top100.asp从ChemWeb检索《化学工程与生物技术文摘》库CEABA (部分免费)/课程材料:MIT生物学超文本教材http://esg-[url]:8001/esgbio/7001main.html[/url]生物材料网 (Biomaterials Network)/生物信息学资源导航,上海生物化学所/bio/index.htm小分子生物活性数据库ChemBank (免费)/英国剑桥医学研究委员会:分子生物学实验室LMB/biology site of the network./。
英文文献|英文期刊数据库|英文硕士论文|英文博士论文论文写作资源SCI论文润色北大核心期刊SCI影响因子化学类英文期刊投稿指南[学术须知] 专业SCI论文修改服务:★先修改后付款;☆语言问题免费重修;★24-72小时交稿;☆正规财务发票;★一分钟下单;☆365日不间断服务化学类英文期刊投稿指南:化学类(Chemistry)1【期刊名称】SENSORS AND ACTUA TORS B: CHEMICAL【所属学科】化学【级别】SCI、EI【期刊主页】/wps/find ... ription#description【投稿方式】email【出版商】elsevier【审稿周期】3-6 months2【期刊名称】Applied Catalysis A: General【所属学科】化学,催化【级别】SCI、EI【投稿主页】/Jour ... 856&Precis=DESC【投稿方式】online submision【影响因子】2.337【出版商】elsevier【审稿周期】3 months【出版周期】half-month journal3【期刊名称】Tetrahedron Letter【所属学科】有机化学Organic Chemistry【级别】SCI【期刊主页】/sci ... c26274c4b9df99e5c0f【投稿方式】email【出版商】elsevier4【期刊名称】Tetrahedron【所属学科】有机化学Organic Chemistry【级别】SCI【期刊主页】/wps/find ... ription#description【投稿方式】email【出版商】elsevier5【期刊名称】The Journal of Organic Chemistry【所属学科】有机化学【级别】SCI【影响因子】6.903【期刊主页】/journals/joceah/index.html【投稿方式】email【出版商】ACS6【期刊名称】Journal of the American Chemical Society【所属学科】化学【级别】SCI【影响因子】3.462【期刊主页】/journals/jacsat/index.html【投稿方式】email【出版商】ACS7【期刊名称】Angewandte Chemie International Edition【所属学科】化学【影响因子】9.161【级别】SCI【期刊主页】/cgi-bin/jhome/26737 【投稿方式】email【出版商】Wiley8【期刊名称】Chemistry - A European Journal【所属学科】化学【级别】SCI【影响因子】4.517【期刊主页】/cgi-bin/jhome/26293 【投稿方式】email【出版商】Wiley 9【期刊名称】European Journal of Organic Chemistry【所属学科】有机化学【级别】SCI【影响因子】2.426【期刊主页】/cgi-bin/jhome/27380 【投稿方式】email【出版商】Wiley10【期刊名称】Journal of Molecular Structure【所属学科】化学,特别是有晶体结构的分子Chemistry【级别】SCI【影响因子】1.0【期刊主页】 ... mp;journal=00222860【投稿方式】email【出版商】elsevier【审稿周期】1-2 week 我师妹的文章是8 天接受的11【期刊名称】The Journal of organic chemistry【所属学科】organic chemistry【级别】SCI【影响因子】3.462【期刊主页】/journals/joceah/index.html【投稿方式】on-line submittion【出版商】American chemistry Society【审稿周期】4-8weeks12【期刊名称】the journal of american chemical society【所属学科】chemistry【级别】SCI【影响因子】6.903【期刊主页】/journals/jacsat/【投稿方式】on-line submittion【出版商】American chemistry Society【审稿周期】4-8weeks13【期刊名称】advanced synthesis & catalysis【所属学科】chemistry【级别】SCI【影响因子】4.482【期刊主页】http///cgi-bin【投稿方式】on-line submittion【出版商】Wiley14【期刊名称】chemical communications【所属学科】chemistry【级别】SCI【影响因子】3.997【期刊主页】/is/journals/current/chemcomm/cccpub.htm 【投稿方式】on-line submittion【出版商】Royal Society of Chemistry【审稿周期】4-8weeks15【期刊名称】Organic &Biomolecular Chmistry【所属学科】有机化学及化学生物学【级别】SCI IF=2.194【期刊主页】/Publishing/Journals/OB/index.asp【投稿方式】email【出版商】RSC【审稿周期】1-2 months16 【期刊名称】Synlett【所属学科】有机化学Organic Chemistry【级别】SCI【期刊主页】/ ... synlett/index.shtml 【出版商】Thieme Stuttgart17【期刊名称】SYNTHESIS【所属学科】有机化学Organic Chemistry【级别】SCI【期刊主页】/ ... nthesis/index.shtml 【投稿方式】email【出版商】Thieme Stuttgart18【期刊名称】Phytochemistry【所属学科】有机化学Organic Chemistry【级别】SCI【期刊主页】/sci ... 7576855b50ec607f058 【投稿方式】email【出版商】elsevier19【期刊名称】Chemical Communications【所属学科】化学【级别】SCI【期刊主页/Publishing/Journals/cc/【投稿方式】email【出版商】RSC20【期刊名称】Green Chemistry【所属学科】化学【级别】SCI【期刊主页】/Publishing/Journals/gc/index.asp【投稿方式】email【出版商】RSC21【期刊名称】Angewandte Chemie International Edition【所属学科】化学【级别】SCI【影响因子】7.996【期刊主页】/cgi-bin/jhome/26737 【投稿方式】email【出版商】Wiley22【期刊名称】Journal of chromatograohy A【所属学科】色谱分析【级别】SCI【影响因子】3.359【期刊主页】/wps/find ... ription#description【投稿方式】email【出版商】elsevier【审稿周期】3-6 months23【期刊名称】Journal of chromatograohy B【所属学科】色谱分析【级别】SCI【影响因子】2.176【期刊主页】/wps/find ... ription#description【投稿方式】email【出版商】elsevier【审稿周期】3-6 months24【期刊名称】Analytical chemistry【所属学科】分析化学【级别】SCI【影响因子】5.450【期刊主页】/journals/ancham/index.html【投稿方式】在线投稿/email【出版商】ACS【审稿周期】unknown25【期刊名称】electrophoresis【所属学科】分析化学【级别】SCI【影响因子】3.743【期刊主页】http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2027/ 【投稿方式】在线投稿/email【出版商】wiley interscience【审稿周期】2 months26【期刊名称】Journal of chromatography A【所属学科】分析化学【级别】SCI【影响因子】3.359【期刊主页】/wps/find ... ription#description【投稿方式】在线投稿/email【出版商】elsevier【审稿周期】3 months27【期刊名称】JOURNAL OF SEPARA TION SCIENCE【所属学科】分析化学【级别】SCI【影响因子】1.927【期刊主页】http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2259/ 【投稿方式】在线投稿/email【出版商】wiley interscience【审稿周期】2-3 months28【期刊名称】Journal of pharmaceutical and biomedical analysis【所属学科】分析化学【级别】SCI【影响因子】1.509【期刊主页】/wps/find ... ription#description【投稿方式】在线投稿/email【出版商】elsevier【审稿周期】1-2 month29【期刊名称】Phytochemical Analysis【所属学科】分析化学【级别】SCI【影响因子】1.385【期刊主页】/WileyCDA/WileyTitle/productCd-PCA.html 【投稿方式】主页上无在线投稿【出版商】wiley interscience【审稿周期】2=3 months30【期刊名称】Electrochemistry Communications【所属学科】Electrochemistry【级别】SCI、EI【影响因子】2.926【期刊主页】/sci ... daa82c9a2b982514b77【投稿方式】在线投稿【出版商】ELSEVIER【审稿周期】1 month31【期刊名称】Electrochimica Acta【所属学科】Electrochemistry【级别】SCI、EI【影响因子】2.341【期刊主页】/sci ... abf8e59c12785940620【投稿方式】在线投稿【出版商】ELSEVIER【审稿周期】1 month32【期刊名称】Journal of The Electrochemical Society【所属学科】Electrochemical science and technology【级别】SCI、EI【影响因子】2.356【期刊主页】/JES【投稿方式】在线投稿【出版商】ECS【审稿周期】1-3 months33【期刊名称】Electrochemical and Solid-State Letters【所属学科】Electrochemical science and technology【级别】SCI、EI【影响因子】2.271【期刊主页】/ESL【投稿方式】在线投稿【出版商】ECS【审稿周期】1-3 months34【期刊名称】Organic Letters【所属学科】有机化学【级别】SCI【影响因子】4.19【期刊主页】/journals/orlef7/index.html【投稿方式】在线投稿【出版商】ACS【审稿周期】1 month35 【期刊名称】Organic Letters(影响因子: 4.195), Journal of the American Chemical Society(影响因子: 6.903)【所属学科】chemistry【级别】SCI【期刊主页】/about.html【投稿方式】on-line submittion,/paragonplus/splash/index.html or https:///paragon/index.jsp 【出版商】American chemistry Society36【期刊名称】Analytic Chimic Acta【所属学科】分析化学【级别】SCI、EI【期刊主页】/ACA【投稿方式】email【出版商】elsevier【审稿周期】3-6 months37【期刊名称】Molecules【所属学科】化学【级别】SCI【影响因子】0.676【期刊主页】/molecules/【投稿方式】在线投稿/email/邮寄【出版商】MDPI【审稿周期】3-6 months38【期刊名称】Catalysis Communications【所属学科】化学&催化【级别】SCI【IF】=1.89【期刊主页】/catcom/【投稿方式】online submission【出版商】elsevier【审稿周期】3-6 months39【期刊名称】Applied Catalysis B: Environmental【所属学科】化学&催化&环境科学【级别】SCI【IF】=4.042【期刊主页】/apcatb/【投稿方式】online submission【出版商】elsevier【审稿周期】3-6 months40【期刊名称】Journal of Catalysis【所属学科】化学&催化【级别】SCI【IF】=4.063【期刊主页】/jcat/【投稿方式】online submission【出版商】elsevier【审稿周期】3-6 months41【期刊名称】Journal of Molecular Catalysis A: Chemical 【所属学科】化学&催化【级别】SCI【IF】=2.316【期刊主页】/molcaa/【投稿方式】online submission【出版商】elsevier【审稿周期】3-6 months42【期刊名称】analytical biochemistry【所属学科】分析【级别】SCI【影响因子】2.370【期刊主页】/wps/find ... ription#description 【投稿方式】email【出版商】elsevier【审稿周期】未知43【期刊名称】analyst【所属学科】分析【级别】SCI【影响因子】2.783【期刊主页】/Publishing/Journals/an/index.asp 【投稿方式】email【出版商】皇家化学会【审稿周期】未知44【期刊名称】analytical sciences【所属学科】分析【级别】SCI【影响因子】1.051【期刊主页】http://wwwsoc.nii.ac.jp/cgi-bin/jsac/analsci/toc/【投稿方式】email【出版商】日本分析化学会【审稿周期】未知45【期刊名称】analytical letters【所属学科】分析【级别】SCI【影响因子】0.915【期刊主页】/newjour/a/msg03705.html【投稿方式】email【Publisher】Marcel Dekker, Inc.【审稿周期】未知46【期刊名称】Analytical Communications【所属学科】分析【级别】SCI【影响因子】1.628【期刊主页】/Publishing/Journals/an/index.asp【投稿方式】email【出版商】皇家化学会【审稿周期】未知47【期刊名称】Macromolecules【所属学科】高分子【级别】SCI, 3.898【期刊主页】/macromolecules/【投稿方式】online submision【出版商】ACS【审稿周期】3-6 months48【期刊名称】Talanta【所属学科】分析化学【级别】SCI、EI,2.532(2004 年)【期刊主页】/tal/【投稿方式】submission on line【出版商】elsevier【审稿周期】3-6 months49【期刊名称】ADV ANCES IN CA TALYSIS【所属学科】化学【级别】SCI,EI【影响因子】9.750【期刊主页】/science/bookseries/03600564 【国际刊号】ISSN: 0360-0564【投稿方式】online【出版商】ELSEVIER ACADEMIC PRESS INC【审稿周期】3~6 months50【期刊名称】CA TALYSIS LETTERS【所属学科】化学&材料【级别】SCI,EI【影响因子】1.904【期刊主页】/east/hom ... 40109-70-35504020-0 【国际刊号】ISSN: 1011-372X【出版商】SPRINGER【审稿周期】3~6 months51【期刊名称】European Polymer Journal【所属学科】化学【影响因子】1.419【期刊主页】 ... mp;journal=00143057【投稿方式】online submision【出版商】elsevier【审稿周期】3-6 months52【期刊名称】Polymer degradation and stability【所属学科】化学【级别】SCI【影响因子】1.685【期刊主页】 ... mp;journal=01413910【投稿方式】online submision【出版商】elsevier【审稿周期】3-6 months53【期刊名称】Green Chemistry【所属学科】化学【级别】SCI Impact Factor:3.5【期刊主页】【投稿方式】email【出版商】RSC【审稿周期】3months54【期刊名称】Journal of Polymer Science Part B: Polymer Physics【所属学科】化学主要高分子类【级别】SCI, 1.39【期刊主页】/cgi-bin/jhome/36698【投稿方式】online submision【出版商】Wiley【审稿周期】2 months55【期刊名称】Journal of Applied Polymer Science【所属学科】化学主要高分子类【级别】SCI, 1.3【期刊主页】/cgi-bin/jhome/30035【投稿方式】online submision【出版商】Wiley【审稿周期】2 months56【期刊名称】EUROPEAN POLYMER JOURNAL【简介】This journal publishes results bearing on the physics and chemistry of natural and synthetic macronuclear substances and also reviews articles covering advances in polymer technology.【所属学科】Chemistry ; Physics ; Materials Science【级别】SCI,EI【影响因子】0.720【期刊主页】/wps/find ... ription#description【投稿方式】online submission【出版商】Elsevier【审稿周期】in a month57【期刊名称】Carbohydrate Research【简介】The journal includes normal length research papers, perspectives, notes, rapid communications and book reviews together with notices of meetings concerned w ith carbohydrates.【所属学科】Chemistry【级别】SCI,EI【影响因子】1.43【期刊主页】/Jour ... 829&Precis=DESC【投稿方式】online submission【出版商】Elsevier【审稿周期】2 month58【期刊名称】Carbohydrate Polymers【简介】Carbohydrate Polymers covers the study and exploitation of the industrial applications of carbohydrate polymers in areas such as food, textiles, paper, wood, adhesives, pharmaceuticals, oil field applications and industrial chemistry.【所属学科】Chemistry【级别】SCI,EI【影响因子】1.71【期刊主页】/Jour ... 871&Precis=DESC【投稿方式】online submission【出版商】Elsevier【审稿周期】2 month59【期刊名称】Journal of Physical Chemistry B【所属学科】化学,物理,材料类【级别】SCI【影响因子】3.834 (2004); 3.679 (2003); 3.611 (2002)【期刊主页】/journals/jpcbfk/index.html【投稿方式】on-line submittion【审稿周期】审稿期限是21 天,超过 1 个月编辑会给通讯联系人发信说明情况。
具体介绍各个催化期刊之前,有必要对现今几大出版社或数据库简要介绍一下(一般催化期刊都是这四个出版社或数据库名下的):(1)Elsevier Science出版社QUOTE:Elsevier 出版的期刊是世界公认的高品位学术期刊,且大多数为核心期刊,被世界上许多著名的二次文献数据库所收录。
SDOS目前收录1700多种数字化期刊,该数据库涵盖了食品、数学、物理、化学、生命科学、商业及经济管理、计算机科学、工程技术、能源科学、环境科学、材料科学和社会科学等众多学科。
该数据库不仅涵盖了以上各个学科的研究成果,还提供了简便易用的智能检索程序。
通过Science Direct Onsite(SDOS)中国集团的数据库支持,用户可以使用Elsevier Science为其特别定制的科学、技术方面的学术期刊并共享资源。
目前 (截止到2005年11月16日)该数据库已有期刊种数1,734,期刊期数145,078 ,文章篇数2,576,316,最早年份为1995年。
这个数据库的服务器是通过专线对中国大陆用户提供服务的。
Elsevier Science是一家非常好的电子出版商,从2001年1月起,就已有28家杰出的学术机构加入了Elsevier SDOS中国集团。
(2)Springer出版社QUOTE:德国施普林格( Springer-Verlag )是世界上著名的科技出版公司,通过Springer Link 系统提供学术期刊及电子图书的在线服务。
全文期刊数据库所收录的学科范围较广,包括:行为科学、生物医药与生命科学、化学与材料科学、计算机科学、商业与经济学、工程学、地球和环境科学、人文科学、社会科学与法律、数学、医学、物理与天文学等 11 个学科,其中许多为核心期刊。
(3)ACS数据库QUOTE:美国化学学会 ----ACS(American Chemical Society)成立于1876年,现已成为世界上最大的科技协会之一,多年来,ACS一直致力于为全球化学研究机构、企业及个人提供高品质的文献及服务,在科学、教育、政策等领域提供了多方位的专业支持,成为享誉全球的科技出版机构。
华南理工大学博士研究生申请学位发表学术论文的规定(经校学位评定委员会七届十二次会议讨论通过)为了促进我校博士研究生科研能力与学术水平的提高,保证博士学位论文的质量,现就我校博士研究生申请博士学位提出如下发表学术论文规定。
理工科类本规定适用于在我校理学、工学门类所有学科申请学位的博士研究生。
一、申请学位论文答辩前,博士研究生以本人为第一作者发表的与学位论文相关的学术论文须达到以下要求之一:1、在国内外SCI、EI(核心)检索源期刊上发表(或被录用)2篇学术论文,或者在国内外学术期刊上发表2篇被SCI、EI(光盘版)收录的学术论文;2、在所属学科指定的国际重要学术会议(见表1)上发表1篇被SCI或EI(光盘版)收录的会议论文(多篇只统计1篇),并另在国内外SCI、EI(核心)检索源期刊上发表(或被录用)1篇学术论文,或者另在国内外学术期刊上发表1篇被SCI、EI(光盘版)收录的学术论文。
博士研究生发表的满足上述要求之一的学术论文中,须至少有1篇学术论文用英文发表,须至少有1篇学术论文已公开发表。
SCI、EI(核心)检索源期刊以学术论文录用时公布的版本为准。
二、学校鼓励博士研究生发表高水平学术论文,博士研究生以本人为第一作者在本学科国际重要学术期刊(见表2)上发表1篇论文,视为达到发表论文的要求。
三、学校鼓励博士研究生申请与学位论文相关的发明专利。
凡以第一发明人获得授权发明专利相当于发表1篇SCI或EI(光盘版)收录的学术论文。
四、本规定适用于2008年9月1日后入学(即2008级开始)的博士研究生和在2011年1月1日后申请学位论文答辩送审的博士研究生。
2008年9月1日前入学(即2007级及以前)且在2011年1月1日前申请学位论文答辩送审的博士研究生,其发表论文的要求按原发表学术论文的规定(华南工研2003[24]号)执行。
一、在《华南理工大学学报》和其他高校学报,以及华南理工大学主办的其他学术期刊上发表的多篇论文只统计1篇,在学术会议上发表多篇会议论文只统计1篇。
外文期刊缩写与全称对照表(总94页)--本页仅作为文档封面,使用时请直接删除即可----内页可以根据需求调整合适字体及大小--外文期刊缩写与全称对照表AAcc. Chem. Res.Accounts of Chemical ResearchACH - Models Chem.ACH - Models in ChemistryACI Mater. J.ACI Materials JournalACS Symp. Ser.ACS Symposium SeriesActa Biochim. Pol.Acta Biochimica PolonicaActa Biotechnol.Acta BiotechnologicaActa Chem. Scand.Acta Chemica ScandinavicaActa Chim. SinicaActa Chimica SinicaActa Cienc. Indica, Chem.Acta Cienceia Indica ChemistryActa Cienc. Indica, Phys.Acta Ciencia Indica PhyicsActa Crystallogr., Sect. A: Found. Crystallogr.Acta Crystallographica Section A: FoundationsActa Crystallogr., Sect. B: Struct. SciActa Crystallographica Section B: Structural ScienceActa Crystallogr., Sect. C: Cryst. Struct. Commun.Acta Crystallographica Section C: Crystal Structure CommunicationsActa Crystallogr., Sect D: Biol. Crystallogr.Acta Crystallographica Section D: Biological CrystallographyActa Crystallogr. Sect. E: Struct. Rep. OnlineActa Crystallographica Section E Structure Reports OnlineActa Hydroch. Hydrob.Acta Hydrochimica et HydrobiologicaActa Mater.Acta MaterialiaActa Metall.Acta MetallurgicaActa Phys. Pol., AActa Physica Polonica AActa Phys. Pol., BActa Physica Polonica BActa Polym.Acta PolymericaActa Polytech. Scand., Chem. Technol. SerActa Polytechnica Scandinavica - Chemical Technology SeriesAdhes. AgeAdhesives AgeAdsorpt. Sci. Technol.Adsorption Science and TechnologyAdv. Appl. Microbiol.Advances in Applied MicrobiologyAdv. At. Mol. Opt. Phy.Advances in Atomic Molecular and Optical PhysicsAdv. Biochem. Eng./Biotechnol.Advances in Biochemical Engineering / BiotechnologyAdv. Carbohydr. Chem. Biochem.Advances in Carbohydrate Chemistry and BiochemistryAdv. Chem. Phys.Advances in Chemical PhysicsAdv. Chem. Ser.Advances in Chemistry SeriesAdv. Chromatogr.Advances in ChromatographyAdv. Colloid Interface Sci.Advances in Colloid and Interface ScienceAdv. Compos. MaterAdvanced Composite MaterialsAdv. Cryog. Eng.Advances in Cryogenic EngineeringAdv. Eng. Mater.Advanced Engineering MaterialsAdv. Enzyme Regul.Advances in Enzyme RegulationAdv. Enzymol. Relat. Areas Mol. Biol.Advances in Enzymology and Related Areas of Molecular BiologyAdv. Filtr. Sep. Technol.Advances in Filtration and Separation TechnologyAdv. Funct. Mater.Advanced Functional MaterialsAdv. Heterocycl. Chem.Advances in Heterocyclic ChemistryAdv. Inorg. Chem.Advances in Inorganic ChemistryAdv. Mass Spectrom.Advances in Mass SpectrometryAdv. Synth. Catal.Advanced Synthesis and CatalysisAdv. Mater.Advanced MaterialsAdv. Mater. Opt. Electron.Advanced Materials for Optics and ElectronicsAdv. Mater. ProcessesAdvanced Materials and ProcessesAdv. Mater. Res.Advances in Materials ResearchAdv. Organomet. Chem.Advances in Organometallic ChemistryAdv. Phys. Org. Chem.Advances in Physical Organic ChemistryAdv. Polym. Sci.Advances in Polymer ScienceAdv. Polym. Tech.Advances in Polymer TechnologyAdv. Powder Technol.Advanced Powder TechnologyAdv. Powder. Metall. Part. Mater.Advances in Powder Metallurgy and Particulate MaterialsAdv. Protein Chem.Advances in Protein ChemistryAdv. Quantum Chem.Advances in Quantum ChemistryAdv. Second Messenger Phosphoprotein Res.Advances in Second Messenger and Phosphoprotein ResearchAdv. Space Res.Advances in Space ResearchAdv. X-Ray Anal.Advances in X-Ray AnalysisAdverse Drug React. Toxicol. Rev.Adverse Drug Reactions and Toxicological ReviewsAerosol Sci. Technol.Aerosol Science and TechnologyAlChE J.AIChE JournalAlChE Symp. Ser.AIChE Symposium SeriesAm. Ceram. Soc. Bull.American Ceramic Society BulletinAm. Ind. Hyg. Assoc. J.American Industrial Hygiene Association JournalAm. J. Respir. Cell Mol. Biol.American Journal of Respiratory Cell and Molecular BiologyAm. Lab.American LaboratoryAm. Mineral.American MineralogistAmmonia Plant Saf. Relat. FacilAmmonia Plant Safety and Related FacilitiesAn. Asoc. Quim. Argent.Anales de la Asociacion Quimica ArgentinaAn. Quim.Anales de QuimicaAnal. Biochem.Analytical BiochemistryAnal. Chem.Analytical ChemistryAnal. Chim.Annali di ChimicaAnal. Chim. ActaAnalytica Chimica ActaAnal. Commun.Analytical CommunicationsAnal. Lett.Analytical LettersAnal. Sci.Analytical SciencesAngew. Chem. Int. Ed.Angewandte Chemie International EditionAngew. Makromol. Chem.Angewandte Makromolekulare ChemieAnn. Chim. (Rome)Annali di ChimicaAnn. Chim. - Sci. Mat.Annales de Chimie - Science des MateriauxAnn. Clin. Biochem.Annals of Clinical BiochemistryAnn. . Acad. Sci.Annals of the New York Academy of Sciences Annu. Rep. Med. Chem. Annual Reports in Medicinal Chemistry Annu. Rep. Prog. Chem. Sect. A: Inorg. Chem. Annual Reports on the Progress of Chemistry, Section A: Inorganic Chemistry Annu. Rep. Prog. Chem. Sect. B: Org. Chem. Annual Reports on the Progress of Chemistry, Section B: Organic Chemistry Annu. Rep. Prog. Chem. Sect. C: Phys. Chem. 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Iron–ceria–zirconia fluorite catalysts for methane selective oxidation to formaldehydeRadka Nedyalkova a ,Daniel Niznansky b ,Anne-Cécile Roger a,*a Laboratoire des Matériaux,Surfaces et Procédés pour la Catalyse,LMSPC-ECPM,25Rue Becquerel,67087Strasbourg Cedex 2,France bDepartment of Inorganic Chemistry,Faculty of Natural Sciences of Charles University,Albertov 6,12843Prague 2,Czech Republica r t i c l e i n f o Article history:Received 17November 2008Received in revised form 15June 2009Accepted 17June 2009Available online 23June 2009Keywords:Selective oxidation of methane to formaldehydeIron–ceria–zirconiaSol–gel method of preparationa b s t r a c tCeria–zirconia catalysts modified by partial substitution of zirconium by iron were investigated for the reaction of the selective oxidation of methane to formaldehyde.The insertion of iron was ensured by the preparation method,based on decomposition of the mixed precursors.The crystalline structure was studied by XRD and the iron state was determined by Mössbauer spectroscopy.The insertion of Fe 3+into the lattice of the mixed oxide and the partial substitution of zirconium ions with iron cations up to 25%have not resulted in any phase rejection of the formed iron oxide.The reducibility of Ce 4+in the modified ternary oxide is enhanced by doping with iron.Despite their low specific surface area,the catalysts are efficient at activating the methane independently of the iron content.The selectivity to formaldehyde strongly depends on the amount of the iron inserted in the mixed oxide.Ó2009Elsevier B.V.All rights reserved.1.IntroductionThe partial oxidation of methane to formaldehyde (MPO)is a promising way of producing high added value compound,avoiding the actual process based on a high energy consuming step of reforming.The direct partial oxidation can be performed at atmo-spheric pressure,using oxygen or air as oxidant,at relatively low temperature (250–600°C).Higher temperatures favour methane activation but lead to the formation of more highly oxidized prod-ucts,which are much more thermodynamically stable than formal-dehyde.As a support material with high surface area,silica was found to ensure high metal oxide dispersion,avoiding a secondary reaction from formaldehyde to CO X [1–6].It was reported that among various reducible metal oxides,molybdenum,vanadium or iron oxide can be used for improving the efficiency of the cata-lysts.In the case of iron,it was demonstrated that the redox cen-tres Fe 3+/Fe 2+of small clusters are responsible for high catalytic selectivity to formaldehyde,while larger iron oxide particles result mainly to deep oxidation into CO 2[7].In a previous work [5]on FeO X /silica catalysts,we proved the beneficial effects of iron inser-tion in the silica matrix under the form of tetrahedral Fe 3+,on the production of formaldehyde in comparison with the simple impregnation of iron oxide on a silica support of high specific area.In the present work,other types of iron-based catalysts for the direct production of formaldehyde from methane were investi-gated.In order to elucidate some of the crucial aspects as towhether the supports with high surface area,such as silica,are really essential for high formaldehyde selectivity of the catalysts or if the reducible Fe 3+integrated into the oxide matrix is the key point,the primary focus of the current work is to correlate the structure and the catalytic activity of the ceria–zirconia system partially substituted by iron.2.Experimental 2.1.Catalysts preparationCe–Zr–Fe mixed oxides were synthesized via a pseudo sol–gel method based on the thermal decomposition of metallic propionates [8,9].In this synthetic procedure,cerium(III)acetate hydrate,zirco-nium(IV)acetylacetonate and iron(II)acetate hydrate were used as starting positions of the obtained mixed oxides are given in the text with general formula as follows:Ce 2Zr 2ÀX Fe X O 8Àd with X =0.1;0.2;0.3;0.4and 0.5.For comparison,a mixed oxide Ce 2Zr 2O 8free of iron (X =0)was prepared in the same conditions.The starting salts were dissolved separately in boiling propionic acid (0.12mol L À1).The solutions were mixed and then the solvent was evaporated until a resin was formed.After that,the product was heated in air at 700°C over 3h (2°C min À1).2.2.Specific surface areaSpecific surface area measurements were carried out by using the BET method based on the N 2physisorption capacity at 77K on a Coulter SA 3100apparatus.1566-7367/$-see front matter Ó2009Elsevier B.V.All rights reserved.doi:10.1016/j.catcom.2009.06.017*Corresponding author.Fax:+33390242768.E-mail address:rogerac@ecpm.u-strasbg.fr (A.-C.Roger).Catalysis Communications 10(2009)1875–1880Contents lists available at ScienceDirectCatalysis Communicationsj ou r na l h om e pa ge :w w w.e lse v ie r.c om /lo c at e /c at c om2.3.Transmission electronic microscopy(TEM)A high resolution microscope EM-002B TOPCON(acceleration tension of200keV)was used,and was coupled to X-rays energy dispersive spectroscopy(XEDS KEVEX Deltapro Quantum)for microanalysis of the samples.2.4.X-ray diffraction(XRD)X-ray powder diffraction(XRD)patterns were recorded on a Siemens D-5000powder diffractometer using nickel-filtered Cu Ka radiation(1.5406Å).2.5.Thermo-programmed reduction(TPR)Temperature programmed reduction(TPR)was conducted using a conventional apparatus equipped with a TCD detector.A 50-mg sample placed in a U-shaped quartz tube(6.0mm i.d.). TPR was performed by heating the samples at15°C minÀ1from 25to900°C in a3%H2–N2mixtureflowing at50mL minÀ1.2.6.Mössbauer spectroscopyThe Mössbauer spectra measurement was carried out in the transmission mode with57Co diffused into an Rh matrix as a source moving with constant acceleration.The spectrometer(Wissel)was calibrated by means of a standard a-Fe foil,and the isomer shift was expressed with respect to this standard at293K.Thefitting of the spectra was performed with the help of the NORMOS program. 2.7.Catalytic activityThe partial oxidation of methane was carried out at the atmo-spheric pressure in a quartz U-shaped tube reactor with an inner diameter of6.6mm,placed within a vertical furnace.The reaction temperature was measured with a thermocouple placed near the catalytic bed.The inlet gas mixture(35mL minÀ1)was prepared with the relation following ratios CH4/O2/N2=7.5/1/4.Helium was used as a diluting gas of the reaction mixture(30.5mL minÀ1). The inlet gases are introduced independently and theirflows are controlled by massflowmeters of the type BROOKS5850with elec-tronic control systems.The catalytic tests were performed at GHSV of42,000hÀ1.A tube was warmed to120°C and used to link the outlet of the reactor to the gas chromatograph to avoid condensation and poly-merisation of the formaldehyde.The reaction products are analyzed by two gas chromatographs. Thefirst chromatograph of type DELSI with a Hayesep column (polymeric porous)and a detector of thermal conductivity(TCD) permits the identification of several products:methane,CO2,eth-ane,ethene,formaldehyde,water and methanol.The second chro-matograph of type VARIAN provides a5Åmolecular mesh and detector TCD that facilitates the resolution related to the identifica-tion of O2and N2and permits the analysis of CH4and CO.A trap is placed between these two chromatographs,containing a methanol solution(15%in water)and maintained at0°C,to pre-vent formaldehyde and methanol from polluting the second col-umn of chromatography.3.Results and discussionA series offive catalysts were prepared by the sol–gel based method(see Section2)with various synthetic Zr/Fe ratios,starting from substitution of zirconium with5%iron into the system Ce2Zr1.9Fe0.1O8to25%for Ce2Zr1.5Fe0.5O8.The theoretical formula and the specific surface area of the materials are given in Table 1.The significantly lower specific surface area(in the range be-tween4and7m2gÀ1)corresponding to the all mixed oxide sam-ples heated at700°C are not strongly affected by the iron content.The diffractograms of the fresh catalysts are presented in Fig.1, as well as a ceria–zirconia oxide free of iron,noted X=0,with a for-mula Ce2Zr2O8.In all cases only a crystalline structure correspond-ing to cubicfluorite is detected.No rejected phase of iron oxide is evidenced.The peaks are highly symmetric and can befitted as sin-gle peaks by a Lorentzian peak-shape function(shown for the main peak of X=0.5in the inset of Fig.1).Thefive oxides X=0.1to X=0.5crystallize with the same cubic lattice parameter of5.26Å(calculated from the four main diffraction peaks at2h=29.4°;34.1°;48.9°and57.9°).As shown in Fig.1by the straight lines, the diffraction peaks are slightly shifted towards higher angles with respect to those of the mixed oxide free of iron X=0.Without iron(X=0,Fig.1),the cubic lattice parameter is5.27Å.The particle size(Table1)remains in the same range for all materials,around 60Å,but tends to increase with increasing iron content in the mixed oxide.Transmission electron microscopy was performed to analyze the micro-homogeneity of the oxides.Fig.2presents the photo-graph obtained by TEM for Ce2Zr1.5Fe0.5O8(X=0.5),which is the catalyst with the highest iron content of the series.The chemical analyses were performed by XEDS using a beam of8.8nm for quantification of local composition.The Ce,Zr and Fe contents for local analyses(results L1,L2,L3and L4in Fig.2)are compared to the global composition of the catalyst(analysis G,large beam) and to the theoretical composition(Th.in Fig.2).The local compo-sitions always correspond to the global composition of the sam-ple.They never reveal zones of composition far from the expected value of12.5%for iron content,which accounts for the homogeneous distribution of iron in the catalyst.This is in good agreement with the XRD results where no phase rejection was evidenced.The reducibility of the catalysts has been studied by tempera-ture programmed reduction.The profiles of H2consumption are given in Fig.3,as well as the reduction profile of Ce2Zr2O8.It is seen that Ce2Zr2O8is characterized by a maximum in the consumed hydrogen for the reduction process around500°C.This low tem-perature reduction is generally assigned to surface cerium reduc-tion[10].The higher temperature reduction(around900°C) assigned to bulk cerium reduction is in our case very small,dueTable1Characterization of the catalysts after synthesis.Samples BET area m2gÀ1Particle size(Å)a H2consumed mmol gÀ1cataCe4+reduction if Fe3+(%)Ce4+reduction if Fe2+(%) Ce2Zr1.5Fe0.5O8Àd 4.168 2.6978.1103.1Ce2Zr1.6Fe0.4O8Àd 4.265 2.5183.8103.8Ce2Zr1.7Fe0.3O8Àd 3.862 2.2785.8100.8Ce2Zr1.8Fe0.2O8Àd7.458 1.9281.691.6Ce2Zr1.9Fe0.1O8Àd 5.663 1.7185.390.3Ce2Zr2O8–560.9052.952.9a Calculated on basis of the X-ray diffraction peaks.1876R.Nedyalkova et al./Catalysis Communications10(2009)1875–1880to the small particle size of the oxide and the consequent high surface/volume ratio.The volume of hydrogen consumption corre-sponds to the reduction of 53%of Ce 4+into Ce 3+.The insertion of iron leads to differentiation of the reduction profile in two separate zones.The first reduction zone begins at lower temperature with increasing Fe content in the mixed oxide.0%20%40%60%80%100%CeZrFe14 23R.Nedyalkova et al./Catalysis Communications 10(2009)1875–18801877Simultaneously,the surface of this peak increases with X .Similar behaviour is also apparent for the high temperature reduction zone.With increasing Fe content,the maximal hydrogen consump-tion shifts from 890°C for X =0and X =0.1to 725°C for X =0.5.The second zone of reduction increases with X ,and corresponds to the reduction of iron cations into Fe [11].The total volumes of hydrogen consumed per gram of catalyst are given in Table 1.By taking into account that iron oxide is totally reduced during the whole TPR process,the degree of reduction of Ce 4+into Ce 3+was calculated.The results are given also in Table 1.Depending on the initial oxidation state of iron in the oxide,the reduction of Ce 4+is estimated between 78%and 104%,an in-crease compared to the value of 53%for the system without iron.Thus,the addition of iron into the ceria–zirconia system favours the cerium reduction in terms of the temperature and as well as in terms of the amount of reduced cerium.Values higher than 100%of cerium reduction,calculated assuming an initial oxidation state of +2for iron in the catalysts,could indicate that either iron in the mixed oxide is +3or a mixture +3/+2.The surface of the high temperature peak was compared to the iron content in the catalyst.For X =0.2,the hydrogen consumption is of 0.33mmol per gram of catalyst (17%of the whole consump-tion).This is in good agreement with the quantity of 0.34mmol of Fe ions per gram of catalyst (assuming Fe 3+in the molar weight calculation).The high temperature reduction would then consist in the reduction of Fe 2+into Fe °.For other catalysts,the two values are not so close,but follow the same tendency:0.47mmol of H 2for 0.52mmol of Fe for X =0.3;0.54mmol of H 2for 0.69mmol of Fe for X =0.4;and 0.69mmol of H 2for 0.87mmol of Fe for X =0.5.The reduction of the Ce–Zr–Fe mixed oxides would then consist of two separate steps :partial Ce 4+reduction (deeper cerium reduction by Fe doping)and Fe 3+reduction into Fe 2+at tempera-tures lower than 600°C;and a final reduction of Fe 2+into Fe 0at temperatures higher then 750°C (temperature decreasing with increasing Fe content).In order to obtain detailed information about the structure and the mechanism of the insertion of iron into the lattice of the Ce–Zr system,the catalyst sample with the highest Fe content (X =0.5)was examined by Mössbauer spectroscopy.The spectrum is given in Fig.4.The details of the fit are presented in Table 2.The spectrum can be fitted by a doublet of isomer shift d equal to 0.33mm/s.This value is in the range of 0.15–0.45mm/s,which is typical for Fe 3+(most probably in octahedral position),when a -Fe is used as internal standard [12].For this sample,the presence of Fe 2+can be excluded (d within the range 0.9–1.8mm/s).This is in good agreement with the conclusions from the TPR analysis,whereFe 2+was assumed to lead to an increasing the cerium reduction higher than 100%.The good fitting of the spectrum by a doublet shows that there is neither hematite nor a separated iron oxide phase.It was found in this case that Fe 3+in the distorted octahedral site is diluted in the matrix and forms a solid solution,which is paramagnetic at room temperature [13].This observation of Fe 3+diluted in a solid solution is also consis-tent with the XRD measurements where no iron oxide phase was detected.The integration of iron in the oxide solid solution is also in accordance with the modification of the cubic lattice parameter in comparison with Ce 2Zr 2O 8.The ionic radius of the octahedral Fe 3+(0.645Å)[14]is lower than that of the cubic Zr 4+,which is equal to 0.84Å.Therefore the partial substitution of Zr by Fe up to 25%for Ce 2Zr 1.5Fe 0.5O 8Àd will result in a contraction of the lat-tice.The insertion of iron ions in the cubic lattice of ceria–zirconia does not follow the conventional Vergard’s law.Some studies on CeO 2–Fe 2O 3solid solutions [13,15–18]showed that the mecha-nism of insertion of the octahedral Fe 3+ions into the cubic lattice of CeO 2depends on the amount of doping.The Fe 3+cations can either substitute a Ce 4+cation in a cubic site and induce vacancy compensation for charge balance,or compensate the charge by additional cation interstitial insertion.Both mechanisms are claimed at high substitution rates.In both mechanisms of substitu-tion,the variation of the lattice parameter is different.Substitution of a smaller cation for Ce 4+induces a lattice contraction,whereas interstitial cations will expand the cubic lattice.In our case,since there is a smaller difference in the ionic radius between Fe 3+and Zr 4+(0.645and 0.84Å,respectively)in comparison with those of Fe 3+and Ce 4+(0.645and 0.97Å,respectively),the substitution of Zr 4+with Fe 3+cations is a more likely process than between Fe 3+and Ce 4+.The ionic size mismatch between Fe 3+and Zr 4+((r dopant Àr host )/r host )is À23%considering an octahedral site forFe 3+.The calculations of doping CeO 2by iron always refer to cubic site.In that case,the ionic size mismatch between Fe 3+and Zr 4+is only À7%.For this value of size difference,both mechanisms of incorporation can take place.This explains why the cubic lattice parameter does not vary linearly with the ironcontent.Fig.4.Mössbauer spectrum of the sample Ce 2Zr 1.5Fe 0.5O 8Àd ,X =0.5.Table 2Mössbauer parameters for the sample Ce 2Zr 1.5Fe 0.5O 8Àd ,X =0.5;values of the fitting.SubspectrumIsomer shift,d0.33mm/s Quadrupole splitting,D EQ 1.09mm/s Hyperfine field,BHf N/A Relative area (%)1001878R.Nedyalkova et al./Catalysis Communications 10(2009)1875–1880The doping by undersized cations has been demonstrated to en-hance the reducibility of cerium by decreasing the activation en-ergy for the reduction Ce4+?Ce3+[17,18].This is the case for ceria–zirconia solid solutions in comparison with ceria.Here,from the TPR experiments,we demonstrated that the incorporation of iron in ceria–zirconia lattice favours the reducibility of Ce4+.We have thus additional favourable effect on reduction by decreasing again the mean ionic radius of the B sites by partially substituting zirconium ions by even smaller iron ions.Another crucial aspect is whether the incorporation of octahe-dral3+cations will not provoke an ordered arrangement of the cat-ions in the pyrochlore structure.In the pyrochlore structure,ceria–zirconia mixed oxides present much better redox properties [19,20]thanfluorite-type ones.Bernal et al.[20]clearly showed that the nuclei of cation-ordered pyrochlore Ce2Zr2O8can be re-duced at a much lower temperature and to a greater extent than purefluorite.This can be related to the different occupancy of the oxygen sites in both structures[21].In the present work,no structural evidence of pyrochlore formation was detected by XRD.However,the small additional reflections associated to the pyrochlore structure expected around2h=29°,38°and45°could be hindered either by the much more intense peak around30°or in the background due to the very small crystallite size,which leads to the large shape of the peaks.The Ce2Zr2ÀX Fe X O8Àd series of catalysts was tested in the reac-tion of methane partial oxidation.The methane conversion versus reaction temperature is given in Fig.5A.All catalysts exhibit the same profile of methane conversion versus temperature.The conversion is negligible up to350°C, and starts increasing and reaches values close to6%at500°C. The amount of iron substitution does not result in any significant changes on the methane conversion rate.By comparison with other iron-based catalysts[5,7],the value of methane conversion is in the same range,whereas the specific surface area values of the catalysts reported were much higher. Under the same reaction conditions,Fe/silica catalysts(0.5wt.%) of850m2gÀ1reach a maximal methane conversion of3.4%at a higher temperature(650°C)than our Ce–Zr–Fe catalysts.CO2,H2O and formaldehyde were the only products detected in these reaction conditions.Neither carbon monoxide nor methanol was formed during the test.The selectivity into formaldehyde ver-sus temperature is given in Fig.5B,where noticeable differences in the behaviour of the catalysts appeared.An increase of the selectiv-ity of the samples into formaldehyde formation was observed depending on the amount of iron substituted to zirconium in the mixed oxide.The maximal selectivity into HCHO is4%for theR.Nedyalkova et al./Catalysis Communications10(2009)1875–18801879Ce2Zr1.8Fe0.2O8Àd at450°C,while the selectivity for the Ce2Zr1.7Fe0.3O8Àd reaches18%at400°C.For both catalysts,highest Fe content resulted in maximal selectivity into formaldehyde,even at lower temperature(300–350°C),and reaches values around 50%.From the TPR experiments,the amount of Ce4+reduction was estimated at around80%for all catalysts.The maximal CH4conver-sion is always around temperature500°C which corresponds to the maximal temperature of the low temperature reduction zone in TPR.The catalysts with high redox properties investigated in this work are able to activate the methane independently of the iron content.The effect of iron appears clearly on formaldehyde selectivity. The high iron dispersion in the redox matrix of the ceria–zirconia catalyst due to its insertion in the mixed oxide lattice under the form of octahedral Fe3+ensures quite high formaldehyde selectiv-ity,even at high level of iron contents.The insertion in the lattice avoids the formation of aggregated Fe2O3species which would pre-vent formaldehyde production[1,20].Arena et al.[22,23]clearly correlates the surface structures of FeOx/SiO2catalysts with their activity–selectivity pattern.They established that isolated Fe3+is the key point for high formalde-hyde selectivity.However,systems that are too isolated react poorly due to low electron transfer efficiency.In our case,the insertion of Fe3+in the reducible host mixed oxide would favour the eÀ-transfer efficiency,in addition with the dispersive effect of the solid solution formation.As shown by TPR experiments,the whole reducibility of cerium is enhanced by Fe doping.The global reducibility of the catalysts as well increases with the iron content, even in the low temperature reduction zone(<600°C)of cerium reduction and Fe3+reduction into Fe2+.Our catalytic systems,when Fe content increases,would then act like the2-d oligomeric patches related by Arena et al.[23].After the catalytic test the mixed oxide structure is preserved as shown by XRD in Fig.6.The cubic lattice parameter of the mixed oxide after the catalytic test for all catalysts was calculated to be 5.25Å,which is slightly smaller than for the fresh oxides(5.26Å).4.ConclusionsDespite the lower specific surface area of the catalytic systems studied in this work than that of the silica-based catalysts,the re-sults showed that these samples are efficient enough to activate the methane with a rate of conversion comparable to that obtained on high surface catalyst.The preparation method based on the decomposition of mixed propionate precursors ensures the effec-tive insertion and dispersion of iron in the cubic lattice of the cer-ia–zirconia mixed oxide in the form of Fe3+.The doping by Fe3+enhances the reducibility of Ce4+in the mixed oxide in terms of the temperature and the reduced amount of Ce4+cations.Despite their low specific surface area,the catalysts convert around6%of the methane,independently of the iron content.On the contrary, the selectivity to formaldehyde strongly depends on the amount of iron inserted in the mixed oxide and increases with the iron content.AcknowledgementThe authors thank the«Ministère de l’Education Nationale,de l’Enseignement Supérieur et de la Recherche»for thefinancial support.References[1]A.Parmaliana,F.Arena,F.Frusteri,A.Martinez-Arias,M.Lopez Granados,J.L.G.Fierro,Appl.Catal.A:General226(2002)163–174.[2]R.G.Herman,Q.Sun,C.Shi,K.Klier,C.Wang,H.Hu,I.E.Wachs,M.Bhasin,Catal.Today37(1997)1–14.[3]A.De Lucas,J.L.Valverde,P.Canizares,L.Rodriguez,Appl.Catal.A:General184(1999)143–152.[4]A.Erdohelyi,K.Fodor,R.Nemeth,A.Hanez,A.Oszko,J.Catal.199(2001)328–337.[5]C.A.Guerrero, D.Niznansky,Y.N’Guyen, C.Courson, A.C.Roger,Catal.Commun.9(2008)864–869.[6]T.Kobayashi,N.Guilhaume,J.Miki,N.Kitamura,M.Haruta,Catal.Today32(1996)171–175.[7]K.Tabata,Y.Takemoto,T.Suzuki,E.Banares,M.A.Pena,J.L.G.Fierro,Catal.Rev.44(2002)1–58.[8]F.Romero-Sarria,J.C.Vargas,A.C.Roger,A.Kiennemann,Catal.Today133(2008)149–153.[9]J.C.Vargas,S.Libs,A.C.Roger,A.Kiennemann,Catal.Today107–108(2005)417–425.[10]J.Kašpar,P.Fornasiero,M.Graziani,Catal.Today50(1999)285–298.[11]L.Bedel,A.C.Roger,C.Estournes,A.Kienneman,Catal.Today85(2003)207–218.[12]F.Menil,J.Phys.Chem.Solids46(1985)7693–7700.[13]G.Li,R.L.Smith Jr.,H.Inomata,J.Am.Chem.Soc.123(2001)11091–11092.[14]R.D.Shannon,Acta Cryst.A32(1976)751–760.[15]R.Li,S.Yabe,M.Yamashita,S.Momose,S.Yoshida,S.Yin,T.Sato,Mater.Chem.Phys.75(2002)39–44.[16]L.Minervini,M.O.Zacate,R.W.Grimes,Solid State Ion.116(1999)339–349.[17]G.Balducci,M.S.Islam,J.Kaspar,P.Fornasiero,M.Graziani,Chem.Mater.15(2003)3781–3785.[18]F.J.Perez-Alonso,M.L.Granados,M.Ojeda,P.Terreros,S.Rojas,T.Herranz,J.L.G.Fierro,Chem.Mater.17(2005)2329–2339.[19]A.Suda,yo,K.Yamamura,H.Sobukawa,T.Sasaki,Y.Nagai,T.Tanabe,M.Sugiura,J.Ceram.Soc.Japan112(2004)586–589.[20]S.Bernal,G.Blanco,J.J.Calvino,J.C.Hernandez,J.A.Perez-Omil,J.M.Pintado,M.P.Yeste,J.Alloys Compd.451(2008)521–525.[21]J.B.Thomson,A.R.Armstrong,P.G.Bruce,J.Solid State Chem.148(1999)56–62.[22]F.Arena,G.Gatti,S.Collucia,G.Martra,A.Parmaliana,Catal.Today91–92(2004)305–309.[23]F.Arena,G.Gatti,G.Martra,S.Collucia,L.Stievano,L.Spadaro,P.Famulari,A.Parmaliana,J.Catal.231(2005)365–380.1880R.Nedyalkova et al./Catalysis Communications10(2009)1875–1880。