射频等离子体诱导合成MoO_2-Mo_2N复合催化剂及其在合成气制低碳醇中的应用
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摘要
通过射频等离子体改性体相Mo_2N制备了MoO_2-Mo_2N复合催化剂,并考察了其在合成气制低碳醇反应中的催化性能。利用XRD、TEM、XPS、CO-TPD对改性前后的催化剂进行了表征,结果发现在等离子体处理过程中,体相Mo_2N可与表面氧原子发生结构重组,产生了更多的活性位点,且生成的MoO_2与Mo_2N间存在一定的相互作用。所制得的MoO_2-Mo_2N复合催化剂的催化性能较体相Mo_2N有所提升,在350℃反应温度下,CO转化率达到32.7%,醇选择性达到34.03%,醇类时空产率达到79.5mg/(g·h)。
MoO_2-Mo_2N composite catalyst was prepared by modifying bulk phase Mo_2N via RF plasma technique,and its catalytic performance in higher alcohols synthesis from syngas was investigated.The catalysts were characterized by XRD,TEM,XPS and CO-TPD.It was found that during the plasma treatment,the bulk phase Mo_2N can recombine with the surface oxygen atoms,which resulted in more active sites on the catalyst.Also there is certain interaction between MoO_2and Mo_2N.The catalytic performance of the prepared MoO_2-Mo_2N composite catalyst is improved compared with that of the bulk phase Mo_2N.At the reaction temperature of 350℃,the CO conversion rate,the alcohol selectivity,and the alcohol space-time yield reach32.7%,34.03%,and 79.5mg/(g·h)respectively.
MoO_2-Mo_2N composite catalyst was prepared by modifying bulk phase Mo_2N via RF plasma technique,and its catalytic performance in higher alcohols synthesis from syngas was investigated.The catalysts were characterized by XRD,TEM,XPS and CO-TPD.It was found that during the plasma treatment,the bulk phase Mo_2N can recombine with the surface oxygen atoms,which resulted in more active sites on the catalyst.Also there is certain interaction between MoO_2and Mo_2N.The catalytic performance of the prepared MoO_2-Mo_2N composite catalyst is improved compared with that of the bulk phase Mo_2N.At the reaction temperature of 350℃,the CO conversion rate,the alcohol selectivity,and the alcohol space-time yield reach32.7%,34.03%,and 79.5mg/(g·h)respectively.
引文
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[2]WANG N,LI J,LIU X,et al.Remarkable enhancement to the catalytic performance of molybdenum sulfide catalysts via in situ decomposition method for higher alcohols synthesis from syngas[J].RSC Advances,2016,6:112356-112362.
[3]BOAHENE P E,SURISETTY V R,SAMMYNAIK-EN R,et al.Higher alcohol synthesis using K-doped CoRhMoS2/MWCNT catalysts:influence of pelletization,particle size and incorporation of binders[J].Topics in Catalysis,2014,57(6):538-549.
[4]HOU G,CHENG B,DING F,et al.Well dispersed silicon nanospheres synthesized by RF thermal plasma treatment and their high thermal conductivity and dielectric constant in polymer nanocomposites[J].RSC Advances,2015,5(13):9432-9440.
[5]KUMAR S,SELVARAJAN V,KUMAR S,et al.Spheroidization of metal and ceramic powders in thermal plasma jet[J].Computational Materials Science,2006,36(4):451-456.
[6]ATTRI P,ARORA B,CHOI E H.Utility of plasma:a new road from physics to chemistry[J].RSC Advances,2013,3(31):12540-12567.
[7]ISHIGAKI T.Synthesis of functional oxide nanoparticles through RF thermal plasma processing[J].Plasma Chemistry&Plasma Processing,2017:1-22.
[8]VOLLATH D.Plasma synthesis of nanopowders[J].Journal of Nanoparticle Research,2008,10(1S):39-57.
[9]MEYYAPPPAN M.Plasma nanotechnology:past,present and future[J].Journal of Physics D:Applied Physics,2011,44(44):174002.
[10]PFENDER E.Thermal plasma technology:where do we stand and where are we going?[J].Plasma Chemistry and Plasma Processing,1999,19(1):1-31.
[11]LI Y L,ISHIGAKI T.Spheroidization of titanium carbide powders by induction thermal plasma processing[J].Journal of the American Ceramic Society,2004,84(9):1929-1936.
[12]OUKACINE L,GITZHOFER F,ABATZOGLOU N,et al.Application of the induction plasma to the synthesis of two dimensional steam methane reforming Ni/Al2O3,catalyst[J].Surface&Coatings Technology,2006,201(5):2046-2053.
[13]ZHANG H,CAO T,CHENG Y.Preparation of fewlayer graphene nanosheets by radio-frequency induction thermal plasma[J].Carbon,2015,86:38-45.
[14]WILDEN J,WANk A,BYKAVA A.DC thermal plasma CVD synthesis of coatings from liquid single source SiBCN and SiCNTi precursors[J].Surface&Coatings Technology,2005,200(1/2/3/4):612-615.
[15]SUZUKI M,KAGAWA M,SYONO Y,et al.Synthesis of ultrafine single-component oxide particles by the spray-ICP technique[J].Journal of Materials Science,1992,27(3):679-684.
[16]KATO Y,KAGAWA M,SYONO Y.Component distribution in plasma-deposited ultrafine powders of binary(Cr2O3,Fe2O3,SnO2)-Al2O3,systems[J].Materials Letters,1998,35(3/4):266-269.
[17]CHAI X,SHANG S,LIU G,et al.Characterization of Ni/γ-Al2O3catalyst prepared by atmospheric high frequency cold plasma jet for CO2 reforming of CH4[J].Chinese Journal of Catalysis,2010,319(3):353-359.
[18]NASEH M V,KHODADADI A A,MORTAZAVI Y,et al.Fast and clean functionalization of carbon nanotubes by dielectric barrier discharge plasma in air compared to acid treatment[J].Carbon,2010,48(5):1369-1379.
[19]ZHANG L,DIAO S,NIE Y,et al.Photocatalytic patterning and modification of graphene[J].Journal of the American Chemical Society,2011,133(8):2706-13.
[20]LIU J,XUE Y,ZHANG M,et al.Graphene-based materials for energy applications[J].MRS Bulletin,2012,37(12(Graphene Fundamentals and Functionalities)):1265-1272.
[21]LAURENT-BROCQ M,JOB N,ESKENAZI D,et al.Pt/C catalyst for PEM fuel cells:control of Pt nanoparticles characteristics through a novel plasma deposition method[J].Applied Catalysis B:Environmental,2014,147(7):453-463.
[22]LIU C J,ZHAO Y,LI Y,et al.Perspectives on electron-assisted reduction for preparation of highly dispersed noble metal catalysts[J].ACS Sustainable Chemistry&Engineering,2014,2:3-13.
[23]HOU G,CHENG B,DING F,et al.Well dispersed silicon nanospheres synthesized by RF thermal plasma treatment and their high thermal conductivity and dielectric constant in polymer nanocomposites[J].RSCAdvances,2015,5(13):9432-9440.
[24]ATTRI P,ARORA B,CHOI E H.Utility of plasma:a new road from physics to chemistry[J].RSC Advances,2013,3(31):12540-12567.
[25]WEI Z B.Surface species and the stability ofγ-Mo2N[J].Solid State Ionics,1997,101:761-767.
[26]YAO M,LI Q,HOU G,et al.Dopant-controlled morphology evolution of WO3polyhedra synthesized by RF thermal plasma and their sensing properties[J].ACS Applied Materials&Interfaces,2015,7(4):2856-2866.
[27]PORTELA L,GRANGE P,DELMON B.XPS and NO adsorption studies on alumina-supported Co-Mo catalysts sulfided by different procedures[J].Journal of Catalysis,1995,156(2):243-254.
[28]WEI Z B Z,GRANGE P,DELMON B.XPS and XRDstudies of fresh and sulfided Mo2N[J].Applied Surface Science,1998,135(1):107-114.
[29]NAGAI M,GOTO Y,IRISAWA A,et al.Catalytic activity and surface properties of nitrided molybdena-alumina for carbazole hydrodenitrogenation[J].Journal of Catalysis,2000,191(1):128-137.
[30]KIM G T,PARK T K,CHUNG H,et al.Growth and characterization of chloronitroaniline crystals for optical parametric oscillators:I.XPS study of Mobased compounds[J].Applied Surface Science,1999,152(1/2):35-43.
[31]LIAKAKOU E T,HERACLEOUS E.Transition metal promoted K/Mo2C as efficient catalysts for CO hydrogenation to higher alcohols[J].Catalysis Science&Technology,2015,6(4):1106-1119.
[32]ZHANG J W.Probing into surface sites of fresh Mo2N/Al2O3,Mo2C/Al2O3and MoP/Al2O3catalysts by CO adsorption and in situ FT-IR spectroscopy[J].China Petroleum Processing&Petrochemical Technology,2010,12(4):43-45.
[33]WU Z,MAROTOVALIENTE A,GUERRERORUIZA,et al.Microcalorimetric and IR spectroscopic studies of CO adsorption on molybdenum nitride catalysts[J].Physical Chemistry Chemical Physics,2003,5(8):1703-1707.