Cu_2O/TiO_2催化甲醛乙炔化反应的载体效应
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摘要
以不同温度焙烧的TiO_2为载体,CuCl_2·2H_2O为铜源,NaOH为沉淀剂,L-抗坏血酸钠为还原剂,采用液相还原-沉积沉淀法制备了Cu_2O/TiO_2,借助X射线粉末衍射(XRD)、H_2程序升温还原(H_2-TPR)、N_2-物理吸附、透射电镜(TEM)、X射线光电子能谱(XPS)等手段,研究了TiO_2载体焙烧温度对Cu_2O/TiO_2甲醛乙炔化反应性能的影响。结果表明,低温焙烧得到的TiO_2载体以锐钛矿相存在,与Cu_2O物种间具有弱的相互作用,使得Cu_2O被过度还原为金属Cu,催化活性较低。随着载体焙烧温度的升高,TiO_2中出现金红石相,Cu_2O与载体间相互作用增强,Cu_2O高效转变为乙炔亚铜活性物种,使催化剂表现出最佳的催化性能。
A series of Cu_2O/TiO_2 catalysts were prepared by liquid reduction-deposition-precipitation technique from copper chloride as copper source, sodium hydroxide as precipitant, sodium L-ascrobate as reducer, and TiO_2 calcined at different temperatures as support. The catalysts were characterized by X-ray diffraction(XRD), H_2-temperature programmed reduction(H_2-TPR), nitrogen physisorption, transmission electron microscopy(TEM), and X-ray photoelectron spectroscopy(XPS). The catalytic activity of these catalysts were studied in formaldehyde ethynylation. The results showed that calcination temperature of TiO_2 support had great influence on the catalytic activity of Cu_2O/TiO_2. TiO_2 calcined at low temperature presented mainly as anatase phase and had weak interaction with Cu_2O, which could cause over reduction of active Cu_2O to inactive metal Cu and result in the decrease of catalytic activity. With the increase of calcination temperature, anatase TiO_2 gradually transformed to rutile TiO_2 which could inhibit over reduction of active Cu_2O due to its strong interaction with Cu_2O. As a result of efficient conversion of Cu_2O to active Cu(I) ethynlate, the Cu_2O/TiO_2 catalyst with TiO_2 support calcined at high temperatures had the best catalytic activity.
A series of Cu_2O/TiO_2 catalysts were prepared by liquid reduction-deposition-precipitation technique from copper chloride as copper source, sodium hydroxide as precipitant, sodium L-ascrobate as reducer, and TiO_2 calcined at different temperatures as support. The catalysts were characterized by X-ray diffraction(XRD), H_2-temperature programmed reduction(H_2-TPR), nitrogen physisorption, transmission electron microscopy(TEM), and X-ray photoelectron spectroscopy(XPS). The catalytic activity of these catalysts were studied in formaldehyde ethynylation. The results showed that calcination temperature of TiO_2 support had great influence on the catalytic activity of Cu_2O/TiO_2. TiO_2 calcined at low temperature presented mainly as anatase phase and had weak interaction with Cu_2O, which could cause over reduction of active Cu_2O to inactive metal Cu and result in the decrease of catalytic activity. With the increase of calcination temperature, anatase TiO_2 gradually transformed to rutile TiO_2 which could inhibit over reduction of active Cu_2O due to its strong interaction with Cu_2O. As a result of efficient conversion of Cu_2O to active Cu(I) ethynlate, the Cu_2O/TiO_2 catalyst with TiO_2 support calcined at high temperatures had the best catalytic activity.
引文
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[26]李忠,刘媛媛,郑华艳,等.固体酸负载CuⅠ催化剂表征及催化甲醇氧化羰基化[J].化工学报,2010,61(6):1443-1449.LI Z,LIU Y Y,ZHENG H Y,et al.Characterization and catalytic performance of CuⅠ/solid acids catalysts in oxidative carbonylation of methanol[J].CIESC Journal,2010,61(6):1443-1449.
[27]王登豪,张传彩,朱明远,等.高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用[J].化工学报,2017,68(7):2739-2745.WANG D H,ZHANG C C,ZHU M Y,et al.Efficient and stable hydrogenation of dimethyl oxalate via copper-nickel catalysts[J].CIESC Journal,2017,68(7):2739-2745.
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[29]LIU Y,WANG Z,HUANG W.Influences of Ti O2 phase structures on the structures and photocatalytic hydrogen production of Cu Ox/Ti O2photocatalysts[J].Applied Surface Science,2016,389:760-767.
[30]WU G,GUAN N,LI L.Low temperature CO oxidation on Cu-Cu_2O/Ti O2 catalyst prepared by photodeposition[J].Catalysis Science&Technology,2011,1:601-608.
[31]CHEN C S,CHEN T C,CHEN C C,et al.Effect of Ti3+on Ti O2-supported Cu catalysts used for CO oxidation[J].Langmuir,2012,28:9996-10006.
[2]NADGERI J M,TELKAR M M,RODE C V.Hydrogenation activity and selectivity behavior of supported palladium nanoparticles[J].Catalysis Communications,2008,9(3):441-446.
[3]TANIELYAN S,SCHMIDT S,MARIN N,et al.Selective hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol over particulate Raney nickel catalysts[J].Topics in Catalysis,2010,53(15):1145-1149.
[4]ZHANG Q,ZHANG Y,LI H T,et al.Heterogeneous Ca O-Zr O2acid-base bifunctional catalysts for vapor-phase selective dehydration of1,4-butanediol to 3-buten-1-ol[J].Applied Catalysis A:General,2013,466:233-239.
[5]SCHULZ A,WENDERLEIN H,REPPE W,et al.Production of aliphatic alcohols:US2335795[P].1943.
[6]王娟芸,蒋毅,谢建川,等.孔雀石催化合成1,4-丁炔二醇的研究[J].Chinese Journal of Synthetic Chemistry,2010,18(B09):26-29.WANG J Y,JIANG Y,XIE J C,et al.The research on preparation of butynediol using self-made malachite[J].Chinese Journal of Synthetic Chemistry,2010,18(B09):26-29.
[7]高玉明,田恒水,朱云峰.Cu O-Bi2O3粉体催化合成1,4-丁炔二醇的研究[J].广东化工,2008,35(9):53-55.GAO Y M,TIAN H S,ZHU Y F.Catalytic synthesis on1,4-butynediol by Cu O-Bi2O3 particles[J].Guangdong Chemical Industry,2008,35(9):53-55.
[8]蒋健,林深,刘春莲.纳米Cu O/Bi2O3粉体的制备及催化性能[J].合成化学,2005,13(1):45-48.JIANG J,LIN S,LIU C L.Preparation and catalytic activity of Cu/Bi2O3 nano-particles[J].Chinese Journal of Synthetic Chemistry,2005,13(1):45-48.
[9]YANG G H,XU Y B,SU X T,et al.MCM-41 supported Cu O/Bi2O3 nanoparticles as potential catalyst for 1,4-butynediol synthesis[J].Ceramics International,2014,40(3):3969-3973.
[10]罗平,赵新明,李海侠,等.Reppe法合成1,4-丁炔二醇EQ-201型炔化催化剂的研究[J].化工设计通讯,2012,38(5):87-93.LUO P,ZHAO X M,LI H X,et al.Research of EQ-201 acetylene catalyst in Reppe synthesizing 1,4-butynediol[J].Chemical Engineering Design Communications,2012,38(5):87-93.
[11]郑艳,孙自瑾,王永钊,等.Cu O-Bi2O3/Si O2-Mg O催化剂的制备及炔化性能[J].分子催化,2012,26(3),233-238.ZHENG Y,SUN Z J,WANG Y Z,et al.Preparation of Cu O-Bi2O3/Si O2-Mg O catalyst and its ethynylation performance[J].Journal of Molecular Catalysis,2012,26(3):233-238.
[12]王俊俊,李海涛,马志强,等.磁性Cu O-Bi2O3/Fe3O4-Si O2-Mg O催化剂的制备及甲醛乙炔化性能[J].化工学报,2015,66(6):2098-2104.WANG J J,LI H T,MA Z Q,et al.Preparation of magnetic Cu O-Bi2O3/Fe3O4-Si O2-Mg O catalyst and its catalytic performance for formaldehyde ethynylation[J].CIESC Journal,2015,66(6):2098-2104.
[13]马志强,张鸿喜,李海涛,等.核壳结构Cu O-Bi2O3@meso-Si O2催化剂的制备及甲醛乙炔化性能[J].工业催化,2015,23(5):344-348.MA Z Q,ZHANG H X,LI H T,et al.Preparation of core-shell Cu O-Bi2O3@meso-Si O2 catalyst and its catalytic performance for formaldehyde ethynylation[J].Industrial Catalysis,2015,23(5):344-348.
[14]罗敏,李海涛,马志强,等.甲醛乙炔化反应中Cu O-Bi2O3/Si O2-Mg O催化剂活化过程研究[J].工业催化,2014,22(5):363-368.LUO M,LI H T,MA Z Q,et al.Researches on activation process of Cu O-Bi2O3/Si O2-Mg O catalyst in formaldehyde ethynylation reaction[J].Industrial Catalysis,2014,22(5):363-368.
[15]HORT E V,PISCATAWAY N J.Ethynylation catalyst and method of production alkynols by low pressure reactions:US3920759[P].1975.
[16]杨国峰,李海涛,张鸿喜,等.Na OH浓度对Cu_2O结构及甲醛乙炔化性能的影响[J].分子催化,2016,30(6):540-546.YANG G F,LI H T,ZHANG H X,et al.Effect of Na OH concentration on structure and catalytic performance of Cu_2O for formaldehyde ethynylation[J].Journal of Molecular Catalysis,2016,30(6):540-546.
[17]林骋,刘明言.铜离子掺杂二氧化钛光催化板式微反应器[J].化工学报,2014,65(11):4325-4332.LIN C,LIU M Y.Photocatalytic planar microreactor of copper ion doped titanium dioxide[J].CIESC Journal,2014,65(11):4325-4332.
[18]GAO H,LIU J,ZHANG J,et al.Influence of carbon and yttrium co-doping on the photocatalytic activity of mixed phase Ti O2[J].Chinese Journal of Catalysis,2017,38:1688-1696.
[19]袁峰,卢士香.金红石Ti O2(011)表面的理论研究进展[J].吉首大学学报(自然科学版),2017,38(4):53-58.YUAN F,LU S X.Review of theoretical research on rutile Ti O2(011)surface[J].Journal of Jishou University(Natural Science Edition),2017,38(4):53-58.
[20]侯静静,赵清华,李刚,等.复合半导体Mo S2/Cu_2O的制备及其光催化性能研究[J].分子催化,2017,31(3):258-266.HOU J J,ZHAO Q H,LI G,et al.Preparation and photocatalytic performance of composite semiconductor Mo S2/Cu_2O[J].Journal of Molecular Catalysis,2017,31(3):258-266.
[21]CHENG S,GAO Z,KOU J,et al.Direct synthesis of isobutanol from syngas over nanosized Cu/Zn O/Al2O3 catalysts derived from hydrotalcite-like materials supported on carbon fibers[J].Energy Fuels,2017,31:8572-8579
[22]LIANG Y,CHEN Z,YAO W,et al.Decorating of Ag and Cu O on Cu nanoparticles for enhanced high catalytic activity to the degradation of organic pollutants[J].Langmuir,2017,33:7606-7614.
[23]辜敏,陈应龙,吴亚珍.Cu O-Si O2和Cu_2O-Si O2薄膜的制备及其光学性能[J].无机化学学报,2017,33(4):576-582.GU M,CHEN Y L,WU Y Z.Preparation and optical properties of Cu O-Si O2 and Cu_2O-Si O2 films[J].Chinese Journal of Inorganic Chemistry,2017,33(4):576-582.
[24]杨自嵘,彭杰庭,韩玉琦,等.表面Cu_2O纳米颗粒修饰高效促进γ-Bi2Mo O6的可见光催化活性[J].物理化学学报,2013,29(4):813-820.YANG Z R,PENG J T,HAN Y Q,et al.Significantly improved visible light photocatalytic activity ofγ-Bi2Mo O6 by surface modification with Cu_2O nanoparticles[J].Acta Physico-Chimica Sinica,2013,29(4):813-820.
[25]陈玉萍,蒋新,卢建刚.微通道反应过程对铜锌催化剂微结构的影响[J].化工学报,2015,66(10):3895-3902.CHEN Y P,JIANG X,LU J G.Effects of reaction progress in microchannel on microstructure of Cu-Zn catalyst[J].CIESC Journal,2015,66(10):3895-3902.
[26]李忠,刘媛媛,郑华艳,等.固体酸负载CuⅠ催化剂表征及催化甲醇氧化羰基化[J].化工学报,2010,61(6):1443-1449.LI Z,LIU Y Y,ZHENG H Y,et al.Characterization and catalytic performance of CuⅠ/solid acids catalysts in oxidative carbonylation of methanol[J].CIESC Journal,2010,61(6):1443-1449.
[27]王登豪,张传彩,朱明远,等.高效稳定的铜镍催化剂在草酸二甲酯加氢中的应用[J].化工学报,2017,68(7):2739-2745.WANG D H,ZHANG C C,ZHU M Y,et al.Efficient and stable hydrogenation of dimethyl oxalate via copper-nickel catalysts[J].CIESC Journal,2017,68(7):2739-2745.
[28]陈捷,刘延,黄磊,等.焙烧温度对Ti O2柱撑膨润土结构、吸附及光催化性能的影响[J].高等学校化学学报,2008,29(7):1406-1411.CHEN J,LIU Y,HUANG L,et al.Influence of calcination temperature on structure and adsorption and photocatalytic activity of titanium oxide pillared bentonite[J].Chemical Journal of Chinese Universities,2008,29(7):1406-1411.
[29]LIU Y,WANG Z,HUANG W.Influences of Ti O2 phase structures on the structures and photocatalytic hydrogen production of Cu Ox/Ti O2photocatalysts[J].Applied Surface Science,2016,389:760-767.
[30]WU G,GUAN N,LI L.Low temperature CO oxidation on Cu-Cu_2O/Ti O2 catalyst prepared by photodeposition[J].Catalysis Science&Technology,2011,1:601-608.
[31]CHEN C S,CHEN T C,CHEN C C,et al.Effect of Ti3+on Ti O2-supported Cu catalysts used for CO oxidation[J].Langmuir,2012,28:9996-10006.