N掺杂对TiO_2负载Cu基催化剂甲醛乙炔化性能的影响
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摘要
以TiO_2及N掺杂的TiO_2为载体、CuCl_2·2H_2O为铜源、NaOH为沉淀剂,采用沉积沉淀法制备了Cu含量(质量分数,下同)为30%的CuO/TiO_2及CuO/N-TiO_2催化剂。结合N_2物理吸附、XRD、XPS、H_2-TPR、CO-IR等表征,研究了N掺杂对TiO_2负载CuO催化剂结构及甲醛乙炔化性能的影响。结果表明,经N掺杂的TiO_2呈现出较多的Ti ~(3+)物种及氧空位,增加了CuO与载体间的相互作用,有利于CuO物种的分散。在炔化反应过程中,CuO原位转变为高分散的Cu~+活性中心,催化剂表现出高的催化活性与使用稳定性。
CuO/TiO_2and CuO/N-TiO_2catalysts with 30%Cu loading were prepared by deposition-precipitation method using copper chloride as copper source,sodium hydroxide as precipitant,and TiO_2and N-TiO_2as supports.Combined with the characterization of N_(2 )physical adsorption-desorption,X-ray diffraction(XRD),H_2-temperature programmed reduction(H_2-TPR),X-ray photoelectron spectroscopy(XPS),CO Fourier transform infrared spectroscopy(CO-IR),and etc,the effects of N doping on the structure of TiO_2supported CuO catalyst and the catalytic performance of formaldehyde ethynylation were studied.The results show that N-doped TiO_2presented more Ti ~(3+)species and oxygen vacant sites,which increased the interaction between CuO and the carrier and was conducive to the dispersion of CuO species.In the process of ethynylation,CuO is transformed into highly dispersed Cu~+active species in situ,and the catalyst shows high catalytic activity and stability.
CuO/TiO_2and CuO/N-TiO_2catalysts with 30%Cu loading were prepared by deposition-precipitation method using copper chloride as copper source,sodium hydroxide as precipitant,and TiO_2and N-TiO_2as supports.Combined with the characterization of N_(2 )physical adsorption-desorption,X-ray diffraction(XRD),H_2-temperature programmed reduction(H_2-TPR),X-ray photoelectron spectroscopy(XPS),CO Fourier transform infrared spectroscopy(CO-IR),and etc,the effects of N doping on the structure of TiO_2supported CuO catalyst and the catalytic performance of formaldehyde ethynylation were studied.The results show that N-doped TiO_2presented more Ti ~(3+)species and oxygen vacant sites,which increased the interaction between CuO and the carrier and was conducive to the dispersion of CuO species.In the process of ethynylation,CuO is transformed into highly dispersed Cu~+active species in situ,and the catalyst shows high catalytic activity and stability.
引文
[1]钟传蓉,卢艾.炔醇的应用与生产[J].油田化学,2000,17(3):285-288.
[2]LI H T,ZHAO Y X,GAO C G,et al.Study on deactivation of Ni/Al2O3catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution[J].Chemical Engineering Journal,2012,181/182:501-507.
[3]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.
[4]ZHANG Q,ZHANG Y,LI H T,et al.Heterogeneous CaO-ZrO2 acid-base bifunctional catalysts for vaporphase selective dehydration of 1,4-butanediol to 3-buten-1-ol[J].Applied Catalysis A:General,2013,466:233-239.
[5]HAAS T,JAEGER B,WEBER R,et al.New diol processes:1,3-propanediol and 1,4-butanediol[J].Applied Catalysis A:General,2005,280(1):83-88.
[6]钟琳,赵明英,吕绍洁,等.炔醛法合成丁炔二醇催化剂研究[J].天然气化工,1989,14(6):5-8.
[7]徐邦澄,葛旭丹,顾其威.淤浆床低压法合成1,4-丁炔二醇的研究-不同载体炔化催化剂的性能[J].华东化工学院学报,1989,15(3):272-276.
[8]林西平,栗洪道.炔醛法合成丁炔二醇催化剂[J].石油化工,1987,16(4):265-269.
[9]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].合成化学,2010,18(B09):26-29.
[10]高玉明,田恒水,朱云峰.CuO-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.
[11]马志强,张鸿喜,李海涛,等.核壳结构CuO-Bi2O3@meso-SiO2催化剂的制备及甲醛乙炔化性能[J].工业催化,2015,23(5):344-348.
[12]杨国峰,李海涛,张鸿喜,等.NaOH浓度对Cu2O结构及甲醛乙炔化性能的影响[J].分子催化,2016,30(6):540-546.
[13]李海涛,牛珠珠,杨国锋,等.Cu2O/TiO2催化甲醛乙炔化反应的载体效应[J].化工学报,2018,69(6):2512-2518.
[14]王俊俊,李海涛,马志强,等.磁性CuO-Bi2O3/Fe3O4-SiO2-MgO催化剂的制备及甲醛乙炔化性能[J].化工学报,2015,66(6):2098-2104.
[15]郑艳,孙自瑾,王永钊,等.CuO-Bi2O3/SiO2-MgO催化剂的制备及炔化性能[J].分子催化,2012,26(3):233-238.
[16]张海鹏,潘庆芝,邹永存.介孔TiO2担载Cu(OH)2及其催化炔烃氧化偶联反应[J].高等学校化学学报,2014,35(6):1307-1310.
[17]阿山,郑家威,刘聚明,等.乙酸修饰Ag/TiO2复合光催化剂的制备及协同催化性能[J].高等学校化学学报,2017,38(8):1450-1457.
[18]孟志宇,张因,赵丽丽,等.不同晶型TiO2负载镍催化剂催化顺酐液相加氢[J].高等学校化学学报,2015,26(9):1779-1785.
[19]唐玉朝.N掺杂TiO2的结构及可见光催化[D].合肥:中国科学技术大学,2008.
[20]刘玉娟,王东哲,张磊,等.载体焙烧气氛对甲醇水蒸气重整制氢CuO/CeO2催化剂的影响[J].燃料化学学报,2018,46(8):992-999.
[21]SHEN W W,MAO D S,LUO Z M,et al.CO oxidation on mesoporous SBA-15supported CuO-CeO2 catalyst prepared by a surfactant-assisted impregnation method[J].RSC Advance,2017,7(44):27689-27698.
[22]LU Y,ZHANG X,CHU Y C,et al.Cu2O nanocrystals/TiO2microspheres film on a rotating disk containing long-afterglow phosphor for enhanced round-theclock photocatalysis[J].Applied Catalysis B:Environmental,2018,224:239-248.
[23]HENSEL J,WANG G,LI Y,et al.Synergistic effect of CdSe quantum dot sensitization and nitrogen doping of TiO2 nanostructures for photoelectrochemical solar hydrogen generation[J].Nano Letters,2010,10:478-483.
[24]CHEN C S,CHEN T C,CHEN C C,et al.Effect of Ti 3+on TiO2-supported Cu catalysts used for CO oxidation[J].Langmuir,2012,28:9996-10006.
[25]ZHU H Y,DONG L,CHEN Y.Effect of titania structure on the properties of its supported copper oxide catalysts[J].Journal of Colloid and Interface Science,2011,357:497-503.
[26]DI W,CHENG J H,TIAN S X,et al.Synthesis and characterization of supported copper phyllosilicatecatalysts for acetic ester hydrogenation to ethanol[J].Applied Catalysis A:General,2016,510:244-259.
[27]HORNS A,BERA P,CMARA A L,et al.CO-TPR-DRIFTS-MS in situ study of CuO/Ce1-xTbxO2-y(x=0,0.2and 0.5)catalysts:support effects on redox properties and CO oxidation catalysis[J].Journal of Catalysis,2009,268:367-375.
[28]MANZOLI M,MONTE R D,BOCCUZZI F,et al.CO oxidation over CuOx-CeO2-ZrO2 catalysts:transient behaviour and role of copper clusters in contact with ceria[J].Applied Catalysis B:Environmental,2005,61:192-205.
[29]XUE J J,WANG X Q,QI G S,et al.Characterization of copper species over Cu/SAPO-34in selective catalytic reduction of NOx with ammonia:relationships between active Cu sites and de-NOx performance at low temperature[J].Journal of Catalysis,2013,297:56-64.
[2]LI H T,ZHAO Y X,GAO C G,et al.Study on deactivation of Ni/Al2O3catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution[J].Chemical Engineering Journal,2012,181/182:501-507.
[3]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.
[4]ZHANG Q,ZHANG Y,LI H T,et al.Heterogeneous CaO-ZrO2 acid-base bifunctional catalysts for vaporphase selective dehydration of 1,4-butanediol to 3-buten-1-ol[J].Applied Catalysis A:General,2013,466:233-239.
[5]HAAS T,JAEGER B,WEBER R,et al.New diol processes:1,3-propanediol and 1,4-butanediol[J].Applied Catalysis A:General,2005,280(1):83-88.
[6]钟琳,赵明英,吕绍洁,等.炔醛法合成丁炔二醇催化剂研究[J].天然气化工,1989,14(6):5-8.
[7]徐邦澄,葛旭丹,顾其威.淤浆床低压法合成1,4-丁炔二醇的研究-不同载体炔化催化剂的性能[J].华东化工学院学报,1989,15(3):272-276.
[8]林西平,栗洪道.炔醛法合成丁炔二醇催化剂[J].石油化工,1987,16(4):265-269.
[9]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].合成化学,2010,18(B09):26-29.
[10]高玉明,田恒水,朱云峰.CuO-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.
[11]马志强,张鸿喜,李海涛,等.核壳结构CuO-Bi2O3@meso-SiO2催化剂的制备及甲醛乙炔化性能[J].工业催化,2015,23(5):344-348.
[12]杨国峰,李海涛,张鸿喜,等.NaOH浓度对Cu2O结构及甲醛乙炔化性能的影响[J].分子催化,2016,30(6):540-546.
[13]李海涛,牛珠珠,杨国锋,等.Cu2O/TiO2催化甲醛乙炔化反应的载体效应[J].化工学报,2018,69(6):2512-2518.
[14]王俊俊,李海涛,马志强,等.磁性CuO-Bi2O3/Fe3O4-SiO2-MgO催化剂的制备及甲醛乙炔化性能[J].化工学报,2015,66(6):2098-2104.
[15]郑艳,孙自瑾,王永钊,等.CuO-Bi2O3/SiO2-MgO催化剂的制备及炔化性能[J].分子催化,2012,26(3):233-238.
[16]张海鹏,潘庆芝,邹永存.介孔TiO2担载Cu(OH)2及其催化炔烃氧化偶联反应[J].高等学校化学学报,2014,35(6):1307-1310.
[17]阿山,郑家威,刘聚明,等.乙酸修饰Ag/TiO2复合光催化剂的制备及协同催化性能[J].高等学校化学学报,2017,38(8):1450-1457.
[18]孟志宇,张因,赵丽丽,等.不同晶型TiO2负载镍催化剂催化顺酐液相加氢[J].高等学校化学学报,2015,26(9):1779-1785.
[19]唐玉朝.N掺杂TiO2的结构及可见光催化[D].合肥:中国科学技术大学,2008.
[20]刘玉娟,王东哲,张磊,等.载体焙烧气氛对甲醇水蒸气重整制氢CuO/CeO2催化剂的影响[J].燃料化学学报,2018,46(8):992-999.
[21]SHEN W W,MAO D S,LUO Z M,et al.CO oxidation on mesoporous SBA-15supported CuO-CeO2 catalyst prepared by a surfactant-assisted impregnation method[J].RSC Advance,2017,7(44):27689-27698.
[22]LU Y,ZHANG X,CHU Y C,et al.Cu2O nanocrystals/TiO2microspheres film on a rotating disk containing long-afterglow phosphor for enhanced round-theclock photocatalysis[J].Applied Catalysis B:Environmental,2018,224:239-248.
[23]HENSEL J,WANG G,LI Y,et al.Synergistic effect of CdSe quantum dot sensitization and nitrogen doping of TiO2 nanostructures for photoelectrochemical solar hydrogen generation[J].Nano Letters,2010,10:478-483.
[24]CHEN C S,CHEN T C,CHEN C C,et al.Effect of Ti 3+on TiO2-supported Cu catalysts used for CO oxidation[J].Langmuir,2012,28:9996-10006.
[25]ZHU H Y,DONG L,CHEN Y.Effect of titania structure on the properties of its supported copper oxide catalysts[J].Journal of Colloid and Interface Science,2011,357:497-503.
[26]DI W,CHENG J H,TIAN S X,et al.Synthesis and characterization of supported copper phyllosilicatecatalysts for acetic ester hydrogenation to ethanol[J].Applied Catalysis A:General,2016,510:244-259.
[27]HORNS A,BERA P,CMARA A L,et al.CO-TPR-DRIFTS-MS in situ study of CuO/Ce1-xTbxO2-y(x=0,0.2and 0.5)catalysts:support effects on redox properties and CO oxidation catalysis[J].Journal of Catalysis,2009,268:367-375.
[28]MANZOLI M,MONTE R D,BOCCUZZI F,et al.CO oxidation over CuOx-CeO2-ZrO2 catalysts:transient behaviour and role of copper clusters in contact with ceria[J].Applied Catalysis B:Environmental,2005,61:192-205.
[29]XUE J J,WANG X Q,QI G S,et al.Characterization of copper species over Cu/SAPO-34in selective catalytic reduction of NOx with ammonia:relationships between active Cu sites and de-NOx performance at low temperature[J].Journal of Catalysis,2013,297:56-64.