基于Cu-Fc配位聚合物衍生的Pt-Cu/Cu_xFe_yO@C催化1,4-丁炔二醇加氢性能研究
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摘要
1,4-丁烯二醇是精细化工领域的重要中间体,有着广泛的应用.采用异丙醇还原氯铂酸制备Pt纳米颗粒,并通过浸渍法将其负载于1,1’-二茂铁二羧酸(Fc)与CuCl_2·2H_2O水热法合成的Cu-Fc配位聚合物,干燥焙烧后制备得到Pt-Cu/Cu_xFe_yO@C催化剂,利用XRD、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析仪(TG)、N_2吸附脱附仪等表征手段对所制备的催化剂进行表征,对比了催化剂焙烧前后加氢效果,并考察了催化剂与底物的物质的量之比对1,4-丁炔二醇加氢制备1,4-丁烯二醇的影响.结果表明,以焙烧后制备的5%Pt-Cu/Cu_xFe_yO@C催化剂,在n催化剂∶n原料=1∶2 000,温度为120℃,H_2压力为4 MPa,反应时间为30 min的条件下,加氢反应的转化率为100%,生成1,4-丁烯二醇选择性为96.1%.
2-butene-1,4-diol is a kind of important intermediate in the field of fine chemical engineering,which has a very wide range of applications. We prepared the Pt nano-particles by using the isopropanol as reductive agent to reduce the( hydro) chloroplatinic acid,and followed by using the impregnation method to load the prepared Pt nanoparticles on the Cu-Fc coordination polymer,which synthetized by using 1,1 '-Ferrocenedicarboxylicacid and CuCl_2·2 H_2O under the condition of hydro-thermal.At last,vacuum was used to dry and calcine the Pt/Cu-Fc coordination polymer under the nitrogen atmosphere to get the catalysts of Pt-Cu/Cu_xFe_yO@ C,then the catalysts were characterized by some comprehensive technical approaches such as XRD,XPS,TEM,SEM,TG,Nitrogen adsorption instrument.We also compared the hydrogenation results of the catalysts before and after calcination,and investigated the effect of molar ratio of catalysts to substrate on the performance of hydrogenation 2-butyne-1,4-diol to 2-butylene-1,4-diol. The results show that using the 5%Pt-Cu/Cu_xFe_yO@ C as catalysts,the molar ratio of catalysts and substrate is 1 ∶ 2 000,the temperature is 120 ℃,H_2 pressure is 4 MPa,the reaction time is 30 min,2-butyne-1,4-diol conversion of 100%,2-butylene-1,4-diolselectivity is 96.1% respectively.
2-butene-1,4-diol is a kind of important intermediate in the field of fine chemical engineering,which has a very wide range of applications. We prepared the Pt nano-particles by using the isopropanol as reductive agent to reduce the( hydro) chloroplatinic acid,and followed by using the impregnation method to load the prepared Pt nanoparticles on the Cu-Fc coordination polymer,which synthetized by using 1,1 '-Ferrocenedicarboxylicacid and CuCl_2·2 H_2O under the condition of hydro-thermal.At last,vacuum was used to dry and calcine the Pt/Cu-Fc coordination polymer under the nitrogen atmosphere to get the catalysts of Pt-Cu/Cu_xFe_yO@ C,then the catalysts were characterized by some comprehensive technical approaches such as XRD,XPS,TEM,SEM,TG,Nitrogen adsorption instrument.We also compared the hydrogenation results of the catalysts before and after calcination,and investigated the effect of molar ratio of catalysts to substrate on the performance of hydrogenation 2-butyne-1,4-diol to 2-butylene-1,4-diol. The results show that using the 5%Pt-Cu/Cu_xFe_yO@ C as catalysts,the molar ratio of catalysts and substrate is 1 ∶ 2 000,the temperature is 120 ℃,H_2 pressure is 4 MPa,the reaction time is 30 min,2-butyne-1,4-diol conversion of 100%,2-butylene-1,4-diolselectivity is 96.1% respectively.
引文
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[19]Das R,Pachfule P,Banerjee R,et al.Metal and metal oxide nanoparticle synthesis from metal organic frameworks(MOFs):Finding the border of metal and metal oxides[J].Nanosc,2012,4(2):591-599.
[20]Zhou Jiao(周姣).Selective hydrogenation of acetylene catalyzed by supported nickel copper catalyst(负载镍铜催化剂催化乙炔选择加氢反应的研究)[D].Master Dissertation of Dalian University of Technology,(辽宁大连理工大学硕士论文),2012.
[21]Wang zhan-qi(王沾祺),Zhou zhi-ming(周志明),Zhang rui(张锐),et al.Selective hydrogenation of phenylacetylene over Pd-Cu/γ-Al2O3catalysts(Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢反应)[J].Acta Phys-Chim Sin(物理化学学报),2014,2014(12):2315-2322.
[2]Wang Shao-hong(王劭泓).Study on preparation of butylene glycol by catalytic hydrogenation of butyne glycol(丁炔二醇催化加氢制备丁烯二醇工艺研究)[D].Master Dissertation of East China University of science and technology(上海华东理工大学硕士论文).2004.
[3]Chaudhari R V,Parande M G,Ramachandran P A,et al.Hydrogenation of butynediol to cis-butenediol catalyzed by Pd-Zn-Ca CO3:Reaction kinetics and modeling of a batch slurry reactor[J].AICh E J,1985,31(11):1891-1903.
[4]MAG M,VMG V,EMS E,et al.CN[P].95193955.6patent,1997.
[5]Telkar M M,Rode C V,Rane V H,et al.Influence of alkali metal doping on selectivity behaviour of platinum catalysts for hydrogenation of 2-butyne-1,4-diol[J].Catal Commun,2005,6(11):725-730.
[6]Xiu jing-hai(修景海),Chen xiao(陈霄),Yang zonghan(杨宗翰),et al.Chemical synthesis of Al-Co intermetallic compound catalysts for selective hydrogenation of alkyne(Al Co金属间催化剂的合成及炔烃选择加氢性能)[J].J Mol Catal(China)(分子催化),2017,31(4):325-333.
[7]a.Hoskins B F,Robson R.Infinite polymeric frameworks consisting of three dimensionally linked rod-like segments[J].J Am Chem Soc,1989,111(15):5962-5964.b.Chen Jun(陈君),Long Ji-lan(隆继兰).Bi-centered MOFs-derived Co-Zn O@CN nano-materialas efficient electrocatalyst for oxygen reduction reaction(双中心MOFs衍生的Co-Zn O@CN纳米材料作为电化学催化剂用于氧还原反应的研究)[J].J Mol Catal(China)(分子催化),2017,31(5):463-471.c.Li He-jian(李和健),Wu Cang-cang(吴藏藏),Zheng Li(郑丽),et al.Selective catalytic oxidation of benzyl alcohol over Cu-BTC and its derivatives(Cu-BTC及其衍生物在苯甲醇选择氧化反应中的催化活性)[J].J Mol Catal(China)(分子催化),2017,31(4):341-347.
[8]Xamena F X L I,Abad A,Corma A,et al.MOFs as catalysts:Activity,reusability and shape-selectivity of a Pd-containing MOF[J].J Catal,2007,250(2):294-298.
[9]Yin D,Li C,Ren H,et al.Efficient Pd@MIL-101(Cr)hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity[J].Rsc Adv,2017,7(3):1626-1633.
[10]Zhang M,Yang Y,Li C,et al.PVP-Pd@ZIF-8 as highly efficient and stable catalysts for selective hydrogenation of 1,4-butynediol[J].Catal Sci Technol,2014,4(2):329-332.
[11]Li C,Zhang M,Di X,et al.One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol[J].Chin J Catal,2016,37(9):1555-1561.
[12]Chaikittisilp W,Ariga K,Yamauchi Y.A new family of carbon materials:synthesis of MOF-derived nanoporous carbons and their promising applications[J].J Mat Chem A,2012,1(1):14-19.
[13]Sun Ruo-li(孙若力).Study on preparation and properties of two ferrocenyl hyperbranched polyether and two ferrocene carboxylic acid coordination polymers(二茂铁基超支化聚醚和二茂铁羧酸基配位聚合物的制备及性能研究)[D].Master Dissertation of Zhejiang University(浙江大学硕士论文).2016.
[14]Li Ming(李明).Preparation and reaction properties of Pd/C@Fe3O4magnetic catalyst(Pd/C@Fe3O4磁性催化剂的制备及反应性能)[D].Master Dissertation of Beijing University of Chemical Technology,(北京化工大学硕士论文),2013.
[15]Zhang Cao(张超).Preparation and properties of nano Pt based core-shell catalysts(纳米Pt基核壳催化剂的制备及性能研究)[D].Master Dissertation of Southeast University,(江苏东南大学硕士论文),2015.
[16]Mandegarzad S,Raoof J B,Hosseini S R,et al.Cu-Pt bimetallic nanoparticles supported metal organic framework-derived nanoporous carbon as a catalyst for hydrogen evolution reaction[J].Electrochim Acta,2016,190:729-736.
[17]Moulder J F,Chastain J,King R C.Handbook of x-ray photoelectron spectroscopy:A reference book of standard spectra for identification and interpretation of XPS Data[J].Chem Phys Lett,1979,220(1):7-10.
[18]Wang Mei-song(王美淞),Zhou Pei-pei(邹培培),Huang Yan-li(黄艳丽),et al.Three-dimensional graphene-based Pt-Cu nanoparticles-containing composite as highly active and recyclable catalyst(高活性、可循环的Pt-Cu@3D石墨烯复合催化剂的制备和催化性能)[J].Acta Phys-Chim Sin(物理化学学报),2017,33(6):1230-1235.
[19]Das R,Pachfule P,Banerjee R,et al.Metal and metal oxide nanoparticle synthesis from metal organic frameworks(MOFs):Finding the border of metal and metal oxides[J].Nanosc,2012,4(2):591-599.
[20]Zhou Jiao(周姣).Selective hydrogenation of acetylene catalyzed by supported nickel copper catalyst(负载镍铜催化剂催化乙炔选择加氢反应的研究)[D].Master Dissertation of Dalian University of Technology,(辽宁大连理工大学硕士论文),2012.
[21]Wang zhan-qi(王沾祺),Zhou zhi-ming(周志明),Zhang rui(张锐),et al.Selective hydrogenation of phenylacetylene over Pd-Cu/γ-Al2O3catalysts(Pd-Cu/γ-Al2O3催化苯乙炔选择性加氢反应)[J].Acta Phys-Chim Sin(物理化学学报),2014,2014(12):2315-2322.