不同晶相TiO_2负载Cu_2O催化甲醛乙炔化反应
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摘要
分别以金红石相和锐钛矿相TiO_2为载体,采用液相还原-沉积法制备了Cu_2O/TiO_2催化剂.采用氮气物理吸附-脱附(N2-physisorption)实验、氢气程序升温还原(H2-TPR)、X射线衍射(XRD)、X射线光电子能谱(XPS)、CO红外光谱(CO-IR)及高分辨透射电子显微镜(HRTEM)等技术,研究了不同晶相TiO_2载体对Cu_2O/TiO_2结构及其催化甲醛乙炔化反应性能的影响.结果表明,以金红石相TiO_2为载体的催化剂炔化活性明显高于以锐钛矿相TiO_2为载体的催化剂,原因在于金红石相TiO_2主要暴露(110)晶面,其与铜物种的配位环境及较高的空位密度形成了更多的Cu—O—Ti结构物种,表现为Cu_2O与TiO_2之间强的相互作用.这导致Cu_2O高效转变为乙炔亚铜活性物种,并保持了较高的分散度与稳定性,抑制了过度还原物种金属Cu的生成,进而使催化剂表现出较高的催化性能.
Cu_2O/TiO_2 catalysts with anatase and rutile titania as supports were prepared by liquid reductiondeposition-precipitation method and applied in 1,4-butynediol synthesis by formaldehyde ethynylation reaction.Effects of different TiO_2 polymorphs on structure and catalytic performance of catalyst were investigated,combined with N2 physical adsorption-desorption,H2-temperature programmed reduction( H2-TPR),high resolution transmission electron microscopy( HRTEM),X-ray diffraction( XRD),X-ray photoelectron spectroscopy( XPS) and CO infrared spectroscopy( CO-IR). The results showed that the ethynylation activity of catalyst with rutile TiO_2 as support was obviously higher than that of anatase TiO_2 as support. This was mainly due to the different surface structures originated from the different crystalline structures of the as-prepared TiO_2. The( 110) planes were preferentially exposed planes for rutile TiO_2. Compared with anatase TiO_2,the higher density vacant sites and different coordination structures of copper species on rutile( 110) planes facilitated the formation of more Cu—O—Ti structures,exhibiting stronger interaction between Cu_2O and the support. Meanwhile,the stronger interaction between Cu_2O and rutile efficiently retained the dispersion of active species and stablized the valence of Cu+,leading to a higher catalytic performance.
Cu_2O/TiO_2 catalysts with anatase and rutile titania as supports were prepared by liquid reductiondeposition-precipitation method and applied in 1,4-butynediol synthesis by formaldehyde ethynylation reaction.Effects of different TiO_2 polymorphs on structure and catalytic performance of catalyst were investigated,combined with N2 physical adsorption-desorption,H2-temperature programmed reduction( H2-TPR),high resolution transmission electron microscopy( HRTEM),X-ray diffraction( XRD),X-ray photoelectron spectroscopy( XPS) and CO infrared spectroscopy( CO-IR). The results showed that the ethynylation activity of catalyst with rutile TiO_2 as support was obviously higher than that of anatase TiO_2 as support. This was mainly due to the different surface structures originated from the different crystalline structures of the as-prepared TiO_2. The( 110) planes were preferentially exposed planes for rutile TiO_2. Compared with anatase TiO_2,the higher density vacant sites and different coordination structures of copper species on rutile( 110) planes facilitated the formation of more Cu—O—Ti structures,exhibiting stronger interaction between Cu_2O and the support. Meanwhile,the stronger interaction between Cu_2O and rutile efficiently retained the dispersion of active species and stablized the valence of Cu+,leading to a higher catalytic performance.
引文
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