不同晶相TiO2负载Cu2O催化甲醛乙炔化反应

doi:10.7503/cjcu20180523

摘要/Abstract

摘要：

分别以金红石相和锐钛矿相TiO₂为载体, 采用液相还原-沉积法制备了Cu₂O/TiO₂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TiO₂载体对Cu₂O/TiO₂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TiO₂为载体的催化剂炔化活性明显高于以锐钛矿相TiO₂为载体的催化剂, 原因在于金红石相TiO₂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Cu₂O与TiO₂之间强的相互作用. 这导致Cu₂O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.

关键词: Cu₂O/TiO₂, 晶相结构, 甲醛乙炔化, 1,4-丁炔二醇

Abstract:

Cu₂O/TiO₂ catalysts with anatase and rutile titania as supports were prepared by liquid reduction-deposition-precipitation method and applied in 1,4-butynediol synthesis by formaldehyde ethynylation reaction. Effects of different TiO₂ 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 TiO₂ as support was obviously higher than that of anatase TiO₂ as support. This was mainly due to the different surface structures originated from the different crystalline structures of the as-prepared TiO₂.The(110) planes were preferentially exposed planes for rutile TiO₂. Compared with anatase TiO₂, 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 Cu₂O and the support. Meanwhile, the stronger interaction between Cu₂O and rutile efficiently retained the dispersion of active species and stablized the valence of Cu⁺, leading to a higher catalytic performance.

Key words: Cu₂O/TiO₂, Phase structure, Formaldehyde ethynylation, 1, 4-Butynediol

中图分类号:

O643

TrendMD:

王志鹏, 牛珠珠, 班丽君, 郝全爱, 张鸿喜, 李海涛, 赵永祥. 不同晶相TiO₂负载Cu₂O催化甲醛乙炔化反应. 高等学校化学学报, 2019, 40(2): 334.

WANG Zhipeng,NIU Zhuzhu,BAN Lijun,HAO Quanai,ZHANG Hongxi,LI Haitao,ZHAO Yongxiang. Formaldehyde Ethynylation Reaction over Cu₂O Supported on TiO₂ with Different Phases^†. Chem. J. Chinese Universities, 2019, 40(2): 334.

图/表 8

Fig.1 Effects of reaction time on conversion of HCHO(A) and yield of BD(B) over different catalystsa. Cu2O/A-TiO2; b. Cu2O/R-TiO2. Reaction conditions: catalyst amount, 2.5 g; reaction temperature, 90 ℃.

Fig.2 XRD patterns of A-TiO2(a) and R-TiO2(b) supports(A), Cu2O/A-TiO2(a) and Cu2O/R-TiO2(b) catalysts(B)

Table 1 Structural and textural data of supported catalysts

Sample	w(Cu)^a(%)	$S BET b$ /(m²·g^-1)	$d C u 2 O c$ /nm	T $i Ⅰ 4 +$ /(T $i Ⅰ 4 +$ +T $i Ⅱ 4 +$ )^d(%)	H₂ consumption^e/ (μmol·g^-1)
C/A-TiO₂	19.7	39.5(53.6)	24	15.6	1588(1539)
C/R-TiO₂	19.3	35.7(44.6)	19	28.3	1567(1508)

Table 1 Structural and textural data of supported catalysts

Sample	w(Cu)^a(%)	$S BET b$ /(m²·g^-1)	$d C u 2 O c$ /nm	T $i Ⅰ 4 +$ /(T $i Ⅰ 4 +$ +T $i Ⅱ 4 +$ )^d(%)	H₂ consumption^e/ (μmol·g^-1)
C/A-TiO₂	19.7	39.5(53.6)	24	15.6	1588(1539)
C/R-TiO₂	19.3	35.7(44.6)	19	28.3	1567(1508)

Fig.3 HRTEM images of TiO2 supports and Cu2O/TiO2 catalysts(A) A-TiO2; (B) Cu2O/A-TiO2; (C) R-TiO2; (D) Cu2O/R-TiO2.

Fig.4 XPS spectra of Cu2p(A) and Ti2p(B) of Cu2O/A-TiO2(a) and Cu2O/R-TiO2(b) catalysts

Fig.5 H2-TPR profiles of prepared Cu2O/A-TiO2(a), Cu2O/R-TiO2(b) catalysts and pure Cu2O(c)

Fig.6 XRD patterns of Cu2O/A-TiO2(a) and Cu2O/R-TiO2(b) catalysts after reaction

Fig.7 CO-IR spectra of Cu2O/A-TiO2(a) and Cu2O/R-TiO2(b) catalysts before(A) and after(B) reaction

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不同晶相TiO₂负载Cu₂O催化甲醛乙炔化反应

Formaldehyde Ethynylation Reaction over Cu₂O Supported on TiO₂ with Different Phases^†

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