Influence of dopants on the structure and catalytic features of
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The Cu-<i>M</i>/ZnO catalysts (<i>M</i> = Zr<sup>4+</sup>, Al<sup>3+</sup> and Mg<sup>2+</sup>) for dimethyl oxalate (DMO) selective hydrogenation to ethylene glycol (EG) were synthesized by the co-precipitation method. The properties of the as-synthesized catalysts were characterized by N<sub>2</sub>-physisorption, N<sub>2</sub>O-titration, XRD, H<sub>2</sub>-TPR, CO<sub>2</sub>-TPD, SEM, FT-IR and XPS. It was found that the Cu dispersion could be effectively promoted by the dopants incorporated in the Cu/ZnO catalyst. Particularly, a trace amount of Mg<sup>2+ </sup>and Al<sup>3+</sup> dopants could significantly reinforce the chemical interaction between the Cu and ZnO phases by embedding into the ZnO lattice, while the Cu/ZrO<sub>2 </sub>interaction could be improved with the introduction of Zr<sup>4+</sup>. For DMO gas-phase hydrogenation, the EG yield of the Cu/ZnO catalyst increased from 75.0% to 85.0% and 90.0% in the presence of Zr<sup>4+ </sup>and Al<sup>3+ </sup>dopants, respectively. Particularly, the EG selectivity of Cu-Mg/ZnO catalyst reached up to 95.0% with DMO completely converted for more than 100 h. The correlation between the catalytic behavior and physicochemical features of the Cu/ZnO based catalysts suggested that the surface Cu<sup>+</sup> sites was vital for the catalytic behavior with adequate Cu<sup>0</sup> sites. Additionally, the strengthened Cu/oxide interaction favored the outstanding stability of the Cu-Zr/ZnO and Cu-Mg/ZnO catalyst for DMO hydrogenation.
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