Structure and properties of amorphous CeO2@TiO2 catalyst and its performance in the selective catalytic reduction of NO with NH3
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摘要: 采用自发沉积法制备了非晶态CeO2@TiO2催化剂，通过XRD、Raman光谱、TEM、N2吸附、H2-TPR、NH3-TPD及FT-IR等手段表征了催化剂结构和表面性质，研究了CeO2@TiO2在选择催化还原脱NO反应中的催化性能。结果表明，非晶态CeO2@TiO2催化剂中Ce与Ti间存在很强的相互作用，能够在原子水平上相互结合，表现出与晶态结构截然不同的还原特性，具备更强的氧化还原能力。同时，与浸渍法制备的CeO2/TiO2相比，CeO2@TiO2还具有更大的比表面积和更强的表面酸性，因而具有更加优异的脱硝性能。在175℃下NO转化率即达到80%以上，在200-400℃脱硝率稳定在96.0%-99.4%；同时，H2O和SO2的阶跃应答实验表明，CeO2@TiO2具有很强的抗水和抗SO2毒化能力。Abstract: Amorphous CeO2@TiO2 catalyst was prepared by spontaneous deposition method and characterized by XRD, Raman spectra, TEM, N2 physisorption, H2-TPR, NH3-TPD and FT-IR; its performance in the selective catalytic reduction (SCR) of NO with NH3 was investigated. The results show that there is a strong interaction between Ce and Ti which are combined at atomic level. In comparison with the crystal CeO2/TiO2 catalyst prepared by impregnation, the amorphous CeO2@TiO2 catalyst exhibits larger surface area and pore volume, excellent redox ability and acidity, and outstanding catalytic performance in SCR. Over the CeO2@TiO2 catalyst, the conversion of NO reaches 80% at 175℃ and retains 96.0%-99.4% at 200-400℃. Moreover, the amorphous CeO2@TiO2 catalyst also shows strong resistance to H2O and SO2 poisoning.
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图 1 催化剂的XRD (a) 和Raman (b) 谱图
Figure 1 XRD patterns (a) and Raman spectra (b) of various catalysts
a: CeO2; b: CeO2@TiO2; c: CeO2/TiO2
图 2 CeO2@TiO2催化剂的TEM (a) 和SAED (b) 照片
Figure 2 TEM (a) and SAED (b) images of the CeO2@TiO2 catalysts
图 3 催化剂的N2吸附-脱附等温线和孔径分布
Figure 3 N2 adsorption-desorption isotherms and pore distribution curves of CeO2@TiO2 (a) and CeO2/TiO2 (b)
图 4 催化剂的H2-TPR谱图
Figure 4 H2-TPR profiles of catalysts
a: CeO2; b: CeO2@TiO2; c: CeO2/TiO2
图 5 催化剂的NH3-TPD谱图
Figure 5 NH3-TPD profiles of catalysts
a: CeO2; b: CeO2@TiO2; c: CeO2/TiO2
图 6 催化剂的SCR性能
Figure 6 Performances of various catalysts in the SCR of NO with NH3
a: CeO2; b: CeO2/TiO2; c: CeO2@TiO2
图 7 CeO2@TiO2、CeO2/TiO2上SO2和H2O的阶跃应答实验
Figure 7 Step transient response of SO2 and H2O in the SCR of NO with NH3
a: CeO2@TiO2; b: CeO2/TiO2
图 8 催化剂的FT-IR谱图
Figure 8 FT-IR spectra of the catalysts before and after the intoxication test
a: CeO2@TiO2; b: CeO2/TiO2; c: CeO2@TiO2-used; d: CeO2/TiO2-used
表 1 催化剂的物理化学性质
Table 1 Textural and surface properties of various catalysts
Catalyst ABET/(m2·g-1) v/(cm3·g-1) dp/nm H2 consumption /(cm3·gcat-1) Acid amount /(mmol·gcat-1) weak acid strong acid CeO2 48.0 0.062 3 3.912 4 18.98 3.69 0.68 CeO2@TiO2 210.03 0.158 5 4.923 9 53.28 12.64 2.85 CeO2/TiO2 51.564 0.124 6 9.667 5 21.77 3.85 - 
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