Performance study of catalytic soot combustion using M0.3Co2.7O4 solid solution nanocrystals
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摘要: 采用水热法制备了过渡金属离子M (M = Cu、Ni)掺杂的M0.3Co2.7O4固溶体纳米晶，系统研究了过渡金属离子M掺杂对Co3O4纳米晶催化净化碳烟颗粒的调控作用。研究表明，Cu0.3Co2.7O4固溶体纳米晶具有最佳碳烟催化净化性能，其Tm为421 ℃、CO2选择性为100%。主要原因在于：1) Cu离子掺杂抑制了Co3O4晶体生长，提高了材料比表面积，进而扩大了催化剂与碳烟颗粒的接触界面；2) Cu离子掺杂提高了催化剂表面Co3+的物质的量比，并使催化剂形成较多缺陷位点，有利于氧物种吸附活化；3) Cu离子掺杂提高了催化剂的氧化还原能力，不但增强了活性氧物种的生成能力，而且促进了NO氧化生成NO2，进而提高碳烟催化净化性能。Cu0.3Co2.7O4固溶体纳米晶同时表现出良好的催化净化碳烟稳定性，为构筑高效柴油机碳烟净化催化剂提供了理论依据。Abstract: Transition-metal ion M (M = Cu、Ni) doped M0.3Co2.7O4 solid solution nanocrystals were prepared by a one-pot hydrothermal route. The effect of M doping on the catalytic performance of Co3O4 nanocrystals for soot combustion was systematically investigated. Results indicate that Cu0.3Co2.7O4 nanocrystals exhibit the optimal catalytic performance with a Tm of 421 ℃ and 100% CO2 selectivity. It was mainly attributed to the following aspects: 1) Cu ion doping inhibited the crystal growth of Co3O4 and increased the specific surface area, thereby expanding the contact between the catalyst and soot particles; 2) Cu ion doping increased the molar ratio of surface Co3+ and created more defect sites, facilitating the adsorption and activation of oxygen species; 3) Cu ion doping enhanced the redox ability of the catalyst, which not only promoted the generation of active oxygen species but also enhanced the oxidation of NO to NO2, thereby improving the soot combustion efficiency. Meanwhile, Cu0.3Co2.7O4 solid solution nanocrystals showed good stability, providing a theoretical basis for designing high-efficiency diesel soot purification catalysts.
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Key words:
- catalytic combustion /
- soot particle /
- transition-metal ions /
- solid solution /
- nanocrystal
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图 2 固溶体纳米晶的N2吸脱附等温线和孔径分布图
Figure 2. N2 sorption isotherms and pore size distributions of solid solution nanocrystals
图 7 基于同质量纳米晶催化净化碳烟曲线和柱状图
Figure 7. Activity curve and histogram of soot combustion over solid solution nanocrystals with the same mass
图 8 基于同表面积纳米晶催化净化碳烟曲线和柱状图
Figure 8. Activity curve and histogram of soot combustion over solid solution nanocrystals with the same surface area
图 9 纳米晶CuCo-NC循环稳定性测试曲线和柱状图
Figure 9. Recycling stability curve and histogram of CuCo-NC for soot combustion
表 1 固溶体纳米晶的物理化学结构参数
Table 1. Physicochemical parameters of solid solution nanocrystals
催化剂 SBET
/(m2·g−1)VP
/(cm3·g−1)DP/
nmCrystallite
size/nmH2消耗量
/(mmol·g−1)Co-NC 4.28 0.0138 15.3 28 3.52 NiCo-NC 5.27 0.0046 15.9 26 6.89 CuCo-NC 7.75 0.0031 16.1 24 12.32 
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表 2 固溶体纳米晶的元素组成及价态参数
Table 2. Elemental compositions and chemical valence states of solid solution nanocrystals
催化剂 Co 2p envelope O 1s envelope Co3+/% Co2+/% Co3+/Co2+ Oads/% Olatt/% Oads/Olatt Co-NC 39 61 0.64 45 55 0.82 NiCo-NC 44 56 0.79 52 48 1.08 CuCo-NC 53 47 1.13 59 41 1.44
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