Putanenko Pavel K, Dorofeeva Natalia V, Kharlamova Tamara S, Grabchenko Maria V, Kulinich Sergei A, Vodyankina Olga V
Department of Physical and Colloid Chemistry, National Research Tomsk State University, Tomsk 634050, Russia.
Research Institute of Science and Technology, Tokai University, Hiratsuka 259-1292, Kanagawa, Japan.
Materials (Basel). 2023 Dec 18;16(24):7701. doi: 10.3390/ma16247701.
The present work is focused on nickel catalysts supported on LaO-CeO binary oxides without and with the addition of Cu to the active component for the dry reforming of methane (DRM). The catalysts are characterized using XRD, XRF, TPD-CO, TPR-H, and low-temperature N adsorption-desorption methods. This work shows the effect of different La:Ce ratios (1:1 and 9:1) and the Cu addition on the structural, acid base, and catalytic properties of Ni-containing systems. The binary LaCeO oxide at a ratio of La:Ce = 1:1 is characterized by the formation of a solid solution with a fluorite structure, which is preserved upon the introduction of mono- or bimetallic particles. At La:Ce = 9:1, LaO segregation from the solid solution structure is observed, and the La excess determines the nature of the precursor of the active component, i.e., lanthanum nickelate. The catalysts based on LaCeO (1:1) are prone to carbonization during 6 h spent on-stream with the formation of carbon nanotubes. The Cu addition facilitates the reduction of the Cu-Ni catalyst carbonization and increases the number of structural defects in the carbon deposition products. The lanthanum-enriched LaCeO (9:1) support prevents the accumulation of carbon deposition products on the surface of CuNi/LaO-CeO 9:1, providing high DRM activity and an H/CO ratio of 0.9.
本工作聚焦于负载在LaO-CeO二元氧化物上的镍催化剂,该催化剂在活性组分中添加或不添加Cu用于甲烷干重整(DRM)。采用XRD、XRF、TPD-CO、TPR-H和低温N吸附-脱附方法对催化剂进行表征。这项工作展示了不同La:Ce比(1:1和9:1)以及添加Cu对含Ni体系的结构、酸碱和催化性能的影响。La:Ce = 1:1的二元LaCeO氧化物的特征是形成具有萤石结构的固溶体,在引入单金属或双金属颗粒时该结构得以保留。在La:Ce = 9:1时,观察到LaO从固溶体结构中偏析出来,并且La的过量决定了活性组分前驱体的性质,即镍酸镧。基于LaCeO(1:1)的催化剂在6小时的运行过程中容易发生碳化并形成碳纳米管。添加Cu有助于减少Cu-Ni催化剂的碳化,并增加碳沉积产物中的结构缺陷数量。富含镧的LaCeO(9:1)载体可防止碳沉积产物在CuNi/LaO-CeO 9:1表面堆积,提供高DRM活性和0.9的H/CO比。