Ma Lei, Yan Li, Lu An-Hui, Ding Yunjie
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology No. 2 Linggong Road Dalian 116024 P. R. China.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences 457 Zhongshan Road Dalian 116023 China
RSC Adv. 2018 Feb 20;8(15):8152-8163. doi: 10.1039/c7ra12891f. eCollection 2018 Feb 19.
In this paper, Ni/AlO catalysts (15 wt% Ni) with different Re loadings were prepared to investigate the effect of Re on the structure and catalytic performance of Ni-Re/AlO catalysts for the reductive amination of monoethanolamine. Reaction results reveal that the conversion and ethylenediamine selectivity increase significantly with increasing Re loading up to 2 wt%. Ni-Re/AlO catalysts show excellent stability during the reductive amination reaction. The characterization of XRD, DR UV-Vis spectroscopy, H-TPR, and acidity-basicity measurements indicates that addition of Re improves the Ni dispersion, proportion of octahedral Ni species, reducibility, and acid strength for Ni-Re/AlO catalysts. The Ni15 and Ni15-Re2 catalysts were chosen for in-depth study. The results from SEM-BSE, TEM, and CO-TPD indicate that smaller Ni particle size and higher Ni surface area are obtained in the reduced Ni-Re/AlO catalysts. Results from XPS and STEM-EDX line scan suggest that Re species show a mixture of various valances and have a tendency to aggregate on the surface of Ni particles. During reaction, the Ni particles on the AlO support are stabilized and the sintering process is effectively suppressed by the incorporation of Re. It could be concluded that sufficient Ni sites, the collaborative effect of Ni-Re, and brilliant stability contribute to the excellent catalytic performance of Ni-Re/AlO catalysts for the reductive amination of monoethanolamine.
本文制备了具有不同Re负载量的Ni/AlO催化剂(Ni含量为15 wt%),以研究Re对用于单乙醇胺还原胺化反应的Ni-Re/AlO催化剂的结构和催化性能的影响。反应结果表明,随着Re负载量增加至2 wt%,转化率和乙二胺选择性显著提高。Ni-Re/AlO催化剂在还原胺化反应过程中表现出优异的稳定性。XRD、DR紫外可见光谱、H-TPR和酸碱性质测量结果表明,添加Re提高了Ni-Re/AlO催化剂的Ni分散度、八面体Ni物种比例、还原性和酸强度。选择Ni15和Ni15-Re2催化剂进行深入研究。SEM-BSE、TEM和CO-TPD结果表明,还原后的Ni-Re/AlO催化剂具有更小的Ni粒径和更高的Ni表面积。XPS和STEM-EDX线扫描结果表明,Re物种呈现多种价态的混合物,并且倾向于在Ni颗粒表面聚集。在反应过程中,AlO载体上的Ni颗粒得以稳定,并且通过引入Re有效地抑制了烧结过程。可以得出结论,充足的Ni位点、Ni-Re的协同作用以及出色的稳定性有助于Ni-Re/AlO催化剂在单乙醇胺还原胺化反应中表现出优异的催化性能。