Centre for Surface Chemistry and Catalysis, Katholieke Universiteit Leuven, Kasteelpark Arenberg 23, 3001 Heverlee, Belgium.
ChemSusChem. 2012 Aug;5(8):1549-58. doi: 10.1002/cssc.201100782. Epub 2012 Jun 22.
Carbon nanofibers (CNFs) are a class of graphitic support materials with considerable potential for catalytic conversion of biomass. Earlier, we demonstrated the hydrolytic hydrogenation of cellulose over reshaped nickel particles attached at the tip of CNFs. The aim of this follow-up study was to find a relationship between the acid/metal balance of the Ni/CNFs and their performance in the catalytic conversion of cellulose. After oxidation and incipient wetness impregnation with Ni, the Ni/CNFs were characterized by various analytical methods. To prepare a selective Ni/CNF catalyst, the influences of the nature of oxidation agent, Ni activation, and Ni loading were investigated. Under the applied reaction conditions, the best result, that is, 76 % yield in hexitols with 69 % sorbitol selectivity at 93 % conversion of cellulose, was obtained on a 7.5 wt % Ni/CNF catalyst prepared by chemical vapor deposition of CH(4) on a Ni/γ-Al(2)O(3) catalyst, followed by oxidation in HNO(3) (twice for 1 h at 383 K), incipient wetness impregnation, and reduction at 773 K under H(2). This preparation method leads to a properly balanced Ni/CNF catalyst in terms of Ni dispersion and hydrogenation capacity on the one hand, and the number of acidic surface-oxygen groups responsible for the acid-catalyzed hydrolysis on the other.
碳纳米纤维(CNFs)是一类石墨支撑材料,在生物质催化转化方面具有很大的潜力。之前,我们已经证明了在 CNFs 尖端附着的重整镍颗粒上进行纤维素的水解氢化反应。本后续研究的目的是寻找 Ni/CNFs 的酸/金属平衡与其在纤维素催化转化性能之间的关系。经过氧化和 Ni 的初始湿浸渍,通过各种分析方法对 Ni/CNFs 进行了表征。为了制备选择性的 Ni/CNF 催化剂,考察了氧化剂种类、Ni 活化和 Ni 负载量的影响。在应用的反应条件下,在纤维素转化率为 93%的情况下,在 7.5wt%Ni/CNF 催化剂上获得了最佳的结果,即己糖醇的收率为 76%,山梨醇的选择性为 69%,该催化剂是通过 Ni/γ-Al(2)O(3)催化剂上 CH(4)的化学气相沉积制备的,然后在 HNO(3)中氧化(在 383K 下两次 1 小时)、初始湿浸渍和 H(2)下在 773K 还原。这种制备方法使得 Ni/CNF 催化剂在 Ni 分散度和加氢能力以及负责酸催化水解的酸性表面氧基团数量之间达到了适当的平衡。