Total hydrogenation of bio-derived furans over supported Ru subnanoclusters prepared via amino acid-assisted deposition
Total hydrogenation of bio-derived furans over supported Ru subnanoclusters prepared via amino acid-assisted deposition
复制标题
通过氨基酸辅助沉积制备的负载 Ru 亚纳米团簇上生物源呋喃的完全氢化
DOI：
10.1039/c9gc02943e
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发表时间：
2020
期刊：
影响因子：
9.8
通讯作者：
Cao Yong
中科院分区：
文献类型：
--
作者：
Qian Yang;Li Ze-Jun;Du Xian-Long;Zhang Qi;Zhao Yi;Liu Yong-Mei;Cao Yong
开发具有减少的贵金属用量的高效且耐用的催化剂对于含呋喃的生物基原料的选择性氢化是极其期望的，这代表了对石化资源的有吸引力且可持续的替代。在这里，我们描述了一种新型的分散良好的Ru亚纳米团簇（约。0.50 wt %）负载在商业P25 TiO 2材料上，该商业P25 TiO 2材料由容易且有效的氨基酸辅助沉积-沉淀策略获得。所合成的催化剂表现出优异的催化活性和选择性，用于工业上重要的糠醛以及一系列结构多样的生物基呋喃化合物直接氢化成其相应的完全氢化的衍生物。在80 ° C和4 MPa H2下获得的平均转换频率（ATOF）值高达367 h − 1，这是报告的最高值。该催化剂在80 ° C下进行的5个反应循环中也显示出稳定的糠醛完全氢化（52 mmol规模，转化数高达12 500）。 在动力学和结构表征方面，超小Ru团簇的关键性能主要来自于表面不饱和Ru原子数量的增加和局部配位环境的改变。我们的工作突出了亚纳米尺寸的Ru簇在推进生物基化学品生产的高效和负担得起的方法中的重要性。
Development of a highly efficient and robust catalyst with reduced usage of noble metals is extremely desirable for selective hydrogenations of furan-containing bio-based feedstocks, which represents an attractive and sustainable alternative to petrochemical resources. Herein, we describe a new type of well-dispersed Ru subnanoclusters (ca. 0.50 wt%) supported on commercial P25 TiO2 material obtained from a facile and effective amino acid-assisted deposition–precipitation strategy. The as-synthesized catalyst exhibits superior catalytic activity and selectivity for direct hydrogenation of industrially important furfural as well as a range of structurally diverse bio-based furanic compounds to their corresponding fully hydrogenated derivatives. An average turnover frequency (ATOF) value as high as 367 h−1 at 80 °C and 4 MPa H2 is obtained, which is the highest reported value. This catalyst also shows stable furfural total hydrogenation in 5 reaction cycles conducted at 80 °C (52 mmol-scale, turnover number up to 12 500). In terms of the kinetic and structural characterizations, the key performances of the ultrasmall Ru clusters are proposed to mainly originate from an enhanced number of unsaturated surface Ru atoms and change in local coordination environment. Our work highlights the importance of the subnanometric size of Ru clusters in the advancement of efficient and affordable approaches towards bio-based chemical production.