Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, P. R. China.
Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Shanghai, 200237, P. R. China.
ChemSusChem. 2020 Sep 18;13(18):4954-4966. doi: 10.1002/cssc.202001600. Epub 2020 Aug 19.
Selective transformation of glycerol to propanal (PA) provides a feasible route towards the sustainable synthesis of high value-added chemicals. In this work, zirconium phosphate (ZrP) was studied as support and Ru and Co as metal sites for glycerol hydrogenolysis in a continuous-flow reactor. It was found that ZrP-supported Co-O species had a moderate selectivity to PA (49.5 %) in glycerol hydrogenolysis. Notably, once Ru species were doped into CoO/ZrP, the resulting catalyst exhibited not only an outstanding catalytic performance for glycerol hydrogenolysis to PA (a selectivity of 80.2 % at full conversion), but also a high stability at least a 50 h long-term performance. The spent catalyst could be regenerated by calcining in air to remove carbonaceous deposits. Characterization indicated that the acid sites on ZrP played a very critical role in the dehydration of glycerol into acrolein (AE), that the distribution of Co was uniform, basically consistent with that of Zr, P and Ru, and that an especially close contact between Co-O and Ru species was formed on Ru/CoO/ZrP catalyst. The further activity tests and characterizations confirmed that there was a strong interaction between the dispersed Co-O species and Ru nanoparticles, which endowed Ru sites with high electronic density. This effect could play a role in facilitating the dissociation of H , and thus in promoting the hydrogenation reaction. Besides, DFT calculations suggested that the Co-O species can adsorb more strongly the C=C bond of the intermediate AE on a highly coordinatively unsaturated Co (Co ) site and thus lead to preferential hydrogenation at the C=C bond of AE to PA.
选择性地将甘油转化为丙醛 (PA) 为可持续合成高附加值化学品提供了可行的途径。在这项工作中，研究了磷酸锆 (ZrP) 作为载体，以及 Ru 和 Co 作为金属位，用于甘油在连续流反应器中的氢解反应。结果表明，ZrP 负载的 Co-O 物种在甘油氢解中对 PA 具有中等选择性（49.5%）。值得注意的是，一旦 Ru 物种掺杂到 CoO/ZrP 中，所得催化剂不仅在甘油氢解生成 PA 方面表现出出色的催化性能（完全转化时的选择性为 80.2%），而且在至少 50 h 的长期稳定性方面也表现出很高的稳定性。通过在空气中煅烧可以再生失活的催化剂，以去除积碳。表征表明，ZrP 上的酸位在甘油脱水生成丙烯醛 (AE) 中起着非常关键的作用，Co 的分布均匀，基本与 Zr、P 和 Ru 一致，并且在 Ru/CoO/ZrP 催化剂上形成了 Co-O 和 Ru 物种之间特别紧密的接触。进一步的活性测试和表征证实，分散的 Co-O 物种和 Ru 纳米颗粒之间存在强烈的相互作用，这赋予了 Ru 位高电子密度。这种效应可以在促进 H 的解离方面发挥作用，从而促进加氢反应。此外，DFT 计算表明，Co-O 物种可以在高度配位不饱和的 Co（Co ）位上更强烈地吸附中间体 AE 的 C=C 键，从而导致 AE 中 C=C 键优先加氢生成 PA。
