Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, YO10 5DD, UK.
School of Chemical and Biological Engineering, Seoul National University, 1 Kwanak-Ro, Kwanak-Gu, Seoul, 151-742, Republic of Korea.
ChemSusChem. 2018 Feb 22;11(4):716-725. doi: 10.1002/cssc.201702207. Epub 2018 Jan 31.
Iron-N-heterocyclic carbene complexes (Fe-NHCs) have come to prominence because of their applicability in diverse catalytic reactions, ranging from C-C cross-coupling and C-X bond formation to substitution, reduction, polymerization, and dehydration reactions. The detailed synthesis, characterization, and application of novel heterogeneous Fe-NHC catalysts immobilized on mesoporous expanded high-amylose corn starch (HACS) and Starbon 350 (S350) for facile fructose conversion into 5-hydroxymethylfurfural (HMF) is reported. Both catalyst types showed good performance for the dehydration of fructose to HMF when the reaction was tested at 100 °C with varying time (10 min, 20 min, 0.5 h, 1 h, 3 h and 6 h). For Fe-NHC/S350, the highest HMF yield was 81.7 % (t=0.5 h), with a TOF of 169 h , fructose conversion of 95 %, and HMF selectivity of 85.7 %, whereas for Fe-NHC/expanded HACS, the highest yield was 86 % (t=0.5 h), with a TOF of 206 h , fructose conversion of 87 %, and HMF selectivity of 99 %. Iron loadings of 0.26 and 0.30 mmol g were achieved for Fe-NHC/expanded starch and Fe-NHC/S350, respectively.
铁-氮杂环卡宾配合物(Fe-NHCs)因其在各种催化反应中的应用而备受关注,这些反应包括 C-C 交叉偶联和 C-X 键形成反应,以及取代、还原、聚合和脱水反应。本文报道了将新型固载在介孔膨化高直链玉米淀粉(HACS)和 Starbon 350(S350)上的非均相 Fe-NHC 催化剂详细合成、表征及其在果糖易位转化为 5-羟甲基糠醛(HMF)中的应用。当在 100°C 下以不同时间(10 min、20 min、0.5 h、1 h、3 h 和 6 h)测试反应时,两种催化剂类型在将果糖脱水生成 HMF 方面均表现出良好的性能。对于 Fe-NHC/S350,最高 HMF 收率为 81.7%(t=0.5 h),TOF 为 169 h ,果糖转化率为 95%,HMF 选择性为 85.7%;而对于 Fe-NHC/膨化 HACS,最高收率为 86%(t=0.5 h),TOF 为 206 h ,果糖转化率为 87%,HMF 选择性为 99%。Fe-NHC/膨化淀粉和 Fe-NHC/S350 的铁负载量分别为 0.26 和 0.30 mmol·g。