Dong Zhen, Zhang Yahui, Xia Haian
Jiangsu Provincial Key Lab for the Chemistry and Utilization of Agro-forest Biomass, College of Chemical Engineering, Nanjing Forestry University Nanjing China
RSC Adv. 2024 May 8;14(21):14982-14991. doi: 10.1039/d4ra02054e. eCollection 2024 May 2.
Catalytic hydrogenolysis of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) has become a hot topic in the bioenergy field in recent years. It remains a challenge to mediate the activation/hydrogenation/hydrogenolysis of C-O and C[double bond, length as m-dash]O bonds of HMF at high temperatures. Herein, bimetallic Ru-Co/AC catalysts were prepared by the "two-step" reduction method and were used to catalyze the hydrogenolysis of HMF to DMF. The effects of different reduction methods, Ru/Co ratios, and Ru loading on the catalytic performances of the Ru-Co/AC catalysts were investigated, and the physicochemical properties of the catalysts were characterized by TEM, XPS, H-TPR, It was found that the catalysts reduced by the "two-step" reduction method exhibited better catalytic activities than those fabricated by a single H or NaBH reduction method. The introduction of Co metals promoted the dispersion of Ru nanoparticles (NPs) on AC and the transfer of electrons from Co to Ru, thereby improving the catalytic activity. An excellent yield of DMF up to 97.9% and 98.7% conversion of HMF were achieved in a short time (1.5 h) under the optimal conditions (200 °C, 1 MPa). Furthermore, the possible reaction pathway for the hydrogenolysis of HMF to DMF over 5%Ru-1%Co/AC catalyst is also discussed. The work shows that the Ru-Co/AC catalysts have great potentials for the conversion of HMF into liquid fuel DMF.
近年来,5-羟甲基糠醛(HMF)催化氢解为2,5-二甲基呋喃(DMF)已成为生物能源领域的一个热门话题。在高温下介导HMF的C-O和C=O键的活化/氢化/氢解仍然是一个挑战。在此,通过“两步”还原法制备了双金属Ru-Co/AC催化剂,并用于催化HMF氢解为DMF。研究了不同还原方法、Ru/Co比和Ru负载量对Ru-Co/AC催化剂催化性能的影响,并通过TEM、XPS、H-TPR对催化剂的物理化学性质进行了表征。结果发现,采用“两步”还原法制备的催化剂比采用单一H或NaBH还原法制备的催化剂具有更好的催化活性。Co金属的引入促进了Ru纳米颗粒(NPs)在AC上的分散以及电子从Co向Ru的转移,从而提高了催化活性。在最佳条件(200℃,1MPa)下,短时间内(1.5h)实现了高达97.9%的DMF产率和98.7%的HMF转化率。此外,还讨论了5%Ru-1%Co/AC催化剂上HMF氢解为DMF的可能反应途径。该工作表明,Ru-Co/AC催化剂在将HMF转化为液体燃料DMF方面具有巨大潜力。