Song Yang, Mobley Justin K, Motagamwala Ali Hussain, Isaacs Mark, Dumesic James A, Ralph John, Lee Adam F, Wilson Karen, Crocker Mark
Department of Chemistry , University of Kentucky , 505 Rose Street , Lexington , KY 40506 , USA.
Center for Applied Energy Research (CAER) , University of Kentucky , 2540 Research Park Drive , Lexington , KY 40511 , USA . Email:
Chem Sci. 2018 Sep 6;9(42):8127-8133. doi: 10.1039/c8sc03208d. eCollection 2018 Nov 14.
A heterogeneous catalyst system, employing Au nanoparticles (NPs) and Li-Al (1 : 2) layered double hydroxide (LDH) as support, showed excellent activity in aerobic oxidation of the benzylic alcohol group in β-O-4 linked lignin model dimers to the corresponding carbonyl products using molecular oxygen under atmospheric pressure. The synergistic effect between Au NPs and the basic Li-Al LDH support induces further reaction of the oxidized model compounds, facilitating facile cleavage of the β-O-4 linkage. Extension to oxidation of γ-valerolactone (GVL) extracted lignin and kraft lignin using Au/Li-Al LDH under similar conditions produced a range of aromatic monomers in high yield. Hydrolysis of the Au/Li-Al LDH oxidized lignin was found to increase the degree of lignin depolymerization, with monomer yields reaching 40% for GVL extracted lignin. Based on these results, the Au/Li-Al LDH + O catalyst system shows potential to be an environmentally friendly means of depolymerizing lignin to low molecular weight aromatics under mild conditions.
一种非均相催化剂体系,以金纳米颗粒(NPs)和锂 - 铝(1∶2)层状双氢氧化物(LDH)为载体,在常压下使用分子氧将β - O - 4连接的木质素模型二聚体中的苄醇基团有氧氧化为相应的羰基产物时表现出优异的活性。金纳米颗粒与碱性锂 - 铝层状双氢氧化物载体之间的协同作用促使氧化后的模型化合物进一步反应,便于β - O - 4键的轻松断裂。在类似条件下,使用金/锂 - 铝层状双氢氧化物对γ - 戊内酯(GVL)提取的木质素和硫酸盐木质素进行氧化反应,能高产率地生成一系列芳香族单体。研究发现,对金/锂 - 铝层状双氢氧化物氧化后的木质素进行水解可提高木质素的解聚程度,GVL提取的木质素单体产率可达40%。基于这些结果,金/锂 - 铝层状双氢氧化物 + 氧气催化剂体系显示出在温和条件下将木质素解聚为低分子量芳烃的环保方法的潜力。