Wang Xiaoxiao, Yang Yanmei, Zhou Zhiqing, Zhong Yuling, Qin Miaomiao, Wang Weiqing, Li Weifeng, Tang Bo
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Centre of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University. Jinan 250014, China.
School of Physics, Shandong University, Jinan, Shandong 250100, China.
ACS Appl Mater Interfaces. 2024 Dec 18;16(50):69125-69132. doi: 10.1021/acsami.4c09672. Epub 2024 Dec 10.
5-hydroxymethylfurfural (HMF) is one of the most promising biomass-based chemicals that is used to produce many kinds of important compounds. Especially, the selective conversion of HMF to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), an important chemical feedstock, has high industrial significance but is technically challenging. In this study, we present a high-performance photocatalyst for selective oxidation of HMF to HMFCA. By integrating an ultrasmall amount of palladium (Pd) nanoclusters (1.12‰ in weight) on defective hexagonal boron nitride nanosheets (Pd/defective h-BN nanosheets (dh-BNs)), outstanding photocatalytic performance can be achieved, resulting in up to a 95% HMF conversion ratio with an 82% HMFCA selectivity. The performance is considerably higher than that of pristine dh-BNs and Pd on defect-free h-BNs. More importantly, this Pd/dh-BNs catalyst maintains a high catalytic activity after eight cycles, demonstrating robust catalytic stability. Density functional theory calculations indicate that Pd/dh-BNs can lower the energy barrier for HMF oxidation and facilitate the desorption of HMFCA, which contributes to the high selectivity catalytic performance. This study not only introduces a promising photocatalyst for sustainable chemical transformations but can also provide valuable insights into the design of advanced photocatalytic material for biorefinery applications.
5-羟甲基糠醛（HMF）是最具潜力的生物质基化学品之一，可用于生产多种重要化合物。特别是，将HMF选择性转化为重要的化学原料5-羟甲基-2-呋喃羧酸（HMFCA）具有很高的工业意义，但在技术上具有挑战性。在本研究中，我们提出了一种用于将HMF选择性氧化为HMFCA的高性能光催化剂。通过在缺陷型六方氮化硼纳米片（Pd/缺陷型h-BN纳米片（dh-BNs））上整合极少量的钯（Pd）纳米团簇（重量为1.12‰），可以实现出色的光催化性能，HMF转化率高达95%，HMFCA选择性为82%。该性能大大高于原始dh-BNs和无缺陷h-BNs上的Pd的性能。更重要的是，这种Pd/dh-BNs催化剂在八个循环后仍保持高催化活性，证明了其强大的催化稳定性。密度泛函理论计算表明，Pd/dh-BNs可以降低HMF氧化的能垒并促进HMFCA的解吸，这有助于实现高选择性催化性能。本研究不仅介绍了一种用于可持续化学转化的有前景的光催化剂，还可以为生物炼制应用中先进光催化材料的设计提供有价值的见解。
