Zhang Yang, Wang Lin, Pan Shengmin, Zhou Lin, Zhang Man, Yang Yaoyue, Cai Wenbin
Key Laboratory of General Chemistry of the National Ethnic Affairs Commission, School of Chemistry and Environment, Southwest Minzu University, Chengdu 610041, China.
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, Fudan University, Shanghai 200438, China.
Molecules. 2024 Aug 16;29(16):3890. doi: 10.3390/molecules29163890.
The electrochemical conversion of glycerol into high-value chemicals through the selective glycerol oxidation reaction (GOR) holds importance in utilizing the surplus platform chemical component of glycerol. Nevertheless, it is still very limited in producing three-carbon chain (C) chemicals, especially glyceric acid/glycerate, through the direct oxidation of its primary hydroxyl group. Herein, Pd microstructure electrodeposited on the Ni foam support (Pd/NF) is designed and fabricated to achieve a highly efficient GOR, exhibiting a superior current density of ca. 120 mA cm at 0.8 V vs. reversible hydrogen electrode (RHE), and high selectivity of glycerate at ca. 70%. The Faradaic efficiency of C chemicals from GOR can still be maintained at ca. 80% after 20 continuous electrolysis runs, and the conversion rate of glycerol can reach 95% after 10-h electrolysis. It is also clarified that the dual-component interfaces constructed by the adjacent Pd and Ni sites are responsible for this highly efficient GOR. Specifically, Ni sites can effectively strengthen the generative capacity of the active adsorbed hydroxyl (OH) species, which can steadily immigrate to the Pd sites, so that the surface adsorbed glycerol species are quickly oxidized into C chemicals, rather than breaking the C-C bond of glycerol; thus, neither form the C/C species. This study may yield fresh perspectives on the electrocatalytic conversion of glycerol into high-value C chemicals, such as glyceric acid/glycerate.
通过选择性甘油氧化反应（GOR）将甘油电化学转化为高价值化学品，对于利用甘油这一过剩的平台化学成分具有重要意义。然而，通过直接氧化甘油的伯羟基来生产三碳链（C）化学品，尤其是甘油酸/甘油酸盐，目前仍然非常有限。在此，设计并制备了电沉积在泡沫镍载体上的钯微观结构（Pd/NF），以实现高效的甘油氧化反应，在相对于可逆氢电极（RHE）为0.8 V时，表现出约120 mA cm的优异电流密度，以及约70%的甘油酸盐高选择性。在连续20次电解运行后，甘油氧化反应生成C化学品的法拉第效率仍可维持在约80%，经过10小时电解后，甘油转化率可达95%。研究还表明，由相邻的钯和镍位点构建的双组分界面是这种高效甘油氧化反应的原因。具体而言，镍位点可以有效增强活性吸附羟基（OH）物种的生成能力，这些物种能够稳定地迁移到钯位点，从而使表面吸附的甘油物种迅速氧化为C化学品，而不会破坏甘油的C-C键；因此，也不会形成C/C物种。这项研究可能为将甘油电催化转化为高价值C化学品，如甘油酸/甘油酸盐，提供新的视角。
