Jang Daehee, Park Minseon, Maeng Junbeom, Ha Jungseub, Choi Sehun, Kim Nayeon, Seo Min Ho, Kim Won Bae
Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), 77 Cheongam-ro, Nam-gu, Pohang, Gyeongbuk, 37673, Republic of Korea.
Department of Nanotechnology Engineering, Pukyong National University, 45 Yongso-ro, Nam-gu, Busan, 48547, Republic of Korea.
Small. 2024 Dec;20(49):e2404540. doi: 10.1002/smll.202404540. Epub 2024 Sep 9.
The ethylene glycol oxidation reaction (EGOR) has attracted attention because ethylene glycol (EG), which exhibits large-scale production and a low market price, can be reformed into valuable glycolic acid (GCA) with the cogeneration of high-purity hydrogen gas during the reaction. In this study, a noble catalyst material of Pt nanoparticles supported on Se-doped porous carbon (Pt/SePC) is prepared and investigated for the selective electrochemical oxidation of EG to GCA. Pt/SePC achieved a maximum EG conversion of 94.6% and GCA selectivity of 84.4% and maintained this high performance with negligible degradation during durability tests. Furthermore, the EGOR required lower overpotential rather than the oxygen evolution reaction, thus the EGOR coupled with the hydrogen evolution reaction can reduce the cell overpotential to 0.60 V, which is much lower than that of water electrolysis (1.58 V). The effect of Se doping is investigated through experimental analyses and density functional theory (DFT) calculations, and they shows that Se modified the binding energy of Pt nanoparticles and the adsorption energy of reactants by lattice deformation and charge density modification. This study provides scientific insights and strategies for electrocatalyst design for the selective oxidation of polyols to value-added chemicals via the cogeneration of hydrogen gas.
乙二醇氧化反应(EGOR)引起了人们的关注,因为大规模生产且市场价格低廉的乙二醇(EG)可以在反应过程中被转化为有价值的乙醇酸(GCA),同时联产高纯度氢气。在本研究中,制备了负载在硒掺杂多孔碳上的铂纳米颗粒(Pt/SePC)这种贵金属催化剂材料,并对其用于EG选择性电化学氧化制备GCA进行了研究。Pt/SePC实现了94.6%的最大EG转化率和84.4%的GCA选择性,并且在耐久性测试期间保持了这种高性能,降解可忽略不计。此外,EGOR所需的过电位低于析氧反应,因此EGOR与析氢反应耦合可将电池过电位降低至0.60 V,这远低于水电解的过电位(1.58 V)。通过实验分析和密度泛函理论(DFT)计算研究了硒掺杂的影响,结果表明硒通过晶格变形和电荷密度改性改变了铂纳米颗粒的结合能和反应物的吸附能。本研究为通过联产氢气将多元醇选择性氧化为增值化学品的电催化剂设计提供了科学见解和策略。