Liu Songliang, Ma Kun, Teng Huaifang, Miao Weixin, Zhou Xiaotong, Cui Xuejing, Zhou Xin, Jiang Luhua, Guo Shaojun
Electrocatalysis & Nanomaterial Laboratory, College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.
Interdisciplinary Research Center for Biology and Chemistry, Liaoning Normal University, Dalian, Liaoning, 116029, P. R. China.
Adv Mater. 2025 Mar;37(10):e2411148. doi: 10.1002/adma.202411148. Epub 2025 Jan 28.
Innovating nanocatalysts with both high intrinsic catalytic activity and high selectivity is crucial for multi-electron reactions, however, their low mass/electron transport at industrial-level currents is often overlooked, which usually leads to low comprehensive performance at the device level. Herein, a Cl/O etching-assisted self-assembly strategy is reported for synthesizing a self-assembled gap-rich PdMn nanofibers with high mass/electron transport highway for greatly enhancing the electrocatalytic reforming of waste plastics at industrial-level currents. The self-assembled PdMn nanofiber shows excellent catalytic activity in upcycling waste plastics into glycolic acid, with a high current density of 223 mA cm@0.75 V (vs RHE), high selectivity (95.6%), and Faraday efficiency (94.3%) to glycolic acid in a flow electrolyzer. Density functional theory calculation, X-ray absorption spectroscopy combined with in situ electrochemical Fourier transform infrared spectroscopy reveals that the introduction of highly oxophilic Mn induces a downshift of the d-band center of Pd, which optimizes the adsorption energy of the reaction intermediates on PdMn surface, thereby facilitating the desorption of glycolic acid as a high-value product. Computational fluid dynamics simulations confirm that the gap-rich nanofiber structure is conducive for mass transfer to deliver an industrial-level current.
开发兼具高本征催化活性和高选择性的纳米催化剂对于多电子反应至关重要，然而，它们在工业级电流下的低质量/电子传输往往被忽视，这通常导致器件层面的综合性能较低。在此，报道了一种Cl/O蚀刻辅助自组装策略，用于合成具有高质量/电子传输通道的自组装富间隙PdMn纳米纤维，以在工业级电流下大幅增强废塑料的电催化重整。自组装的PdMn纳米纤维在将废塑料升级循环为乙醇酸方面表现出优异的催化活性，在流动电解槽中，在0.75 V（相对于可逆氢电极）时具有223 mA cm的高电流密度、对乙醇酸的高选择性（95.6%）和法拉第效率（94.3%）。密度泛函理论计算、X射线吸收光谱结合原位电化学傅里叶变换红外光谱表明，高亲氧性Mn的引入导致Pd的d带中心下移，优化了反应中间体在PdMn表面的吸附能，从而促进了作为高价值产物的乙醇酸的脱附。计算流体动力学模拟证实，富间隙纳米纤维结构有利于传质以输送工业级电流。
