College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082, China.
ACS Appl Mater Interfaces. 2023 Mar 8;15(9):11631-11641. doi: 10.1021/acsami.2c16656. Epub 2023 Feb 28.
Composition optimization, structural design, and introduction of external magnetic fields into the catalytic process can remarkably improve the oxygen evolution reaction (OER) performance of a catalyst. NiFeO@(Ni, Fe)S/P materials with a heterogeneous core-shell structure were prepared by the sulfide/phosphorus method based on spinel-structured NiFeO nanomicrospheres. After the sulfide/phosphorus treatment, not only the intrinsic activity of the material and the active surface area were increased but also the charge transfer resistance was reduced due to the internal electric field. The overpotential of NiFeO@(Ni, Fe)P at 10 mA cm (iR correction), Tafel slope, and charge transfer resistance were 261 mV, 42 mV dec, and 3.163 Ω, respectively. With an alternating magnetic field, the overpotential of NiFeO@(Ni, Fe)P at 10 mA cm (without iR correction) declined by 45.5% from 323 mV (0 mT) to 176 mV (4.320 mT). Such enhancement of performance is primarily accounted for the enrichment of the reactive ion OH on the electrode surface induced by the inductive electric potential derived from the Faraday induction effect of the AMF. This condition increased the electrode potential and thus the charge transfer rate on the one hand and weakened the diffusion of the active substance from the electrolyte to the electrode surface on the other hand. The OER process was dominantly controlled by the charge transfer process under low current conditions. A fast charge transfer rate boosted the OER performance of the catalyst. At high currents, diffusion exerted a significant effect on the OER process and low OH diffusion rates would lead to a decrease in the OER performance of the catalyst.
通过对催化剂的催化过程进行组成优化、结构设计和外加磁场引入,可以显著提高其析氧反应(OER)性能。以尖晶石结构的 NiFeO 纳米微球为前驱体,采用硫化/磷化法制备了具有核壳异质结构的 NiFeO@(Ni,Fe)S/P 材料。经过硫化/磷化处理后,不仅提高了材料的本征活性和比表面积,还降低了电荷转移电阻,这是由于内部电场的存在。NiFeO@(Ni,Fe)P 在 10 mA cm(iR 校正)、Tafel 斜率和电荷转移电阻下的过电势分别为 261 mV、42 mV dec 和 3.163 Ω。施加交变磁场后,NiFeO@(Ni,Fe)P 在 10 mA cm(无 iR 校正)下的过电势从 323 mV(0 mT)降低到 176 mV(4.320 mT),降低了 45.5%。这种性能的增强主要归因于外加磁场的感应电动势引起的感生电场导致电极表面反应离子 OH 的富集,从而增加了电极电位和电荷转移速率,另一方面,削弱了活性物质从电解质向电极表面的扩散。在低电流条件下,OER 过程主要受电荷转移过程控制。快速的电荷转移速率可以提高催化剂的 OER 性能。在高电流下,扩散对 OER 过程有显著影响,低的 OH 扩散速率会导致催化剂的 OER 性能下降。