Li Jie, Yi Zhi-Bin, Li Nuo-Tong, Yu Na-Na, Geng Hao-Ran
School of Materials Science and Engineering, University of Jinan, No. 336 West Road of Nan Xinzhuang, Jinan 250022, Shandong Province, China.
Department of Mechanical and Aerospace Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
Phys Chem Chem Phys. 2023 Jul 26;25(29):19492-19500. doi: 10.1039/d3cp02373g.
This work reports the refinement of nanoporous copper (NPC) ligaments by introducing the sodium dodecyl sulfate (SDS) surfactant in the dealloying process. The AlCu (at%) alloy precursor is chemically dealloyed in a mixed solution of NaOH and SDS surfactant, producing NPC with a hierarchical microstructure. Micron-scaled skeletons that build up higher level networks consist of geometrically similar nano-scaled bi-continuous ligament-pore networks at the lower level. It has been found that the size of the ligaments in the lower level networks reduces from ∼32 nm to ∼24 nm with increasing SDS concentration to 1 mM. Further increasing the SDS concentration to 5 mM only leads to a slight ligament size decrease to ∼21 nm. Remarkably, nano-sized cones are formed on the lower level network surface in the dealloying solution containing 1 mM SDS, and the cone number greatly rises when the SDS concentration increases to 5 mM. The surface diffusivity of Cu adatoms is evaluated based on the experimental data, and the refinement of the ligament as well as the formation of cones are associated with the decreased surface diffusivity and the retarded Cu adatom motions with the addition of SDS. Quantum chemical calculations and molecular dynamics simulations are performed to model the adsorption behavior of SDS. It has been found that the SDS-substrate interaction increases with the number of SDS molecules before SDS reaches saturation.
这项工作报道了通过在脱合金过程中引入十二烷基硫酸钠(SDS)表面活性剂来细化纳米多孔铜(NPC)韧带。AlCu(原子百分比)合金前驱体在NaOH和SDS表面活性剂的混合溶液中进行化学脱合金,生成具有分级微观结构的NPC。构成更高层次网络的微米级骨架由较低层次几何形状相似的纳米级双连续韧带-孔隙网络组成。研究发现,随着SDS浓度增加到1 mM,较低层次网络中韧带的尺寸从约32 nm减小到约24 nm。进一步将SDS浓度增加到5 mM只会导致韧带尺寸略微减小到约21 nm。值得注意的是,在含有1 mM SDS的脱合金溶液中,较低层次网络表面形成了纳米级圆锥体,当SDS浓度增加到5 mM时,圆锥体数量大幅增加。基于实验数据评估了Cu原子的表面扩散率,韧带的细化以及圆锥体的形成与添加SDS后表面扩散率降低和Cu原子运动受阻有关。进行了量子化学计算和分子动力学模拟以模拟SDS的吸附行为。研究发现,在SDS达到饱和之前,SDS与底物的相互作用随着SDS分子数量的增加而增强。