Liu Yidan, Yodsin Nuttapon, Li Ting, Wu Haocheng, Jia Rongrong, Shi Liyi, Lai Zhuangchai, Namuangruk Supawadee, Huang Lei
Research Center of Nano Science and Technology, College of Sciences, Shanghai University, Shanghai 200444, P. R. China.
College of Textile Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China.
Mater Horiz. 2024 Apr 22;11(8):1964-1974. doi: 10.1039/d3mh02041j.
The rational design of heterostructured nanocrystals (HNCs) is of great significance for developing highly efficient hydrogen evolution reaction (HER) electrocatalysts. However, a significant challenge still lies in realizing the controllable synthesis of desired HNCs directly onto a support and exploring their structure-activity-dependent HER performance. Herein, we reported various controllable Pd@Pt core-shell HNCs with optimal hybrid structures a photochemical deposition strategy. The growth patterns of a Pt shell can be finely controlled by adjusting the growth kinetics, resulting in a varying deposition rate. In particular, the as-prepared Pd@Pt HNCs with a Pt shell in the Stranski-Krastanov mode showed the best performances over a wide pH range media, delivering low overpotentials of 33, 18 and 49 mV, resulting in a catalytic current density of 10 mA cm at a low effective catalyst loading of 0.021 mg cm. The resulting Tafel slopes were 23.1, 52.6 and 42.7 mV dec in 0.5 M HSO, 1.0 M phosphate-buffered saline (PBS) and 1.0 M KOH electrolyte, respectively. It was found that the increased fraction of unsaturated coordination of Pt islands in the resultant material is the key to the enhanced and robust HER activity, which has been confirmed through density functional theory (DFT) calculations. This strategy could be extended to the rational design and synthesis of other heterostructured catalysts for energy conversion and storage.
异质结构纳米晶体（HNCs）的合理设计对于开发高效析氢反应（HER）电催化剂具有重要意义。然而，一个重大挑战仍然在于直接在载体上实现所需HNCs的可控合成，并探索其结构-活性依赖的HER性能。在此，我们报道了通过光化学沉积策略制备的具有最佳混合结构的各种可控Pd@Pt核壳HNCs。通过调节生长动力学可以精细控制Pt壳的生长模式，从而导致沉积速率的变化。特别地，以Stranski-Krastanov模式制备的具有Pt壳的Pd@Pt HNCs在宽pH范围的介质中表现出最佳性能，在低有效催化剂负载量为0.021 mg cm时，提供33、18和49 mV的低过电位，从而产生10 mA cm的催化电流密度。在0.5 M HSO、1.0 M磷酸盐缓冲盐水（PBS）和1.0 M KOH电解质中，所得的塔菲尔斜率分别为23.1、52.6和42.7 mV dec。研究发现，所得材料中Pt岛的不饱和配位分数增加是HER活性增强和稳健的关键，这已通过密度泛函理论（DFT）计算得到证实。该策略可扩展到用于能量转换和存储的其他异质结构催化剂的合理设计和合成。
