Su Jiaqi, Feng Jie, Feng Yonggang, Liu Shangheng, Xu Bingyan, Lin Yue, Ye Jinyu, Zhang Ying, Li Youyong, Shao Qi, Huang Xiaoqing
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.
Institute of Functional Nano & Soft Materials (FUNSOM), Soochow University, Jiangsu 215123, China.
Precis Chem. 2023 Jul 3;1(6):363-371. doi: 10.1021/prechem.3c00055. eCollection 2023 Aug 28.
Developing a catalyst to break the tradeoff relationship between the catalytic activity and antipoisoning property toward the ethanol oxidation reaction (EOR) is of critical importance to the development of direct ethanol fuel cells (DEFCs), but remains challenging. Here, we developed a unique class of single-site Cu-doped PdSn wavy nanowires (denoted as SS Cu-PdSn WNWs) with promoted activity and durability toward alkaline EOR. Detailed characterizations reveal the atomic isolation of Cu species dispersed on the surface of the PdSn WNWs with distinct wavy structure and grain boundaries. The created SS Cu-PdSn WNWs exhibit an enhanced EOR performance in terms of mass activity, which is higher than those of PdSn WNWs, commercial Pd black, and commercial Pd/C, respectively. Moreover, the SS Cu-PdSn WNWs can also show improved stability as compared to other catalysts due to the improved antipoisoning property from the unique surface anchoring structure. Further investigations demonstrate that the doped SS Cu can strongly inhibit the adsorption of CO and promote the reaction process of EOR. DFT results reveal that the doped Cu shifts down the d-band center of PdSn, thereby modifying the adsorption of intermediates and reducing the reaction barrier of EOR. This work maps a pathway for optimally boosting EOR performance with surface engineering via atomic doping.
开发一种能够打破乙醇氧化反应（EOR）催化活性与抗中毒性能之间权衡关系的催化剂，对于直接乙醇燃料电池（DEFC）的发展至关重要，但仍然具有挑战性。在此，我们开发了一类独特的单原子掺杂铜的钯锡波浪状纳米线（记为SS Cu-PdSn WNWs），其对碱性EOR具有增强的活性和耐久性。详细表征揭示了分散在具有独特波浪状结构和晶界的钯锡WNWs表面的铜物种的原子级隔离。所制备的SS Cu-PdSn WNWs在质量活性方面表现出增强的EOR性能，分别高于钯锡WNWs、商业钯黑和商业钯/碳。此外，由于独特的表面锚固结构提高了抗中毒性能，SS Cu-PdSn WNWs与其他催化剂相比也表现出更好的稳定性。进一步研究表明，掺杂的SS Cu可以强烈抑制CO的吸附并促进EOR的反应过程。密度泛函理论（DFT）结果表明，掺杂的铜使钯锡的d带中心下移，从而改变了中间体的吸附并降低了EOR的反应势垒。这项工作通过原子掺杂表面工程为优化提高EOR性能开辟了一条途径。
