Sun Hui-Ying, Ding Yu, Yue Ya-Qi, Xue Qi, Li Fu-Min, Jiang Jia-Xing, Chen Pei, Chen Yu
Key Laboratory of Macromolecular Science of Shaanxi Province, Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an 710062, PR China.
ACS Appl Mater Interfaces. 2021 Mar 24;13(11):13149-13157. doi: 10.1021/acsami.0c22106. Epub 2021 Mar 10.
The rational design of advanced electrocatalysts and energy-saving electrolysis strategies is highly desirable for achieving high-efficiency electrochemical H generation yet challenging. In this work, we report highly branched Pd hydride nanodendrites (PdH-NDs) formed by a very facial solvothermal method and a succedent chemical H intercalation method in ,-dimethylformamide. The electrocatalytic performance of PdH-NDs is experimentally and theoretically correlated with the morphology and composition, which has demonstrated substantially enhanced electrochemical activity and stability for formate oxidation reaction and hydrogen evolution reaction in alkaline electrolyte compared with Pd nanodendrites. Density functional theory calculations suggest a downshift of the Pd d-band center of PdH-NDs due to the dominant Pd-H ligand effects that weaken the binding energies of the intermediate catalytic species and toxic carbon monoxide. The asymmetric formate electrolyzer based on bifunctional PdH-ND electrocatalysts is first constructed, which only requires a low voltage of 0.54 V at 10 mA cm for continuous H generation. This study reveals significant insights about the morphology/composition-performance relationship for palladium hydrides with bifunctional electroactivity.
合理设计先进的电催化剂和节能电解策略对于实现高效电化学产氢至关重要，但仍具有挑战性。在这项工作中，我们报道了通过一种非常简便的溶剂热法以及后续在N，N-二甲基甲酰胺中的化学氢嵌入法形成的高度分支的氢化钯纳米枝晶（PdH-NDs）。通过实验和理论将PdH-NDs的电催化性能与形态和组成相关联，结果表明，与钯纳米枝晶相比，其在碱性电解质中对甲酸氧化反应和析氢反应具有显著增强的电化学活性和稳定性。密度泛函理论计算表明，由于占主导地位的Pd-H配体效应，PdH-NDs的Pd d带中心下移，这削弱了中间催化物种和有毒一氧化碳的结合能。首次构建了基于双功能PdH-ND电催化剂的不对称甲酸盐电解槽，在10 mA cm²下连续产氢仅需0.54 V的低电压。这项研究揭示了关于具有双功能电活性的钯氢化物的形态/组成-性能关系的重要见解。
