Xiaoxiao Wang, Hao Yang, Moxuan Liu, Zhaojun Liu, Kai Liu, Zerui Mu, Yan Zhang, Tao Cheng* and Chuanbo Gao*,
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引用次数: 0
摘要
贵金属纳米晶体在有效催化以电化学乙醇氧化反应(EOR)为代表的多步骤、多电子转移过程方面面临挑战,原因是中间产物的结合能之间存在线性比例关系,阻碍了单个元素步骤的独立优化。在此,我们开发了具有一系列接近的局部表面结合亲和力的贵金属纳米晶体,以克服这一挑战。实验证明,通过对钯表面施加拉伸应变并用离散的金原子进行装饰,就能在客体分子附近形成具有不同亲和力的多种结合位点,这一点已通过二氧化碳探测和密度泛函理论计算得到证实。这种表面可使反应中间产物根据每个元素步骤的需要在不同结合位点之间迁移,从而与在单一位点上的反应相比,降低了整个 EOR 的能量障碍。在这些定制表面上,我们在 EOR 中获得了 32.7 mA cm-2 和 47.8 A mgPd-1 的比活度和质量活度,分别是商用 Pd/C 的 10.9 倍和 43.8 倍,超过了最先进的钯基催化剂。这些结果凸显了这种方法在改善各种多步骤、多电子转移反应方面的前景,而这些反应对于能源转换应用至关重要。
Noble metal nanocrystals face challenges in effectively catalyzing electrochemical ethanol oxidation reaction (EOR)-represented multistep, multielectron transfer processes due to the linear scaling relationship among binding energies of intermediates, impeding independent optimization of individual elemental steps. Herein, we develop noble metal nanocrystals with a range of local surface binding affinities in close proximity to overcome this challenge. Experimentally, this is demonstrated by applying tensile strain to a Pd surface and decorating it with discrete Au atoms, forming a diversity of binding sites with varying affinities in close proximity for guest molecules, as evidenced by CO probing and density functional theory calculations. Such a surface enables reaction intermediates to migrate between different binding sites as needed for each elemental step, thereby reducing the energy barrier for the overall EOR when compared to reactions at a single site. On these tailored surfaces, we attain specific and mass activities of 32.7 mA cm–2 and 47.8 A mgPd–1 in EOR, surpassing commercial Pd/C by 10.9 and 43.8 times, respectively, and outperforming state-of-the-art Pd-based catalysts. These results highlight the promise of this approach in improving a variety of multistep, multielectron transfer reactions, which are crucial for energy conversion applications.
期刊介绍:
ACS Nano, published monthly, serves as an international forum for comprehensive articles on nanoscience and nanotechnology research at the intersections of chemistry, biology, materials science, physics, and engineering. The journal fosters communication among scientists in these communities, facilitating collaboration, new research opportunities, and advancements through discoveries. ACS Nano covers synthesis, assembly, characterization, theory, and simulation of nanostructures, nanobiotechnology, nanofabrication, methods and tools for nanoscience and nanotechnology, and self- and directed-assembly. Alongside original research articles, it offers thorough reviews, perspectives on cutting-edge research, and discussions envisioning the future of nanoscience and nanotechnology.