Zhu Dandan, Huang Yu, Shi Xianjin, Li Rong, Wang Zhenyu, Peng Wei, Cao Junji, Lee Shuncheng
Key Laboratory of Aerosol Chemistry and Physics, State Key Laboratory of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an 710061, China.
Center for Excellence in Quaternary Science and Global Change, Chinese Academy of Sciences, Xi'an 710061, China.
PNAS Nexus. 2025 Jan 6;4(1):pgae594. doi: 10.1093/pnasnexus/pgae594. eCollection 2025 Jan.
Modulating the electronic structure of noble metals via electronic metal-support interaction (EMSI) has been proven effectively for facilitating molecular oxygen activation and catalytic oxidation reactions. Nevertheless, the investigation of the fundamental mechanisms underlying activity enhancement has primarily focused on metal oxides as supports, especially in the catalytic degradation of volatile organic compounds. In this study, a novel Pt catalyst supported on nitrogen-doped carbon encapsulating FeNi alloy, featuring ultrafine Pt nanoparticles, was synthesized. This catalyst demonstrated exceptional catalytic activity (92%), recyclability, and water tolerance for the deep oxidation of formaldehyde at room temperature. Structural analyses and theoretical calculations revealed a directional electron transfer from FeNi alloy to Pt, even there is no direct contact between them. This electron penetration effect, mediated by carbon, conferred electron-rich properties to Pt, leading to the activation of molecular oxygen by elongating O-O bond length (1.405 Å). Consequently, efficient formaldehyde removal was achieved with an ultra-low Pt loading. This investigation offers a novel perspective on modulating the electronic structure of Pt by engineering a unique EMSI effect between a nonoxide support and active species, thereby enabling efficient oxygen activation for air purification.
通过电子金属-载体相互作用（EMSI）调节贵金属的电子结构已被证明能有效促进分子氧活化和催化氧化反应。然而，对活性增强背后基本机制的研究主要集中在金属氧化物作为载体上，特别是在挥发性有机化合物的催化降解方面。在本研究中，合成了一种负载在包裹FeNi合金的氮掺杂碳上的新型Pt催化剂，其具有超细Pt纳米颗粒。该催化剂在室温下对甲醛深度氧化表现出优异的催化活性（92%）、可回收性和耐水性。结构分析和理论计算表明，即使FeNi合金与Pt之间没有直接接触，也存在从FeNi合金到Pt的定向电子转移。这种由碳介导的电子穿透效应赋予Pt富电子特性，通过延长O-O键长度（1.405 Å）导致分子氧活化。因此，在超低Pt负载量下实现了高效的甲醛去除。本研究通过设计非氧化物载体与活性物种之间独特的EMSI效应，为调节Pt的电子结构提供了新的视角，从而实现了用于空气净化的高效氧活化。
