Rational catalyst structure design is expected to solve the low O utilization and poor molecular mass transfer efficiency in heterogeneous catalytic ozonation (HCO). Herein, Pt/CMK-3 catalyst with confined space to enhance mass transfer was synthesized and employed for CHSH removal. Unlike fully free diffusion in 0–2.0 wt% Pt/CMK-3 and bulk phase diffusion in 10.0 wt% Pt/CMK-3, removal efficiency of 5.0 wt% Pt/CMK-3 was significantly improved to 97.0%, which was attributed to the effective interfacial diffusion of O and CHSH through local microenvironment modulation of Pt/Pt nanoclusters (NCs) inducing synchronous mass transfer. Experimental and DFT calculations confirmed the strong electronic interactions between O and Pt facilitated charge redistribution and preferential O activation. AIMD simulation demonstrated that the synchronous difference in mean-square displacements (MSD) and diffusion coefficient (Dc) of CHSH (Dc=0.022) and O (Dc=0.0046) in the confined Pt/CMK-3 system could facilitate CHSH migrate to Pt through interfacial diffusion. Especially, the d-orbital electrons of Pt NCs interact sequentially with p-orbital electrons of CHSH and O to maintain redox of Pt/Pt. This study provides novel insights on effective mass transfer and kinetic properties of gaseous reaction between oxidant and pollutant by constructing unique interfacial diffusion behaviors.

中文翻译：

---

Pt0/Pt2+纳米团簇的局部微环境调节诱导同步传质效应以促进催化臭氧化


合理的催化剂结构设计有望解决多相催化臭氧化（HCO）中氧气利用率低和分子传质效率差的问题。在此，合成了具有有限空间以增强传质的 Pt/CMK-3 催化剂，并将其用于 CHSH 去除。与 0-2.0wt% Pt/CMK-3 中的完全自由扩散和 10.0wt% Pt/CMK-3 中的体相扩散不同，5.0wt% Pt/CMK-3 的去除效率显着提高至 97.0%，这归因于通过 Pt/Pt 纳米团簇 (NC) 的局部微环境调节诱导同步传质，实现 O 和 CHSH 的有效界面扩散。实验和 DFT 计算证实了 O 和 Pt 之间的强电子相互作用促进了电荷重新分布和优先 O 激活。 AIMD模拟表明，约束Pt/CMK-3系统中CHSH（Dc=0.022）和O（Dc=0.0046）的均方位移（MSD）和扩散系数（Dc）的同步差异可以促进CHSH向Pt迁移通过界面扩散。特别是，Pt NCs 的 d 轨道电子依次与 CHSH 和 O 的 p 轨道电子相互作用，以维持 Pt/Pt 的氧化还原。这项研究通过构建独特的界面扩散行为，为氧化剂和污染物之间的气态反应的有效传质和动力学特性提供了新的见解。