Unraveling the synergistic effects of trapping and active sites on SO₂/H₂O-resistance of transition-metal modified Ce-TiO₂ dual-site catalysts via DFT calculation

IF 5.4 2区化学 Q2 CHEMISTRY, PHYSICAL

Colloids and Surfaces A: Physicochemical and Engineering Aspects Pub Date : 2025-07-17 DOI:10.1016/j.colsurfa.2025.137790

Guomeng Zhang , Ye Jiang , Yichao Xu , Jiayao Song , Yingyuan Zhuang , Weihong Wu , Zhengda Yang

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引用次数: 0

Abstract

Achieving SO₂/H₂O resistance in Ce-based catalysts remains challenging for stationary source NO_x elimination. This study proposes dual-functional CMT catalysts with separated SO₂/H₂O-trapping sites (M-O_2 C-Ti) and active Ce sites. The density functional theory (DFT) was applied to screen the optimal modified CMT catalysts by calculating the adsorption properties, electronic interactions and reaction pathways. The M-O_2 C-Ti structure is employed to trap SO₂/H₂O to avoid sulfation/hydration of the Ce site. Among seventeen transition-metals, Cr, Mn, Fe, Co, Ni-modulated M-O_2 C-Ti structures exhibit excellent SO₂/H₂O-trapping ability. This is attributed to more electron transfer at trapping sites. The NH₃-SCR reaction pathways contain five processes: NH₃ adsorption, NH₃ dissociation, N-N coupling, H transfers, and N-O breaking. NH₃ dissociation and H transfers were the most difficult elementary reactions to perform. Through the calculation of adsorption energy difference and free energy barrier, it is found that the Co doping can not only safeguard active Ce site from sulfation/hydration with Co-O_2 C-Ti structure as SO₂/H₂O-trapping site, but also exhibit excellent SO₂/H₂O-resistance for NH₃-SCR performance of active Ce site even after sulfation/hydration. The research results provide new insights into the mechanism of transition metal doping on the resistance of catalysts to SO₂/H₂O, giving theoretical guidance for the rational design of catalysts.

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通过DFT计算揭示了捕获和活性位点对过渡金属修饰Ce-TiO 2双位点催化剂so2 /H 2阻力的协同效应

实现铈基催化剂的SO2/H2O抗性仍然是固定源NOx消除的挑战。本研究提出了具有分离SO2/ h2o捕获位点（M-O2 C-Ti）和活性Ce位点的双功能CMT催化剂。利用密度泛函理论（DFT）对改性CMT催化剂的吸附性能、电子相互作用和反应途径进行了筛选。M-O2 C-Ti结构被用来捕获SO2/H2O，以避免Ce位点的磺化/水化。在17种过渡金属中，Cr, Mn, Fe, Co， ni调制的M-O2 C-Ti结构表现出优异的SO2/ h2o捕获能力。这是由于在捕获点有更多的电子转移。NH3- scr反应途径包括5个过程：NH3吸附、NH3解离、N-N偶联、H转移和N-O断裂。NH3解离和H转移是最难进行的基本反应。通过对吸附能差和自由能势的计算，发现Co掺杂不仅可以保护活性Ce位点不受Co- o2 C-Ti结构作为SO2/ h2o捕集位点的硫磺化/水化作用，而且在硫磺化/水化作用后活性Ce位点的NH3-SCR性能也表现出优异的SO2/ h2o抗性。研究结果为过渡金属掺杂对催化剂抗SO2/H2O性能的影响机理提供了新的认识，为催化剂的合理设计提供了理论指导。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Colloids and Surfaces A: Physicochemical and Engineering Aspects 化学-物理化学

CiteScore

8.70

自引率

9.60%

发文量

2421

审稿时长

56 days

期刊介绍： Colloids and Surfaces A: Physicochemical and Engineering Aspects is an international journal devoted to the science underlying applications of colloids and interfacial phenomena. The journal aims at publishing high quality research papers featuring new materials or new insights into the role of colloid and interface science in (for example) food, energy, minerals processing, pharmaceuticals or the environment.