A combined DFT calculation and experimental study of the mechanism of the SCR of NOx by NH3 over Fe-doped CoMn2O4.

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-06-18 DOI:10.1039/d5cp01422k

Yulong Deng,Jiacheng Zheng,Wenting Chen,Xu Wang,Chengliao Deng,Xiaoming Cai,Jinming Cai,Honglin Tan

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引用次数: 0

Abstract

NH3 selective catalytic reduction (SCR) is a promising method for NOx removal, but its low-temperature effectiveness and narrow operating window limit industrial use. This study demonstrates, through DFT calculations and experimental validation, that Fe-doped CoMn2O4 (CoFe0.1Mn1.9O4) catalysts can effectively enhance catalytic activity. Through the in-depth study of NH3-SCR, it was found that the NH3 adsorption on the catalyst surface might be significantly enhanced by the doping of Fe (Eads = -1.29 eV → -1.42 eV), and it was also further demonstrated that the NH3 had a better adsorption energy on the surface of the CoFe0.1Mn1.9O4 catalyst through the electron difference density (EDD) and partial density of states (PDOS). In addition to this, the CoFe0.1Mn1.9O4 catalyst not only reduces the first step of the dehydrogenation reaction of NH3 (Eα = 0.86 eV → 0.83 eV), but also lowers the energy barrier of the NH3-SCR (Eα = 1.11 eV → 0.86 eV). All these calculations demonstrate that Fe doping has the potential to significantly enhance catalytic performance. CoMn2O4 and Fe-doped CoMn2O4 (CoFe0.02Mn1.98O4) catalysts were synthesized using sol-gel and impregnation techniques, respectively. Through characterization and performance testing, CoFe0.02Mn1.98O4 is found to exhibit a more efficient NOx conversion (87% at 250 °C), and its N2 selectivity is also slightly improved (64%), which matches with the calculation results. In this study, a method to improve the denitrification efficiency of CoMn2O4 spinel catalysts was proposed, which provides a new idea for the development of CoMn2O4 catalysts.

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结合DFT计算和实验研究了NH3在掺铁CoMn2O4上SCR NOx的机理。

氨选择性催化还原（NH3 selective catalytic reduction， SCR）是一种很有前途的脱硝方法，但其低温效率低、操作窗口窄限制了其工业应用。本研究通过DFT计算和实验验证表明，fe掺杂的CoMn2O4 （cofe0.1 mn1.90 o4）催化剂可以有效提高催化活性。通过对NH3- scr的深入研究，发现Fe的掺杂（Eads = -1.29 eV→-1.42 eV）可以显著增强催化剂表面对NH3的吸附，并通过电子差密度（EDD）和偏态密度（PDOS）进一步证明了NH3在cofe0.1 mn1.90 o4催化剂表面具有更好的吸附能。此外，cofe0.1 mn1.90 o4催化剂不仅降低了NH3脱氢反应的第一步反应（Eα = 0.86 eV→0.83 eV），而且降低了NH3- scr的能垒（Eα = 1.11 eV→0.86 eV）。所有这些计算表明，Fe掺杂具有显著提高催化性能的潜力。采用溶胶-凝胶法和浸渍法分别合成了CoMn2O4和fe掺杂CoMn2O4 （CoFe0.02Mn1.98O4）催化剂。通过表征和性能测试，发现CoFe0.02Mn1.98O4在250℃时具有更高的NOx转化率（87%），其N2选择性也略有提高（64%），这与计算结果相吻合。本研究提出了一种提高CoMn2O4尖晶石催化剂脱氮效率的方法，为CoMn2O4催化剂的发展提供了新的思路。

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

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.