Quantifying the Two-Dimensional Driving Patterns of Chemisorbed Oxygen and Particle Size on NO Reduction Activity and Mechanism.
Quantifying the Two-Dimensional Driving Patterns of Chemisorbed Oxygen and Particle Size on NO Reduction Activity and Mechanism.
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DOI：
10.1021/acsami.3c05162
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发表时间：
2023-07
影响因子：
9.5
通讯作者：
Wentao Mu;Shichao Ma;Hao Chen;Tengfei Liu;Jinxing Long;Q. Zeng;Xue-hui Li
中科院分区：
文献类型：
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作者：
Wentao Mu;Shichao Ma;Hao Chen;Tengfei Liu;Jinxing Long;Q. Zeng;Xue-hui Li
非均相催化剂的构效关系和反应机理的活性描述符驱动模式的量化仍然是一个巨大的挑战，迫切需要解决。本文以典型的mn基催化剂为例，基于活性规律和诸多表征，提出了化学吸附氧密度（ρOβ）和粒径（dTEM）作为NO选择性催化还原的二维描述符，其作用分别是量化空位缺陷的含量和位于平台或界面上的活性位点的数量。它们可以用来构建和量化NO还原的构效关系和反应机制的驱动模式。因此，用拟合函数定量地描述了ρOβ和dTEM对Ea的互补调制。此外，基于原位漫反射红外傅里叶变换光谱（DRIFTS）的构效关系和量化规律，确定了特定组合nox -中间体的反应效率（RE）是驱动Langmuir-Hinshelwood机制的触发因素，并根据拟合的量化函数由描述子互补协同调节。两个描述符中的任何一个在其低值处都对Ea和RE起主导作用，并且主导因子是逐步演变的：当采用Ea和RE对描述符的依赖性来识别主导因子和域时，dTEM↔dTEM与ρOβ相耦合。因此，这项工作已经定量地解释了活性调节的本质，并可能为反应活性的定量驱动模式和机制提供见解。
Quantification in the driving patterns of activity descriptors on structure-activity relationships and reaction mechanisms over heterogeneous catalysts is still a great challenge and needs to be addressed urgently. Herein, with the example of typical Mn-based catalysts, based on the activity regularity and many characterizations, the chemisorbed oxygen density (ρOβ) and particle size (dTEM) have been proposed as the two-dimensional descriptors for selective catalytic reduction of NO, whose role is in quantifying the contents of vacancy defects and the amounts of active sites located on terraces or interfaces, respectively. They can be utilized to construct and quantify the driving patterns for the structure-activity relationships and reaction mechanisms of NO reduction. As a consequence, a complementary modulation for Ea by ρOβ and dTEM is described quantitatively in terms of the fitted functions. Moreover, based on the structure-activity relationships and the quantification laws of in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the reaction efficiency (RE) of the specific combined NOx-intermediate is identified as the trigger to drive the Langmuir-Hinshelwood mechanism and modulated by the descriptors complementally and collaboratively following the fitted quantification functions. Either of the two descriptors at its lower values plays a dominant role in regulating Ea and RE, and the dominant factor evolves progressively: dTEM ↔ coupling dTEM with ρOβ ↔ ρOβ, when the dependency of Ea and RE on the descriptors is adopted to identify the dominant factor and domains. Therefore, this work has quantitatively accounted for the essence of activity modulation and may provide insight into the quantitative driving patterns for reaction activity and mechanism.