突破金属催化剂火山形活度曲线的峰高限制：不同表面结构对过渡金属氧化物的作用,The Journal of Physical Chemistry C

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突破金属催化剂火山形活度曲线的峰高限制：不同表面结构对过渡金属氧化物的作用
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2021-12-21 , DOI: 10.1021/acs.jpcc.1c08089
Jianfu Chen ₁ , Menglei Jia _{1,

2} , Jinglin Wang ₁ , Peijun Hu _{1,

2} , Haifeng Wang ₁

Affiliation

火山形活性曲线长期以来一直用于揭示不同催化剂之间的活性趋势，是催化剂筛选的基本工具。虽然通常曲线的峰值高度被认为是可能的最高活动，但对其起源和内在约束的理解仍然是一个相对开放的问题。在此，基于微动力学分析和第一性原理计算，我们定量证明了峰高受催化剂表面结构特征的强烈影响，并且可以通过减少 Brønsted-Evans-Polanyi (BEP) 的截距来大大提高关系。我们以各种过渡金属氧化物（TMO）为重点，探索了小分子解离的 BEP 关系，发现截距小于扁平金属的截距。这种截距的减少源于氧化物表面独特的局部结构，这导致了较弱的结合能力和更多的终态过渡态。以NO氧化为例，我们说明金红石型氧化物的活性曲线在典型的中高温下明显高于金属，表明金红石型氧化物具有固有的优越活性。此外，还讨论了 TMO 在突破金属分子解离活性极限方面的一般应用。我们说明金红石型氧化物的活性曲线在典型的中高温下明显高于金属，这表明金红石型氧化物具有固有的优越活性。此外，还讨论了 TMO 在突破金属分子解离活性极限方面的一般应用。我们说明金红石型氧化物的活性曲线在典型的中高温下明显高于金属，这表明金红石型氧化物具有固有的优越活性。此外，还讨论了 TMO 在突破金属分子解离活性极限方面的一般应用。

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Breaking through the Peak Height Limit of the Volcano-Shaped Activity Curve for Metal Catalysts: Role of Distinct Surface Structures on Transition Metal Oxides

The volcano-shaped activity curve has long been used to reveal the activity trends among different catalysts and is a fundamental tool for catalyst screening. Although generally the peak height of the curve is considered as the highest possible activity, the understanding for its origin and inherent constraints is still a comparatively open issue. Herein, on the basis of microkinetic analysis and first-principles calculations, we quantitatively demonstrate that the peak height is strongly affected by the structural features of catalyst surfaces and could be largely improved by reducing the intercept of the Brønsted–Evans–Polanyi (BEP) relation. Focusing on various transition metal oxides (TMOs), we explore the BEP relations for the dissociation of small molecules, and the intercepts are shown to be smaller than those of flat metals. This reduction in intercept originates from the distinct local structure of oxide surfaces, which contributes to the weak binding ability and more final-state-like transition state. Taking NO oxidation as an example, we illustrate that the activity curve of rutile-type oxides is obviously higher than metals at typical medium–high temperatures, suggesting that rutile-type oxides possess inherently superior activity. Furthermore, general application of TMOs in breaking through the activity limit of metals for molecule dissociation is discussed.

更新日期：2022-01-13

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