Understanding trends in C-H bond activation in heterogeneous catalysis
Understanding trends in C-H bond activation in heterogeneous catalysis
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DOI：
10.1038/nmat4760
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发表时间：
2017-02-01
期刊：
影响因子：
41.2
通讯作者：
Norskov, Jens K.
中科院分区：
文献类型：
--
作者：
Latimer, Allegra A.;Kulkarni, Ambarish R.;Norskov, Jens K.
尽管对能够将甲烷直接转化为更高价值的商品化学品和液体燃料的催化剂的研究已经活跃了超过世纪，但是用于选择性甲烷活化的可行的工业方法还有待开发（1）。电子结构计算在这一研究中发挥着越来越重要的作用，但大规模的材料筛选工作受到计算昂贵的过渡态势垒计算的阻碍。本函有两个目的。首先，我们表明，对于广泛的催化剂，通过自由基中间体进行，可以建立一个统一的框架，预测C-H活化障碍，使用一个单一的通用描述符。其次，我们结合联合收割机这种缩放方法与活性位点形成的热力学分析，以提供甲烷活化率的地图。我们的模型成功地合理化现有的经验数据，并奠定了基础，为未来的催化剂设计策略，超越不同的催化剂类。
While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed(1). Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.