Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors
Biomass hydrodeoxygenation catalysts innovation from atomistic activity predictors
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DOI：
10.1098/rsta.2020.0056
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发表时间：
2020-07
期刊：
影响因子：
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通讯作者：
Fabian Morteo-Flores;Julien Engel;A. Roldan
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文献类型：
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作者：
Fabian Morteo-Flores;Julien Engel;A. Roldan
循环经济强调转化涉及经济增长的产品和改善生态系统的思想，以减少过度使用原材料造成的负面后果。这可以通过使用将工农业废物转化为散装化学品的第二代生物质来实现。使用催化过程对于从木质纤维生物质中实现生物燃料的可行升级至关重要。我们用密度泛函理论计算了13种过渡金属作为催化剂的性质与它们对氢和氧的亲和力之间的关系，它们是生物质价态中的关键物种。这些参数的关系将决定生物质衍生化合物加氢脱氧(HDO)过程的趋势。我们发现，在最稳定位置的氢和氧的吸附能与这些金属的电子性质呈线性关系，这将使表面结合生物质衍生化合物的能力合理化，并打破C-O键。这将加速用于生物质衍生物(如愈创木酚和苯甲醚等)的低温高效HDO工艺的催化剂创新。在所考察的单金属催化剂中，标度关系表明，根据d带中心和d带宽度模型，Ni具有良好的氢氧亲和力平衡。将计算的参数与愈创木酚在被调查表面上的吸附强度进行比较表明，仅凭d带性质并不能很好地描述这一趋势。相反，我们发现功函数和d波段属性的线性组合提供了显著更好的相关性。本文是一个名为“实现循环经济的科学”讨论会议议题的一部分。
Circular economy emphasizes the idea of transforming products involving economic growth and improving the ecological system to reduce the negative consequences caused by the excessive use of raw materials. This can be achieved with the use of second-generation biomass that converts industrial and agricultural wastes into bulk chemicals. The use of catalytic processes is essential to achieve a viable upgrade of biofuels from the lignocellulosic biomass. We carried out density functional theory calculations to explore the relationship between 13 transition metals (TMs) properties, as catalysts, and their affinity for hydrogen and oxygen, as key species in the valourization of biomass. The relation of these parameters will define the trends of the hydrodeoxygenation (HDO) process on biomass-derived compounds. We found the hydrogen and oxygen adsorption energies in the most stable site have a linear relation with electronic properties of these metals that will rationalize the surface's ability to bind the biomass-derived compounds and break the C–O bonds. This will accelerate the catalyst innovation for low temperature and efficient HDO processes on biomass derivates, e.g. guaiacol and anisole, among others. Among the monometallic catalysts explored, the scaling relationship pointed out that Ni has a promising balance between hydrogen and oxygen affinities according to the d-band centre and d-band width models. The comparison of the calculated descriptors to the adsorption strength of guaiacol on the investigated surfaces indicates that the d-band properties alone are not best suited to describe the trend. Instead, we found that a linear combination of work function and d-band properties gives significantly better correlation. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.