Nguyen Vu, Etz Brian D, Pylypenko Svitlana, Vyas Shubham
Department of Chemistry, Colorado School of Mines, 1012 14th Street, Golden, Colorado 80401, United States.
ACS Omega. 2021 Oct 15;6(42):28215-28228. doi: 10.1021/acsomega.1c04306. eCollection 2021 Oct 26.
This study explored the fundamental chemical intricacies behind the interactions between metal catalysts and carbon supports with graphitic nitrogen defects. These interactions were probed by examining metal adsorption, specifically, the location of adsorption and the electronic structure of metal catalysts as the basis for the metal-support interactions (MSIs). A computational framework was developed, and a series of 12 transition metals was systematically studied over various graphene models with graphitic nitrogen defect(s). Different modeling approaches served to provide insights into previous MSI computational discrepancies, reviewing both truncated and periodic graphene models. The computational treatment affected the magnitudes of adsorption energies between the metals and support; however, metals generally followed the same trends in their MSI. It was found that the addition of the nitrogen dopant improved the MSI by promoting electronic rearrangement from the metals' d- to s-orbitals for greater orbital overlap with the carbon support, shown with increased favorable adsorption. Furthermore, the study observed periodic trends that were adept descriptors of the MSI fundamental chemistries.
本研究探讨了金属催化剂与具有石墨氮缺陷的碳载体之间相互作用背后的基本化学复杂性。通过研究金属吸附来探究这些相互作用，具体而言，吸附位置以及金属催化剂的电子结构作为金属-载体相互作用（MSIs）的基础。开发了一个计算框架，并在具有石墨氮缺陷的各种石墨烯模型上系统地研究了一系列12种过渡金属。不同的建模方法有助于深入了解先前MSI计算中的差异，同时回顾了截断和周期性石墨烯模型。计算处理影响了金属与载体之间吸附能的值；然而，金属在其MSI中通常遵循相同的趋势。研究发现，氮掺杂剂的加入通过促进电子从金属的d轨道重排到s轨道，以与碳载体实现更大的轨道重叠，从而改善了MSI，表现为有利吸附增加。此外该研究观察到了周期性趋势，这些趋势是MSI基本化学的合适描述符。
