Performance of density functional theory for describing hetero‐metallic active‐site motifs for methane‐to‐methanol conversion in metal‐exchanged zeolites
Performance of density functional theory for describing hetero‐metallic active‐site motifs for methane‐to‐methanol conversion in metal‐exchanged zeolites
复制标题
密度泛函理论的性能用于描述金属交换沸石中甲烷向甲醇转化的异金属活性位点基序
DOI：
10.1002/jcc.25714
复制
发表时间：
2018
影响因子：
3
通讯作者：
Odoh, Samuel O.
中科院分区：
文献类型：
--
作者：
Dandu, Naveen K.;Adeyiga, Olajumoke;Panthi, Dipak;Bird, Shaina A.;Odoh, Samuel O.
通过铜交换沸石可以以高甲醇选择性促进甲烷至甲醇转化（MMC）。然而，关于使用这些沸石来促进MMC方法，存在两个开放的问题。第一个问题是在逐步MMC工艺中通过这些沸石以等温方式操作三个循环的可能性。第二个问题是通过用其他地球上丰富的过渡金属系统地取代这些活性位点中的一些铜中心来提高甲醇产率的可能性。量子力学计算可用于比较氧化铜物种和类似混合金属系统的甲烷活化。为了进行这样的筛选，重要的是我们使用准确且计算负担得起的理论方法来描述异金属催化物质的性质。我们已经研究了47个交换相关密度泛函的性能，用于预测六种异质金属[M-O-Cu]2+和[M-O2-Cu]2+（其中M = Co，Fe和Ni）的相对自旋态能量和化学反应性，通过与耦合团簇理论（包括迭代单，双激发以及三重激发的微扰处理）CCSD（T）进行比较。我们还对其中一些系统进行了多参考计算。我们考虑了与MMC相关的两种类型的反应（氢加成和氧加成）。我们建议使用τ-HCTH和OLYP来确定异金属基序中的自旋态能量分裂。ω B 97、ω B 97 X、ω B 97 X-D3和MN 15在预测氢和氧加成反应的能量方面表现最好。相比之下，局部和半局部泛函的化学反应性较差。使用[Fe-O-Cu]2+作为测试，我们看到非局部泛函对甲烷C = H活化势垒表现良好。相比之下，半局部泛函的表现相当差。© 2018 Wiley Periodicals，Inc.
Methane‐to‐methanol conversion (MMC) can be facilitated with high methanol selectivities by copper‐exchanged zeolites. There are however two open questions regarding the use of these zeolites to facilitate the MMC process. The first concerns the possibility of operating the three cycles in the stepwise MMC process by these zeolites in an isothermal fashion. The second concerns the possibility of improving the methanol yields by systematic substitution of some copper centers in these active sites with other earth‐abundant transition metals. Quantum‐mechanical computations can be used to compare methane activation by copper oxide species and analogous mixed‐metal systems. To carry out such screening, it is important that we use theoretical methods that are accurate and computationally affordable for describing the properties of the hetero‐metallic catalytic species. We have examined the performance of 47 exchange‐correlation density functionals for predicting the relative spin‐state energies and chemical reactivities of six hetero‐metallic [M‐O‐Cu]2+and [M‐O2‐Cu]2+, (where MCo, Fe, and Ni), species by comparison with coupled cluster theory including iterative single, double excitations as well as perturbative treatment of triple excitations, CCSD(T). We also performed multireference calculations on some of these systems. We considered two types of reactions (hydrogen addition and oxygen addition) that are relevant to MMC. We recommend the use of τ‐HCTH and OLYP to determine the spin‐state energy splittings in the hetero‐metallic motifs. ωB97, ωB97X, ωB97X‐D3, and MN15 performed best for predicting the energies of the hydrogen and oxygen addition reactions. In contrast, local, and semilocal functionals do poorly for chemical reactivity. Using [Fe‐O‐Cu]2+as a test, we see that the nonlocal functionals perform well for the methane CH activation barrier. In contrast, the semilocal functionals perform rather poorly. © 2018 Wiley Periodicals, Inc.
登录
查看更多内容
DOI：
10.1063/1.4981521
发表时间：
2017-04
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Masaaki Saitow;Ute Becker;Christoph Riplinger;Edward F. Valeev;F. Neese
通讯作者：
Masaaki Saitow;Ute Becker;Christoph Riplinger;Edward F. Valeev;F. Neese
一种新的直接 CI 方法，用于小轨道空间中的大 CI 扩展
DOI：
--
发表时间：
1984
期刊：
影响因子：
--
作者：
P. Siegbahn
通讯作者：
P. Siegbahn
DOI：
10.1021/jp058212b
发表时间：
2005-12
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
M. Liao;J. Watts;Ming-Ju Huang
通讯作者：
M. Liao;J. Watts;Ming-Ju Huang
多构型自洽场论和密度泛函理论能否正确预测金属-金属键配合物的基态？
影响因子：
5.5
作者：
Rebecca K. Carlson;S. Odoh;Stephen J. Tereniak;Connie C. Lu;L. Gagliardi
通讯作者：
L. Gagliardi
使用从头计算和离子淌度质谱法分析糖肽离子的分子结构
DOI：
--
发表时间：
2019
期刊：
影响因子：
--
作者：
中村賀美;竹内孝江
通讯作者：
竹内孝江