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Reaction of CO2 with Groups 4 and 6 Transition Metal Oxide Clusters
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpca.7b09462 Luis A. Flores 1 , Julia G. Murphy 1 , William B. Copeland 1 , David A. Dixon 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-11-07 00:00:00 , DOI: 10.1021/acs.jpca.7b09462 Luis A. Flores 1 , Julia G. Murphy 1 , William B. Copeland 1 , David A. Dixon 1
Affiliation
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Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the addition of CO2 to group 4 (MO2)n and group 6 (MO3)n (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid–base addition (physisorption) and formation of CO32– (chemisorption) of CO2 to these clusters were predicted. Physisorption and chemisorption of CO2 are predicted to be thermodynamically allowed for group 4 (MO2)n clusters, with chemisorption being more favored energetically. Correlations of the ligand binding energies (LBEs) for the group 4 clusters are made with the fluoride affinities and M–O and M═O bond strengths of the clusters. The LBEs for chemisorption on the Zr and Ti clusters are consistent with published experimental and computational studies of bulk solids. Physisorption LBEs for the Ti and Zr clusters are more exothermic than the bulk values, as the cluster models allow for better relaxation at the metal sites. Chemisorption is not predicted to occur with group 6 (MO3)n clusters, as the larger chemisorbed structures were all found to be metastable. CO2 is predicted to weakly physisorb to (WO3)n with physisorption correlating with the Lewis acidity of the metal site.
中文翻译：
CO 2与4和6族过渡金属氧化物簇的反应
密度泛函理论（DFT）和耦合聚类理论（CCSD（T））用于研究将CO 2添加到第4组（MO 2）n和第6组（MO 3）n（n = 1，2，3）纳米团簇。预测了路易斯酸碱添加（物理吸附）和向这些团簇形成CO 3 2–（化学吸附）CO 2所产生的结构和能量。预测第4组（MO 2）n在热力学上允许CO 2的物理吸附和化学吸附。团簇，化学吸附在能量上更受青睐。第4组团簇的配体结合能（LBE）与团簇的氟化物亲和力和M–O和M = O键强度相关。用于Zr和Ti团簇化学吸附的LBE与散装固体的已发表的实验和计算研究一致。Ti和Zr团簇的物理吸附LBE比散装值放热得多，因为团簇模型允许在金属部位更好地松弛。预计第6组（MO 3）n簇不会发生化学吸附，因为发现较大的化学吸附结构都是亚稳的。预计CO 2弱吸收到（WO 3）n 其物理吸附与金属位点的路易斯酸度有关。
更新日期：2017-11-08
中文翻译：
CO 2与4和6族过渡金属氧化物簇的反应
密度泛函理论（DFT）和耦合聚类理论（CCSD（T））用于研究将CO 2添加到第4组（MO 2）n和第6组（MO 3）n（n = 1，2，3）纳米团簇。预测了路易斯酸碱添加（物理吸附）和向这些团簇形成CO 3 2–（化学吸附）CO 2所产生的结构和能量。预测第4组（MO 2）n在热力学上允许CO 2的物理吸附和化学吸附。团簇，化学吸附在能量上更受青睐。第4组团簇的配体结合能（LBE）与团簇的氟化物亲和力和M–O和M = O键强度相关。用于Zr和Ti团簇化学吸附的LBE与散装固体的已发表的实验和计算研究一致。Ti和Zr团簇的物理吸附LBE比散装值放热得多，因为团簇模型允许在金属部位更好地松弛。预计第6组（MO 3）n簇不会发生化学吸附，因为发现较大的化学吸附结构都是亚稳的。预计CO 2弱吸收到（WO 3）n 其物理吸附与金属位点的路易斯酸度有关。
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