Actinyl-Modified g-C3N4 as CO2 Activation Materials for Chemical Conversion and Environmental Remedy via an Artificial Photosynthetic Route.,Inorganic Chemistry

当前位置： X-MOL 学术 › Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Actinyl-Modified g-C3N4 as CO2 Activation Materials for Chemical Conversion and Environmental Remedy via an Artificial Photosynthetic Route.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-05-29 , DOI: 10.1021/acs.inorgchem.0c00791
Raza Ullah Shah Bacha ₁ , Li Li ₁ , Yuan-Ru Guo ₂ , Liqiang Jing ₁ , Qing-Jiang Pan ₁

Affiliation

With the reported CO₂ activation for the oxidation of benzene to phenol (-ENE → -OL) by the graphitic carbon nitride g-C₃N₄ (CN) via an artificial photosynthetic route as inspiration, high-valent actinyls (An^mO₂)ⁿ⁺ (An = U, Np, Pu; m = VI, V; n = 2, 1) have been introduced for its further modification. Our calculations indicate thermodynamic spontaneity in the feasibility of g-C₃N₄-(An^mO₂)ⁿ⁺ (CN-An^m) formation. The magnificent structural and electronic properties of CN-An^m are utilized for CO₂ activation in terms of the rarely studied -ENE → -OL conversion. The calculated free energies show that most steps of the catalytic cycle are favored by CN-An^m complexes. The first step (carbamate formation) is slightly endothermic in all cases, where CN-U is 0.51 eV higher than CN and CN-Pu is −0.01 eV lower. All benzene addition reactions release energy, with that for CN-U being the lowest. The phenolate formation is favored by some actinyl complexes over CN, and CN-U is only 0.23 eV higher. The phenol release (resulting in formamide complexes) and CO desorption are exothermic for all CN-An^m. The overall process suggests the improved catalytic performance of actinyl-modified CN materials, and the slightly depleted uranyl-carbon nitride could be one of the promising catalysts.

中文翻译：

in系修饰的g-C3N4作为CO2活化材料，可通过人工光合作用途径进行化学转化和环境修复。

据报道，通过人工光合作用的石墨碳氮化物gC ₃ N ₄（CN）激发了CO ₂活化苯氧化为苯酚（-ENE→-OL）的作用，因此，高价act化基（An ^m O ₂）ⁿ⁺（An = U，Np，Pu; m = VI，V; n = 2，1）已被引入以作进一步修改。我们的计算表明在gC ₃ N _4-（An ^m O ₂）ⁿ⁺（CN-An ^m）形成。就很少研究的-ENE→-OL转化而言，CN-An ^m的出色的结构和电子性质可用于CO ₂活化。计算出的自由能表明，CN-An ^m配合物有利于催化循环的大多数步骤。在所有情况下，第一步（氨基甲酸酯形成）都略有吸热，其中CN-U比CN高0.51 eV ，CN-Pu低-0.01 eV。所有苯加成反应均释放能量，其中CN-U的能量最低。某些act基配合物比CN和CN-U更有利于酚盐的形成仅高出0.23 eV。所有CN-An ^m的苯酚释放（导致甲酰胺络合物）和CO解吸是放热的。整个过程表明，in化基改性的CN材料具有更高的催化性能，略微耗尽的铀酰-碳氮化物可能是有前途的催化剂之一。

更新日期：2020-05-29

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南