Flexible Single‐Atom Cesium Sites on Amorphous MgO Nano‐Cushions for Enhanced CO2‐Involved Multi‐Step Reactions DOI

Qiuyan Cao,

Wenqiang Sun, Zhen Yin

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Abstract Single atomic sites (SAs) face challenges in catalyzing complex chemical processes involving multiple intermediates due to rigid coordination environments, steric hindrances, and limited activation behaviors. Herein, an alloying‐mediated element repartition method is developed synthesize flexible cesium single‐atom catalysts, anchoring Cs single on precisely controlled amorphous‐MgO/crystalline NbC hetero‐phase nano‐supports. The amorphousMgO(a‐MgO) equipped 1 ‐a‐MgO/NbC achieves 91% yield the cyclization of CO 2 with 2‐aminobenzonitrile within a gas–liquid–solid triphasic system, outperforming its counterpart fabricated crystalline MgO, ‐c‐MgO/NbC catalyst (only 23%). shows excellent tolerance various functional groups sustainable catalysis, especially removing traditional requirement for high‐pressure conditions additives. Operando spectroscopic characterizations theoretical calculations demonstrate that sandwich‐structural enhances consecutive through vertically adsorbed configurations during C‐N coupling N‐heterocyclic ring formation. SAs supported by a‐MgO nano‐cushions allow adaptability dynamic transformations via tensile Cs‐O compressive Mg─O bonds, ultimately reducing energy barriers critical rearrangement isomerization steps. This study provides valuable insights into designing SACs overcome limitations support interfaces, thereby enhancing performance toward multi‐intermediate conversion heterogeneous catalytic transformations.

Language: Английский

Unusual 1,1‐Dicarboxylation Selectivity in the Domino Hydrocarboxylation of Alkynes with Formate and Application in Polyimide Photoresists DOI Open Access
Yaxin Sun, Peng Yang, Jian‐Biao Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

We report for the first time a photoinduced domino 1,1-dicarboxylation of alkynes synthesis malonic acid derivatives using cesium formate solution (80% w/w in water), which is different from previous 1,2-dicarboxylation methods that usually produce succinic acids. Cesium malonate precipitated directly diluted reaction mixture and was collected by filtration without further purification. Interestingly, solid with additional water led to mono-carboxylation product. The solubility alkaline environment are two key factors contributing outcome. A series acids, propionic acids drug intermediates were synthesized good yields. Mechanism experiments DFT calculations indicate formed through α-selective addition CO2 •- cinnamate intermediate. This method enables direct preparation water-soluble carboxylate-functionalized molecules polymers hydrophobic alkyne-containing precursors, showing potential usability photolithography semiconductor manufacturing.

Language: Английский

Citations

1
Encapsulation of chiral CoII(R,R)(salen) in mesocellular foam as an efficient heterogeneous catalyst for asymmetric electrocarboxylation of 1-phenylethyl chloride with CO2 DOI

M. J. Li,

Feng Zhang, Baoen Shan

et al.

Journal of Organometallic Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 123621 - 123621

Published: March 1, 2025

Language: Английский

Citations

0
Flexible Single‐Atom Cesium Sites on Amorphous MgO Nano‐Cushions for Enhanced CO2‐Involved Multi‐Step Reactions DOI

Qiuyan Cao,

Wenqiang Sun, Zhen Yin

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Abstract Single atomic sites (SAs) face challenges in catalyzing complex chemical processes involving multiple intermediates due to rigid coordination environments, steric hindrances, and limited activation behaviors. Herein, an alloying‐mediated element repartition method is developed synthesize flexible cesium single‐atom catalysts, anchoring Cs single on precisely controlled amorphous‐MgO/crystalline NbC hetero‐phase nano‐supports. The amorphousMgO(a‐MgO) equipped 1 ‐a‐MgO/NbC achieves 91% yield the cyclization of CO 2 with 2‐aminobenzonitrile within a gas–liquid–solid triphasic system, outperforming its counterpart fabricated crystalline MgO, ‐c‐MgO/NbC catalyst (only 23%). shows excellent tolerance various functional groups sustainable catalysis, especially removing traditional requirement for high‐pressure conditions additives. Operando spectroscopic characterizations theoretical calculations demonstrate that sandwich‐structural enhances consecutive through vertically adsorbed configurations during C‐N coupling N‐heterocyclic ring formation. SAs supported by a‐MgO nano‐cushions allow adaptability dynamic transformations via tensile Cs‐O compressive Mg─O bonds, ultimately reducing energy barriers critical rearrangement isomerization steps. This study provides valuable insights into designing SACs overcome limitations support interfaces, thereby enhancing performance toward multi‐intermediate conversion heterogeneous catalytic transformations.

Language: Английский

Citations

0