Bifunctional Catalysts with Core–Shell Distributed ZrO2 and Co Nanoparticles Derived from MOF-on-MOF Heterostructures for Economical One-Pot Tandem CO2 Fixation,ACS Catalysis

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Bifunctional Catalysts with Core–Shell Distributed ZrO2 and Co Nanoparticles Derived from MOF-on-MOF Heterostructures for Economical One-Pot Tandem CO2 Fixation
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-06-08 , DOI: 10.1021/acscatal.3c01604
Ze Qin _{1,

2} , Liyu Chen _{1,

2} , Yingwei Li _{1,

2} , Kui Shen _{1,

2}

Affiliation

The N-formylation of aryl amines with CO₂ is an emerging strategy to simultaneously reduce carbon emission and produce high-value formamides. Considering that aryl amines are usually produced from the hydrogenation of their corresponding nitroarenes in the chemical industry, the one-pot tandem hydrogenation–formylation of nitroarenes with CO₂ to formamides is obviously a much more economical but still unexploited strategy for efficient CO₂ fixation. Herein, we report the rational synthesis of bifunctional catalysts with core–shell distributed ZrO₂ and Co nanoparticles (NPs) from the controlled pyrolysis of a ZIF-67-on-UiO-66 heterostructure for this one-pot tandem reaction. To fabricate such MOF-on-MOF heterostructures, we develop a facile surfactant-assisted strategy to seed ZIF-8 nuclei on the UiO-66 surface, followed by the successful growth of a thickness-controlled ZIF-67 shell on the UIO-66 core. Based on further pyrolysis, the highly mesoporous derivants with core–shell distributed ZrO₂ and Co NPs can be obtained, of which the reductive Co and Lewis basic ZrO₂ can serve as highly active sites for the hydrogenation of nitroarenes and the N-formylation of aryl amines with CO₂, respectively, due to their favorable electronic structures and good mass diffusion of reactants/intermediates. Impressively, the optimized core–shell catalyst achieves a much higher yield of N-(4-methoxyphenyl)formamide (99.5%) than its ZrO₂/C (0%), Co-NC (14.1%), and physically mixed counterparts (52.3%) for the one-pot tandem hydrogenation–formylation between 4-nitroanisole and CO₂ with good recyclability and a broad substrate scope, shedding light on the rational design of efficient bifunctional catalysts for this tandem CO₂ fixation reaction.

中文翻译：

具有源自 MOF-on-MOF 异质结构的核壳分布 ZrO2 和 Co 纳米颗粒的双功能催化剂，用于经济的一锅串联 CO2 固定

芳胺与CO ₂的N-甲酰化是一种新兴策略，可同时减少碳排放并生产高价值甲酰胺。_{考虑到化学工业中芳胺通常是通过相应硝基芳烃的氢化生产的，硝基芳烃与CO 2}的一锅串联氢化-甲酰化反应生成甲酰胺显然是一种更经济但尚未开发的有效CO 2固定_策略。在此，我们报道了核壳分布ZrO _{2双功能催化剂的合理合成}和 Co 纳米颗粒 (NP)，来自 ZIF-67-on-UiO-66 异质结构的受控热解，用于这一一锅串联反应。为了制造这种 MOF-on-MOF 异质结构，我们开发了一种简便的表面活性剂辅助策略，在 UiO-66 表面上接种 ZIF-8 核，然后在 UIO-66 上成功生长厚度控制的 ZIF-67 壳核。通过进一步热解，可以获得核壳分布的ZrO _{2和Co NPs的高介孔衍生物，其中还原性Co和Lewis碱性ZrO}₂可以作为硝基芳烃加氢和N-甲酰化的高活性位点。芳基胺与CO ₂分别由于其良好的电子结构和反应物/中间体良好的质量扩散。令人印象深刻的是，优化的核壳催化剂实现了比 ZrO ₂ /C (0%)、Co-NC (14.1%) 和物理混合催化剂更高的N- (4-甲氧基苯基)甲酰胺产率 (99.5%) （ 52.3%）用于4-硝基苯甲醚和CO ₂之间的一锅串联加氢-甲酰化反应，具有良好的可回收性和广泛的底物范围，为该串联CO ₂固定反应的高效双功能催化剂的合理设计提供了思路。

更新日期：2023-06-08

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