A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis
Abstract The rational synthesis of a two‐dimensional (2D) porous aromatic framework (PAF) with a controllable growth direction remains a challenge to overcome the limitation of traditional stacked 2D materials. Herein, a step‐growth strategy is developed to fabricate a vertically oriented nitrogen‐r...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2023-10-01
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| Series: | Carbon Energy |
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| Online Access: | https://doi.org/10.1002/cey2.357 |
| _version_ | 1797510972338864128 |
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| author | Xiugang Li Qilu Yao Rongwei Shi Minsong Huang Zhang‐Hui Lu |
| author_facet | Xiugang Li Qilu Yao Rongwei Shi Minsong Huang Zhang‐Hui Lu |
| author_sort | Xiugang Li |
| collection | DOAJ |
| description | Abstract The rational synthesis of a two‐dimensional (2D) porous aromatic framework (PAF) with a controllable growth direction remains a challenge to overcome the limitation of traditional stacked 2D materials. Herein, a step‐growth strategy is developed to fabricate a vertically oriented nitrogen‐rich porous aromatic framework on graphene oxide (V‐PAF‐GO) using monolayer benzidine‐functionalized GO (BZ‐GO) as a molecular pillar. Then, the confined Co nanoparticle (NP) catalysts are synthesized by encapsulating ultra‐small Co into the slit pores of V‐PAF‐GO. Due to the high nitrogen content, large specific surface area, and adequate slit pores, the optimized vertical nanocomposites V‐PAF‐GO provide abundant anchoring sites for metal NPs, leading to ultrafine Co NPs (1.4 nm). The resultant Co/V‐PAF‐GO catalyst shows an extraordinary catalytic activity for ammonia borane (AB) methanolysis, yielding a turnover frequency value of 47.6 min−1 at 25°C, comparable to the most effective non‐noble‐metal catalysts ever reported for AB methanolysis. Experimental and density functional theory studies demonstrate that the electron‐donating effect of N species of PAF positively corresponds to the low barrier in methanol molecule activation, and the cleavage of the O–H bond in CH3OH has been proven to be the rate‐determining step for AB methanolysis. This work presents a versatile step‐growth strategy to prepare a vertically oriented PAF on GO to solve the stacking problem of 2D materials, which will be used to fabricate other novel 2D or 2D–2D materials with controllable orientation for various applications. |
| first_indexed | 2024-03-10T05:38:48Z |
| format | Article |
| id | doaj.art-e33bcfa16746442ab02fc6f7723ba7e5 |
| institution | Directory Open Access Journal |
| issn | 2637-9368 |
| language | English |
| last_indexed | 2024-03-10T05:38:48Z |
| publishDate | 2023-10-01 |
| publisher | Wiley |
| record_format | Article |
| series | Carbon Energy |
| spelling | doaj.art-e33bcfa16746442ab02fc6f7723ba7e52023-11-22T22:45:00ZengWileyCarbon Energy2637-93682023-10-01510n/an/a10.1002/cey2.357A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysisXiugang Li0Qilu Yao1Rongwei Shi2Minsong Huang3Zhang‐Hui Lu4Key Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Key Laboratory of Energy Catalysis and Conversion of Nanchang, National Engineering Research Center for Carbohydrate Synthesis, College of Chemistry and Chemical Engineering Jiangxi Normal University Nanchang ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Key Laboratory of Energy Catalysis and Conversion of Nanchang, National Engineering Research Center for Carbohydrate Synthesis, College of Chemistry and Chemical Engineering Jiangxi Normal University Nanchang ChinaCollege of Material and Chemical Engineering Tongren University Tongren ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Key Laboratory of Energy Catalysis and Conversion of Nanchang, National Engineering Research Center for Carbohydrate Synthesis, College of Chemistry and Chemical Engineering Jiangxi Normal University Nanchang ChinaKey Lab of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Key Laboratory of Energy Catalysis and Conversion of Nanchang, National Engineering Research Center for Carbohydrate Synthesis, College of Chemistry and Chemical Engineering Jiangxi Normal University Nanchang ChinaAbstract The rational synthesis of a two‐dimensional (2D) porous aromatic framework (PAF) with a controllable growth direction remains a challenge to overcome the limitation of traditional stacked 2D materials. Herein, a step‐growth strategy is developed to fabricate a vertically oriented nitrogen‐rich porous aromatic framework on graphene oxide (V‐PAF‐GO) using monolayer benzidine‐functionalized GO (BZ‐GO) as a molecular pillar. Then, the confined Co nanoparticle (NP) catalysts are synthesized by encapsulating ultra‐small Co into the slit pores of V‐PAF‐GO. Due to the high nitrogen content, large specific surface area, and adequate slit pores, the optimized vertical nanocomposites V‐PAF‐GO provide abundant anchoring sites for metal NPs, leading to ultrafine Co NPs (1.4 nm). The resultant Co/V‐PAF‐GO catalyst shows an extraordinary catalytic activity for ammonia borane (AB) methanolysis, yielding a turnover frequency value of 47.6 min−1 at 25°C, comparable to the most effective non‐noble‐metal catalysts ever reported for AB methanolysis. Experimental and density functional theory studies demonstrate that the electron‐donating effect of N species of PAF positively corresponds to the low barrier in methanol molecule activation, and the cleavage of the O–H bond in CH3OH has been proven to be the rate‐determining step for AB methanolysis. This work presents a versatile step‐growth strategy to prepare a vertically oriented PAF on GO to solve the stacking problem of 2D materials, which will be used to fabricate other novel 2D or 2D–2D materials with controllable orientation for various applications.https://doi.org/10.1002/cey2.3572D–2D materialsammonia boranegraphene oxidemethanolysisporous aromatic frameworks |
| spellingShingle | Xiugang Li Qilu Yao Rongwei Shi Minsong Huang Zhang‐Hui Lu A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis Carbon Energy 2D–2D materials ammonia borane graphene oxide methanolysis porous aromatic frameworks |
| title | A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis |
| title_full | A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis |
| title_fullStr | A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis |
| title_full_unstemmed | A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis |
| title_short | A step‐growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide: Hybrid material‐confined Co for ammonia borane methanolysis |
| title_sort | step growth strategy to grow vertical porous aromatic framework nanosheets on graphene oxide hybrid material confined co for ammonia borane methanolysis |
| topic | 2D–2D materials ammonia borane graphene oxide methanolysis porous aromatic frameworks |
| url | https://doi.org/10.1002/cey2.357 |
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