Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes
Heteroatom-rich porous-organic-polymers (POPs) comprising highly cross-linked robust skeletons with high physical and thermal stability, high surface area, and tunable pore size distribution have garnered significant research interest owing to their versatile functionalities in a wide range of appli...
| Main Authors: | , , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2022
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| Online Access: | https://hdl.handle.net/10356/161704 |
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| author | Paul, Ratul Shit, Subhash Chandra Singh, Arunima Wong, Roong Jien Dao, Duy Quang Joseph, Boby Liu, Wen Bhattacharya, Saswata Mondal, John |
| author2 | School of Chemical and Biomedical Engineering |
| author_facet | School of Chemical and Biomedical Engineering Paul, Ratul Shit, Subhash Chandra Singh, Arunima Wong, Roong Jien Dao, Duy Quang Joseph, Boby Liu, Wen Bhattacharya, Saswata Mondal, John |
| author_sort | Paul, Ratul |
| collection | NTU |
| description | Heteroatom-rich porous-organic-polymers (POPs) comprising highly cross-linked robust skeletons with high physical and thermal stability, high surface area, and tunable pore size distribution have garnered significant research interest owing to their versatile functionalities in a wide range of applications. Here, we report a newly developed organogel-assisted porous-organic-polymer (POP) supported Cu catalyst (Cu@TpRb-POP). The organogel was synthesized via a temperature induced gelation strategy, employing Schiff-base coupling between 2,4,6-triformylphloroglucinol aldehyde (Tp) and pararosaniline base (Rb). The gel is subsequently transformed to hierarchical porous organic structures without the use of any additive, thereby offering advantageous features including extremely low density, high surface area, a highly cross-linked framework, and a heteroatom-enriched backbone of the polymer. During the semi-hydrogenation of terminal and internal alkynes, the Cu@TpRb-POP-B catalyst with Cu embedded in the TpRb-POP structure consistently demonstrated improved selectivity towards alkenes compared to Cu@TpRb-POP-A, which contains Cu NPs exposed at the exterior surfaces of the POP support. Additionally, Cu@TpRb-POP-B showed higher stability and reusability than Cu@TpRb-POP-A. The superior performance of the Cu@TpRb-POP-B catalyst is attributed to the steric hindrance effect, which controls the product selectivity, as well as the synergistic interaction between the heteroatom-rich POP framework and the embedded Cu NPs. Both the effects are corroborated by experimental characterization of the catalysts and density functional theory (DFT) calculations. |
| first_indexed | 2024-10-01T05:30:48Z |
| format | Journal Article |
| id | ntu-10356/161704 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T05:30:48Z |
| publishDate | 2022 |
| record_format | dspace |
| spelling | ntu-10356/1617042023-12-29T06:49:19Z Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes Paul, Ratul Shit, Subhash Chandra Singh, Arunima Wong, Roong Jien Dao, Duy Quang Joseph, Boby Liu, Wen Bhattacharya, Saswata Mondal, John School of Chemical and Biomedical Engineering Engineering::Chemical engineering Catalyst Selectivity Heteroatoms Heteroatom-rich porous-organic-polymers (POPs) comprising highly cross-linked robust skeletons with high physical and thermal stability, high surface area, and tunable pore size distribution have garnered significant research interest owing to their versatile functionalities in a wide range of applications. Here, we report a newly developed organogel-assisted porous-organic-polymer (POP) supported Cu catalyst (Cu@TpRb-POP). The organogel was synthesized via a temperature induced gelation strategy, employing Schiff-base coupling between 2,4,6-triformylphloroglucinol aldehyde (Tp) and pararosaniline base (Rb). The gel is subsequently transformed to hierarchical porous organic structures without the use of any additive, thereby offering advantageous features including extremely low density, high surface area, a highly cross-linked framework, and a heteroatom-enriched backbone of the polymer. During the semi-hydrogenation of terminal and internal alkynes, the Cu@TpRb-POP-B catalyst with Cu embedded in the TpRb-POP structure consistently demonstrated improved selectivity towards alkenes compared to Cu@TpRb-POP-A, which contains Cu NPs exposed at the exterior surfaces of the POP support. Additionally, Cu@TpRb-POP-B showed higher stability and reusability than Cu@TpRb-POP-A. The superior performance of the Cu@TpRb-POP-B catalyst is attributed to the steric hindrance effect, which controls the product selectivity, as well as the synergistic interaction between the heteroatom-rich POP framework and the embedded Cu NPs. Both the effects are corroborated by experimental characterization of the catalysts and density functional theory (DFT) calculations. Submitted/Accepted version R. P. and S. C. S. acknowledge DST-INSPIRE (GAP-0799) and the Council of Scientific and Industrial Research (CSIR), New Delhi, for their respective senior research fellowships. J. M. acknowledges the Department of Science and Technology, India, for the DST-INSPIRE Faculty Research Project Grant (GAP-0522), CSIR-YSA Research Grant (reference no. HRDG/ YSA-19/02/21(0045)/2019) and Focused Basic Research (FBR) Grant under the CLP theme (reference no. 34/1/TD-CLP/ NCP-FBR 2020-RPPBDD-TMD-SeMI) for financial support at CSIR-IICT, Hyderabad. 2022-09-15T08:45:16Z 2022-09-15T08:45:16Z 2022 Journal Article Paul, R., Shit, S. C., Singh, A., Wong, R. J., Dao, D. Q., Joseph, B., Liu, W., Bhattacharya, S. & Mondal, J. (2022). Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes. Nanoscale, 14(4), 1505-1519. https://dx.doi.org/10.1039/d1nr07255b 2040-3364 https://hdl.handle.net/10356/161704 10.1039/d1nr07255b 35029265 2-s2.0-85123901521 4 14 1505 1519 en Nanoscale © 2022 The Royal Society of Chemistry. All rights reserved. This paper was published in Nanoscale and is made available with permission of The Royal Society of Chemistry. application/pdf |
| spellingShingle | Engineering::Chemical engineering Catalyst Selectivity Heteroatoms Paul, Ratul Shit, Subhash Chandra Singh, Arunima Wong, Roong Jien Dao, Duy Quang Joseph, Boby Liu, Wen Bhattacharya, Saswata Mondal, John Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title | Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title_full | Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title_fullStr | Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title_full_unstemmed | Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title_short | Organogel-assisted porous organic polymer embedding Cu NPs for selectivity control in the semi hydrogenation of alkynes |
| title_sort | organogel assisted porous organic polymer embedding cu nps for selectivity control in the semi hydrogenation of alkynes |
| topic | Engineering::Chemical engineering Catalyst Selectivity Heteroatoms |
| url | https://hdl.handle.net/10356/161704 |
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