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...

Full description

Saved in:
Bibliographic Details
Main Authors: Paul, Ratul, Shit, Subhash Chandra, Singh, Arunima, Wong, Roong Jien, Dao, Duy Quang, Joseph, Boby, Liu, Wen, Bhattacharya, Saswata, Mondal, John
Other Authors: School of Chemical and Biomedical Engineering
Format: Article
Language:English
Published: 2022
Subjects:
Online Access:https://hdl.handle.net/10356/161704
Tags: Add Tag
No Tags, Be the first to tag this record!
Institution: Nanyang Technological University
Language: English
id sg-ntu-dr.10356-161704
record_format dspace
spelling sg-ntu-dr.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
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Chemical engineering
Catalyst Selectivity
Heteroatoms
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
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.
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
format Article
author 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
title 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_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_sort organogel-assisted porous organic polymer embedding cu nps for selectivity control in the semi hydrogenation of alkynes
publishDate 2022
url https://hdl.handle.net/10356/161704
_version_ 1787136613905596416