Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites
The thermolytic transformation of lignocellulosic spent coffee grounds to superior redox-active carbocatalyst (denoted as NBC) via nitrogen functionalization in a pyrolytic environment at various temperatures was investigated. The intrinsic (e.g. surface chemistry, degree of graphitization, etc.) an...
| Main Authors: | , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2020
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| Online Access: | https://hdl.handle.net/10356/138360 |
| _version_ | 1811691661022986240 |
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| author | Oh, Wen-Da Lisak, Grzegorz Webster, Richard David Liang, Yen-Nan Veksha, Andrei Giannis, Apostolos Moo, James Guo Sheng Lim, Jun-Wei Lim, Teik-Thye |
| author2 | School of Civil and Environmental Engineering |
| author_facet | School of Civil and Environmental Engineering Oh, Wen-Da Lisak, Grzegorz Webster, Richard David Liang, Yen-Nan Veksha, Andrei Giannis, Apostolos Moo, James Guo Sheng Lim, Jun-Wei Lim, Teik-Thye |
| author_sort | Oh, Wen-Da |
| collection | NTU |
| description | The thermolytic transformation of lignocellulosic spent coffee grounds to superior redox-active carbocatalyst (denoted as NBC) via nitrogen functionalization in a pyrolytic environment at various temperatures was investigated. The intrinsic (e.g. surface chemistry, degree of graphitization, etc.) and extrinsic (e.g. specific surface area, morphology, etc.) properties of the catalysts were systematically studied using various characterization techniques. The three main N configurations conducive to redox reactions, namely pyrrolic N, pyridinic N and graphitic N were present at different compositions in all the NBCs prepared at pyrolysis temperature ≥500 °C. The NBCs were used as peroxymonosulfate (PMS) activator for degrading bisphenol A. It was found that NBC-1000 (prepared at 1000 °C) has the highest catalytic performance (kapp = 0.072 min−1) due to the relatively higher specific surface area (438 m2 g−1), excellent degree of graphitization, and optimum N bonding configuration ratio. Based on the radical scavenger and electron paramagnetic resonance studies, the nonradical pathway involving 1O2 generation is identified as the prevailing pathway while the radical pathway involving SO4[rad]−and [rad]OH generation is the recessive pathway. Further investigation of the durability of surface active sites revealed that the active sites undergo N bonding configuration reconstruction and cannibalistic oxidation (increase in surface oxygen content) during PMS activation reaction. The graphitic N manifest greater catalytic activity and stability compared to pyridinic N and pyrrolic N under oxidizing environment. The results demonstrated that reaction optimization is critical to improve the durability of the catalyst. This study provides useful insights in converting lignocellulosic biomass waste into functional catalytic material, and the strategy to improve the durability of carbocatalysts for redox-based reactions. |
| first_indexed | 2024-10-01T06:23:26Z |
| format | Journal Article |
| id | ntu-10356/138360 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:23:26Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1383602020-05-05T02:10:47Z Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites Oh, Wen-Da Lisak, Grzegorz Webster, Richard David Liang, Yen-Nan Veksha, Andrei Giannis, Apostolos Moo, James Guo Sheng Lim, Jun-Wei Lim, Teik-Thye School of Civil and Environmental Engineering School of Physical and Mathematical Sciences Nanyang Environment and Water Research Institute Science::Chemistry Lignocellulosic Waste Peroxymonosulfate The thermolytic transformation of lignocellulosic spent coffee grounds to superior redox-active carbocatalyst (denoted as NBC) via nitrogen functionalization in a pyrolytic environment at various temperatures was investigated. The intrinsic (e.g. surface chemistry, degree of graphitization, etc.) and extrinsic (e.g. specific surface area, morphology, etc.) properties of the catalysts were systematically studied using various characterization techniques. The three main N configurations conducive to redox reactions, namely pyrrolic N, pyridinic N and graphitic N were present at different compositions in all the NBCs prepared at pyrolysis temperature ≥500 °C. The NBCs were used as peroxymonosulfate (PMS) activator for degrading bisphenol A. It was found that NBC-1000 (prepared at 1000 °C) has the highest catalytic performance (kapp = 0.072 min−1) due to the relatively higher specific surface area (438 m2 g−1), excellent degree of graphitization, and optimum N bonding configuration ratio. Based on the radical scavenger and electron paramagnetic resonance studies, the nonradical pathway involving 1O2 generation is identified as the prevailing pathway while the radical pathway involving SO4[rad]−and [rad]OH generation is the recessive pathway. Further investigation of the durability of surface active sites revealed that the active sites undergo N bonding configuration reconstruction and cannibalistic oxidation (increase in surface oxygen content) during PMS activation reaction. The graphitic N manifest greater catalytic activity and stability compared to pyridinic N and pyrrolic N under oxidizing environment. The results demonstrated that reaction optimization is critical to improve the durability of the catalyst. This study provides useful insights in converting lignocellulosic biomass waste into functional catalytic material, and the strategy to improve the durability of carbocatalysts for redox-based reactions. 2020-05-05T02:10:47Z 2020-05-05T02:10:47Z 2018 Journal Article Oh, W.-D., Lisak, G., Webster, R. D., Liang, Y.-N., Veksha, A., Giannis, A., . . . Lim, T.-T. (2018). Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites. Applied Catalysis B: Environmental, 233, 120-129. doi:10.1016/j.apcatb.2018.03.106 0926-3373 https://hdl.handle.net/10356/138360 10.1016/j.apcatb.2018.03.106 2-s2.0-85044843289 233 120 129 en Applied Catalysis B: Environmental © 2018 Elsevier B.V. All rights reserved. This paper was published in Applied Catalysis B: Environmental and is made available with permission of Elsevier B.V. |
| spellingShingle | Science::Chemistry Lignocellulosic Waste Peroxymonosulfate Oh, Wen-Da Lisak, Grzegorz Webster, Richard David Liang, Yen-Nan Veksha, Andrei Giannis, Apostolos Moo, James Guo Sheng Lim, Jun-Wei Lim, Teik-Thye Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title | Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title_full | Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title_fullStr | Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title_full_unstemmed | Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title_short | Insights into the thermolytic transformation of lignocellulosic biomass waste to redox-active carbocatalyst : durability of surface active sites |
| title_sort | insights into the thermolytic transformation of lignocellulosic biomass waste to redox active carbocatalyst durability of surface active sites |
| topic | Science::Chemistry Lignocellulosic Waste Peroxymonosulfate |
| url | https://hdl.handle.net/10356/138360 |
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