Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols
In recent years, the development of green mechanochemical processes for the synthesis of new catalysts with higher catalytic efficacy and selectivity has received manifest interest. In continuation of our previous study, in which graphene oxide (GRO) and highly reduced graphene oxide (HRG) based nan...
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| Format: | Article |
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MDPI AG
2020-10-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/10/10/1136 |
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| author | Mufsir Kuniyil J. V. Shanmukha Kumar Syed Farooq Adil Mohamed E. Assal Mohammed Rafi Shaik Mujeeb Khan Abdulrahman Al-Warthan Mohammed Rafiq H. Siddiqui Aslam Khan Muhammad Bilal Hafiz M. N. Iqbal Waheed A. Al-Masry |
| author_facet | Mufsir Kuniyil J. V. Shanmukha Kumar Syed Farooq Adil Mohamed E. Assal Mohammed Rafi Shaik Mujeeb Khan Abdulrahman Al-Warthan Mohammed Rafiq H. Siddiqui Aslam Khan Muhammad Bilal Hafiz M. N. Iqbal Waheed A. Al-Masry |
| author_sort | Mufsir Kuniyil |
| collection | DOAJ |
| description | In recent years, the development of green mechanochemical processes for the synthesis of new catalysts with higher catalytic efficacy and selectivity has received manifest interest. In continuation of our previous study, in which graphene oxide (GRO) and highly reduced graphene oxide (HRG) based nanocomposites were prepared and assessed, herein, we have explored a facile and solvent-less mechanochemical approach for the synthesis of N-doped graphene (NDG)/mixed metal oxide (MnCO<sub>3</sub>–ZrO<sub>2</sub>) ((X%)NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub>), as the (X%)NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> nano-composite was synthesized using physical grinding of separately synthesized NDG and pre-calcined (300 °C) MnCO<sub>3</sub>–ZrO<sub>2</sub> via green milling method. The structures of the prepared materials were characterized in detail using X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Analysis (EDX), Fourier-transform infrared spectroscopy (FTIR), Raman, Thermogravimetric analysis (TGA), and N<sub>2</sub> adsorption-desorption isotherm analysis. Besides, the obtained nanocomposites were employed as heterogeneous oxidation catalyst for the alcohol oxidation using green oxidant O<sub>2</sub> without involving any surfactants or bases. The reaction factors were systematically studied during the oxidation of benzyl alcohol (PhCH<sub>2</sub>OH) as the model reactant to benzaldehyde (PhCHO). The NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> exhibits premium specific activity (66.7 mmol·g<sup>−1</sup>·h<sup>−1</sup>) with 100% conversion of PhCH<sub>2</sub>OH and > 99.9% selectivity to PhCHO after only 6 min. The mechanochemically prepared NDG based nanocomposite exhibited notable improvement in the catalytic efficacy as well as the surface area compared to the pristine MnCO<sub>3</sub>–ZrO<sub>2</sub>. Under the optimal circumstances, the NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> catalyst could selectively catalyze the aerobic oxidation of a broad array of alcohols to carbonyls with full convertibility without over-oxidized side products like acids. The NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> catalyst were efficiently reused for six subsequent recycling reactions with a marginal decline in performance and selectivity. |
| first_indexed | 2024-03-10T15:53:46Z |
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| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T15:53:46Z |
| publishDate | 2020-10-01 |
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| series | Catalysts |
| spelling | doaj.art-3f729649ff1540adbc0dd876d1b9e8672023-11-20T15:48:35ZengMDPI AGCatalysts2073-43442020-10-011010113610.3390/catal10101136Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of AlcoholsMufsir Kuniyil0J. V. Shanmukha Kumar1Syed Farooq Adil2Mohamed E. Assal3Mohammed Rafi Shaik4Mujeeb Khan5Abdulrahman Al-Warthan6Mohammed Rafiq H. Siddiqui7Aslam Khan8Muhammad Bilal9Hafiz M. N. Iqbal10Waheed A. Al-Masry11Department of Chemistry, Koneru Lakshmaiah Education Foundation, Vaddeswaram, Guntur 522502, AP, IndiaDepartment of Chemistry, Koneru Lakshmaiah Education Foundation, Vaddeswaram, Guntur 522502, AP, IndiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh 11451, Saudi ArabiaKing Abdullah Institute for Nanotechnology, King Saud University, Riyadh 11451, Saudi ArabiaSchool of Life Science and Food Engineering, Huaiyin Institute of Technology, Huaian 223003, ChinaTecnologico de Monterrey, School of Engineering and Sciences, Campus Monterrey, Ave. Eugenio Garza Sada 2501, Monterrey CP 64849, N.L., MexicoChemical Engineering Department, College of Engineering, King Saud University, P.O. 800, Riyadh 11451, Saudi ArabiaIn recent years, the development of green mechanochemical processes for the synthesis of new catalysts with higher catalytic efficacy and selectivity has received manifest interest. In continuation of our previous study, in which graphene oxide (GRO) and highly reduced graphene oxide (HRG) based nanocomposites were prepared and assessed, herein, we have explored a facile and solvent-less mechanochemical approach for the synthesis of N-doped graphene (NDG)/mixed metal oxide (MnCO<sub>3</sub>–ZrO<sub>2</sub>) ((X%)NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub>), as the (X%)NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> nano-composite was synthesized using physical grinding of separately synthesized NDG and pre-calcined (300 °C) MnCO<sub>3</sub>–ZrO<sub>2</sub> via green milling method. The structures of the prepared materials were characterized in detail using X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), Energy Dispersive X-Ray Analysis (EDX), Fourier-transform infrared spectroscopy (FTIR), Raman, Thermogravimetric analysis (TGA), and N<sub>2</sub> adsorption-desorption isotherm analysis. Besides, the obtained nanocomposites were employed as heterogeneous oxidation catalyst for the alcohol oxidation using green oxidant O<sub>2</sub> without involving any surfactants or bases. The reaction factors were systematically studied during the oxidation of benzyl alcohol (PhCH<sub>2</sub>OH) as the model reactant to benzaldehyde (PhCHO). The NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> exhibits premium specific activity (66.7 mmol·g<sup>−1</sup>·h<sup>−1</sup>) with 100% conversion of PhCH<sub>2</sub>OH and > 99.9% selectivity to PhCHO after only 6 min. The mechanochemically prepared NDG based nanocomposite exhibited notable improvement in the catalytic efficacy as well as the surface area compared to the pristine MnCO<sub>3</sub>–ZrO<sub>2</sub>. Under the optimal circumstances, the NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> catalyst could selectively catalyze the aerobic oxidation of a broad array of alcohols to carbonyls with full convertibility without over-oxidized side products like acids. The NDG/MnCO<sub>3</sub>–ZrO<sub>2</sub> catalyst were efficiently reused for six subsequent recycling reactions with a marginal decline in performance and selectivity.https://www.mdpi.com/2073-4344/10/10/1136ZrO<sub>2</sub>MnCO<sub>3</sub>N-doped graphenenanocompositescatalystalcohols |
| spellingShingle | Mufsir Kuniyil J. V. Shanmukha Kumar Syed Farooq Adil Mohamed E. Assal Mohammed Rafi Shaik Mujeeb Khan Abdulrahman Al-Warthan Mohammed Rafiq H. Siddiqui Aslam Khan Muhammad Bilal Hafiz M. N. Iqbal Waheed A. Al-Masry Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols Catalysts ZrO<sub>2</sub> MnCO<sub>3</sub> N-doped graphene nanocomposites catalyst alcohols |
| title | Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols |
| title_full | Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols |
| title_fullStr | Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols |
| title_full_unstemmed | Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols |
| title_short | Eco-Friendly and Solvent-Less Mechanochemical Synthesis of ZrO<sub>2</sub>–MnCO<sub>3</sub>/N-Doped Graphene Nanocomposites: A Highly Efficacious Catalyst for Base-Free Aerobic Oxidation of Various Types of Alcohols |
| title_sort | eco friendly and solvent less mechanochemical synthesis of zro sub 2 sub mnco sub 3 sub n doped graphene nanocomposites a highly efficacious catalyst for base free aerobic oxidation of various types of alcohols |
| topic | ZrO<sub>2</sub> MnCO<sub>3</sub> N-doped graphene nanocomposites catalyst alcohols |
| url | https://www.mdpi.com/2073-4344/10/10/1136 |
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