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Efficient aerial oxidation of different types of alcohols using ZnO nanoparticle–MnCO3-graphene oxide composites
Authors:Syed Farooq Adil  Mohamed E Assal  Mohammed Rafi Shaik  Mufsir Kuniyil  Azhar Hashmi  Mujeeb Khan  Aslam Khan  Muhammad Nawaz Tahir  Abdulrahman Al-Warthan  Mohammed Rafiq H Siddiqui
Institution:1. Chemistry Department, College of Science, King Saud University, P.O. 2455, Riyadh, 11451 Kingdom of Saudi Arabia;2. SABIC Technology and Innovation, Riyadh, Kingdom of Saudi Arabia;3. King Abdullah Institute for Nanotechnology, King Saud University, Riyadh, 11451 Kingdom of Saudi Arabia;4. Chemistry Department, King Fahd University of Petroleum and Minerals, Dhahran, 31261 Kingdom of Saudi Arabia
Abstract:Graphene–metal nanocomposites have been found to remarkably enhance the catalytic performance of metal nanoparticle-based catalysts. In continuation of our previous report, in which highly reduced graphene oxide (HRG)-based nanocomposites were synthesized and evaluated, we present nanocomposites of graphene oxide (GRO) and ZnO nanoparticle-doped MnCO3 (ZnO–MnCO3/(1%)GRO]) synthesized via a facile, straightforward co-precipitation technique. Interestingly, it was noticed that the incorporation of GRO in the catalytic system could noticeably improve the catalytic efficiency compared to a catalyst (ZnO–MnCO3) without GRO, for aerial oxidation of benzyl alcohol (BzOH) employing O2 as a nature-friendly oxidant under base-free conditions. The impacts of various reaction factors were thoroughly explored to optimize reaction conditions using oxidation of BzOH to benzaldehyde (BzH) as a model substrate. The catalysts were characterized using X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, Energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET), and Raman spectroscopy. The (1%)ZnO–MnCO3/(1%)GRO exhibited significant specific activity (67 mmol.g−1.hr−1) with full convversion of BzOH and >99% BzH selectivity within just 6 min. The catalytic efficiency of the (1%)ZnO–MnCO3/(1%)GRO nanocomposite was significantly better than the (1%)ZnO–MnCO3/(1%)HRG and (1%)ZnO–MnCO3 catalysts, presumably due to the existence of oxygen-possessing groups on the GRO surface and as well as a very high surface area that could have been instrumental in uniformly dispersing the active sites of the catalyst, i.e., ZnO–MnCO3. Under optimum circumstances, various kinds of alcohols were selectively transformed to respective carbonyls with full convertibility over the (1%)ZnO–MnCO3/(1%)GRO catalyst. Furthermore, the highly effective (1%)ZnO–MnCO3/(1%)GRO catalyst could be successfully reused and recycled over five consecutive runs with a marginal reduction in its performance and selectivity.
Keywords:graphene  MnCO3  nanocomposite  oxidation  ZnO nanoparticles
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