Solventless Mechanochemical Fabrication of ZnO–MnCO3/N-Doped Graphene Nanocomposite: Efficacious and Recoverable Catalyst for Selective Aerobic Dehydrogenation of Alcohols under Alkali-Free Conditions

Catalysts

Mufsir Kuniyil¹  Abdulrahman Al-Warthan¹  Mohamed E. Assal¹  Mohammed Rafi Shaik¹  Mohammed Rafiq H. Siddiqui¹  Syed Farooq Adil¹  Mujeeb Khan¹  Aslam Khan²  Hamid Shaikh³  Zeeshan Nawaz⁴  Abdulrahman I. Alharthi⁵ 

[1] Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia;King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2454, Riyadh 11451, Saudi Arabia;SABIC Polymer Research Center (SPRC), Department of Chemical Engineering, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia;SABIC Technology & Innovation, P.O. Box 5101, Riyadh 11422, Saudi Arabia;The Department of Chemistry, College of Sciences and Humanities, Prince Sattam Bin Abdulaziz University, P.O. Box 173, Al-Kharj 11942, Saudi Arabia;

关键词: ZnO nanoparticles;    nitrogen doped graphene;    nanocomposite;    MnCO₃;    oxidation;    catalyst;   

DOI  :  10.3390/catal11070760

来源: DOAJ

【 摘 要 】

Catalytic efficacy of metal-based catalysts can be significantly enhanced by doping graphene or its derivatives in the catalytic protocol. In continuation of previous work regarding the catalytic properties of highly-reduced graphene oxide (HRG), graphene-oxide (GO) doped mixed metal oxide-based nanocomposites, herein we report a simple, straightforward and solventless mechanochemical preparation of N-doped graphene (NDG)/mixed metal oxide-based nanocomposites of ZnO–MnCO₃ (i.e., ZnO–MnCO₃/(X%-NDG)), wherein N-doped graphene (NDG) is employed as a dopant. The nanocomposites were prepared by physical milling of separately fabricated NDG and ZnO–MnCO₃ calcined at 300 °C through eco-friendly ball mill procedure. The as-obtained samples were characterized via X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FT-IR), Raman, Field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDX) and surface area analysis techniques. To explore the effectiveness of the obtained materials, liquid-phase dehydrogenation of benzyl alcohol (BOH) to benzaldehyde (BH) was chosen as a benchmark reaction using eco-friendly oxidant (O₂) without adding any harmful surfactants or additives. During the systematic investigation of reaction, it was revealed that the ZnO–MnCO₃/NDG catalyst exhibited very distinct specific-activity (80 mmol/h.g) with a 100% BOH conversion and <99% selectivity towards BH in a very short time. The mechanochemically synthesized NDG-based nanocomposite showed remarkable enhancement in the catalytic performance and increased surface area compared with the catalyst without graphene (i.e., ZnO–MnCO₃). Under the optimum catalytic conditions, the catalyst successfully transformed various aromatic, heterocyclic, allylic, primary, secondary and aliphatic alcohols to their respective ketones and aldehydes with high selectively and convertibility without over-oxidation to acids. In addition, the ZnO–MnCO₃/NDG was also recycled up to six times with no apparent loss in its efficacy.

【 授权许可】

Unknown