Nanostructured Al2O3/Graphene Additive in Bio-Based Lubricant: A Novel Approach to Improve Engine Performance

Personal and industrial use of internal combustion engines (ICEs) is projected to continue until 2050 and beyond. Yet demands to reduce global dependence on petrochemicals and fossil fuel-derived lubricants are increasing and environmentally necessary. New strategies for maintaining and enhancing ICE performance by reducing friction, wear, fuel consumption, and exhaust emissions will reduce the depletion of mineral and fossil fuel reserves and environmental pollution. This paper reports the tribological enhancement of nano-bio lubricants formulated using 2D nanocomposites of Al2O3/graphene as novel additives in coconut oil, whose performance as a lubricant compares favourably with the mineral-based engine oil 15W40. Structural, compositional, and morphological characterization of an Al2O3/graphene nanocomposite synthesized via thermal annealing revealed an ultra-fine particle size (<10 nm) with spherical/laminar morphology and a rich sp2 domain, exhibiting a consistent colloidal stability when formulated as nanofluid. Through the use of various characterisation techniques, including friction and wear analysis we gained valuable insight into the tribological mechanism. Our optimisation of 2D tribological system using coconut oil formulation resulted significant reductions in the coefficient of friction (28%), specific fuel consumption (8%), and exhaust pollutants (CO, SO2, and NOx) emissions. This work demonstrates the benefits of using nano-bio lubricant formulated using coconut oil and 2D based hybrids as base stock and additives, delivering solutions to global challenges such as improving fuel consumption while reducing environmental pollution; solutions that can be transferred to other areas where lubricants are a necessity

Next frontiers in cleaner synthesis: 3D printed graphene-supported CeZrLa mixed-oxide nanocatalyst for CO2 utilisation and direct propylene carbonate production

A rapidly-growing 3D printing technology is innovatively employed for the manufacture of a new class of heterogenous catalysts for the conversion of CO2 into industrially relevant chemicals such as cyclic carbonates. For the first time, directly printed graphene-based 3D structured nanocatalysts have been developed combining the exceptional properties of graphene and active CeZrLa mixed-oxide nanoparticles. It constitutes a significant advance on previous attempts at 3D printing graphene inks in that it does not merely explore the printability itself, but enhances the efficiency of industrially relevant reactions, such as CO2 utilisation for direct propylene carbonate (PC) production in the absence of organic solvents. In comparison to the starting powder, 3D printed GO-supported CeZeLa catalysts showed improved activity with higher conversion and no noticeable change in selectivity. This can be attributed to the spatially uniform distribution of nanoparticles over the 2D and 3D surfaces, and the larger surface area and pore volume of the printed structures. 3D printed GO-supported CeZeLa catalysts compared to unsupported 3D printed samples exhibited higher selectivity and yield owing to the great number of new weak acid sites appearing in the supported sample, as observed by NH3-TPD analysis. In addition, the catalyst's facile separation from the product has the capacity to massively reduce materials and operating costs resulting in increased sustainability. It convincingly shows the potential of these printing technologies in revolutionising the way catalysts and catalytic reactors are designed in the general quest for clean technologies and greener chemistry

Continuous Hydrothermal Flow Synthesis of Blue-Luminescent, Excitation-Independent N-doped Carbon Quantum Dots as Nanosensors

Blue-luminescent N-doped carbon quantum dots (NCQDs) exhibiting rarely observed excitation independent optical properties are synthesised from citric acid in the presence of ammonia via a Continuous Hydrothermal Flow Synthesis (CHFS) approach. CHFS is an eco-friendly, rapid synthetic approach (within fractions of a second) facilitating ease of scale-up industrialization as well as offering materials with superior properties. The synthesised CQDs readily disperse in aqueous solution, have an average particle size of 3.3 ± 0.7 nm, with highest emission intensity at 441 nm (and a narrow full width at half maximum, FWHM ~78 nm) under a 360 nm excitation wavelength. Carbon quantum dots, without any further modification, exhibited a high selectivity and sensitivity as a nano-sensor for the highly toxic and carcinogenic chromium(VI) ions. The nano-chemo-sensor delivers significant advantages including simplicity of manufacturing via a continuous, cleaner technology (using targeted biomass precursor), high selectivity, sensitivity and fast response leading to potential applications in environmental industry as well photovoltaics, bio-tagging, bio-sensing and beyond

Engineering Nitrogen-Doped Carbon Quantum Dots: Tailoring Optical and Chemical Properties through Selection of Nitrogen Precursors

The process of N-doping is frequently employed to enhance the properties of carbon quantum dots. However, the precise requirements for nitrogen precursors in producing high-quality N-doped carbon quantum dots (NCQDs) remain undefined. This research systematically examines the influence of various nitrogen dopants on the morphology, optical features, and band structure of NCQDs. The dots are synthesized using an efficient, eco- friendly, and rapid continuous hydrothermal flow technique. This method offers unparalleled control over synthesis and doping, while also eliminating convention-related issues. Citric acid is used as the carbon source, and urea, trizma base, beta-alanine, L-arginine, and EDTA are used as nitrogen sources. Notably, urea and trizma produced NCQDs with excitation-independent fluorescence, high quantum yields (up to 40%), and uniform dots with narrow particle size distributions. Density functional theory (DFT) and time-dependent DFT modelling established that defects and substituents within the graphitic structure have a more significant impact on the NCQDs’ electronic structure than nitrogen-containing functional groups. Importantly, for the first time, this work demonstrates that the conventional approach of modelling single-layer structures is insufficient, but two layers suffice for replicating experimental data. This study, therefore, provides essential guidance on the selection of nitrogen precursors for NCQD customization for diverse applications

Investigating the effect of N‐doping on carbon quantum dots structure, optical properties and metal ion screening

Carbon quantum dots (CQDs) derived from biomass, a suggested green approach for nanomaterial synthesis, often possess poor optical properties and have low photoluminescence quantum yield (PLQY). This study employed an environmentally friendly, cost-effective, continuous hydrothermal flow synthesis (CHFS) process to synthesise efficient nitrogen-doped carbon quantum dots (N-CQDs) from biomass precursors (glucose in the presence of ammonia). The concentrations of ammonia, as nitrogen dopant precursor, were varied to optimise the optical properties of CQDs. Optimised N-CQDs showed significant enhancement in fluorescence emission properties with a PLQY of 9.6% compared to pure glucose derived-CQDs (g-CQDs) without nitrogen doping which have PLQY of less than 1%. With stability over a pH range of pH 2 to pH 11, the N-CQDs showed excellent sensitivity as a nano-sensor for the highly toxic highly-pollutant chromium (VI), where efficient photoluminescence (PL) quenching was observed. The optimised nitrogen-doping process demonstrated effective and efficient tuning of the overall electronic structure of the N-CQDs resulting in enhanced optical properties and performance as a nano-sensor

Next frontiers in cleaner synthesis: 3D printed graphene-supported CeZrLa mixed-oxide nanocatalyst for CO2 utilisation and direct propylene carbonate production

A rapidly-growing 3D printing technology is innovatively employed for the manufacture of a new class of heterogenous catalysts for the conversion of CO2 into industrially relevant chemicals such as cyclic carbonates. For the first time, directly printed graphene-based 3D structured nanocatalysts have been developed combining the exceptional properties of graphene and active CeZrLa mixed-oxide nanoparticles. It constitutes a significant advance on previous attempts at 3D printing graphene inks in that it does not merely explore the printability itself, but enhances the efficiency of industrially relevant reactions, such as CO2 utilisation for direct propylene carbonate (PC) production in the absence of organic solvents. In comparison to the starting powder, 3D printed GO-supported CeZeLa catalysts showed improved activity with higher conversion and no noticeable change in selectivity. This can be attributed to the spatially uniform distribution of nanoparticles over the 2D and 3D surfaces, and the larger surface area and pore volume of the printed structures. 3D printed GO-supported CeZeLa catalysts compared to unsupported 3D printed samples exhibited higher selectivity and yield owing to the great number of new weak acid sites appearing in the supported sample, as observed by NH3-TPD analysis. In addition, the catalyst's facile separation from the product has the capacity to massively reduce materials and operating costs resulting in increased sustainability. It convincingly shows the potential of these printing technologies in revolutionising the way catalysts and catalytic reactors are designed in the general quest for clean technologies and greener chemistry

Outstanding visible light photocatalysis by nano-TiO2 hybrids with nitrogen-doped carbon quantum dots and/or reduced graphene oxide

Historically, titanium dioxide (TiO2) has been one of the most extensively studied metal oxide photocatalyst, however, it suffers from a large bandgap and fast charge recombination. We report for the first time the use of green, rapid, single-step continuous hydrothermal flow synthesis for the preparation of TiO2, and TiO2 hybrids with reduced graphene oxide (rGO) and/or N-doped carbon quantum dots (NCQD) with leap step enhancement in photocatalytic activity. Using a solar light generator under ambient conditions with no extra oxygen gas added, we observed the evolution reaction of the model pollutant (methylene blue) in real time. Tailoring of the light adsorption to match of that solar spectrum, was achieved by a combination of materials of nano-TiO2 hybrids of nitrogen-doped carbon quantum dots and graphene in its reduced form with a photocatalytic rate constant of ca. 25 x 10-5 s-1. Using a diversity of state-of-the-art techniques including high-resolution transmission electron microscopy, transient photoluminescence, X-ray photoelectron spectroscopy and high accuracy, sophisticated hybrid density functional theory calculations we have gained substantial insight into the charge transfer and modulation of the energy band edges of anatase due to the presence of graphene or carbon dots, parameters which play a key role in improving drastically the photocatalytic efficiencies when compared to pristine titania. More importantly, we prove that a combination of features and materials display the best photocatalytic behaviour. This performance is delivered in a greener synthetic process, that not only produces photocatalytic materials with optimised properties and tailored visible light adsorption and efficiency, but also provides a path to industrialization

London Doctoral Academy Postgraduate Research Summer School 2020

‘Interdisciplinarity: the importance of collaboration and agile thinking’ Each year London South Bank University’s (LSBU) postgraduate research students submit research posters for inclusion in a research poster competition and exhibition as part of the Research Summer School. This provides an opportunity for researchers to showcase the important research undertaken across the University. At LSBU our research is highly applied and focuses on real-world challenges