Structural Characterization of Polycrystalline Titania Nanoparticles on C. striata Biosilica for Photocatalytic POME Degradation.

The biosilica shell of marine diatoms has emerged as a unique matrix for photocatalysis, owing to its sophisticated architecture with hierarchical nanopores and large surface area. Although the deposition of titania nanoparticles on diatom biosilica has been demonstrated previously, their photocatalytic activity has been tested only for degradation of pure compounds, such as dyes, nitrogen oxide, and aldehydes. The efficiency of such photocatalysts for degradation of mixtures, for instance, industrial wastewaters, is yet to be investigated. Furthermore, reports on the lattice structures and orientation of nanotitania crystals on biosilica are considerably limited, especially for the underexplored tropical marine diatoms. Here, we report an extensive characterization of titania-loaded biosilica from the tropical Cyclotella striata diatom, starting from freshly grown cell cultures to photodegradation of wastewaters, namely, the palm oil mill effluent (POME). As Indonesia is the largest palm oil producer in the world, photocatalytic technology could serve as a sustainable alternative for local treatment of POME. In this study, we achieved a 54% loading of titania on C. striata TBI strain biosilica, as corroborated by XRF analyses, which was considerably high compared to previous studies. Through visualization using HR-TEM, supported by SAED and XRD analyses, nanocrystal TiO2 appeared to be trapped in an anatase phase with polycrystalline characteristics and distinct crystallographic orientations. Importantly, the presence of C. striata biosilica lowered the band gap of titania from 3.41 eV to around 3.2 eV upon deposition, enabling photodegradation of POME using a broad-range xenon lamp as the light source, mimicking the sunlight. Kinetic analyses revealed that POME degradation using the photocatalysts followed quasi-first-order kinetics, in which the highest titania content resulted in the highest photocatalytic activity (i.e., up to 47% decrease in chemical oxygen demand) and exhibited good photostability throughout the reaction cycles. Unraveling the structure and photoactivity of titania-biosilica catalysts allows transforming marine diatoms into functional materials for wastewater photodegradation.

Recent Advances in Photocatalytic Oxidation of Methane to Methanol.

Methane is one of the promising alternatives to non-renewable petroleum resources since it can be transformed into added-value hydrocarbon feedstocks through suitable reactions. The conversion of methane to methanol with a higher chemical value has recently attracted much attention. The selective oxidation of methane to methanol is often considered a "holy grail" reaction in catalysis. However, methanol production through the thermal catalytic process is thermodynamically and economically unfavorable due to its high energy consumption, low catalyst stability, and complex reactor maintenance. Photocatalytic technology offers great potential to carry out unfavorable reactions under mild conditions. Many in-depth studies have been carried out on the photocatalytic conversion of methane to methanol. This review will comprehensively provide recent progress in the photocatalytic oxidation of methane to methanol based on materials and engineering perspectives. Several aspects are considered, such as the type of semiconductor-based photocatalyst (tungsten, titania, zinc, etc.), structure modification of photocatalyst (doping, heterojunction, surface modification, crystal facet re-arrangement, and electron scavenger), factors affecting the reaction process (physiochemical characteristic of photocatalyst, operational condition, and reactor configuration), and briefly proposed reaction mechanism. Analysis of existing challenges and recommendations for the future development of photocatalytic technology for methane to methanol conversion is also highlighted.

Coke-Resistant Ni/CeZrO2 Catalysts for Dry Reforming of Methane to Produce Hydrogen-Rich Syngas.

Dry reforming of methane was studied over high-ratio zirconia in ceria-zirconia-mixed oxide-supported Ni catalysts. The catalyst was synthesized using co-precipitation and impregnation methods. The effects of the catalyst support and Ni composition on the physicochemical characteristics and performance of the catalysts were investigated. Characterization of the physicochemical properties was conducted using X-ray diffraction (XRD), N2-physisorption, H2-TPR, and CO2-TPD. The results of the activity and stability evaluations of the synthesized catalysts over a period of 240 min at a temperature of 700 °C, atmospheric pressure, and WHSV of 60,000 mL g−1 h−1 showed that the 10%Ni/CeZrO2 catalyst exhibited the highest catalytic performance, with conversions of CH4 and CO2 up to 74% and 55%, respectively, being reached. The H2/CO ratio in the product was 1.4, which is higher than the stoichiometric ratio of 1, indicating a higher formation of H2. The spent catalysts showed minimal carbon deposition based on the thermo-gravimetry analysis, which was <0.01 gC/gcat, so carbon deposition could be neglected.

Sustainable Diesel from Pyrolysis of Unsaturated Fatty Acid Basic Soaps: The Effect of Temperature on Yield and Product Composition.

The production of sustainable diesel without hydrogen addition remains a challenge for low-cost fuel production. In this work, the pyrolysis of unsaturated fatty acid (UFA) basic soaps was studied for the production sustainable diesel (bio-hydrocarbons). UFAs were obtained from palm fatty acids distillate (PFAD), which was purified by the fractional crystallization method. Metal hydroxides were used to make basic soap composed of a Ca, Mg, and Zn mixture with particular composition. The pyrolysis reactions were carried out in a batch reactor at atmospheric pressure and various temperatures from 375 to 475 °C. The liquid products were obtained with the best yield (58.35%) at 425 °C and yield of diesel fraction 53.4%. The fatty acids were not detected in the pyrolysis liquid product. The gas product consisted of carbon dioxide and methane. The liquid products were a mixture of hydrocarbon with carbon chains in the range of C7 and C20 containing n-alkane, alkene, and iso-alkane.

Photocatalytic Degradation of Palm Oil Mill Effluent (POME) Waste Using BiVO4 Based Catalysts.

Disposal of palm oil mill effluent (POME), which is highly polluting from the palm oil industry, needs to be handled properly to minimize the harmful impact on the surrounding environment. Photocatalytic technology is one of the advanced technologies that can be developed due to its low operating costs, as well as being sustainable, renewable, and environmentally friendly. This paper reports on the photocatalytic degradation of palm oil mill effluent (POME) using a BiVO4 photocatalyst under UV-visible light irradiation. BiVO4 photocatalysts were synthesized via sol-gel method and their physical and chemical properties were characterized using several characterization tools including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), surface area analysis using the BET method, Raman spectroscopy, electron paramagnetic resonance (EPR), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of calcination temperature on the properties and photocatalytic performance for POME degradation using BiVO4 photocatalyst was also studied. XRD characterization data show a phase transformation of BiVO4 from tetragonal to monoclinic phase at a temperature of 450 °C (BV-450). The defect site comprising of vanadium vacancy (Vv) was generated through calcination under air and maxima at the BV-450 sample and proposed as the origin of the highest reaction rate constant (k) of photocatalytic POME removal among various calcination temperature treatments with a k value of 1.04 × 10-3 min-1. These findings provide design guidelines to develop efficient BiVO4-based photocatalyst through defect engineering for potential scalable photocatalytic organic pollutant degradation.

Preparation and Characterizations of Carbon Nanospheres Derived from Activated Carbons and Palm Oil as Anode Materials of Lithium Secondary Batteries.

Carbon nanospheres (CNSs) with diameter of around 100 nm were synthesized by pyrolysis technique using activated carbon as Fe-catalyst support and palm oil as carbon precursors with various ratios. Firstly, the Fe catalyst were deposited onto the activated carbon by incipient wetness impregnation method using Fe(NO3)2 x 9H2O as precursors with various content of catalyst (5%, 7% and 10% with respect to the carbon support). The carbon products were characterized by X-ray diffraction, transmission electron microscope, scanning electron microscope, Raman spectroscopy, nitrogen adsorption and X-ray photoelectron spectroscopy. Preliminary electrochemical characteristics of as-synthesized CNSs as anode materials of lithium secondary batteries were conducted using Cyclic Voltammetry to observe the mechanism of Li-ion insertion/extraction during charge-discharge tests.