The article reviews the mechanism, how Schottky barrier and the SPR phenomena help to improve a photoreaction, focusing on the paradox between the Schottky barrier and SPR in the matter of the way of electron flow in the metal/semiconductor system.

Glycerol steam reforming has been performed in a fixed-bed microreactor containing bimetallic Co−Ni/Al2O3 catalyst using a wide range of steam-to-glycerol ratios (3 ≤ STGR ≤ 12) for reaction temperatures between 773 and 823 K at atmospheric pressure. Physicochemical characterization revealed the presence of both Lewis and Brönsted acid sites on the catalyst although the catalyst appears to have a net surface acidity (acid:basic site concentration ratio = 9.0). Co and Ni oxides as well as the metal aluminates were identified from XRD pattern with crystallite size (131.5 nm) similar to that obtained from H2 chemisorption experiments (136.0 nm). Glycerol consumption rate data analysis implicates fractional orders with respect to both glycerol (0.25) and steam (0.36) with an activation energy of 63.3 kJ mol−1. Similar treatment for H2, CO2, CO, and CH4 production rate evinced positive fractional orders for both reactants with the exception of CO which has mild inhibition by steam (−0.065). Mechanistic considerations and associated Langmuir−Hinshelwood and Eley−Rideal kinetic models were derived for both single- and dual-site adsorption modes. However, statistical discrimination as well as thermodynamic evaluation of the associated parameter estimates suggest that the most adequate representation involved molecular adsorption of glycerol and steam on two different sites with surface reaction as the rate-controlling step consistent with the presence of both Brönsted acid and basic sites on the catalyst. Carbon deposition during reaction appeared to be responsible for the loss in surface area and pore volume of the used catalysts. However, these attributes were nearly recovered after regeneration (>90%) using TPR−TPO−TPR−TPO cycles. Significantly, carbon deposition is a strong function of glycerol partial pressure but somewhat insensitive to the presence of steam, suggesting that the carbon residue was probably unreactive with steam under the reaction conditions. Indeed, temperature-programmed heat treatment (TPO−TPR−TPO−TPR and TPR−TPO−TPR−TPO) revealed at least two types of carbonaceous deposits. However, one of these carbon pools was resistant to removal with H2.

Primarily produced via transesterification of lipid sources, fatty acid methyl ester (FAME) of biodiesel derived from insect larvae has gained momentum in a great deal of research done over other types of feedstock. From the self-harvesting nature of black soldier fly larvae (BSFL), research had, however, only concentrated on the harvest of BSFL on sixth instar. Through rearing BSFL on coconut endosperm waste (CEW), 100 BSFL were harvested at the fifth and sixth instar, then modification on CEW with mixed-bacteria powder was carried out. It was found that the fifth instar BSFL had 34% lipid content, which was 8% more than the sixth instar. Both instars had similar corrected protein contents around 35–38%. The sixth instar BSFL contained around 19% of chitin, which was about 11% more than the fifth instar. Biodiesel products from both instars showed no differences in terms of FAME content. With modification on CEW, at 0.5 wt% of mixed-bacteria powder concentration, the maximum waste-to-biomass conversion (WBC) and protein conversion (PC) were achieved at 9% and 60%, respectively. Moreover, even with the shorter fermentation time frame of CEW, it did not affect the development of BSFL in terms of its WBC and PC when fed with 14 and 21 days fermented medium. FAME from all groups set, which predominantly constituted about C12:0 at around 60%, followed by C14:0 at around 15%, C16:0, and C18:1 both at 10% on average. Lastly, the FAME yield from BSFL was improved from 25% (sixth instar) to 33% (fifth instar) and showed its highest at 38.5% with modification on raw CEW with 0.5 wt% mixed-bacteria powder and fermented for 21 days. Thus, harvesting BSFL at earlier instar is more beneficial and practical, as it improves the FAME yield from the BSFL biomass.

A 3 wt% La-promoted Ni/Al2O3 catalyst was prepared via wet co-impregnation technique and physicochemically-characterized. Lanthanum was responsible for better metal dispersion; hence higher BET specific surface area (96.0 m2 g−1) as compared to the unpromoted Ni/Al2O3 catalyst (85.0 m2 g−1). In addition, the La-promoted catalyst possessed finer crystallite size (9.1 nm) whilst the unpromoted catalyst measured 12.8 nm. Subsequently, glycerol dry reforming was performed at atmospheric pressure and temperatures ranging from 923 to 1123 K employing CO2-to-glycerol ratio from zero to five. Significantly, the reaction results have yielded syngas as main gaseous products with H2:CO ratios always below than 2.0 with concomitant maximum 96% glycerol conversion obtained at the CO2-toglycerol ratio of 1.67. In addition, the glycerol consumption rate can be adequately captured using power law modelling with the order of reactions equal 0.72 and 0.14 with respect to glycerol and CO2 whilst the activation energy was 35.0 kJ mol−1. A 72 h longevity run moreover revealed that the catalyst gave a stable catalytic performance.

a b s t r a c tMicrowave pyrolysis was performed on waste engine oil pre-mixed with different amounts of metallicchar catalyst produced previously from a similar microwave pyrolysis process. The metallic-char catalyst was first prepared by pretreatment with calcination followed by analyses to determine its various properties. The heating characteristics of the mixture of waste oil and metallic-char during the pyrolysis were investigated, and the catalytic influence of the metallic-char on the yield and characteristics of the pyrolysis products are discussed with emphasis on the composition of oil and gaseous products. The metallic-char, detected to have a porous structure and high surface area (124 m 2 /g), showed high thermal stability in a N 2 atmosphere and it was also found to have phases of metals and metal oxides attached or adsorbed onto the char, representing a potentially suitable catalyst to be used in pyrolysis cracking process. The metallic-char initially acted as an adsorptive-support to adsorb metals, metal oxides and waste oil. Then, the char became a microwave absorbent that absorbed microwave energy and heated up to a high temperature in a short time and it was found to generate arcing and sparks during microwave pyrolysis of the waste oil, resulting in the formation of hot spots (high temperature sites with temperature up to 650 • C) within the reactor under the influence of microwave heating. The presence of this high temperature metallic-char, the amounts of which are likely to increase when increasing amounts of metallic-char were added to the waste oil (5, 10, and 20 wt% of the amount of waste oil added to the reactor), had provided a reducing chemical environment in which the metallic-char acted as an intermediate reductant to reduce the adsorbed metals or metal oxides into metallic states, which then functioned as a catalyst to provide more reaction sites that enhanced the cracking and heterogeneous reactions that occurred during the pyrolysis to convert the waste oil to produce higher yields of light hydrocarbons, H 2 and CO gases in the pyrolysis products, recording a yield of up to 74 wt% of light C 5 -C 10 hydrocarbons and 42 vol% of H 2 and CO gases. The catalytic microwave pyrolysis produced 65-85 wt% yield of pyrolysis-oil containing C 5 -C 20 hydrocarbons that can potentially be upgraded to produce transport-grade fuels. In addition, the recovered pyrolysis-gases (up to 33 wt%) were dominated by aliphatic hydrocarbons (up to 78 vol% of C 1 -C 6 hydrocarbons) and significant amounts of valuable syngas (up to 42 vol% of H 2 and CO in total) with low heating values (LHV) ranging from 4.7 to 5.5 MJ/m 3 , indicating that the pyrolysis-gases could also be used as a gaseous fuel or upgraded to produce more hydrogen as a second-generation fuel.The results indicate that the metallic-char shows advantages for use as a catalyst in microwave pyrolysis treatment of problematic waste oils.