Single-Step Fabrication of BiOI Nanoplates as Gas Diffusion Electrodes for CO2 Electroreduction to Formate: Effects of Spray Pyrolysis Temperature on Activity and Flooding Propensity.

Bismuth-based electrocatalysts for carbon dioxide (CO2) reduction are notable for their high formate selectivity, scalability, affordability, and low toxicity. Here, we introduced a facile spray pyrolysis method to fabricate catalyst-coated gas diffusion electrodes (GDE) in one step. Our study revealed that deposition temperatures significantly affected the morphology, crystal orientation, and impurity of bismuth oxyiodide (BiOI) nanoplates. Specifically, BiOI prepared at 250 °C (BiOI-250) exhibited exceptional Faradaic efficiency (>90%) for formate production at a high current range (100-300 mA cm-2) and demonstrated outstanding stability (>30 h). In situ Raman spectroscopy indicated that BiOI-250's superior performance stemmed from its resilience to microscopic flooding, a failure mechanism observed in low-temperature BiOI. X-ray absorption spectroscopy (XAS) showed that BiOI-250 predominantly consisted of the active Bi2O2CO3 phase, while low-temperature BiOI contained a mixture of Bi2O2CO3 and the less active Bi metal, formed via the reduction of the Bi2O3 impurity. This impurity led to increased catalyst resistivity, uneven potential distribution, and restructuring, contributing to flooding. Our study underscores the crucial role of catalyst structures in determining electrode performance and flooding propensity, offering key insights for optimizing bismuth-based electrocatalysts for CO2 reduction.

Potassium Permanganate-Impregnated Amorphous Silica-Alumina Derived from Sugar Cane Bagasse Ash as an Ethylene Scavenger for Extending Shelf Life of Mango Fruits.

Ethylene, a plant hormone, is a gas that plays a crucial role in fruit ripening and senescence. In this work, a novel ethylene scavenger was prepared from amorphous silica-alumina derived from sugar cane bagasse ash (SC-ASA) and used to prolong the shelf life of mango fruits during storage. KMnO4 at 2, 4, or 6 wt %/w was loaded on SC-ASA using an impregnation method. The results showed that 4% w/w KMnO4 loaded on SC-ASA (4KM/SC-ASA) was superior for ethylene removal at an initial ethylene concentration of 400 µL L-1 for 120 min under ambient conditions (25-27 °C and 70-75% relative humidity), resulting in 100% ethylene removal. The kinetic study of ethylene removal showed that the adsorption data were best fitted with a pseudo-first-order kinetic model. The effects of 4KM/SC-ASA as sachets on the quality changes of the mango fruits were investigated, with the results showing that mango fruits packed in cardboard boxes with 4KM/SC-ASA had significantly delayed ripening, low levels of ethylene production, respiration, and weight loss, high fruit firmness, low total soluble solids, and high acidity compared to those of the control treatment. These findings should contribute to developing an ethylene scavenger to extend the shelf life of fruits, reduce the waste of the sugar and ethanol industries, and make it a valuable material.

Insight into the effects of different oxygen heteroatoms on nicotine adsorption from cigarette mainstream smoke.

Cigarette smoke contains many chemicals, including nicotine, which is harmful and can cause health problems such as carcinogenesis disease, cardiovascular, respiratory, renal, and reproductive systems. Removal of nicotine from mainstream smoke can be done through adsorption with filters or solid adsorbents. In this study, we explored the use of activated carbons for the removal of nicotine from cigarette mainstream smoke. Activated carbons were prepared from dried hemp (Cannabis sativa) stem at an activation temperature of 350-550 °C using phosphoric acid as an activating agent. The results showed that the activated carbons with variable surface functional groups and porosity exhibited high efficiency for nicotine adsorption, removing 68-88% of nicotine from cigarette mainstream smoke. Through X-ray photoelectron spectroscopy and temperature-programmed desorption analyses, we identified that oxygen-containing functional groups, particularly carboxylic groups, exhibited a superior ability to adsorb nicotine. The computational analysis with DFT simulations further supported the importance of oxygen-containing surface functional groups in facilitating nicotine adsorption, with the carboxylic group providing the lowest adsorption energy among other functional groups.

Structural Evolution of Iron-Loaded Metal-Organic Framework Catalysts for Continuous Gas-Phase Oxidation of Methane to Methanol.

Catalytic partial oxidation of methane presents a promising route to convert the abundant but environmentally undesired methane gas to liquid methanol with applications as an energy carrier and a platform chemical. However, an outstanding challenge for this process remains in developing a catalyst that can oxidize methane selectively to methanol with good activity under continuous flow conditions in the gas phase using O2 as an oxidant. Here, we report a Fe catalyst supported by a metal-organic framework (MOF), Fe/UiO-66, for the selective and on-stream partial oxidation of methane to methanol. Kinetic studies indicate the continuous production of methanol at a superior reaction rate of 5.9 × 10-2 µmolMeOH gFe-1 s-1 at 180 °C and high selectivity toward methanol, with the catalytic turnover verified by transient methane isotopic measurements. Through an array of spectroscopic characterizations, electron-deficient Fe species rendered by the MOF support is identified as the probable active site for the reaction.

Cigarette Butt Waste as Material for Phase Inverted Membrane Fabrication Used for Oil/Water Emulsion Separation.

The increasing rate of oil and gas production has contributed to a release of oil/water emulsion or mixtures to the environment, becoming a pressing issue. At the same time, pollution of the toxic cigarette butt has also become a growing concern. This study explored utilization of cigarette butt waste as a source of cellulose acetate-based (CA) polymer to develop a phase inverted membrane for treatment of oil/water emulsion and compare it with commercial polyvinylidene difluoride (PVDF) and polysulfone (PSF). Results show that the CA-based membrane from waste cigarette butt offers an eco-friendly material without compromising the separation efficiency, with a pore size range suitable for oil/water emulsion filtration with the rejection of >94.0%. The CA membrane poses good structural property similar to the established PVDF and PSF membranes with equally asymmetric morphology. It also poses hydrophilicity properties with a contact angle of 74.5°, lower than both PVDF and PSF membranes. The pore size of CA demonstrates that the CA is within the microfiltration range with a mean flow pore size of 0.17 µm. The developed CA membrane shows a promising oil/water emulsion permeability of 180 L m-2 h-1 bar-1 after five filtration cycles. However, it still suffers a high degree of irreversible fouling (>90.0%), suggesting potential future improvements in terms of membrane fouling management. Overall, this study demonstrates a sustainable approach to addressing oil/water emulsion pollution treated CA membrane from cigarette butt waste.

Development of Polyvinylidene Fluoride Membrane via Assembly of Tannic Acid and Polyvinylpyrrolidone for Filtration of Oil/Water Emulsion.

Wastewater containing oil/water emulsion has a serious ecological impact and threatens human health. The impact worsens as its volume increases. Oil/water emulsion needs to be treated before it is discharged or reused again for processing. A membrane-based process is considered attractive in effectively treating oil/water emulsion, but progress has been dampened by the membrane fouling issue. The objective of this study is to develop polyvinylidene fluoride (PVDF) membranes customized for oil/water emulsion separation by incorporating assembly of tannic acid (TA) and polyvinylpyrrolidone (PVP) in the polymer matrix. The results show that the assembly of TA/PVP complexation was achieved as observed from the change in colour during the phase inversion and as also proven from the characterization analyses. Incorporation of the TA/PVP assembly leads to enhanced surface hydrophilicity by lowering the contact angle from 82° to 47°. In situ assembly of the TA/PVP complex also leads to enhanced clean water permeability by a factor of four as a result of enhanced mean flow pore size from 0.2 to 0.9 µm. Owing to enhanced surface chemistry and structural advantages, the optimum hydrophilic PVDF/TA/PVP membrane poses permeability of 540.18 L/(m2 h bar) for oil/water emulsion filtration, three times higher than the pristine PVDF membrane used as the reference.

Polyvinylidene Fluoride Membrane Via Vapour Induced Phase Separation for Oil/Water Emulsion Filtration.

Membrane-based technology is an attractive option for the treatment of oily wastewater because of its high oil removal efficiency, small footprint and operational simplicity. However, filtration performance is highly restricted by membrane fouling, especially when treating oil/water emulsion as a result of strong interaction between oil droplets and the hydrophobic property of the membrane. This study explores the fabrication of polyvinylidene fluoride (PVDF)-based membrane via the vapour induced phase separation (VIPS) method while incorporating polyvinyl pyrrolidone (PVP) as a hydrophilic additive to encounter membrane fouling issues and improve membrane filterability. The resulting membranes were characterized and tested for oil/water emulsion filtration to evaluate their hydraulic, rejection and anti-fouling properties. Results show that the changes in membrane morphology and structure from typical macrovoids with finger-like substructure to cellular structure and larger membrane pore size were observed by the prolonged exposure time from 0 to 30 min through the VIPS method. The enhanced clean water permeability is attributed to the addition of PVP-LiCl in the dope solution that enlarges the mean flow pore size from 0.210 ± 0.1 to 7.709 ± 3.5 µm. The best performing membrane was the VIPS membrane with an exposure time of 5 min (M-5), showing oil/water emulsion permeability of 187 Lm-2 h-1 bar-1 and oil rejection of 91.3% as well as an elevation of 84% of clean water permeability compared to pristine PVDF developed using a typical non-solvent induced phase separation (NIPS) method. Despite the relatively high total fouling, M-5 was able to maintain its high permeability by water flushing as a simple operation for membrane fouling control. The performance was achieved thanks to combination of the large mean flow pore size and hydrophilic property from residual PVP in the membarne matrix. Overall, the results demonstrate the potential of the optimum VIPS method in the presence of PVP and LiCl additives for oil/water emulsion treatment.

Effect of Water and Glycerol in Deoxygenation of Coconut Oil over Bimetallic NiCo/SAPO-11 Nanocatalyst under N2 Atmosphere.

The catalytic deoxygenation of coconut oil was performed in a continuous-flow reactor over bimetallic NiCo/silicoaluminophosphate-11 (SAPO-11) nanocatalysts for hydrocarbon fuel production. The conversion and product distribution were investigated over NiCo/SAPO-11 with different applied co-reactants, i.e., water (H2O) or glycerol solution, performed under nitrogen (N2) atmosphere. The hydrogen-containing co-reactants were proposed here as in-situ hydrogen sources for the deoxygenation, while the reaction tests under hydrogen (H2) atmosphere were also applied as a reference set of experiments. The results showed that applying co-reactants to the reaction enhanced the oil conversion as the following order: N2 (no co-reactant) < N2 (H2O) < N2 (aqueous glycerol) < H2 (reference). The main products formed under the existence of H2O or glycerol solution were free fatty acids (FFAs) and their corresponding Cn-1 alkanes. The addition of H2O aids the triglyceride breakdown into FFAs, whereas the glycerol acts as hydrogen donor which is favourable to initiate hydrogenolysis of triglycerides, causing higher amount of FFAs than the former case. Consequently, those FFAs can be deoxygenated via decarbonylation/decarboxylation to their corresponding Cn-1 alkanes, showing the promising capability of the NiCo/SAPO-11 to produce hydrocarbon fuels even in the absence of external H2 source.

Development of Polysulfone Membrane via Vapor-Induced Phase Separation for Oil/Water Emulsion Filtration.

The discharge of improperly treated oil/water emulsion by industries imposes detrimental effects on human health and the environment. The membrane process is a promising technology for oil/water emulsion treatment. However, it faces the challenge of being maintaining due to membrane fouling. It occurs as a result of the strong interaction between the hydrophobic oil droplets and the hydrophobic membrane surface. This issue has attracted research interest in developing the membrane material that possesses high hydraulic and fouling resistance performances. This research explores the vapor-induced phase separation (VIPS) method for the fabrication of a hydrophilic polysulfone (PSF) membrane with the presence of polyethylene glycol (PEG) as the additive for the treatment of oil/water emulsion. Results show that the slow nonsolvent intake in VIPS greatly influences the resulting membrane structure that allows the higher retention of the additive within the membrane matrix. By extending the exposure time of the cast film under humid air, both surface chemistry and morphology of the resulting membrane can be enhanced. By extending the exposure time from 0 to 60 s, the water contact angle decreases from 70.28 ± 0.61° to 57.72 ± 0.61°, and the clean water permeability increases from 328.70 ± 8.27 to 501.89 ± 8.92 (L·m-2·h-1·bar-1). Moreover, the oil rejection also improves from 85.06 ± 1.6 to 98.48 ± 1.2%. The membrane structure was transformed from a porous top layer with a finger-like macrovoid sub-structure to a relatively thick top layer with a sponge-like macrovoid-free sub-structure. Overall results demonstrate the potential of the VIPS process to enhance both surface chemistry and morphology of the PSF membrane.

Parametric Study on Microwave-Assisted Pyrolysis Combined KOH Activation of Oil Palm Male Flowers Derived Nanoporous Carbons.

Oil palm male flowers (PMFs), an abundant agricultural waste from oil palm plantation in Thailand, have been utilized as an alternative precursor to develop nanoporous carbons (NPCs) via microwave-assisted pyrolysis combined potassium hydroxide (KOH) activation. The influences of relevant processing variables, such as activating agent ratio, microwave power, and activation time on the specific pore characteristics, surface morphology, and surface chemistry of PMFs derived nanoporous carbons (PMFCs) have been investigated to explore the optimum preparation condition. The optimum condition under a microwave radiation power of 700 W, activation holding time of 6 min, and activating agent ratio of 2:1 obtained the PMFC with the highest Brunauer-Emmett-Teller (BET) surface area and total pore volume approximately of 991 m2/g and 0.49 cm3/g, composed of a carbon content of 74.56%. Meanwhile, PMFCs have a highly microporous structure of about 71.12%. Moreover, activating agent ratio and microwave radiation power indicated a significant influence on the surface characteristics of PMFCs. This study revealed the potential of oil palm male flowers for the NPCs' production via microwave-assisted KOH activation with a short operating-time condition.

Coke-resistant defect-confined Ni-based nanosheet-like catalysts derived from halloysites for CO2 reforming of methane.

In this study, halloysites, one of the most abundant clays, with hollow nanotube features were reconstructed by selectively etching silica from the outermost layer of the halloysites associated with unzipping the nanotubes to nanosheets via ball milling, and then, nickel nanoparticles were confined by the resulting defects in the nanosheets to boost charge transfer by a wet impregnation method. The obtained materials were developed as coke-resistant defect-confined Ni-based nanosheet-like catalysts for CO2 reforming of methane (CRM) for the first time. The as-prepared catalyst exhibited good coke and sintering resistance performance in CRM, and especially, there was almost no loss of activity even after a 20 h stability test due to the strong interaction between the Ni nanoparticles and the support. The present investigations may provide a new pathway for the design and application of highly coke-resistant CRM catalysts.

Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst.

Catalytic hydrotreating of palm oil (refined palm olein type) to produce bio-hydrogenated diesel (BHD) was carried out in a continuous-flow fixed-bed reactor over NiMoS2/γ-Al2O3 catalyst. Effects of dominant hydrotreating parameters: temperature: 270-420°C; H2 pressure: 15-80 bar; LHSV: 0.25-5.0 h(-1); and H2/oil ratio: 250-2000 N(cm(3)/cm(3)) on the conversion, product yield, and a contribution of hydrodeoxygenation (HDO) and decarbonylation/decarboxylation (DCO/DCO2) were investigated to find the optimal hydrotreating conditions. All calculations including product yield and the contribution of HDO and DCO/DCO2 were extremely estimated based on mole balance corresponding to the fatty acid composition in feed to fully understand deoxygenation behaviors at different conditions. These analyses demonstrated that HDO, DCO, and DCO2 reactions competitively occurred at each condition, and had different optimal and limiting conditions. The differences in the hydrotreating reactions, liquid product compositions, and gas product composition were also discussed.

Biodiesel production from transesterification of palm oil with methanol over CaO supported on bimodal meso-macroporous silica catalyst.

Calcium oxide-loaded porous materials have shown promise as catalysts in transesterification. However, the slow diffusion of bulky triglycerides through the pores limited the activity of calcium oxide (CaO). In this work, bimodal meso-macroporous silica was used as a support to enhance the accessibility of the CaO dispersed inside the pores. Unimodal porous silica having the identical mesopore diameter was employed for the purpose of comparison. Effects of CaO content and catalyst pellet size on the yield of fatty acid methyl esters (FAME) were investigated. The basic strength was found to increase with increasing the CaO content. The CaO-loaded bimodal porous silica catalyst with the pellet size of 325µm achieved a high %FAME of 94.15 in the first cycle, and retained an excellent %FAME of 88.87 after five consecutive cycles.