In situ hydro-deoxygenation onto nickel-doped HZSM-5 zeolite catalyst for upgrading pyrolytic oil.

Global energy demand has drastically increased due to urbanization and industrialization; thus, developing alternative renewable energy sources is urgently required. In the present work, upgrading the pyrolytic oil (PO) derived from fresh palm fruit was performed by the catalytic in situ hydrodeoxygenation (in situ HDO) process. Preparation of nickel-doped HZSM-5 zeolite (SiO2/Al2O3 = 40) was achieved by incipient wetness impregnation techniques using different weight percents of nickel dopant into HZSM-5. Nickel-doped HZSM-5 zeolite (Ni-HZSM-5) was further subjected to chemical reduction for 5 h in the oxygen-free environment (10% H2 and 90% N2) at 550 °C. The structural properties showed a potential reduction of NiO-HZSM-5 to Ni-HZSM-5, enhancing the catalytic potential. The morphological characterizations showed spherical-shaped Ni agglomerated onto HZSM-5. Acidity and oxygen contents in the pyrolytic oil were achieved by catalyst-aided HDO process at 220 °C for 6 h using methanol as a hydrogen donor. The catalytically upgraded pyrolytic oil (UPO) was analyzed for density, HHV, CHNO, and TGA. The best upgrading oil was distilled following ASTM D86 to separate gasoline, kerosene, and diesel. The acidity, density, HHV, and viscosity were measured before and after the upgradation processes. The results showed the potential impact of Ni with 10% doped on HZSM-5 on HDO reaction and illustrated the lowest oxygen content in upgraded pyrolytic oil products. Considerable decrease in viscosity and density level indicated that in situ HDO not only reduced oxygen content but also cracked pyrolytic oil to small molecules. The distilled product of upgrading oil was higher than pyrolytic oil by approximately 15% in volume. The viscosity, density, and HHV were under standard specifications of kerosene and diesel, except for acidity. However, the acidity was reduced by over 60% compared with raw material.

Novel gC3N4/MgZnAl-MMO derived from LDH for solar-based photocatalytic ammonia production using atmospheric nitrogen.

The development of catalysis technologies for sustainable environmental applications, especially an alternative to ammonia (NH3) production under the Haber-Bosch process, has gained a lot of scope in recent days. The current work demonstrated a green synthesis of graphitic carbon nitride (gC3N4) containing magnesium-zinc-aluminium mixed metal oxides (MgZnAl-MMO) derived from layered double hydroxide (LDH) for visible light aided catalytic production of ammonia. Pyrolysis-hydrothermal techniques were adopted for the synthesis and fabrication of the gC3N4/MgZnAl-MMO catalytic composite. Characterization results of field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), UV-visible spectroscopy, photoluminescence (PL), etc. showed the desired properties and functionalities like semi-crystalline structure with rough surface morphology that enhance the sorption reactions. Catalytic composite gC3N4/MgZnAl-MMO showed a bandgap energy of 2.16 eV that is considerably shifted toward the visible range when compared to gC3N4 (2.39 eV) and MgZnAl-MMO (2.93 eV). The results were also well complied with XPS results obtained that promote solar-based photocatalysis. The gC3N4/MgZnAl-MMO assisted photocatalytic production of NH3 in an aqueous media proved to be acceptable by the production of a maximum 47.56 µmol/L NH3 under visible spectrum employing a light emitting diode (LED) source. The results showed that the advancement of catalyst for desired functionalities and NH3 production using LED simulating solar light-aided catalysis would be an alternative to the Haber-Bosch process and solar-based sustainable processes for NH3 production.

Photocatalytic transfer of aqueous nitrogen into ammonia using nickel-titanium-layered double hydroxide.

The development of solar-driven transfer of atmospheric nitrogen into ammonia is one of the green and sustainable strategies in industrial ammonia production. Nickel-titanium-layered double hydroxide (NiTi-LDH) was synthesised using the soft-chemical process for atmospheric nitrogen fixation application under photocatalysis in an aqueous system. NiTi-LDH was investigated using advanced characterisation techniques and confirmed the potential oxygen vacancies and/or surface defects owing to better photocatalytic activity under the solar spectrum. It also exhibited a bandgap of 2.8 eV that revealed its promising visible-light catalytic activities. A maximum of 33.52 µmol L-1 aqueous NH3 was obtained by continuous nitrogen (99.9% purity) supply into the photoreactor under an LED light source. Atmospheric nitrogen supply (≈78%) yielded 14.67 µmol L-1 aqueous NH3 within 60 min but gradually reduced to 3.6 µmol L-1 at 330 min. Interestingly, in weak acidic pH, 20.90 µmol L-1 NH3 was produced compared to 11.51 µmol L-1 NH3 in basic pH. The application of NiTi-LDH for visible-light harvesting capability and photoreduction of atmospheric N2 into NH3 thereby opens a new horizon of eco-friendly NH3 production using natural sunlight as alternative driving energy.

Insight into the photocatalytic reduction of hexavalent chromium using photodeposited metal nanoparticle-TiO2 photocatalysis.

Hexavalent chromium (Cr(VI)) is carcinogenic to organisms. It is widely used in several industries. In this work, we investigated the Cr(VI) photocatalytic reaction with a scavenger on Pt and Cu-TiO2 photocatalysts. Metal-deposited TiO2 was successfully synthesized by a photodeposition method. TEM-EDX, XRD, and UV-DR were analyzed to study the changes in morphology, crystallinity, and the electronic properties of photocatalysts. The rate of charge recombination during reduction and photoluminescence (PL) spectroscopy was used to examine the catalysts in depth. Cu-TiO2 demonstrates the highest photocatalytic activity for 63.74% of Cr(VI) removal. To understand the photoreduction of Cr(VI), the fate transformation of Cr species during the adsorption and reaction was investigated using in situ XANES. The results demonstrated that the Cr(III) was noticeably main component adsorbed over the catalyst, particularly in Cu-TiO2. The presence of humic acid can boost the Cr(VI) removal efficiency and enhanced the Cr(VI) reduction to Cr(III). We believe that the extensive research on Cr(VI) photoreduction on metal-TiO2 heterojunction will provide a comprehensive understanding of catalytic behaviors, paving the way for rationally designed novel Cr reduction catalysts.

Valorization of cannabis waste via hydrothermal carbonization: solid fuel production and characterization.

Hydrothermal carbonization (HTC) was employed to convert cannabis waste into valuable solid fuel (hydrochar) under different operating conditions, including reaction temperature (170-230 °C), biomass-water ratio (1:10-1:20), and residence time of 60 min. The produced hydrochar was examined for their fuel properties including calorific value (HHV), proximate and ultimate analysis, thermal stability and combustion behavior, etc. The results revealed higher HTC temperature led to a higher degree of carbonization, which is beneficial for increasing carbon content and HHV of the hydrochar. The HHV of the hydrochar improved significantly up to 24.65 MJ/kg after the HTC compared to 17.50 MJ/kg for cannabis waste. The energy yield of hydrochar from the HTC process was in a range of 70.41-82.23%. The optimal HTC condition was observed at 230 °C and a biomass-water ratio of 1:10, producing high-quality hydrochar with 24.24 MJ/kg HHV and 72.28% energy yield. The hydrochar had similar fuel characteristics to lignite coal with significantly lower ash content. Additionally, recirculation of liquid effluent showed a positive influence on the HHV of hydrochar besides minimizing the release of wastewater from the HTC process. The study revealed that HTC is a promising technique for valorization of cannabis waste into high-value solid fuel, which can be potentially an alternative to coal.

Dynamically driven perovskite La-Fe-modified SrTiO3 nanocubes and their improved photoresponsive activity under visible light: influence of alkaline environment.

Visible-light active La-Fe-SrTiO3 (La0.01Sr0.99Fe0.01Ti0.99O3) photocatalysts were synthesized via a dynamic hydrothermal route under different NaOH concentrations (2, 3, 4, 5, and 6 M). The results showed that altering NaOH concentrations changed the physicochemical characteristics of the materials. Namely, the decrease in particle size was observed when the NaOH levels were increased. The specific surface area of the photocatalysts changed with an increased concentration of NaOH, and the maximum value was 17.10 m2/g in 5 M of NaOH. The crystal structure of all prepared samples remained unaffected when altered the NaOH concentration or when incorporated La and Fe in the lattice of SrTiO3. Namely, all samples synthesized under various NaOH concentrations crystallized and maintained in the standard cubic perovskite structure of SrTiO3. The increased NaOH concentration slightly altered the absorption wavelength towards a longer wavelength region. The La atom, replacing some Sr2+ in the structure of modified SrTiO3, was confirmed to be in the La3+ valence state. Simultaneously, Fe atoms demonstrating oxidation states of Fe3+ can also be incorporated into the SrTiO3 network. The photocatalytic degradation of ciprofloxacin antibiotic revealed that the highest performance was approximately 75% within 9 h over the La0.01Sr0.99Fe0.01Ti0.99O3 sample prepared at 5 M of NaOH via the dynamic hydrothermal process. Meanwhile, this photocatalyst also displayed greater activity than the pristine SrTiO3, the single-doped samples (SrFe0.01Ti0.99O3 and La0.01Sr0.99TiO3), and the La0.01Sr0.99Fe0.01Ti0.99O3 sample prepared through a static hydrothermal technique under the same synthesis condition.

Degradation of doxycycline antibiotics using lanthanum copper oxide microspheres under simulated sunlight.

In this study, lanthanum copper oxide was synthesized under hydrothermal techniques and characterized for doxycycline degradation. The catalyst exhibited enhanced photocatalytic doxycycline degradation under visible light owing to its compatible bandgap energy (1.7 eV). The XRD data revealed high crystallinity of the material with no noticeable impurities. Three-dimensional microspheres of varying sizes (average diameter of 2.52 µm) were observed from SEM. EDX confirms the successful synthesis of La2CuO4. The effect of DC concentration, catalyst dosage, and initial pH on the degradation rate of DC was studied methodically. Interestingly, about 85% of doxycycline (10 mg/L) was degraded within 120 min of light-emitting diode irradiation at pH 10. Oxygen vacancies and surface defects were determined through photoluminescence spectra. The recyclability experiments suggested that the catalyst is capable of degrading DC for three consecutive runs. Radical trapping trials suggested that holes (h+), superoxide radicals (●O2-), and hydroxyl radicals (●OH) are involved in the photodegradation of DC. Herein, the novel approach of La2CuO4 synthesis and the efficient visible-light harvesting capability of as-prepared catalyst reveal the potentiality for DC degradation thereby opening a new horizon of research employing La2CuO4 used for various environmental applications.

Insight into the Roles of Metal Loading on CO2 Photocatalytic Reduction Behaviors of TiO2.

The photocatalytic reduction of carbon dioxide (CO2) into value-added chemicals is considered to be a green and sustainable technology, and has recently gained considerable research interest. In this work, titanium dioxide (TiO2) supported Pt, Pd, Ni, and Cu catalysts were synthesized by photodeposition. The formation of various metal species on an anatase TiO2 surface, after ultraviolet (UV) light irradiation, was investigated insightfully by the X-ray absorption near edge structure (XANES) technique. CO2 reduction under UV-light irradiation at an ambient pressure was demonstrated. To gain an insight into the charge recombination rate during reduction, the catalysts were carefully investigated by the intensity modulated photocurrent spectroscopy (IMPS) and photoluminescence spectroscopy (PL). The catalytic behaviors of the catalysts were investigated by density functional theory using the self-consistent Hubbard U-correction (DFT+U) approach. In addition, Mott-Schottky measurement was employed to study the effect of energy band alignment of metal-semiconductor on CO2 photoreduction. Heterojunction formed at Pt-, Pd-, Ni-, and Cu-TiO2 interface has crucial roles on the charge recombination and the catalytic behaviors. Furthermore, it was found that Pt-TiO2 provides the highest methanol yield of 17.85 µmol/gcat/h, and CO as a minor product. According to the IMPS data, Pt-TiO2 has the best charge transfer ability, with the mean electron transit time of 4.513 µs. We believe that this extensive study on the junction between TiO2 could provide a profound understanding of catalytic behaviors, which will pave the way for rational designs of novel catalysts with improved photocatalytic performance for CO2 reduction.

Enhancing the catalytic performance of calcium-based catalyst derived from gypsum waste for renewable light fuel production through a pyrolysis process: A study on the effect of magnesium content.

The thermochemical conversion of abundant renewable resources through pyrolytic catalysis cracking (PCC) is one of the most promising technologies for producing green biofuels. In this study, the pyrolysis of palm oil was investigated over a sustainable CaO-based catalyst derived from waste gypsum. PCC was conducted in a continuous packed-bed reactor under atmospheric pressure without purge gas. The effects of Mg doping and reaction temperature were also examined. A wet ball milling process was used to prepare the well-mixed catalysts and to subsequently form a heterojunction structure between the CaO and MgO particles. CaO was synthesized using the Ca(OH)2 derived from the reaction between gypsum and sodium hydroxide. The pyrolytic oil was separated from the crude oil to remove water and other impurities. The pyrolytic oil was then distilled following ASTM D86, and the three separated products were classified as bio-gasoline, bio-kerosene, and bio-diesel. The highest renewable light fuel volume (bio-gasoline and bio-kerosene) of about 75% (74 %wt.) was obtained at a reaction temperature of 525 °C with 10% MgCO3 content. The percent volume of light fuel increased with increasing reaction temperature. Renewable light fuel production over the Mg-doped CaO-based catalyst was related to both the Mg content and reaction temperature.

Correction to: Influence of iron mining activity on heavy metal contamination in the sediments of the Aqyazi River, Iran.

The original version of this article unfortunately contained an error in the affiliation section and missing acknowledgment statement.

Optimizing chemical oxygen demand removal from synthesized wastewater containing lignin by catalytic wet-air oxidation over CuO/Al2O3 catalysts.

UNLABELLED: In this study, 10% CuO/Al2O3 catalyst was used in a catalytic wet-air oxidation process to remove chemical oxygen demand (COD) and color from experimentally designed wastewater containing lignin. The catalyst was prepared using an impregnation method and was characterized by X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), and Brunauer-Emmett-Teller method (BET) for surface area before use. A series of Box-Behnken design (BBD) experiments were used to identify the conditions (temperature, pressure, reaction time, and catalysts) necessary for the COD removal process. The predicted model had R2 and R2adj correlation coefficients of 0.98 and 0.97, respectively. Pressure only and the interaction effect between temperature and pressure were found to have a significant effect on COD removal (both confidence interval [CI] 95%). Finally, response surface methodology (RSM)-optimized results suggested that 92% of COD could be removed in 1 L of experimental wastewater with a lignin concentration 350 g/L in 120 min under the following conditions: a reaction temperature of 185 °C, a pressure of 10 bars, and catalyst loading of 1 mg/L. The experiment, performed in triplicate, yielded a COD removal of 90±2%. The results are believed to be of importance to pulp and paper industrial wastewater treatment and other similar applications. IMPLICATIONS: Catalytic wet-air oxidation (CWAO) has been used as an alternative to overcome problems related to the high temperatures and pressures required by the traditional wet-air oxidation. CWAO has been widely applied to treat various industrial wastewaters. To reduce the overall operational cost, it is necessary to identify the optimal condition required when designing wastewater treatment plant processes. In this work, the authors had successfully demonstrated the application of response surface methodology (RSM) with the Box-Behnken design (BBD) as a means of elucidating the complicated interaction effects between parameters.

Synthesis and characterization of Fe-MCM-41 from rice husk silica by hydrothermal technique for arsenate adsorption.

Rice husk (RH) agro-waste was used as a raw material for synthesizing mesoporous molecular sieves, MCM-41. The Fe-MCM-41 was prepared by the hydrothermal technique (HT), resulting in a higher surface area and crystallinity than when prepared under ambient conditions. In addition, a hexagonal structure was clearly seen with hydrothermal technique (HT) preparation. The adsorption of arsenate by HT-Fe-MCM-41 was investigated. The factors studied affecting arsenate adsorption capacity were ferric content in MCM-41, contact time, pH of solution, and initial arsenate concentration. It was found that HT-Fe-MCM-41 at the Si/Fe mole ratio of 10 gave the highest adsorption capacity. Arsenate adsorption reached equilibrium within 4 h. The adsorption capacity of HT-Fe-MCM-41 (Si/Fe = 10) was affected by the initial pH value and the initial arsenate concentration. The adsorption capacity was highest at pH 3 and decreased thereafter with increases in the pH of solution value. The Langmuir model fit the arsenate adsorption isotherm well. The maximum adsorption capacity for arsenate was 1,111 microg g(-1).