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.

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.

Growth and biosorption of Purple guinea and Ruzi grasses in arsenic contaminated soils.

Increasing mining and industrial discharge of untreated wastewater, as well as excessive use of fertilizers for agricultural purposes, and heavy metal contamination in soil have become one of the serious environmental problems worldwide. In the present study, pot experiments were conducted to evaluate the influence of arsenic contamination and other factors on the growth and development of local forage grasses like Purple guinea and Ruzi grasses under controlled conditions. Influence of arsenic concentration, soil properties, and fertilizers on biosorption and withstanding potential of grasses was studied using model soil and real-time arsenic-contaminated mine soil. High arsenic contents in soil significantly affected the growth as well as biomass production of grasses and declined the overall biomass production concerning exposure durations. Purple guinea and Ruzi grasses showed growth tolerance in arsenic-contaminated soils with concentrations of 100 and 150 mg/kg respectively. Grass species, soil compositions, and properties, fertilizers, growth duration, etc. potentially influenced arsenic accumulation in grasses. Both local forage grasses showed <1 bio-accumulation factor (BAF) and bio-concentration factor (BCF) after 45 days that indicates the minimum harvesting time of 45 days, and biosorption rate was found significant to the exposure duration. Maximum translocation factor (TF) values observed in Purple guinea and Ruzi grasses were 0.65 and 0.95, respectively which are < 1, therefore, these local forage grasses could be labeled as arsenic-metallophytes and ability to tolerate high levels of heavy metals without much biosorption. The results confirmed that local forage grasses have much growth tolerance potential against arsenic in real-time mine soil with desired fertilizers and these species could be used for sustainable management of ecological health of the Thung Kum gold mine area in Thailand.

Recent advances in photocatalytic remediation of emerging organic pollutants using semiconducting metal oxides: an overview.

Many untreated and partly treated wastewater from the home and commercial resources is being discharged into the aquatic environment these days, which contains numerous unknown and complex natural and inorganic compounds. These compounds tend to persist, initiating severe environmental problems, which affect human health. Conventionally, physicochemical treatment methods were adopted to remove such complex organic chemicals, but they suffer from critical limitations. Over time, photocatalysis, an advanced oxidation process, has gained its position for its efficient and fair performance against emerging organic pollutant decontamination. Typically, photocatalysis is a green technology to decompose organics under UV/visible light at ambient conditions. Semiconducting nanometal oxides have emerged as pioneering photocatalysts because of large active surface sites, flexible oxidation states, various morphologies, and easy preparation. The current review presents an overview of emerging organic pollutants and their effects, advanced oxidation processes, photocatalytic mechanism, types of photocatalysts, photocatalyst support materials, and methods for improving photodegradation efficiency on the degradation of complex emerging organic pollutants. In addition, the recent reports of metal-oxide-driven photocatalytic remediation of emerging organic pollutants are presented in brief. This review is anticipated to reach a broader scientific community to understand the first principles of photocatalysis and review the recent advancements in this field.

Sonochemical synthesis of graphitic carbon nitride-manganese oxide interfaces for enhanced photocatalytic degradation of tetracycline hydrochloride.

The present study focuses on the sonochemical synthesis of graphitic carbon nitride-manganese oxide (GCN/MnO2) nanocomposite for photocatalytic degradation of an environmentally hazardous pharmaceutical compound, tetracycline hydrochloride (TcH). The sonochemical synthesis aided in tailoring the morphology of GCN/MnO2. The characterization results of SEM/FESEM, XRD, FTIR, UV-Vis spectra, EIS, CV, etc., revealed on the morphology, composition, crystallinity, and other photo-electro-intrinsic properties of the materials. The synergy of GCN and MnO2 results in rapid electron transfer, efficient visible-light absorption, and slower electron-hole pair recombination through its photo-responsive traits against TcH. It was noted that ~ 93% TcH (20 mg L-1) degradation was achieved for 30-mg catalyst dose under light-emitting diode (LED) irradiation (9 W, 220 V) in 135-min duration. The TcH mineralization results were well fit to pseudo-first-order kinetics with a rate constant of 0.02 min-1 (R2 = 0.994). In addition, the composite possessed fair reusability for consequent cycles. Hence, the as-synthesized composite applied for photocatalysis and photoelectrocatalysis fosters a fit-for-purpose and reliable system in the decontamination of TcH in environmental samples. Graphical Abstract.

Quantification, distribution, and effects of di (2-ethylhexyl) phthalate contamination: Risk analysis and mitigation strategies in urban environment.

Phthalate acid ester, di (2-ethylhexyl) phthalate (DEHP) is ubiquitously detected contaminant of emerging concerns (CECs) in all the environmental samples. The present study attempted to understand the fate and transport of DEHP in urban areas by evaluating the quantities, distribution, risk, and effects in the Mysuru city, India. The study is anticipated to serve as a vital document for local and national regulators to frame a robust DEHP management plan and mitigate the risks associated. Liquid-liquid microextraction followed by gas chromatographic analysis was adopted to determine the concentrations of DEHP. The risk quotient method was adopted to assess potential risk, and a conceptual planning model framework was designed to mitigate the DEHP contamination. The municipal wastewater contained 115 ± 9.2 µg/L, whereas treated municipal wastewater showed 95 ± 7.6 µg/L DEHP that was attributed to the inefficiency of the treatment plant. Further, sediments in surface water, as well as groundwater samples of the study area, showed 8 ± 0.64 to 12 ± 0.96 µg/L and 32 ± 2.56 to 40 ± 3.2 µg/kg of DEHP, respectively. The risk quotient of 19.17 for samples in around treatment indicated highest risk, whereas groundwater samples had a risk quotient of 1-2 indicating relative risk to aquatic organisms. In addition, the study highlighted the source, possible entry pathways, and management strategies including treatment aspects to draw an understanding of the distribution and potential ecological imbalances with contamination of DEHP in the urban sector. PRACTITIONER POINTS: Understand the fate and transportation of DEHP in urban wastewater. Primary investigation and assessment to possible health and environmental risks of DEHP contamination in urban wastewater. Revealed the associated health risks and proposed possible management strategies.