Although liquid products derived from the pyrolysis of biomass are promising for the production of petroleum-like hydrocarbon fuels, the catalytic burden of hydrodeoxygenation must be reduced to achieve feasible upgrading processes. Herein, mild hydrotreating of an acid-rich biomass pyrolysis oil (bio-oil) with an unusually high total acid number (588 mg KOH/g bio-oil) was performed to stabilize the low-quality bio-oil. Ru-added TiO₂-supported transition metal catalysts stabilized the bio-oil by reducing its acidity more compared to what could be achieved by Ru-free catalysts; this process also leads to lower loss of organic compounds compared to when using a Ru/TiO₂ catalyst. Based on the performance of transition metal catalysts, including Ni, Co, and Cu, supported on TiO₂, tungstate-zirconia, or SiO₂, supported bimetallic catalysts were prepared by adding Ru to the TiO₂-supported metal catalysts. The bimetallic catalysts Ru/Ni/TiO₂ and Ru/Co/TiO₂ exhibited good decarboxylation activity for the removal of carboxylic acids and a higher yield of organic compounds compared to that provided by Ru, which can be deemed appropriate for feedstocks when hydrodeoxygenation needs to suppress the loss of organic reactants. Using these catalysts, the carboxylic acid concentration was reduced to 319–323 mg KOH/g bio-oil with organic yields of 62–63 wt% at reaction temperatures 150–170 °C lower than the temperature required for direct conversion of carboxylic acids to alcohols or deoxygenates. The improved catalytic hydrotreating activity of Ru-added transition metals can be attributed to the high acid site densities of these catalysts along with their improved hydrogenation activities.

This study investigated the factors that regulated the degradation of perfluorooctanoic acid (PFOA) in laccase-catalyzed oxidative humification reactions with 1-hydroxybenzotriazole (HBT) as a mediator. The reaction rates were examined under conditions with key factors varied, including initial PFOA concentrations, laccase and HBT dosages, and the ionic contents of the reaction solutions. The PFOA degradation followed pseudo-first order kinetics, and the rate constants (k) were similar for the high (100 μmol L⁻¹) and low (1.00 μmol L⁻¹) initial PFOA concentrations, respectively at 0.0040 day⁻¹ (r² = 0.98) and 0.0042 day⁻¹ (r² = 0.86) under an optimum reaction condition tested in this study. The metal ions contained in the reaction solution appeared to have a strong impact on PFOA degradation. Differential UV-Vis spectrometry revealed that Cu²⁺ can complex with PFOA, which plays an essential role to enable PFOA degradation, probably by bridging the negatively charged PFOA and laccase, so that the free radicals of HBT that are released from laccase can reach and react with PFOA. It was also found that Fe³⁺ plays a similar role as Cu²⁺ to enable PFOA degradation in the laccase-HBT reaction system. In contrast, Mg²⁺ and Mn²⁺ cannot complex with PFOA under the investigated conditions, and do not enable PFOA degradation in the laccase-HBT system. Fluoride and partially fluorinated compounds were detected as PFOA degradation products using ion chromatography and high resolution mass spectrometry. The structures of the products suggest the reaction pathways involving free-radical initiated decarboxylation, rearrangement, and cross-coupling.

Novel copper-nickel ferrite nanocatalyst loaded on multi-walled carbon nanotube (MWCNTs-CuNiFe₂O₄) was synthesized and applied to activate peroxymonosulfate (PMS) in the degradation of the reactive black 5 (RB5). The structure of the catalyst was well characterized by scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray powder diffraction (XRD). The MWCNTs-CuNiFe₂O₄/PMS system showed a high performance in the degradation of RB5 with a kinetic rate of 1.5–2.5 times higher than homogeneous and heterogeneous systems. Maximum degradation efficiency (99.60%) was obtained at an initial pH of 7, catalyst dosage of 250 mg/L, PMS dosage of 4 mM, the temperature of 25 °C, and reaction time of 15 min. Anion experiments emphasized that the presence of nitrate, carbonate, and phosphate in the solution reduced the degradation efficiency by producing reactive species with low oxidation potential. The RB5 degradation rate evolved with temperature, and the activation energy was obtained to be 44.48 kJ/mol. The mechanism of PMS activation and production of free radicals was proposed based on tert-butyl alcohol (TBA), ethanol (EtOH), and potassium iodide (KI) scavengers. Trapping experiments showed that both sulfate (SO₄•⁻) and hydroxyl (•OH) radicals are involved in the catalytic degradation of RB5. The effective treatment of real wastewater and tap water by the MWCNTs-CuNiFe₂O₄/PMS system requires a long reaction time. Gas chromatography-mass spectrometry (GC-MS) analysis indicated that RB5 can be degraded via methylation, decarboxylation, hydroxylation, and ring/chain cleavage pathways. The stable catalytic activity after three consecutive cycles suggested that MWCNTs-CuFe₂O₄ is a novel reusability catalyst in PMS activation.

Chlorinated aromatic organic compounds are extremely toxic to the environment and cause cancer to the human body. Pentachlorophenol (PCP) is a hydrophobic and ionic organic compound that is employed as a production material in various industries. Although the Taiwanese government has banned the use of PCP for years, large PCP-contaminated areas remain in Southern Taiwan. Chemical oxidation, which has been proposed as a viable method for restoring PCP-contaminated areas, involves the use of micronanosize birnessite (δ-MnO₂), which is a type of manganese oxide and a natural mineral in soil environments. The goal of this study was to simulate the decontamination of the underlying soil of the PCP-contaminated areas, which is situated in anaerobic and lightless environment. Through the use of a self-developed gas release and absorption reaction flask, the oxidative mineral decarboxylation and dechlorination effects of δ-MnO₂ on PCP in aerobic and anaerobic (with oxygen removed through the use of nitrogen) environments without light were investigated. Results indicated that adding δ-MnO₂ facilitated the oxidative decarboxylation and dechlorination of PCP and the release of Cl⁻ in an aerobic, lightless environment without microbial activity. In the anaerobic environment, the oxidative decarboxylation effect of δ-MnO₂ on PCP decreased significantly, and the dechlorination effect was the primary reaction. Accordingly, adding δ-MnO₂ inorganically destroys aromatic benzene and releases CO₂ and Cl⁻. The molar ratio between CO₂ and Cl⁻ was calculated to assess the mechanisms of the distinct reaction systems. The parameters and data acquired from the experiment, which involved simulating the conditions of the contaminated areas, can be used in planning the on-site management of the PCP contamination; in particular, these parameters and data provide a reference for eliminating PCP from underlying soil—including groundwater-saturated layers.

Non-edible Ceiba oil has the potential to be a sustainable biofuel resource in tropical countries that can replace a portion of today’s fossil fuels. Catalytic deoxygenation of the Ceiba oil (high O/C ratio) was conducted to produce hydrocarbon biofuel (high H/C ratio) over NiO-CaO₅/SiO₂-Al₂O₃ catalyst with aims of high diesel selectivity and catalyst reusability. In the present study, response surface methodology (RSM) technique with Box-Behnken experimental designs (BBD) was used to evaluate and optimize liquid hydrocarbon yield by considering the following deoxygenation parameters: catalyst loading (1–9 wt. %), reaction temperature (300–380 °C) and reaction time (30–180 min). According to the RSM results, the maximum yield for liquid hydrocarbon n-(C₈–C₂₀) was found to be 77% at 340 °C within 105 min and 5 wt. % catalyst loading. In addition, the deoxygenation model showed that the catalyst loading-reaction time interaction has a major impact on the deoxygenation activity. Based on the product analysis, oxygenated species from Ceiba oil were successfully removed in the form of CO₂/CO via decarboxylation/decarbonylation (deCOx) pathways. The NiO-CaO₅/SiO₂-Al₂O₃ catalyst rendered stable reusability for five consecutive runs with liquid hydrocarbon yield within the range of 66–75% with n-(C₁₅ + C₁₇) selectivity of 64–72%. Despite this, coke deposition was observed after several times of catalyst usage, which is due to the high deoxygenation temperature (> 300 °C) that resulted in unfavourable polymerization side reaction.

Advanced oxidation processes (AOPs) using various energy sources and oxidants to produce reactive oxygen species are widely used for the destruction of recalcitrant water contaminants. The current study is about the degradation of two emerging pollutants—salicylic acid (SA) and methyl paraben (MP)—by high-frequency ultrasonication followed by identification of the oxidation byproducts and modeling of the reaction mechanisms using the density functional theory (DFT). The study also encompasses prediction of the aquatic toxicity and potential risk of the identified byproducts to some aquatic organisms bussing the ECOSAR (Ecological Structure Activity Relationships) protocol. It was found that the degradation of both compounds was governed by •OH attack and the pathways consisted of a cascade of reactions. The rate determining steps were decarboxylation (~ 60 kcal mol⁻¹) and bond breakage reactions (~ 80 kcal mol⁻¹), which were triggered by the stability of the reaction byproducts and overcome by the applied reaction conditions. Estimated values of the acute toxicities showed that only few of the byproducts were harmful to aquatic organisms, implying the environmental friendliness of the experimental method.

Br⁻and nitrogen-containing organic pollutants, such as amino acids, protein, etc., were often detected in water and wastewater treatment plants using advanced oxidation technologies. All these technologies have one common characteristic, that is, the removal processes involve ·OH. Therefore, it is necessary to study the different reaction pathways among ·OH, Br⁻, and amino acids. In this research, glycine was chosen as the representative of amino acids and H₂O₂was selected as ·OH precursor. Results showed that Br⁻had a shielding effect on H of α-carbon in glycine, when it was abstracted by ·OH. The main reaction pathway in the system containing Br⁻was the abstraction of H from amino group in glycine by ·OH, contributing 85 % of total abstracted H. This system had a prominent phenomenon of decarboxylation and performed as alkali production dominating. However, in the system not containing Br⁻, the main reaction pathway was the abstraction of H from α-carbon in glycine by ·OH, contributing 97 % of total abstracted H. This system performed as acid production dominating. By laser flash photolysis, the second-order rate constants of abstraction of H from both α-carbon and amino group in glycine by ·OH were obtained as (3.3 ± 0.5) × 10⁷M⁻¹·s⁻¹and (8.2 ± 0.8) × 10⁸ M⁻¹·s⁻¹, respectively. The second-order rate constants of the reaction between H₂NCH₂COO⁻, HṄCH₂COO⁻ and H₂O₂ were (1.5 ± 1.1) × 10⁷ M⁻¹·s⁻¹and (4.4 ± 0.3) × 10⁷ M⁻¹·s⁻¹, respectively. In addition, Br⁻was found to play a catalytic role in the decomposition of H₂O₂under UV radiation. The results mentioned above were significant for the application of advanced oxidation technologies for water containing both amino acids and Br⁻in water and wastewater treatment plants.

The acidity of Ultisols (pH <5) is detrimental to crop production. Technologies should be explored to promote base saturation and liming effect for amelioration of Ultisol pH. Column leaching experiments were conducted to investigate the amelioration effects of canola straw (CS) and peanut straw (PS) in single treatment and in combination whether with alkaline slag (AS) or with lime on Ultisol profile acidity. The treatment without liming materials was set as control, and the AS and lime in single treatment are set for comparison. Results indicated that all the liming materials increase soil profile pH and soil exchangeable base cations at the 0–40-cm depth, except that the lime had amelioration effect just on 0 to 15-cm profile. The amelioration effect of the liming materials on surface soil acidity was mainly dependent on the ash alkalinity in organic materials or acid neutralization capacity of inorganic materials. Specific adsorption of sulfate (SO₄ ²⁻) or organic anions, decarboxylation of organic acids/anions, and the association of H⁺ with organic anions induced a “liming effect” of crop residues and AS on subsoil acidity. Moreover, SO₄ ²⁻ and chloride (Cl⁻) in PS, CS, and AS primarily induced base cations to move downward to subsoil and exchange with exchangeable aluminum (Al³⁺) and protons (H⁺). These anions also promoted the exchangeable Al to leach out of the soil profile. The CS was more effective than PS in decreasing soil acidity in the subsoil, which mainly resulted from higher sulfur (S) and Cl content in CS compared to PS. The CS combined with AS was the better amendment choice in practical agricultural systems.

Hydrogen peroxide (H₂O₂) electrogenerated via two-electron oxygen reduction reaction at cathode plays an important role in electrochemical advanced oxidation processes for organic pollutants removal from wastewater. Herein, multi-walled carbon nanotubes and carbon black co-modified graphite felt electrode (MWCNTs-CB/GF) was prepared as an efficient cathode for H₂O₂ electrogeneration and amoxicillin removal by anodic oxidation with hydrogen peroxide (AO-H₂O₂) and electro-Fenton (EF) under mild pH condition. Besides, the physicochemical and electrochemical properties of MWCNTs-CB/GF were characterized by scanning electron microscopy, N₂ adsorption and desorption experiment, contact angle measurement, X-ray photoelectron spectroscopy, and linear sweep voltammetry. Compared with GF, MWCNTs-CB/GF showed a higher H₂O₂ generation of 309.0 mg L⁻¹ with a current efficiency of 60.9% (after 120 min) and more effective amoxicillin removal efficiencies of 97.5% (after 120 min) and 98.7% (after 30 min) in AO-H₂O₂ and EF (with 0.5 mM Fe²⁺) processes, under the condition of current density 12 mA cm⁻² and initial pH 5.5. Meanwhile, the TOC removal efficiency was 45.2% during EF process after 120 min. Anodic oxidation, H₂O₂ oxidation, and methanol capture indicated that ∙OH generated via electro-activation reaction at MWCNTs-CB/GF and Fenton reaction in solution played the dominant role in amoxicillin removal. Moreover, the TOC removal was associated with ∙OH generated during Fenton reaction in the solution. The major intermediates of AMX degradation by EF process were identified using LC-MS and the possible degradation pathways were proposed containing of β-lactam ring opening, hydroxylation reaction, decarboxylation reaction, methyl groups in the thiazolidine ring oxidation reaction, bond cleavage, and rearrangement processes. All of the above results proved that MWCNTs-CB/GF was an excellent cathode for AMX degradation under mild pH condition.

This study evaluates the treatment of the antibiotic cloxacillin (CLX) in water by means of electrochemical oxidation, TiO₂ photocatalysis, and the photo-Fenton system. The three treatments completely removed cloxacillin and eliminated the residual antimicrobial activity from synthetic pharmaceutical wastewater containing the antibiotic, commercial excipients, and inorganic ions. However, significant differences in the degradation routes were found. In the photo-Fenton process, the hydroxyl radical was involved in the antibiotic removal, while in the TiO₂ photocatalysis process, the action of both the holes and the adsorbed hydroxyl radicals degraded the pollutant. In the electrochemical treatment (using a Ti/IrO₂ anode in sodium chloride as supporting electrolyte), oxidation via HClO played the main role in the removal of CLX. The analysis of initial by-products showed five different mechanistic pathways: oxidation of the thioether group, opening of the central β-lactam ring, breakdown of the secondary amide, hydroxylation of the aromatic ring, and decarboxylation. All the oxidation processes exhibited the three first pathways. Moreover, the aromatic ring hydroxylation was found in both photochemical treatments, while the decarboxylation of the pollutant was only observed in the TiO₂ photocatalysis process. As a consequence of the degradation routes and mechanistic pathways, the elimination of organic carbon was different. After 480 and 240 min, the TiO₂ photocatalysis and photo-Fenton processes achieved ∼45 and ∼15 % of mineralization, respectively. During the electrochemical treatment, 100 % of the organic carbon remained even after the antibiotic was treated four times the time needed to degrade it. In contrast, in all processes, a natural matrix (mineral water) did not considerably inhibit pollutant elimination. However, the presence of glucose in the water significantly affected the degradation of CLX by means of TiO₂ photocatalysis.