Highly Exposed NH2 Edge on Fragmented g-C3 N4 Framework with Integrated Molybdenum Atoms for Catalytic CO2 Cycloaddition: DFT and Techno-Economic Assessment.

This study focuses on the applicability of single-atom Mo-doped graphitic carbon nitride (GCN) nanosheets which are specifically engineered with high surface area (exfoliated GCN), NH2 rich edges, and maximum utilization of isolated atomic Mo for propylene carbonate (PC) production through CO2 cycloaddition of propylene oxide (PO). Various operational parameters are optimized, for example, temperature (130 °C), pressure (20 bar), catalyst (Mo2 GCN), and catalyst mass (0.1 g). Under optimal conditions, 2% Mo-doped GCN (Mo2 GCN) has the highest catalytic performance, especially the turnover frequency (TOF) obtained, 36.4 h-1 is higher than most reported studies. DFT simulations prove the catalytic performance of Mo2 GCN significantly decreases the activation energy barrier for PO ring-opening from 50-60 to 4.903 kcal mol-1 . Coexistence of Lewis acid/base group improves the CO2 cycloaddition performance by the formation of coordination bond between electron-deficient Mo atom with O atom of PO, while NH2 surface group disrupts the stability of CO2 bond by donating electrons into its low-level empty orbital. Steady-state process simulation of the industrial-scale consumes 4.4 ton h-1 of CO2 with PC production of 10.2 ton h-1 . Techno-economic assessment profit from Mo2 GCN is estimated to be 60.39 million USD year-1 at a catalyst loss rate of 0.01 wt% h-1 .

Organic pollutants degradation using plasma with simultaneous ammonification assisted by electrolytic two-cell system.

Atmospheric non-thermal dielectric barrier discharge (DBD) plasma has gained considerable attention due to its cost-efficiency, environmental friendliness, and simplicity. However, certain deficiencies restrict its broad application. Herein, the DBD plasma was used to disrupt three model pharmaceutically active compounds (PhACs), sulfamethoxazole (SMX), ibuprofen (IBP), and norfloxacin (NFX), by varying parameters, such as gas type (Ar, N2, O2, and air) and flow rate (1-4 L min-1). The air plasma discharge had the highest degradation efficiency, and the air flow rate was optimized at 2 L min-1. However, only 10% of IBP was removed by the sole plasma, whereas NFX and SMX were entirely removed after 30 min. Since the air plasma discharge generates reactive oxygen and nitrogen species in a chained reaction, the remaining NO2- and NO3- in the aqueous phase were problematic. Therefore, by coupling plasma with electrolysis using Cu/reduced Cu nanowire (R-CuNw) as the anode/cathode, all three PhACs were removed within 30 min, and NO2- and NO3- were completely reduced to NH3 with cathodic reduction. Moreover, the electrical energy per order (EEO, 0.04 kWh L-1) and treatment cost (0.003 USD L-1) were much lower than those of the single system. This system demonstrates great potential for water remediation, and the production of NH3 as a value-added by-product remarkably improves its practicality and is of great importance in agriculture and energy-related industries.

In situ Fenton remediation for diesel contaminated clayey zone assisted by thermal plasma blasting: Synergism and cost estimation.

Thermal plasma blasting technology has been widely applied for rock cracking. Though, the application for environmental remediation has yet to be reported. Since the delivery of remediation agents into diesel contaminated clayey zones are exceptionally challenging, herein, this study explores the effect of pilot-scale thermal plasma blasting for soil fracturing and concurrently dispersing the Fenton reagent into the diesel contaminated silty soils. Six times plasma blasting with sole H2O2 at 20 kV had the highest degradation of diesel (>97%) with an equilibrium time of 3 h, and the final diesel concentration was below the South Korean regulated health standard (500 mg kg-1). This study highlights plasma blasting able to deliver H2O2 instantaneously and homogeneously into contaminated zone while promoting Fenton reaction synergism (fsyn: 2.04) between H2O2 and ≡Fe surface for effective remediation. Furthermore, the remediation cost (USD 4 metric ton-1) is much lower than most reported in situ technologies.

Sulfur-anchored palm shell waste-based activated carbon for ultrahigh sorption of Hg(II) for in-situ groundwater treatment.

This study utilized a facile and scalable one-pot wet impregnation method for Hg(II) adsorption to prepare sulfur-anchored palm shell waste activated carbon powder (PSAC-S). The experimental results revealed that the sulfur precursors promote the surface charge on the PSAC and enhance Hg(II) removal via the Na2S > Na2S2O4 > CH3CSNH2 sequence. PSAC-S prepared using Na2S had significant Hg(II) sorption efficiencies, achieving a maximum sorption capacity of 136 mg g-1 from the Freundlich model. Compared to PSAC, PSAC-S had an enhancement in Hg(II) sorption behavior for heterogeneous interactions with sulfur. PSAC-S also demonstrated high Hg(II) sorption capacities over a wide range of solution pH, while ionic strength had an insignificant impact on Hg(II) removal efficiencies. Through various spectroscopic analyses, we identified the mechanisms of Hg(II) removal by PSAC-S as electrostatic interactions, Hg-Cl complexation, and precipitation as HgSO4. Moreover, PSAC-S unveiled high adsorption affinity and Hg(II) stability in actual groundwater (even in µg L-1 level). These overall results show the potentials of PSAC-S as an alternative, easily scalable material for in-situ Hg(II) remediation.

Degradation synergism between sonolysis and photocatalysis for organic pollutants with different hydrophobicity: A perspective of mechanism and application for high mineralization efficiency.

Despite extensive studies, the fundamental understanding of synergistic mechanisms between sonolysis and photocatalysis for the abatement of persistent organic pollutants (POPs) remains uncertain. As different phases formed under ultrasound irradiation, hydrophilic POPs, sulfamethoxazole (SMX, Kow: 0.89), predominantly resides in bulk liquid and is ineffectively degraded by sonolysis (kUS = 3.33 × 10-3 min-1) since <10% of hydroxyl radicals (·OH) formed at the gas-liquid interface of cavitation is diffused into the bulk, whereas the other fraction rapidly recombines into hydrogen peroxide (H2O2). This study provides a proof-of-concept for the mechanism by presenting various analytical results, endorsing the synergistic role of photoexcited electrons in splitting sonolysis-induced H2O2 into ·OH, particularly in the bulk phase. In a sonophotocatalytic system, the hydrophobic POPs such as bisphenol A (BPA) and atrazine (ATZ) were mainly degraded in gas-liquid interface indicated by the low synergistic values correlation compared to SMX [i.e., SMX has a higher synergistic factor, fsyn (3.26) than BPA (1.30) and ATZ (1.35)]. Also, fsyn was found linearly correlated with the contribution factor of photocatalysis to split H2O2. Three times of consecutive kinetics using an effluent of municipal (MP) wastewater spiked by POPs presented >98% POPs and >96% total organic carbon (TOC) removal.

Granular Mg-Fe layered double hydroxide prepared using dual polymers: Insights into synergistic removal of As(III) and As(V).

Controlling the particle size and aggregation of nanosheet layers in layered double hydroxides (LDHs) is critical for their application. Herein, we report the preparation of Mg-Fe LDH through a co-precipitation method. The LDH was embedded using polyacrylamide (PAM) and polyvinyl alcohol (PVA; the LDH was designated as PAM/PVA-LDH) for As(III) and As(V) removal. We found that doping with 0.3 mL PVA (2 g L-1) and 0.4 mL (20 g L-1) PAM solution delaminated the nanosheet layers of 1 g of the LDH (PAM40/PVA30-LDH) and restructured the crystal phase from monoclinic to orthorhombic. This increased the surface area and pore volume. Furthermore, PAM40/PVA30-LDH exhibited higher affinity for As(III) and As(V) removal with maximum adsorption capacities of 14.1 and 22.8 mg g-1, respectively, compared to LDH alone with adsorption capacities of 7.1 and 7.9 mg g-1, respectively. It was found that the highest adsorption capacities of As(III) and As(V) using PAM40/PVA30-LDH occurred at pH ∼7 and pH 2.5, respectively. X-ray photoelectron spectroscopy analysis revealed that the removal of As(III) and As(V) on PAM40/PVA30-LDH was mainly attributable to ion exchange with intercalated SO42-, hydrogen bonding, and complexation mechanisms. These findings illustrate that PAM40/PVA30-LDH would be an excellent adsorbent for the remediation of arsenic-polluted wastewater.

Unexpected discovery of superoxide radical generation by oxygen vacancies containing biomass derived granular activated carbon.

Herein, we discovered and reported oxygen vacancies in silicon oxycarbide containing granular palm shell activated carbon (Si-PSAC) as a photocatalyst under UV irradiation. A strong correlation between the atomic content of Si1+, oxygen vacancies and photocatalytic performance of Si-PSAC was obtained. Based on the electron paramagnetic resonance and photoluminescence analyses, Si-PSAC under UVA365 irradiation exhibited a higher donor density, better charge transfer and lower electron-hole recombination than that under the other light sources, leading to a higher O2· production efficiency. Si-PSAC exhibited effective removal performance for various anionic dyes and endocrine-disrupting chemicals under UVA365 irradiation. Continuous-flow column tests revealed the life span of Si-PSAC under UVA365 irradiation was extended by more than 16-fold compared to adsorption column. Since the oxygen vacancies can be created from the naturally present Si in the biomass derived Si-PSAC during the activation, this unexpected discovery of O2· production can extend commercially-available Si-PSAC into the full-scale photocatalysis.

Fluoride removal by palm shell waste based powdered activated carbon vs. functionalized carbon with magnesium silicate: Implications for their application in water treatment.

In this study, palm shell activated carbon powder (PSAC) and magnesium silicate (MgSiO3) modified PSAC (MPSAC) were thoroughly investigated for fluoride (F-) adsorption. F- adsorption isotherms showed that PSAC and MPSAC over-performed some other reported F- adsorbents with adsorption capacities of 116 mg g-1 and 150 mg g-1, respectively. Interestingly, the MgSiO3 impregnated layer changed the adsorption behavior of F- from monolayer to heterogeneous multilayer based on the Langmuir and Freundlich isotherm models verified by chi-square test (X2). Thermodynamic parameters indicated that the F- adsorption on PSAC and MPSAC was spontaneous and exothermic. PSAC and MPSAC were characterized using FESEM-EDX, XRD, FTIR and XPS to investigate the F- adsorption mechanism. Based on the regeneration tests using NaOH (0.01 M), PSAC exhibited poor regeneration (<20%) while MPSAC had steady adsorption efficiencies (∼70%) even after 5 regeneration cycles. This is due to highly polarized C-F bond was found on PSAC while Mg-F bond was distinguished on MPSAC, evidently denoting that the F- adsorption is mainly resulted from the exchange of hydroxyl (-OH) group. It was concluded that PSAC would be a potential adsorbent for in-situ F- groundwater remediation due to its capability to retain F- without leaching out in a wide range pH. MPSAC would be an alternative adsorbent for ex-situ F- water remediation because it can easily regenerate with NaOH solution. With the excellent F- adsorption properties, both PSAC and MPSAC offer as promising adsorbents for F- remediation in the aqueous phase.

Sonocatalytic reduction of nitrate using magnetic layered double hydroxide: Implications for removal mechanism.

In this study, magnetic layered double hydroxides (mag-LDHs) were synthesized through compositing magnetite with three different metals (Mg, Cu and Al) under ultrasound (US, 100 kHz frequency and 50 W power). For the first time, mag-LDHs were applied to sonocatalytic reduction of nitrate (NO3-) and the reduction mechanism were determined by conducting kinetic tests and various spectroscopic analyses. Based on the kinetic data, NO3- reduction and the selectivity for N2 highly depends on the ratio between Mg/Al, solution pH and sonication frequency. The best condition for sonocatalytic denitrification was found to be pH 7 operated under 100 kHz (50% power) using the catalyst with lowest amount of Al (mag-LDH-Al0.3Mg1.5). As a proposed mechanism, NO3- is initially reduced to NO2- by Cu0, and then further reduced to N2/NH4+ by Mg0. Hypothetically Al0 could provide sorption sites for hydrogen radicals (·H) dissociated from ultrasound, hence served as reducing sites in denitrification process. The XPS analysis showed an increased peak of Cu0 after the sonocatalytic reduction when catalyst has lower amount of Al. The excessive hydrogen adsorbed on Al0 might spill-over to the adjacent Cu, thus reducing the CuO into Cu0 at high temperature created by the implosion of the microbubbles. Without the use of consumable reducing agents (i.e. H2 gas), sonocatalytic reduction could be a potential candidate of remediation method to treat NO3- polluted water with high N2 selectivity and easy magnetic recovery.

Sonophotocatalytic degradation of bisphenol A and its intermediates with graphitic carbon nitride.

Since bisphenol A (BPA) exhibits endocrine disrupting action and high toxicity in aqueous system, there are high demands to remove it completely. In this study, the BPA removal by sonophotocatalysis coupled with nano-structured graphitic carbon nitride (g-C3N4, GCN) was conducted with various batch tests using energy-based advanced oxidation process (AOP) based on ultrasound (US) and visible light (Vis-L). Results of batch tests indicated that GCN-based sonophotocatalysis (Vis-L/US) had higher rate constants than other AOPs and especially two times higher degradation rate than TiO2-based Vis-L/US. This result infers that GCN is effective in the catalytic activity in Vis-L/US since its surface can be activated by Vis-L to transport electrons from valence band (VB) for utilizing holes (h+VB) in the removal of BPA. In addition, US irradiation exfoliated the GCN effectively. The formation of BPA intermediates was investigated in detail by using high-performance liquid chromatography-mass spectrometry (HPLC/MS). The possible degradation pathway of BPA was proposed.

Titanium dioxide-based sonophotocatalytic mineralization of bisphenol A and its intermediates.

In this study, bisphenol A (BPA) removal by sonophotocatalysis coupled with commercially available titanium dioxide (TiO2, P25) was assessed in batch tests using energy-based advanced oxidation combining ultrasound (US) and ultraviolet (UV). The kinetics of BPA removal were systematically evaluated by changing operational parameters, such as US frequency and power, mechanical stirring speed, and temperature, but also comparison of single and coupled systems under the optimum US conditions (35 kHz, 50 W, 300 rpm stirring speed, and 20 °C). The combination of US/UV/P25 exhibited the highest BPA removal rate (28.0 × 10-3 min-1). In terms of the synergy index, the synergistic effect of sonophotocatalysis was found to be 2.2. This indicated that sonophotocatalysis has a considerably higher removal efficiency than sonocatalysis or photocatalysis. The removal of BPA was further investigated to identify BPA byproducts and intermediates using high-performance liquid chromatography-mass spectrometry. Five main intermediates were formed during sonophotocatalytic degradation, and complete removal of BPA and its intermediates was obtained after 3 h of operation. The degradation pathway of BPA by sonophotocatalysis was also elucidated.

An efficient and economical treatment for batik textile wastewater containing high levels of silicate and organic pollutants using a sequential process of acidification, magnesium oxide, and palm shell-based activated carbon application.

Considering the chemical properties of batik effluents, an efficient and economical treatment process was established to treat batik wastewater containing not only high levels of Si and chemical oxygen demand (COD), but also toxic heavy metals. After mixing the effluents obtained from the boiling and soaking steps in the batik process, acidification using concentrated hydrochloric acid (conc. HCl) was conducted to polymerize the silicate under acidic conditions. Consequently, sludge was produced and floated. XRD and FT-IR analyses showed that wax molecules were coordinated by hydrogen bonding with silica (SiO2). The acidification process removed ∼78-95% of COD and ∼45-50% of Si, depending on the pH. In the next stage, magnesium oxide (MgO) was applied to remove heavy metals completely and almost 90% of the Si in the liquid phase. During this step, about 70% of COD was removed in the hydrogel that arose as a consequence of the crosslinking characteristics of the formed nano-composite, such as magnesium silicate or montmorillonite. The hydrogel was composed mainly of waxes with polymeric properties. Then, the remaining Si (∼300 mg/L) in the wastewater combined with the effluents from the rinsing steps was further treated using 50 mg/L MgO. As a final step, palm-shell activated carbon (PSAC) was used to remove the remaining COD to < 50 mg/L at pH 3. Overall, the sequential process of acidification and MgO/PSAC application developed could serve as an economical and effective treatment option for treating heavily polluted batik effluents.

Phenyl-functionalized magnetic palm-based powdered activated carbon for the effective removal of selected pharmaceutical and endocrine-disruptive compounds.

Triethoxyphenylsilane (TEPS)-functionalized magnetic palm-based powdered activated carbon (MPPAC-TEPS) was prepared and characterized using various spectroscopic methods, and then tested for the removal of bisphenol A, carbamazepine, ibuprofen and clofibric acid. Magnetite film on MPPAC-TEPS was homogeneously coated on the outer surface of palm-based powdered activated carbon (PPAC) through a hydrothermal co-precipitation technique. Followed by silanization of phenyl-functionalized organosilane on MPPAC's magnetic film. As results, micro/mesopore surface area and volume increased without significant pore clogging and iron (Fe) dissolution under the acidic conditions was greatly decreased. The unique structural and chemical features of MPPAC-TEPS were found to be the main reasons for the enhanced adsorption rates and removal capacities of POPs. The presence of electrolytes and different pH values greatly affected the sorption efficiencies. The dominant sorption mechanism of POPs by MPPAC-TEPS was determined to be π-π interaction (physisorption), based on thermodynamic (ΔG°) and differential scanning calorimetry (DSC). Thermal regeneration at a low temperature (350 °C) was an effective method to desorb the retained POPs and enabled to reactivate MPPAC-TEPS with sustained sorption rates and capacities, whereas PPAC was largely exhausted. As a new type of sorbent for POPs, MPPAC-TEPS has operational advantages, such as magnetic separation and stable regeneration.

Enhanced Recyclable Magnetized Palm Shell Waste-Based Powdered Activated Carbon for the Removal of Ibuprofen: Insights for Kinetics and Mechanisms.

A novel preparation method of magnetized palm shell waste-based powdered activated carbon (MPPAC, avg. size 112 µm) was developed. The prepared MPPAC was assessed by several physicochemical analyses, and batch tests were performed for ibuprofen (IBP) removal. Field emission scanning electron microscopy (FESEM) and N2 gas isotherms revealed that magnetite and maghemite were homogeneous and deposited mostly on the surface of PPAC without a significant clogging effect on the micropores. Isotherm results showed that 3.8% Fe (w/w) impregnated PPAC [MPPAC-Fe(3.8%)] had about 2.2-fold higher maximum sorption capacity (157.3 mg g-1) and a 2.5-fold higher sorption density (0.23 mg m-2) than pristine PPAC. Both Fourier-transform infrared spectroscopy (FTIR) and isotherm data indicated that the high sorption capacity and density of IBP by MPPAC was primarily attributable to donor-acceptor complexes with the C = O group and dispersive π-π interactions with the carbon surface. Based on kinetic and repeated adsorption tests, pore diffusion was the rate-limiting step, and MPPAC-Fe(3.8%) had about 1.9~2.8- and 9.1~15.8-fold higher rate constants than MPPAC-Fe(8.6%) and palm shell-waste granular activated carbon (PGAC, avg. size 621 µm), respectively. MPPAC showed almost eight fold greater re-adsorption capacity than PPAC due to a thermal catalytic effect of magnetite/maghemite.