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Mitigation of hazardous toluene via ozone-catalyzed oxidation using MnOx/Sawdust biochar catalyst
2022
Cha, Jin Sun | Kim, Young-Min | Lee, Im Hack | Choi, Yong Jun | Rhee, Gwang Hoon | Song, Hocheol | Jeon, Byong-Hun | Lam, Su Shiung | Khan, Moonis Ali | Andrew Lin, Kun-Yi | Chen, Wei-Hsin | Park, Young-Kwon
This study investigated catalytic ozone oxidation using a sawdust char (SDW) catalyst to remove hazardous toluene emitted from the chemical industry. The catalyst properties were analyzed by proximate, ultimate, nitrogen adsorption-desorption isotherms, Fourier-transform infrared, and X-ray photoelectron spectroscopy analyses. In addition, hydrogen-temperature programmed reduction experiments were conducted to analyze the catalyst properties. The specific area and formation of micropores of SDC were improved by applying KOH treatment. MnOx/SDC-K3 exhibited a higher toluene removal efficiency of 89.7% after 100 min than MnOx supported on activated carbon (MnOx/AC) with a removal efficiency of 6.6%. The higher (Oₐdₛ (adsorbed oxygen)+Oᵥ(vacancy oxygen))/OL (lattice oxygen) and Mn³⁺/Mn⁴⁺ ratios of MnOx/SDC-K3 than those of MnOx/AC seemed to be important for the catalytic oxidation of toluene.
Show more [+] Less [-]Mechanism of biochar functional groups in the catalytic reduction of tetrachloroethylene by sulfides
2022
Yang, Yadong | Piao, Yunxian | Wang, Ruofan | Su, Yaoming | Qiu, Jinrong | Liu, Na
In recent years, biochar has become of considerable interest for environmental applications, it can be used as a catalyst for sulfides reduction of perchloroethylene, but the crucial role of biochar properties played in catalyzing dechlorination remained ambiguous investigation. To pinpoint the critical functional groups, the modified biochars were respectively produced by HNO₃, KOH and H₂O₂ with similar dimensional structures but different functional groups. Combined with the adsorption and catalytic results of different biochars, the acid-modified biochar had the best catalytic performance (99.9% removal) due to the outstanding specific surface area and ample functional groups. According to characterization and DFT results, carboxyl and pyridine nitrogen exhibited a positive correlation with the catalytic rate, indicating that their contribution to catalytic performance. Customizing biochar with specific functional groups removed depth demonstrated that the carboxyl was essential component. Further, alkaline condition was conducive to catalytic reduction, while tetrachloroethylene cannot be reduced under acidic conditions, because HS⁻ and S²⁻ mainly existed in alkaline environment and the sulfur-containing nucleophilic structure formed with biochar was more stable under this condition. Overall, this study opens new perspectives for in situ remediation by biochar in chlorinated olefin polluted anoxic environment and promotes our insight of modifying for biochar catalyst design.
Show more [+] Less [-]Catalytic hydrogenolysis of plastic to liquid hydrocarbons over a nickel-based catalyst
2022
Zhao, Zhigang | Li, Zheng | Zhang, Xiangkun | Li, Tan | Li, Yuqing | Chen, Xingkun | Wang, Kaige
The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO₂ catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate. As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C₄–C₂₂. The gas products are primarily CH₄ along with a small amount of C₂H₆ and C₃H₈. High yield of CH₄ as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.
Show more [+] Less [-]Microwave-responsive SiC foam@zeolite core-shell structured catalyst for catalytic pyrolysis of plastics
2022
Chen, Zhaohui | Monzavi, Mohammad | Latifi, Mohammad | Samih, Said | Chaouki, J.
Catalytic pyrolysis is a promising chemical recycling technology to supplement mechanical recycling since plastics can be broken down into monomers or converted to the required fuels and chemicals. In this study, a microwave (MW) -responsive SiC foam@zeoltie core-shell structured catalyst was proposed for the catalytic pyrolysis of polyolefins. Under microwave irradiation, the SiC foam core works as both microwave adsorber and catalyst support, thus concentrating the generated heat energy on the ZSM-5 zeolite shell, where the catalytic reaction takes place. SiC foam with an open cellular structure can also improve the global transport of mass and heat during plastics pyrolysis. In this work, the effects of the SiO₂/Al₂O₃ ratio and alkaline treatment of ZSM-5 zeolite coated SiC foam under MW irradiation on the variations in product distribution from low-density polyethylene (LDPE) pyrolysis were investigated at 450 °C. The results indicated that the appropriate acidity and pore structure were crucial to upgrading gas and liquid products. Particularly, the creation of a mesoporous structure in ZSM-5 zeolite via alkaline treatment could improve the diffusion of large molecules and products, thus significantly increasing the selectivity of high-valued light olefins and aromatics while inhibiting the formation of unwanted alkanes, which are expected in the chemical industry. Concretely, the concentration of olefins in gas increased to 51.0 vol% for ZSM-5(50)-0.25AT, and 65.6 vol% for ZSM-5 (50)-0.50AT, compared with 45.2 vol% for the parent ZSM-5(50). The relative concentration of aromatics in liquid decreased from 96.6% for ZSM-5(50) to 75.9% for ZSM-5(50)-0.25AT, and 71.1% for ZSM-5(50)-0.50AT. Given the respective yield of gas and liquid, the total selectivity of C2–C4 olefins and aromatics for mesoporous ZSM-5 zeolites could reach 58.6–64.9% during LDPE pyrolysis, which were higher than that for the parent ZSM-5 zeolite.
Show more [+] Less [-]Cooperation of multiple active species generated in hydrogen peroxide activation by iron porphyrin for phenolic pollutants degradation
2022
Yang, Xiaorong | Hu, Jingping | Wu, Longsheng | Hou, Huijie | Liang, Sha | Yang, Jiakuan
The narrow acid pH range and the nonselectivity of the dominant •OH limit the Fenton systems to remediate the organic wastewater. Inspired by the role of heme in physiological processes, we employed iron porphyrin as a novel homogeneous catalyst to address this issue. Multiple active species are identified during the activation of H₂O₂, including high-valent iron porphyrin ((por)Fe(IV)) species ((por)Fe(IV)–OH, (por)⁺•Fe(IV)=O) and oxygen-centered radicals (•OH, HO₂•/•O₂⁻), as well as atomic hydrogen (*H) and carbon-centered radicals. With the cooperation of these active species, the degradation of pollutants could be resistant to the interference of concomitant ions and proceed over a wide pH range. This cooperative behavior is further verified by intermediates identified from bisphenol A degradation. Specifically, the presence of *H could facilitate the cleavage of the C–C bond and the addition of unsaturated or aromatic molecules. (Por)⁺•Fe(IV)=O could hydroxylate substrates with an oxygen rebound mechanism. Hydrogen atom abstraction of contaminants could be performed by (por)Fe(IV)–OH to form desaturated products by attacking oxygen-centered radicals. The ecotoxicity of bisphenol A could be significantly decreased through degradation. This study would provide a new approach to wastewater treatment and shed light on the interaction between metalloporphyrin and peroxide in an aqueous solution.
Show more [+] Less [-]Remediation techniques for uranium removal from polluted environment – Review on methods, mechanism and toxicology
2022
Akash, S. | Sivaprakash, Baskaran | Raja, V.C Vadivel | Rajamohan, Natarajan | Muthusamy, Govarthanan
Uranium, a radionuclide, is a predominant element utilized for speciality requirements in industrial applications, as fuels and catalyst. The radioactive properties and chemical toxicity of uranium causes a major threat to the ecosystem. The hazards associated with Uranium pollution includes the cancer in bones, liver, and lungs. The toxicological properties of Uranium are discussed in detail. Although there are many methods to eliminate those hazards, this research work is aimed to describe the application of bioremediation methods. Bioremediation methods involve elimination of the hazards of uranium, by transforming into low oxidation form using natural microbes and plants. This study deeply elucidates the methods as bioleaching, biosorption, bioreduction and phytoremediation. Bioleaching process involves bio-oxidation of tetravalent uranium when it gets in contact with acidophilic metal bacterial complex to obtain leach liquor. In biosorption, chitin/chitosan derived sorbents act as chelators and binds with uranium by electrostatic attraction. Bio reduction employs a bacterial transformation into enzymes which immobilize and reduce uranium. Phytoremediation includes phytoextraction and phytotranslocation of uranium through xylems from soil to roots and shoots of plants. The highest uranium removal and uptake reported using the different methods are listed as follows: bioleaching (100% uranium recovery), biosorption (167 g kg⁻¹ uranium uptake), bioreduction (98.9% uranium recovery), and phytoremediation (49,639 mg kg⁻¹ uranium uptake). Among all the techniques mentioned above, bioleaching has been proved to be the most efficient for uranium remediation.
Show more [+] Less [-]Metal-free single heteroatom (N, O, and B)-doped coconut-shell biochar for enhancing the degradation of sulfathiazole antibiotics by peroxymonosulfate and its effects on bacterial community dynamics
2022
Hung, Chang-Mao | Chen, Chiu-Wen | Huang, Jinbao | Dong, Cheng-Di
Metal-free single heteroatom (N, O, and B)-doped coconut-shell biochar (denoted as N-CSBC, O-CSBC, and B-CSBC, respectively) were fabricated in a one-step pyrolysis process to promote peroxymonosulfate (PMS) activation for the elimination of sulfathiazole (STZ) from aquaculture water. B-CSBC exhibited remarkably high catalytic activity with 92% of STZ degradation in 30 min attributed to the presence of meso-/micro-pores and B-containing functional groups (including B–N, B–C, and B₂O₃ species). Radical quenching tests revealed SO₄•⁻, HO•, and ¹O₂ being the major electron acceptors contributing to STZ removal by PMS over B-CSBC catalyst. The B-CSBC catalyst has demonstrated high sustainability in multiple consecutive treatment cycles. High salinity and the presence of inorganic ions such as chloride, enhanced the performance of the sulfate radical-carbon-driven advanced oxidation processes (SR–CAOPs) as pretreatment strategy that significantly facilitated the removal of STZ from aquaculture water. Furthermore, a potential sulfonamide-degrading microorganism, Cylindrospermum_stagnale, belonging to the phylum Cyanobacteria, was the dominant functional bacteria according to the results of high-throughput 16S rRNA gene sequencing conducted after the B-CSBC/PMS treatment. This study provides new insights into the SR–CAOP combined with bioprocesses for removing STZ from aqueous environments.
Show more [+] Less [-]CO2-assisted catalytic pyrolysis of cellulose acetate using Ni-based catalysts
2021
Cho, Seong Heon | Jung, Sungyup | Rinklebe, Jörg | Kwon, Eilhann E.
Cellulose acetate (CA) is one of widely used polymers for chemical and medical applications due to its versatile physico-chemical functionalities. Although its recycle is available after a deacetylation process, the recycle process releases a huge amount of wastewater. Thus, this study investigated a direct disposal process of CA with its valorization to syngas (H₂ and CO) through pyrolysis. To construct more environmentally benign process, CO₂ was used as a co-feedstock with CA to simultaneously convert them into syngas. Pyrolysis of CA in N₂ was performed as a reference study to examine the effectiveness of CO₂ on valorization of CA. Acetic acid and methyl acetate were main volatile pyrolysates (VPs) from CA pyrolysis, and the further thermal cracking of VPs resulted in syngas and CH₄ formations under both N₂ and CO₂ conditions. To expedite syngas formations, multi-stage pyrolysis (two-stage pyrolysis) and catalytic pyrolysis were employed. With the increased thermal energy through two-stage pyrolysis, four times more production of syngas was shown, comparing to the result of a single-stage pyrolysis. With Ni catalysts, the syngas formation was the two orders of magnitude higher than the single-stage pyrolysis, and the significant enhancement of CO formation was shown in the presence of CO₂ due to combined effects of CO₂ and the Ni-based catalysts. This CO enhancement resulted from catalytically expedited gas phase reactions between CO₂ and VPs evolved from CA. In addition, the CO₂ contributed to the suppression of coke deposition on the catalyst, thereby suggesting more technical and environmental benefits of CO₂ as a reactive co-feedstock of pyrolysis in reference to N₂. Therefore, this study proved the direct and versatile technical platform to convert CA and CO₂ into syngas.
Show more [+] Less [-]Visible light driven exotic p (CuO) - n (TiO2) heterojunction for the photodegradation of 4-chlorophenol and antibacterial activity
2021
Gnanasekaran, Lalitha | Pachaiappan, Rekha | Kumar, P Senthil | Hoang, Tuan K.A. | Rajendran, Saravanan | Durgalakshmi, D. | Soto-Moscoso, Matias | Cornejo-Ponce, Lorena | Gracia, F.
The treatment of industrial waste and harmful bacteria is an important topic due to the release of toxins from the industrial pollutants that damage the water resources. These harmful sources frighten the life of every organism which was later developed as the carcinogenic and mutagenic agents. Therefore, the current study focuses on the breakdown or degradation of 4-chlorophenol and the antibacterial activity against Escherichia coli (E. coli). As a well-known catalyst, pure titanium-di-oxide (TiO₂) had not shown the photocatalytic activity in the visible light region. Hence, band position of TiO₂ need to be shifted to bring out the absorption in the visible light region. For this purpose, the n-type TiO₂ nanocrystalline material's band gap got varied by adding different ratios of p-type CuO. The result had appeared in the formation of p (CuO) – n (TiO₂) junction synthesized from sol-gel followed by chemical precipitation methods. The optical band gap value was determined by Kubelka-Munk (K-M) plot through UV–Vis diffusive reflectance spectroscopy (DRS). Further, the comprehensive mechanism and the results of photocatalytic and antibacterial activities were discussed in detail. These investigations are made for tuning the TiO₂ catalyst towards improving or eliminating the existing various environmental damages.
Show more [+] Less [-]Co-oxidative removal of arsenite and tetracycline based on a heterogeneous Fenton-like reaction using iron nanoparticles-impregnated biochar
2021
Fu, Dun | Kurniawan, Tonni Agustiono | Li, Heng | Wang, Haitao | Wang, Yuanpeng | Li, Qingbiao
A highly efficient, eco-friendly and relatively low-cost catalyst is necessary to tackle bottlenecks in the treatment of industrial wastewater laden with heavy metals and antibiotic such as livestock farm and biogas liquids. This study investigated co-oxidative removal of arsenite (As(III)) and tetracycline (TC) by iron nanoparticles (Fe NP)-impregnated carbons based on heterogeneous Fenton-like reactions. The composites included Fe NP@biochar (BC), Fe NP@hydrochar (HC), and Fe NP@HC-derived pyrolysis char (HDPC). The functions of N and S atoms and the loading mass of the Fe NP in the Fe NP@BC in heterogeneous Fenton-like reactions were studied. To sustain its cost-effectiveness, the spent Fe NP@BC was regenerated using NaOH. Among the composites, the Fe NP@BC achieved an almost complete removal of As(III) and TC under optimized conditions (1.0 g/L of dose; 10 mM H₂O₂; pH 6; 4 h of reaction; As(III): 50 μM; TC: 50 μM). The co-oxidative removal of As(III) and TC by the Fe NP@ BC was controlled by the synergistic interactions between the Fe NPs and the active N and S sites of the BC for generating reactive oxygen species (ROS). After four consecutive regeneration cycles, about 61 and 95% of As(III) and TC removal were attained. This implies that the spent carbocatalyst still has reasonable catalytic activities for reuse. Overall, this suggests that adding technological values to unused biochar as a carbocatalyst like Fe NP@BC was promising for co-oxidative removal of As(III) and TC from contaminated water.
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