A multiple Kirkendall strategy for converting nanosized zero-valent iron to highly active Fenton-like catalyst for organics degradation.

Nanosized zero-valent iron (nZVI) is a promising persulfate (PS) activator, however, its structurally dense oxide shell seriously inhibited electrons transfer for O-O bond cleavage of PS. Herein, we introduced sulfidation and phosphorus-doped biochar for breaking the pristine oxide shell with formation of FeS and FePO4-containing mixed shell. In this case, the faster diffusion rate of iron atoms compared to shell components triggered multiple Kirkendall effects, causing inward fluxion of vacancies with further coalescing into radial nanocracks. Exemplified by trichloroethylene (TCE) removal, such a unique "lemon-slice-like" nanocrack structure favored fast outward transfer of electrons and ferrous ions across the mixed shell to PS activation for high-efficient generation and utilization of reactive species, as evidenced by effective dechlorination (90.6%) and mineralization (85.4%) of TCE. [Formula: see text] contributed most to TCE decomposition, moreover, the SnZVI@PBC gradually became electron-deficient and thus extracted electrons from TCE with achieving nonradical-based degradation. Compared to nZVI/PS process, the SnZVI@PBC/PS system could significantly reduce catalyst dosage (87.5%) and PS amount (68.8%) to achieve nearly complete TCE degradation, and was anti-interference, stable, and pH-universal. This study advanced mechanistic understandings of multiple Kirkendall effects-triggered nanocrack formation on nZVI with corresponding rational design of Fenton-like catalysts for organics degradation.

A novel PEI-grafted N-doping magnetic hydrochar for enhanced scavenging of BPA and Cr(VI) from aqueous phase.

Herein, polyethyleneimine (PEI)-grafted nitrogen-doping magnetic hydrochar (PEIMW@MNHC) was synthesized for hexavalent chromium (Cr(VI)) and bisphenol A (BPA) elimination from water. Characterizations exhibited that abundant amino functional groups, intramolecular heterocyclic N, azo and Fe-NX structures were successfully introduced into the inherent structure of hydrochar. The obtained PEIMW@MNHC presented maximum uptake of 205.37 and 180.79 mg/g for Cr(VI) and BPA, respectively, and was highly tolerant to various co-existing ions. Mechanism investigation revealed that the protonated amino, intramolecular heterocyclic N and Fe(II) participated in Cr(VI) reduction, and the N/O-containing groups and Fe(III) fixed Cr(III) onto PEIMW@MNHC by the formation of complexes and precipitates. On the other hand, azo, Fe-NX and graphitic N structures contributed to the removal of BPA via pore filling, hydrogen bonding and π-π interactions. Additionally, PEIMW@MNHC maintained over 85.0% removal efficiency for Cr(VI) and BPA after four cycles, manifesting that PEIMW@MNHC was an ideal adsorbent with outstanding practical application potential.

One-pot synthesis of porous N-doped hydrochar for atrazine removal from aqueous phase: Co-activation and adsorption mechanisms.

KOH-activated N-doped hydrochar (KHCN) was synthesized via co-activation method to eliminate atrazine (AT) in water efficiently. Compared to primitive HC, KHCN had advantages of splendid specific surface area (1205.82 m2/g) and developed microsphere structures on the surface. Specially for KHCN, the extra melamine added strengthened and preserved partial structure of polar oxygen-containing groups that were decomposed in the process of pore making. Besides, the estimated uptake amount of AT onto KHCN (216.50 mg/g) was remarkably superior to KHC (114.25 mg/g). KHCN exhibited the pH-dependence for AT removal, and presented excellent uptake capacity at a relatively neutral environment. Notably, the proposed mechanisms for AT removal by KHCN included electrostatic attraction, pore filling, π-π EDA, H-bond as well as hydrophilic effect. Hence, the porous N-doped hydrochar was a kind of adsorbent which was easy to prepare and had the application prospect for AT removal in natural water.

Polyethylenimine-grafted nitrogen-doping magnetic biochar for efficient Cr(VI) decontamination: Insights into synthesis and adsorption mechanisms.

Herein, polyethylenimine (PEI)-grafted nitrogen (N)-doping magnetic biochar (PEIMW@MNBCBM) was synthesized, and characterization results showed that the microwave-assisted PEI grafting and ball milling-assisted N doping introduced abundant amino, pyridine N and pyrrole N structures onto biochar, which possessed high affinity to Cr(VI) in the anion form. The as-prepared PEIMW@MNBCBM displayed pH-dependence adsorption performance and high tolerance to co-existing ions with maximum uptake capacity of Cr(VI) identified as 183.02 mg/g. Furthermore, PEIMW@MNBCBM could bind Cr(VI) through electrostatic attraction, complexion, precipitation, reduction and pore filling. Especially, effective reduction of Cr(VI) was ascribed to cooperative electron transfer of partial oxygen-containing functional groups, intramolecular pyridine/pyrrole N, protonated amino and Fe2+ on the adsorbent, while oxygen-containing and amino functional groups from N-doping biochar and PEI synergistically complexed Cr(III) via providing lone pair electrons to form coordinate bonds. Furthermore, the stable precipitation was formed between Fe3+ and Cr(III). Additionally, the Cr(VI) elimination efficiency could maintain 95.83% even after four adsorption-desorption cycles, suggesting PEIMW@MNBCBM as a high-performance adsorbent for Cr(VI) contaminated water remediation.

Microwave-assisted synthesis of polyethylenimine-grafted nanocellulose with ultra-high adsorption capacity for lead and phosphate scavenging from water.

Herein, polyethylenimine-grafted nanocellulose (PEIMW@NCMW) was synthetized through microwave-assisted synthesis, which was employed for Pb(II) and phosphate scavenging from water. Characterization results exhibited that the original pomegranate peel-derived cellulose could be transformed to nanometer level by microwave radiation and the amino groups were successfully grafted on the nanocellulose evenly. The adsorption performance of PEIMW@NCMW possessed outstanding improvements over that of original nanocellulose with maximum adsorption capacities reaching 916.02 mg/g for Pb(II) and 278.89 mg/g for phosphate. Furthermore, the PEIMW@NCMW had high tolerance to various co-existing ions and could maintain over 94% removal efficiency during four regeneration cycles. Additionally, the Pb(II) uptake onto PEIMW@NCMW was associated with electrostatic attraction, complexation and pore-filling, whereas high phosphate capture was achieved via H-bonding, complexation and electrostatic attraction. In summary, PEIMW@NCMW was deemed as a potential adsorbent with excellent adsorption capacity for remediation of Pb(II) and phosphate polluted water.

Hydrothermal carbonization of alfalfa: role of processing variables on hydrochar properties.

Hydrothermal carbonization of alfalfa is a potential way to reuse agricultural waste. However, the effects of hydrothermal conditions on the properties of alfalfa-derived hydrochar are not clear. Herein, this study investigated the impact of different synthesis conditions (e.g., heating temperature, heating time, and solid to liquid ratio) on the formation and properties of hydrochar. Characterization and thermogravimetric analysis results revealed that with the increase of hydrothermal temperature and the extension of time, cellulose in alfalfa broken down more completely, and the number of carbon spheres and the aromatization degree increased, while the functional groups decreased. Furthermore, there was a surge in the carbon content, fixed carbon yield, high heating value, reduced oxygen, and volatile content. Additionally, the enhancement solid-liquid ratio could effectively improve the energy and mass yields. In all, by adjusting the process parameters of hydrochar, cleaner and higher productivity products could be obtained. This study provides theory basis for the production of target hydrochar that is used to soil amendments, adsorbents, and energy sources in the future.

Pinecone-derived magnetic porous hydrochar co-activated by KHCO3 and K2FeO4 for Cr(VI) and anthracene removal from water.

Herein, magnetic porous pinecone-derived hydrochar (MPHCMW) co-activated by KHCO3 and K2FeO4 through one-step microwave-assisted pyrolysis was innovatively synthesized for hexavalent chromium (Cr(VI)) and anthracene (ANT) removal from water. The analyses of characterization consequences and co-activation mechanisms not merely proved the high specific surface area (703.97 m2/g) and remarkable microporous structures of MPHCMW caused by the synergistic chemical activation of KHCO3 and K2FeO4, but also testified successful loading of Fe0 and Fe3O4 on MPHCMW by the process of carbothermal reduction between K2FeO4 and carbon matrix of hydrochar. The resultant MPHCMW possessed pH-dependence for Cr(VI), while adsorption for ANT was hardly impacted by the pH of solution. Moreover, the adsorption processes of MPHCMW could attain equilibrium within 60 min for Cr(VI) and 30 min for ANT with multiple kinetics, and the corresponding adsorption capacity for Cr(VI) and ANT was 128.15 and 60.70 mg/g, respectively. Additionally, the adsorption percentages of MPBCMW for Cr(VI)/ANT was maintained at 87.87/82.64% after three times of adsorption-desorption cycles. Furthermore, pore filling, complexation, electrostatic interaction, reduction and ion exchange were testified to enhance the removal of Cr(VI), while the ANT removal was achieved via π-π stacking, complexation, pore filling and hydrogen bonding force.

Two-step ball milling-assisted synthesis of N-doped biochar loaded with ferrous sulfide for enhanced adsorptive removal of Cr(â ¥) and tetracycline from water.

Nitrogen-doped biochar loaded with FeS (FeS@NBCBM) was synthesized by two-step ball milling processes. Characterization results revealed that N-doping process successfully introduced pyridinic, pyrrolic, and graphitic N structures, and FeS was subsequently embedded in N-doped biochar (NBCBM). The resultant FeS@NBCBM presented predominant adsorption capacity for Cr(VI) (194.69 mg/g) and tetracycline (TC, 371.29 mg/g) compared with BC (27.28 and 37.89 mg/g) and NBCBM (71.26 and 81.26 mg/g). In addition, the Cr(VI)/TC elimination process by FeS@NBCBM was basically stable with multiple co-existing ions with slight decrease on adsorption performance after three desorption-regeneration cycles. Most importantly, FeS@NBCBM was found to achieve Cr(VI) elimination not only by electrostatic attraction, ion exchange and complexation, but also by electrons-triggered reduction provided by different species of N, Fe2+ as well as S(Ⅱ). Meantime, pore filling, hydrogen bonding, and π-π stacking interactions were demonstrated to contribute to TC adsorption. These results suggested the co-modification of N-doping and FeS loading by ball milling as an innovative decorating method for biochar to adsorptive purification of Cr(VI) and TC-contaminated water.