Designing Magnesium Phosphate Cement for Stabilization/Solidification of Zn-Rich Electroplating Sludge.

Electroplating sludge is a hazardous waste due to its high potential to leach toxic elements into the natural environment. To alleviate this issue, we tailored magnesium phosphate cement (MPC) as a low-carbon material for stabilization/solidification (S/S) of Zn-rich electroplating sludge. The interaction between MPC and ZnO was investigated to clarify the precipitate chemistry, microstructure transition, and chemical environment of Zn species in the MPC-treated Zn sludge system. Comprehensive characterization (by X-ray diffraction (XRD), 31P nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure spectroscopy (EXAFS)) and thermodynamic modeling results revealed that the incorporated ZnO preferentially reacted with phosphate to form Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O, changing the orthophosphate environment in the MPC system. Stronger chemical bonding between Zn and phosphate in comparison to the bonding between Mg and phosphate also resulted in the formation of amorphous Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O. Zn3(PO4)2·4H2O precipitate appears to predominate at high {K+}{H+}{HPO42-} values, and the formation of Zn3(PO4)2·2H2O/Zn3(PO4)2·4H2O competed for the Mg sites in the MPC system, leading to the inhibition of formation of Mg-phosphate precipitates. Overall, this work uncovers the precipitate chemistry and microstructure transition of Zn species in the MPC system, providing new insights into the sustainable S/S of Zn-contaminated wastes by adopting MPC.

Electroactive Fe-biochar for redox-related remediation of arsenic and chromium: Distinct redox nature with varying iron/carbon speciation.

Electroactive Fe-biochar has attracted significant attention for As(III)/Cr(VI) immobilization through redox reactions, and its performance essentially lies in the regulation of various Fe/C moieties for desired redox performance. Here, a series of Fe-biochar with distinct Fe/C speciation were rationally produced via two-step pyrolysis of iron minerals and biomass waste at 400-850 °C (BCX-Fe-Y, X and Y represented the first- and second-step pyrolysis temperature, respectively). The redox transformation of Cr(VI) and As(III) by Fe-biochar was evaluated in simulated wastewater under oxic or anoxic conditions. Results showed that more effective Cr(VI) reduction could be achieved by BCX-Fe-400, while a higher amount of As (III) was oxidized by BCX-Fe-850 under the anoxic environment. Besides, BCX-Fe-400 could generate more reactive oxygen species (e.g.,•OH) by reducing the O2, which enhanced the redox-related transformation of pollutants under the oxic situation. The evolving redox performance of Fe-biochar was governed by the transition of the redox state from reductive to oxidative related to the Fe/C speciation. The small-sized amorphous/low-crystalline ferrous minerals contributed to a higher electron-donating capacity (0.43-1.28 mmol g-1) of BCX-Fe-400. In contrast, the oxidative surface oxygen-functionalities (i.e., carboxyl and quinoid) on BCX-Fe-850 endowed a stronger electron-accepting capacity (0.71-1.39 mmol g-1). Moreover, the graphitic crystallites with edge-type defects and porous structure facilitated the electron transfer, leading to a higher electron efficiency of BCX-Fe-850. Overall, we unveiled the roles of both Fe and C speciation in maneuvering the redox reactivity of Fe-biochar, which can advance our rational design of electroactive Fe-biochar for redox-related environmental remediation.

Stoichiometric carbocatalysis via epoxide-like C-S-O configuration on sulfur-doped biochar for environmental remediation.

Heteroatom doping is a promising technique to enhance biochar for effective environmental remediation. However, development of electroactive heteroatom-doped biochars, e.g., sulfur-doped biochar, has been hindered due to complex nature of non-stoichiometric biomass-derived carbon and changeable electrochemical state of dopants. Herein, we produced a series of wood waste-derived biochars with customized levels of minerals and redox-active moieties, aiming to unravel the crucial factors for sulfur doping. Calcium (Ca) in biochar was found to preferentially coordinate with sulfur to form inactive inorganic sulfur minerals (i.e., CaSO4 and CaS) with inferior catalytic reactivity. After diminishing the inherent Ca minerals beforehand, we could introduce surface phenoxyl-type radicals (C-O•) and vacancy defects on the biochar to develop an electrophilic C-S-O bonding configuration, which guaranteed a high affinity towards peroxymonosulfate (PMS, 2.08 mM g-1, 30 min) and efficient removal of bisphenol A (BPA, 91.1%, 30 min). Scavenging experiments and in-situ Raman analyses indicated that the epoxide-like C-S-O structure induced nucleophilic addition of PMS to generate surface-bound singlet oxygen (1O2, major) and hydroxyl radicals (•OH, minor) through a preservative and stoichiometric interfacial reaction. Overall, the proposed approach overcomes the major hurdles in science-informed fabrication of sulfur-doped biochar and advances its development for environmental remediation.

Interactions between biochar and clay minerals in changing biochar carbon stability.

The science-informed design of stable carbonaceous materials as 'green' soil amendment will be indispensable for improving the soil fertility and carbon sequestration ability. In this study, a series of biochars were prepared from mineral-rich cellulosic corn straw (C), lignocellulosic pine wood (P), and lignin-rich walnut shell (W) at 500 or 700 °C. Their change of carbon stability after 90-day interaction with two typical soil clay minerals (i.e., kaolinite or montmorillonite) under a field-relevant condition (mass ratio of biochar to soil clay at 1:5) was evaluated as carbon loss (%) determined by the K2CrO7-H2SO4 oxidation method. The spectroscopic analyses demonstrated that the highly graphitized and microporous W-biochars exhibited a high carbon stability (35.6-40.2% C loss) that could be further enhanced in the presence of kaolinite or montmorillonite. This promotion was probably ascribed to the transformation from the aromatic CC/CC functionality to the ester CO and methyl CH configurations on the biochar surface forming stable organo-mineral complexes (i.e., COAl) with the clay minerals. In contrast, a substantial level of labile C fraction was observed in the C- and P-biochars (e.g., 94.8% C loss of P700-M) after incubation with the clay minerals, especially for montmorillonite with high CEC, swelling capacity, and week interlayer bonding. This adverse impact was possibly attributed to the aliphatic CC/CC bonding with low oxidation resistance after co-precipitation with the clay minerals. The results of this study can provide deeper insight into the evolution of physicochemical properties, porous structure, and carbon interactions during long-term biochar application for carbon sequestration and sustainable development.

Insights into the adsorption of pharmaceuticals and personal care products (PPCPs) on biochar and activated carbon with the aid of machine learning.

The science-informed design of 'green' carbonaceous materials (e.g., biochar and activated carbon) with high removal capacity of recalcitrant organic contaminants (e.g., pharmaceuticals and personal care products (PPCPs)) is indispensable for promoting sustainable wastewater treatment. In this study, machine learning (ML) incorporating PPCPs and biochar properties as well as adsorption conditions were applied to build adsorption prediction models and explore the contributions of various biochar's inherent properties to their PPCPs adsorption capacity. The results demonstrated that the models developed by detailed biochar properties (e.g., surface functionality and hierarchical porous structure) from advanced microscopic and spectroscopic techniques were more accurate (i.e., the root-mean-square error decreased by 18-24%) than those by general information such as bulk elemental composition and total pore volume. The relative importance of surface carbon functionalities ranked in the order of C-O bond > CO bond > non-polar carbon for predicting the adsorption capacity. According to the partial dependence analysis, the average pore diameters of adsorbents that were larger than the maximum diameter of PPCPs molecules by 1.5-fold to 2.5-fold favored the PPCPs adsorption. This study reveals new insights into the adsorption of PPCPs and provides a comprehensive reference for the sustainable engineering of biochar adsorbents for PPCPs wastewater treatment.

A review on percarbonate-based advanced oxidation processes for remediation of organic compounds in water.

Sodium percarbonate (SPC) is considered a potential alternative to liquid hydrogen peroxide (H2O2) in organic compounds contaminated water/soil remediation due to its regularly, transportable, economical, and eco-friendly features. The solid state of SPC makes it more suitable to remediate actual soil and water with a milder H2O2 release rate. Apart from its good oxidative capacity, alkaline SPC can simultaneously remediate acidized solution and soil to the neutral condition. Conventionally, percarbonate-based advanced oxidation process (P-AOPs) system proceed through the catalysis under ultraviolet ray, transition metal ions (i.e., Fe2+, Fe3+, and V4+), and nanoscale zero-valent metals (iron, zinc, copper, and nickel). The hydroxyl radical (•OH), superoxide radical (•O2-), and carbonate radical anion (•CO3-) generated from sodium percarbonate could attack the organic pollutant structure. In this review, we present the advances of P-AOPs in heterogeneous and homogeneous catalytic processes through a wide range of activation methods. This review aims to give an overview of the catalysis and application of P-AOPs for emerging contaminants degradation and act as a guideline of the field advances. Various activation methods of percarbonate are summarized, and the influence factors in the solution matrix such as pH, anions, and cations are thoroughly discussed. Moreover, this review helps to clarify the advantages and shortcomings of P-AOPs in current scientific progress and guide the future practical direction of P-AOPs in sustainable carbon catalysis and green chemistry.

Critical Impact of Nitrogen Vacancies in Nonradical Carbocatalysis on Nitrogen-Doped Graphitic Biochar.

Nitrogen-doped graphitic biochar (NBC) has boosted the development of nonradical peroxymonosulfate (PMS) activation in environmental remediation. However, the specific role of nitrogen species played in NBC-based nonradical carbocatalysis remains vaguely interpreted. To pinpoint the critical nitrogen speciation, a sophisticated thermo-mechanochemical manipulation was exploited to prepare a series of NBCs with similar dimensional structures and oxygen levels but different nitrogen species (i.e., dopants and vacancies). Different from conventional perspectives, nonradical NBC-based carbocatalysis was found to be preferably determined by the nitrogen vacancies more than their parent nitrogen dopants. Raman depth analysis evidenced that a complete transformation of nitrogen dopants into nitrogen vacancies could be achieved at 800 °C, where an excellent nonradical abatement of 4-chlorophenol (4-CH, 90.9% removal) was found for the NBC800 with a low PMS consumption (1.24 mM). According to PMS adsorption experiments, nitrogen vacancies exhibited the highest affinity toward the PMS molecules compared to nitrogen dopants, which accounted for the superior carbocatalysis. Electron paramagnetic resonance and Raman spectroscopic analyses indicated that the original PMS molecules were bound to positively charged nitrogen vacancies, and a robust metastable complex (*HSO5-) evolved subsequently via hydrogen abstraction by adjacent persistent free radicals. In situ Raman techniques could be adopted to estimate the level of nitrogen vacancies associated with the polarization of electron distribution. The flexible feature and practical prospects of nitrogen vacancy-based carbocatalysis were also observed in the remediation of simulated phenolic industrial wastewater. Overall, this study unravels the dilemma in the current NBC-based nonradical carbocatalysis and advances our understanding of nitrogen doping technology for next-generation biochar design.

Performance indicators for a holistic evaluation of catalyst-based degradation-A case study of selected pharmaceuticals and personal care products (PPCPs).

Considerable efforts have been made to develop effective and sustainable catalysts, e.g., carbon-/biochar-based catalyst, for the decontamination of organic pollutants in water/wastewater. Most of the published studies evaluated the catalytic performance mainly upon degradation efficiency of parent compounds; however, comprehensive and field-relevant performance assessment is still in need. This review critically analysed the performance indicators for carbon-/biochar-based catalytic degradation from the perspectives of: (1) degradation of parent compounds, i.e., concentrations, kinetics, reactive oxidative species (ROS) analysis, and residual oxidant concentration; (2) formation of intermediates and by-products, i.e., intermediates analysis, evolution of inorganic ions, and total organic carbon (TOC); and (3) impact assessment of treated samples, i.e., toxicity evolution, disinfection effect, and biodegradability test. Five most frequently detected pharmaceuticals and personal care products (PPCPs) (sulfamethoxazole, carbamazepine, ibuprofen, diclofenac, and acetaminophen) were selected as a case study to articulate the performance indicators for a holistic evaluation of carbon-/biochar-based catalytic degradation. This review also encourages the development of alternative performance indicators to facilitate the rational design of catalysts in future studies.

Simultaneous degradation of p-arsanilic acid and inorganic arsenic removal using M-rGO/PS Fenton-like system under neutral conditions.

In this study, magnetic material based reduced graphene oxide (M-rGO) was prepared through co-precipitation and displayed high catalytic efficiency together with persulfate (PS) for simultaneous p-arsanilic acid (p-ASA) decomposition and arsenic removal. Linear sweep voltammetry and chronoamperometric measurements with M-rGO revealed that PS was effectively bound to M-rGO surface and probably formed charge transfer complex, in which M-rGO was pivotal in mediating facile electron transfer. The effects of pH, temperatures, anions, p-ASA concentration, PS, and M-rGO dosages on p-ASA decomposition were studied in the system. Excellent degradation of p-ASA was carried out at a wide range of pH values, which was unattainable by other Fenton-like processes. Under optimal conditions, M-rGO exhibited prominent removal of both p-ASA (98.8 %) and inorganic arsenic (89.8 %). M-rGO had reasonably excellent repeatability and stability, and 77.7 % p-ASA degraded in the third recovered catalyst. The advantages of environmental friendliness, short reaction time, and straightforward synthesis of M-rGO will facilitate the development of heterogeneous Fenton-like catalysts under neutral conditions.

Ball milling as a mechanochemical technology for fabrication of novel biochar nanomaterials.

Mechanochemical synthesis of nano-biochar by ball-milling technology is gaining attention for the sake of its low-cost and eco-friendly nature. Ball milling as a non-/less-solvent technology can propel environmental sustainability and waste valorization into engineered biochar for advanced applications. Scalable production of biochar nanomaterials with superior properties (e.g., 400-500 m2 g-1 surface area and 0.5-1000 nm pore sizes) enables diverse applications in the field of energy and environment. This review critically evaluates the synthesis, characterization, and application of ball-milled biochar nanomaterials based on the latest findings. Limitations such as feedstock selection, process optimization, product homogeneity and reusability, environmental risks, and sustainability assessment remain challenging for further studies. This work highlights the recent advances on mechanochemical biochar technology and offer insights into opportunities and future prospects related to sustainable and facile synthesis of biochar-based novel materials for achieving sustainable development goals.

Fabrication of sustainable manganese ferrite modified biochar from vinasse for enhanced adsorption of fluoroquinolone antibiotics: Effects and mechanisms.

An effective adsorbent towards fluoroquinolone antibiotics was synthesized via a facile two-step approach, the co-precipitation of Fe, Mn with vinasse wastes and then pyrolysis under controlled conditions which denoted as FMB. Its adsorption behavior was examined based on a batch adsorption experiment of fluoroquinolone antibiotics pefloxacin (PEF) and ciprofloxacin (CIP). Experimental factors, such as pH, adsorbent dose, ionic strength, contact time and temperature have done a great deal to influence the adsorption of PEF and CIP. The FMB demonstrated excellent performance in reusability tests towards to both PEF and CIP, which showed that the recycling efficiency of PEF and CIP could remain ~55% and ~80% after five recycle cycles, respectively. The dominated adsorption mechanisms included pore filling effect, π-π stacking interaction, π-π EDA, hydrogen bonding and hydrophobicity. Overall, this work presented FMB was recognized as an effective, environmental-friendly and magnetically separable adsorbent for alleviating fluoroquinolone antibiotics contamination from water.

Concurrent adsorption and micro-electrolysis of Cr(VI) by nanoscale zerovalent iron/biochar/Ca-alginate composite.

This study introduced a new approach for simultaneously enhancing Cr(VI) removal performance and mitigating release of dissolved Fe during nanoscale zero-valent iron (nZVI)-mediated reactions. After entrapping nZVI-impregnated biochar (BC) in the matrix of calcium-alginate (CA) bead, the physicochemical characterization of nZVI/BC/CA composites revealed that nZVI/BC particles were embedded inside CA having a spherical shape and several cracks on its outer layer. The multi-functionality of nZVI/BC/CA composites consisting of reductant (nZVI), porous adsorbent (BC), and external screening layer (CA) enhanced the removal of Cr(VI) with the maximum adsorption capacity of 86.4 mg/g (based on the Langmuir isotherm) and little release of dissolved Fe. With the XPS analysis and fitting results of kinetics (pseudo second order) and isotherms (Redlich-Peterson model), plausible removal mechanisms of Cr(VI) were simultaneous adsorption and micro-electrolysis reactions by nZVI/BC/CA composites. The practical applicability of nZVI/BC/CA composites was further demonstrated through the fixed-bed column experiments. These results provide new insights into the design of high-performance engineered biochar for wastewater treatment.

Concurrent reduction-adsorption of chromium using m-phenylenediamine-modified magnetic chitosan: kinetics, isotherm, and mechanism.

Magnetic chitosan particles (MCS) were chemically grafted by m-phenylenediamine (mPD) forming a distinctive shell layer with abundant nitrogenous functional groups and used as an adsorbent for the effective removal of Cr(VI) from aqueous solution. By interaction among functional groups in the facile oxidative polymerization process, the grafting of mPD and its polymers on MCS surface was innovatively realized. Through Fourier-transformed infrared spectroscopy, energy dispersive spectrometer, X-ray photoelectron spectroscopy, etc., the chemical properties of MCS before and after modification were characterized and the concurrent reduction-adsorption mechanism in Cr(VI) adsorption by mPD-MCS was carefully analyzed. The maximal Cr(VI) removal performance of mPD-MCS reached 227.27 mg/g, which was significantly better than that of the original MCS. The analysis indicated that Cr(VI) could be efficiently reduced to Cr(III) and the removal of Cr(VI) and Cr(III) was through adsorption and chelation simultaneously by mPD-MCS. Results also indicated that the concurrent reduction-adsorption was enhanced by protonation of nitrogenous functional groups under low pH. The obtained results suggest that mPD-MCS has a good potential in removal and detoxication of Cr(VI) from aqueous solutions.