Biochar has triggered a black gold rush in environmental studies as a carbon-rich material with well-developed porous structure and tunable functionality. While much attention has been placed on its ...apparent ability to store carbon in the ground, immobilize soil pollutants, and improve soil fertility, its temporally evolving in situ performance in these roles must not be overlooked. After field application, various environmental factors, such as temperature variations, precipitation events and microbial activities, can lead to its fragmentation, dissolution, and oxidation, thus causing drastic changes to the physicochemical properties. Direct monitoring of biochar-amended soils can provide good evidence of its temporal evolution, but this requires long-term field trials. Various artificial aging methods, such as chemical oxidation, wet–dry cycling and mineral modification, have therefore been designed to mimic natural aging mechanisms. Here we evaluate the science of biochar aging, critically summarize aging-induced changes to biochar properties, and offer a state-of-the-art for artificial aging simulation approaches. In addition, the implications of biochar aging are also considered regarding its potential development and deployment as a soil amendment. We suggest that for improved simulation and prediction, artificial aging methods must shift from qualitative to quantitative approaches. Furthermore, artificial preaging may serve to synthesize engineered biochars for green and sustainable environmental applications.
Biochars have demonstrated great potential for water decontamination and soil remediation; however, their redox reactivity toward trace contaminants and the corresponding redox-active moieties (RAMs, ...i.e., phenolic −OH, semiquinone-type persistent free radicals (PFRs), and quinoid CO) remain poorly understood. Here we investigated the roles of the RAMs on biochar in oxidation of As(III) under varying pH and O2 conditions. The results showed that the promoted oxidation of As(III) by the RAMs is strongly pH dependent. Under acidic and neutral conditions, only the oxidation of As(III) by •OH and H2O2 produced from activation of O2 by phenolic −OH and semiquinone-type PFRs occurred. In contrast, the oxidation by semiquinone-type PFRs, quinoid CO, and H2O2 (if O2 was introduced) appeared under alkaline conditions. This pH-dependent oxidation behavior was attributed to the varying redox activities of RAMs, as confirmed by multiple characterization and validation experiments using biochar with tuned RAMs compositions, as well as thermodynamics evaluation. Our findings provide new insights into the roles of the RAMs on biochar in the promoted oxidation of trace As(III) over a broader pH range under both anoxic and oxic conditions. This study also paves a promising way to oxidize As(III) with biochar.
Acceleration of the anaerobic digestion (AD) process is crucial to achieving energy-efficient recycling of organic wastes. Hydrochar is produced by hydrothermal liquefaction of biomass, yet its ...application in the AD process is rarely reported. The present study showed that sewage sludge-derived hydrochar (SH) enhanced the methane production rate of glucose by 37%. SH increased the methane production rate from acetate but did not affect acidification and the methane production rate from H2/CO2. SH enhanced hydrogenotrophic methanogenesis, which could be due to direct interspecies electron transfer (DIET) by converting H+, e–, and CO2 to methane. Trichococcus and Methanosaeta were dominant in the AD process with SH. Label-free proteomic analysis showed Methanosaeta was involved in DIET as reflected by the up-regulation of proteins involved in hydrogenotrophic methanogenesis. Hydrochars derived from corn straw (CH), Enteromorpha algae (EH), and poplar wood (PH), as well as activated carbon (AC), were also tested in the AD process. SH, CH, and EH obviously increased the methane production rates, which were 39%, 15%, and 20% higher than the control experiment, respectively. It was neither electrical conductivity nor the total redox property of hydrochars and AC but the abundances of surface oxygen-containing functional groups that correlated to the methane production rates.
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.
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•Lignin structures vary with different extraction process and affect product yields.•Native lignin enables effective valorization towards chemicals and biofuels.•Valorization ...strategies in relation to initial lignin structures are evaluated.•Advances in analytical technologies hold promise for lignin valorization.
Lignin is one of the most promising renewable sources for aromatic hydrocarbons, while effective depolymerization towards its constituent monomers is a particular challenge because of the structural complexity and stability. Intensive research efforts have been directed towards exploiting effective valorization of lignin for the production of bio-based platform chemicals and fuels. The present contribution aims to provide a critical review of key advances in the identification of exact lignin structure subjected to various fractionation technologies and demonstrate the key roles of lignin structures in depolymerization for unique functionalized products. Various technologies (e.g., thermocatalytic approaches, photocatalytic conversion, and mechanochemical depolymerization) are reviewed and evaluated in terms of feasibility and potential for further upgrading. Overall, advances in pristine lignin structure analysis and conversion technologies can facilitate recovery and subsequent utilization of lignin towards tailored commodity chemicals and fungible fuels.
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•The porous biochar carrier can facilitate the TCE removal by alleviating aggregation of iron nanoparticles and enhancing PMS activation.•The biochar catalysts manifested a superior ...catalytic performance of PMS activation for TCE degradation.•The catalytic performance of Fe-CB600 out-performed other fabricated catalysts.•The superoxide radical and singlet oxygen were validated as predominant ROSs and oxygen containing group played the key role in PMS activation.
High-efficiency and cost-effective catalysts are critical to completely mineralization of organic contaminants for in-situ groundwater remediation via advanced oxidation processes (AOPs). The engineered biochar is a promising method for waste biomass utilization and sustainable remediation. This study engineers maize stalk (S)- and maize cob (C)-derived biochars (i.e., SB300, SB600, CB300, and CB600, respectively) with oxygen-containing functional groups as a carbon-based support for nanoscale zero-valent iron (nZVI). Morphological and physiochemical characterization showed that nZVI could be impregnated within the framework of the synthesized Fe-CB600 composite, which exhibited the largest surface area, pore volume, iron loading capacity, and Fe0 proportion. Superior degradation efficiency (100% removal in 20 min) of trichloroethylene (TCE, 0.1 mM) and fast pseudo-first-order kinetics (kobs =22.0 h−1) were achieved via peroxymonosulfate (PMS, 5 mM) activation by the Fe-CB600 (1 g L−1) under groundwater condition (bicarbonate buffer solution at pH = 8.2). Superoxide radical and singlet oxygen mediated by Fe0 and oxygen-containing group (i.e., CO) were demonstrated as the major reactive oxygen species (ROSs) responsible for TCE dechlorination. The effectiveness and mechanism of the Fe/C composites for rectifying organic-contaminated groundwater were depicted in this study.
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•Biomass conversion to HMF significantly depends on catalysts and solvents.•Bifunctional catalyst caters for tandem hydrolysis, isomerization, and dehydration.•Lewis-to-Brønsted acid ...ratio and acid strength primarily determine HMF selectivity.•Co-solvents are kinetically and thermodynamically favourable for HMF production.•Biphasic system enhances HMF selectivity by suppressing side reactions.
Conversion of biomass waste to hydroxymethylfurfural (HMF), a value-added platform chemical, has captured great research interests driven by the economic and environmental incentives. This review evaluates the recent development of biomass conversion systems for high HMF yield and selectivity, with a focus on the performance of emerging catalysts and solvents from a mechanistic view. We highlight that the ratio and strength of Brønsted and Lewis acid in bifunctional catalyst are critical for maximizing HMF production by selective improvement in the kinetics of desirable reactions (hydrolysis, isomerization, and dehydration) over undesirable reactions (rehydration, polymerization). The characteristics of solvent mixture such as functional groups and speciation govern the reactivity of substrate towards desirable reactions and stability of HMF and intermediates against side reactions. Research efforts to unravel the interactions among co-catalysts/co-solvents and between catalysts and solvents are encouraged, thereby engineering a synergistic conversion system for biomass valorization.
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•Corn stalk biochar is engineered with hydrophilic functionality and hierarchical pores.•Fe0-HCS composites combine advantages of porous biochar with iron nanoparticles.•Fast kinetics ...and high adsorption capacity of Pb2+, Cu2+ and Zn2+ are demonstrated.•Multiple mechanisms are involved in metal removal by Fe0-HCS composites.
Pyrolyzing low-cost agro-waste into biochar is a promising means for waste biomass utilization. This study engineers corn stalk-derived biochar with abundant hydrophilic functional groups as a support material for iron nanoparticles impregnation (nZVI-HCS). Surface chemistry and morphology of nZVI-HCS composites is characterized by SEM, TEM, TG, XRD, FTIR, XPS, and BET techniques, which helps to elucidate the mechanisms of Pb2+, Cu2+ and Zn2+ removal from single and mixed-metal solutions in batch experiments. Equilibrium adsorption capacities can reach 195.1, 161.9 and 109.7 mg·g−1 for Pb2+, Cu2+ and Zn2+ at neutral medium after 6-h process, respectively. The engineered biochar with hierarchical pores can impregnate iron nanoparticles, serve as an adsorbent, and enhance metal reduction/precipitation. Rapid removal and high performance can be maintained after five regeneration/reuse cycles. Multiple interaction mechanisms including adsorption, precipitation, reduction and complexation are responsible for metal removal by nZVI-HCS composites, which can be a novel biowaste-derived material for wastewater treatment.
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•Corn stalk biochar is engineered with crystalline Zn/Al, Mg/Al, and Ni/Fe LDH flakes.•BC-M-LDH composites combine advantages of porous biochar with LDH minerals.•Fast kinetics and ...high adsorption capacity of phosphorus are demonstrated.•Interlayer ion exchange and surface complexation are involved in phosphorus recovery.
Highly efficient and cost-effective adsorbents for phosphate (P) recovery are the key to control eutrophication and recover phosphorus from waste streams to enhance food production. This study assembled corn stalk-derived biochar (BC) with various forms of layered double hydroxides (LDHs) (B-M-LDH) through simultaneous pyrolysis of waste biomass and metal (i.e., Zn/Al, Mg/Al, and Ni/Fe) hydroxide precipitates. Batch sorption experiments evaluated the kinetics and isotherms of phosphate adsorption as well as the influence of pH value and co-existing anions. Morphological characterization showed that crystalline LDH flakes were impregnated within the framework of fabricated B-M-LDH composites. Superior P adsorption capacity (152.1 mg (P) g−1) and fast Elovich kinetics (5925 mg g−1 h−1) could be achieved by the B-Zn/Al-LDH composite at pH 5. The P adsorption onto BC-LDHs was pH dependent and subjected to adverse influence of co-existing anions. Interlayer anion exchange and surface complexation were probably the predominant adsorption mechanisms at the studied phosphate concentration. Therefore, BC can be functionalized as mineral composites for enhancing P recovery and wastewater treatment.
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