Unveiling the Effects of Carbon-Based Nanomaterials on Crop Growth: From Benefits to Detriments.

To systematically assess the impact of typical CNMs on the growth effects of cereal crops, we conducted a meta-analysis of 48 independent studies worldwide. The pooled results showed that shoot weight (13.39%) and antioxidant metabolite content (SOD: 106.32%, POD: 32.29%, CAT: 22.63%) of cereal crops exposed to the presence of CNMs were significantly increased, but phytohormones secretion (17.84%) was inhibited. The results of subgroup analysis showed that there were differences in the results of different CNM types with the same exposure concentration on growth effects. Short-term exposure adversely affected the root and photosynthetic capacity of the crop, but prolonged exposure instead showed a promoting effect. Multiple linear regression analysis showed that the concentration of CNMs and cereal variety variables were significantly associated with changes in multiple growth effect values. This work could offer references and fresh perspectives for investigating how nanoparticles and crops interact.

Catalyst-Free Photochemical Activation of Peroxymonosulfate in Xanthene-Rich Systems for Fenton-Like Synergistic Decontamination: Efficacy of Proton Transfer Process.

Catalyst-free visible light assisted Fenton-like catalysis offers opportunities to achieve the sustainable water decontamination, but the synergistic decontamination mechanisms are still unclear, especially the effect of proton transfer process (PTP). The conversion of peroxymonosulfate (PMS) in photosensitive dye-enriched system was detailed. The photo-electron transfer between excited dye and PMS triggered the efficient activation of PMS and enhanced the production of reactive species. Photochemistry behavior analysis and DFT calculations revealed that PTP was the crucial factor to determine the decontamination performance, leading to the transformation of dye molecules. The excitation process inducing activation of whole system was composed of low energy excitations, and the electrons and holes were almost contributed by LUMO and HOMO. This work provided new ideas for the design of catalyst-free sustainable system for efficient decontamination.

Insight into the effect of pyrolysis temperature on photoreactivity of biochar-derived dissolved organic matter: Impacts of aromaticity and carbonyl groups.

Practical application of biochar may result in more biochar-derived dissolved organic matter (denoted as BDOM) inevitably release into surface waters by infiltration and surface runoff. The photochemical reaction of BDOM has gained intense attention, which played a key role in the fate of organic contaminants. However, the relationships between specific characteristics of BDOM and its photoreactivity are still uncertain. In this study, the characteristics of BDOM pyrolyzed from rice husk derived biochar at different temperature (from 400 °C to 700 °C) and their effect on the photodegradation of oxytetracycline (OTC) were carefully investigated. The 13C NMR and EEM results indicated the dominated component of BDOM was gradually turned from humic acid like substances with low aromaticity to high aromaticity with abundant oxygen-containing functional groups as pyrolytic temperature increases. Experimental results showed that the apparent rate constants (kobs) of BDOM700 (4.53 × 10-2 min-1) for OTC photodegradation was approximately one order of magnitude higher than BDOM400 (4.52 × 10-3 min-1), which was closely correlated with their aromaticity (R2 = 0.944). It was found that 3BDOM* rather than 1O2 played the major role in BDOM mediated photodegradation of OTC (80.13 % vs 14.34 %), and the carbonyl-containing group was identified as the main 3BDOM* precursor by NaBH4 reduction experiment. This work highlighted both aromaticity and carbonyl group contents were critical indicators for assessing the potential to generate 3BDOM* and corresponding photoreactivity.

Periodate activated by manganese oxide/biochar composites for antibiotic degradation in aqueous system: Combined effects of active manganese species and biochar.

Developing efficient catalysts for oxytetracycline (OTC) degradation is an ideal strategy to tackle environmental pollution, and advanced oxidation processes (AOPs) have been widely used for its degradation. However, the studies on the activation of periodate (PI) by biochar and its composites in recent years have been scarcely reported. In this study, we focused on the degradation of OTC by PI activation with manganese oxide/biochar composites (MnxOy@BC). Experimental results showed that the OTC degradation rate of MnxOy@BC/PI system reached almost 98%, and the TOC removal efficiency reached 75%. Various characteristic analysis proved that PI could be activated efficiently by surface functional groups and manganese-active species (Mn(II), Mn(III), and Mn(IV)) on biochar, and various reactive species such as singlet oxygen (1O2), hydroxyl radical (∙OH), and superoxide radical (O2∙-) can be observed via radical quenching experiments. Based on this, three degradation pathways were proposed. Furthermore, MnxOy@BC and PI were combined to degrade environmental pollutants, which achieved excellent practical benefits and had great practical application potential. We hope that it can provide new ideas for advanced oxidation processes (AOPs) applying for wastewater treatment in the future.

Effects of biochar-based materials on the bioavailability of soil organic pollutants and their biological impacts.

Motivated by the unique structure and superior properties, biochar-based materials, including pristine biochar and composites of biochar with other functional materials, are considered as new generation materials for diverse multi-functional applications, which may be intentionally or unintentionally released to soil. The influencing mechanism of biochar-based material on soil organisms is a key aspect for quantifying and predicting its benefits and trade-offs. This work focuses on the effects of biochar-based materials on soil organisms within the past ten years. 206 sources are reviewed and available knowledge on biochar-based materials' impacts on soil organisms is summarized from a diverse perspective, including the pollutant bioavailability changes in soil, and potential effects of biochar-based materials on soil organisms. Herein, effects of biochar-based materials on the bioavailability of soil organic pollutants are detailed, from the perspective of plant, microorganism, and soil fauna. Potential biological effects of pristine biochar (PBC), metal/metal compounds-biochar composites (MBC), clay minerals-biochar composites (CMBC), and carbonaceous materials-biochar composites (CBC) on soil organisms are highlighted for the first time. And possible mechanisms are presented based on the different characters of biochar-based materials as well as various environmental interactions. Finally, the bottleneck and challenges of risk assessment of biochar-based materials as well as future prospects are proposed. This work not only promotes the development of risk assessment system of biochar-based materials, but broadens the strategy for the design and optimization of environmental-friendly biochar materials.

Lignocellulosic biomass derived N-doped and CoO-loaded carbocatalyst used as highly efficient peroxymonosulfate activator for ciprofloxacin degradation.

Burning lignocellulosic biomass wastes in an outdoor atmosphere has placed heavy burden on ecological environment and increased risk on human health. Converting solid agricultural wastes into functional materials is a research hotspot. In this study, N-doped and CoO-loaded carbocatalyst (CoO-N/BC) was successfully synthesized from the cotton stalk biomass via a simple synthesis process of impregnation and carbonization. Compared with cotton stalk biomass derived pristine biochar, the CoO-N/BC possessed a higher specific surface area (466.631 m2 g-1vs 286.684 m2 g-1) as well as a better catalytic performance in the activation of peroxymonosulfate (PMS) for CIP degradation. The superior catalytic efficiency was ascribed to the directional flow of electrons on the well-organized carbon network of CoO-N/BC, which accelerated electron migration and improved electron conduction ability. Based on the results of radical quenching experiment and electron paramagnetic resonance (EPR), both radical and non-radical process conjointly led to the stepwise decomposition of CIP, and singlet oxygen (1O2) mediated non-radical pathway was discovered to play a dominant role. Besides, the carbon-bridge mediated non-radical pathway was proved to accelerate this degradation process through the experiments of prolong the time of adding CIP at different time intervals. Nitrogen doped sites and CoO active sites as well as defects formed in sp2-hybridized carbon network were supposed to be the active sites for PMS. Furthermore, EIS and LSV were employed to confirm the electron transfer mediated non-radical process of reaction system. This work provides a modified strategy for the disposition of lignocellulosic biomass wastes and illuminates the underlying mechanism of heterogeneous catalysis by CoO-N/BC.

Catalyst-free activation of permanganate under visible light irradiation for sulfamethazine degradation: Experiments and theoretical calculation.

In this study, visible light (VL) was adopted for permanganate (PM) activation without additional catalyst, where sulfamethazine (SMT) was selected as the probe compound. Experiment results showed that the VL/PM system can effectively degrade SMT through pseudo-first-order reaction kinetics. Influencing factors including PM dosage, solution pH, humid acid (HA) and coexisting anions (CO32-, SO42-, Cl- and NO3-) which affect SMT photo-degradation were also examined. Pyrophosphate (PP) had an inhibitory effect on SMT degradation due to the complexation of PP with Mn (III). Electron spin resonance (ESR) spectrometry and UV-Vis spectrophotometer proved that VL can activate PM to generate ·O2- and Mn (III) reactive species. Furthermore, based on the active site prediction, intermediates identification and Density Functional Theory (DFT) calculation, two main degradation pathways involving SMT molecular rearrangement and cleavage of S-N bond were proposed. Moreover, the energy barriers of the two degradation pathways were also calculated. This study offers a novel approach for aqueous SMT removal and deepens our understanding of the degradation mechanism of SMT through DFT calculation, which hopes to shed light on the future development of VL/PM treatment.

Sustainable hydrogen production by molybdenum carbide-based efficient photocatalysts: From properties to mechanism.

Hydrogen is considered to be a promising energy carrier to solve the issue of energy crisis. Molybdenum carbide (MoxC) is the typical material, which has similar properties of Pt and thought to be an attractive alternative to noble metals for H2 evolution. The study of MoxC as alternative catalyst for H2 production is almost focused on electrocatalytic field, while the application of MoxC as a co-catalyst in photocatalytic H2 evolution has received in-depth research in recent years. Particularly, MoxC exhibits significant enhancement in the H2 production performance of semiconductors under visible light irradiation. However, a review discussing MoxC serving as a co-catalysts in the photocatalytic H2 evolution is still absent. Herein, the recent progress of MoxC on photocatalytic H2 evolution is reviewed. Firstly, the preparation methods including chemical vapor deposition, temperature programming, and organic-inorganic hybridization are detailly summarized. Then, the fundamental structure, electronic properties, and specific conductance of MoxC are illustrated to illuminate the advantages of MoxC as a co-catalyst for H2 evolution. Furthermore, the different heterojunctions formed between MoxC and other semiconductors for enhancing the photocatalytic performance are emphasized. Finally, perspectives regarding the current challenges and the future research directions on the improvement of catalytic performance of MoxC-based photocatalysts are also presented.