Colloidal Behaviors of Two-Dimensional Titanium Carbide in Natural Surface Waters: The Role of Solution Chemistry.

Although two-dimensional titanium carbide (Ti3C2Tx MXene) has emerged as a shining star material in various communities, its environmental behaviors and fate remain unknown. Herein, the colloidal properties and stability of Ti3C2Tx MXene are explored in aquatic systems for the first time, considering the roles of solution chemistry conditions (e.g., pH, ionic types, and strength). It was found that pH had no effect on the stability of Ti3C2Tx in the range of 5.0-11.0, whereas ionic valence and concentrations displayed significant effects on the aggregation behavior of Ti3C2Tx. By employing time-resolved dynamic light scattering measurements, the critical coagulation concentration (CCC) value of Ti3C2Tx was determined to be 12 mM for NaCl. The divalent cations Ca2+ and Mg2+ exhibited higher destabilizing capacity to Ti3C2Tx, as evidenced by the lower CCC values (0.3 and 0.4 mM for CaCl2 and MgCl2, respectively) and faster coagulation rates. Long-term stability studies implied that Ti3C2Tx MXene was less likely to be transported over long distances in the synthetic or natural waters. These findings provided significant insights into the fate and transport of Ti3C2Tx in the aquatic environment.

A computational study on the tunability of woven covalent organic frameworks for photocatalysis.

A newly reported woven covalent organic framework (COF-505) with a stable and flexible structure is believed to be a promising candidate for photocatalysis. Here, we carried out density functional theory calculations to investigate the properties of COF-505 related to photocatalysis. We first investigated the ability of visible light absorption by this COF-505. Variations of central metal ions and the dihedral angle between two adjacent ligand groups were respectively taken into account for adjusting its light harvesting capabilities. Replacing the original Cu(i) ions with Pd(ii) ions causes a red shift in the visible light region. Increasing the dihedral angle results in an increase of the band gap for COF-505 with Cu(i) and a decrease for COF-505 with Pd(ii), respectively. The potential of COF-505 as a photocatalyst was furthermore explored by studying the adsorption of H2, CO2 and H2O on it. All molecules can be stably adsorbed. In particular, COF-505 with Pd(ii) exhibits appreciable O-H activation of the adsorbed H2O in the presence of a positive charge, which is promising for initiating water splitting. Overall, our results suggest that COF-505 holds great potential for photocatalytic applications.

Metal-organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions.

Highly efficient removal of metal ion pollutants, such as toxic and nuclear waste-related metal ions, remains a serious task from the biological and environmental standpoint because of their harmful effects on human health and the environment. Recently, highly porous metal-organic frameworks (MOFs), with excellent chemical stability and abundant functional groups, have represented a new addition to the area of capturing various types of hazardous metal ion pollutants. This review focuses on recent progress in reported MOFs and MOF-based composites as superior adsorbents for the efficient removal of toxic and nuclear waste-related metal ions. Aspects related to the interaction mechanisms between metal ions and MOF-based materials are systematically summarized, including macroscopic batch experiments, microscopic spectroscopy analysis, and theoretical calculations. The adsorption properties of various MOF-based materials are assessed and compared with those of other widely used adsorbents. Finally, we propose our personal insights into future research opportunities and challenges in the hope of stimulating more researchers to engage in this new field of MOF-based materials for environmental pollution management.

Nanoscale zero-valent iron/magnetite carbon composites for highly efficient immobilization of U(VI).

Nanoscale zerovalent iron/magnetic carbon (NZVI/MC) composites were successfully synthesized by simply calcining yellow pine and iron precursors. NZVI/MC pyrolyzed at 800°C (NZVI/MC800) had a higher percentage of NZVI and displayed better resistance to aggregation and oxidation of NZVI than samples prepared at other temperatures. The NZVI/MC800 material was applied for the elimination of U(VI) from aqueous solutions. The results suggested that the NZVI/MC800 displayed excellent adsorption capacity (203.94 mg/g) toward U(VI). The significant adsorption capacity and fast adsorption kinetics were attributed to the presence of well-dispersed NZVI, which could quickly reduce U(VI) into U(IV), trapping the guest U(IV) in the porous biocarbon matrix. The removal of U(VI) on the NZVI/MC samples was strongly affected by solution pH. The NZVI/MC samples also displayed outstanding reusability for U(VI) removal after multiple cycles. These findings indicate that NZVI/MC has great potential for remediation of wastewater containing U(VI).

Exploring the Aggregation Mechanism of Graphene Oxide in the Presence of Radioactive Elements: Experimental and Theoretical Studies.

In this study, the aggregation kinetics, aggregate morphology, and aggregation mechanisms of graphene oxide (GO) in the presence of Cs+, Sr2+, UO22+, Eu3+, or Th4+ are characterized by using time-resolved dynamic light scattering, transmission electron microscopy (TEM)-element mapping, redispersion of GO aggregates, and density functional theory (DFT) calculations. The destabilization capability of Cs+, Sr2+, UO22+, Eu3+, and Th4+ and the corresponding values of the critical coagulation concentration (CCC) are obtained for the first time. Polyacrylic acid is used as a dispersant to investigate the reversion of GO aggregates induced by various radioactive elements. The combined results of the poly(acrylic acid) effect and TEM-element mapping show that Cs+ induces the aggregation of GO through electric double-layer suppression and weak binding with oxygen-containing functional groups. By employing DFT calculations, we find that the electrostatic potential distribution and the charge transfer rather than coordination with oxygen-containing functional groups control the destabilizing ability of radioactive elements with a higher valence. A comprehensive process of experimental and theoretical studies is considered to better elucidate the colloidal behavior, self-assembly process, application as a novel adsorbent, and environmental risks of GO.

New Synthesis of nZVI/C Composites as an Efficient Adsorbent for the Uptake of U(VI) from Aqueous Solutions.

New nanoscale zerovalent iron/carbon (nZVI/C) composites were successfully prepared via heating natural hematite and pine sawdust at 800 °C under nitrogen conditions. Characterization by SEM, XRD, FTIR, and XPS analyses indicated that the as-prepared nZVI/C composites contained a large number of reactive sites. The lack of influence of the ionic strength revealed inner-sphere complexation dominated U(VI) uptake by the nZVI/C composites. Simultaneous adsorption and reduction were involved in the uptake process of U(VI) according to the results of XPS and XANES analyses. The presence of U-C/U-U shells demonstrated that innersphere complexation and surface coprecipitation dominated the U(VI) uptake at low and high pH conditions, respectively. The uptake behaviors of U(VI) by the nZVI/C composites were fitted well by surface complexation modeling with two weak and two strong sites. The maximum uptake capacity of U(VI) by the nZVI/C composites was 186.92 mg/g at pH 4.0 and 328 K. Additionally, the nZVI/C composites presented good recyclability and recoverability for U(VI) uptake in regeneration experiments. These observations indicated that the nZVI/C composites can be considered as potential adsorbents to remove radionuclides for environmental remediation.

Plasma-Facilitated Synthesis of Amidoxime/Carbon Nanofiber Hybrids for Effective Enrichment of 238U(VI) and 241Am(III).

Plasma- and chemical-grafted amidoxime/carbon nanofiber hybrids (p-AO/CNFs and c-AO/CNFs) were utilized to remove 238U(VI) and 241Am(III) from aqueous solutions, seawater, and groundwater. Characteristic results indicated more nitrogen-containing groups in p-AO/CNFs compared to c-AO/CNFs. The maximum adsorption capacities of p-AO/CNFs at pH 3.5 and T = 293 K (588.24 mg of 238U(VI)/g and 40.79 mg of 241Am(III)/g from aqueous solutions, respectively) were significantly higher than those of c-AO/CNFs (263.18 and 22.77 mg/g for 238U(VI) and 241Am(III), respectively), which indicated that plasma-grafting was a highly effective, low-cost, and environmentally friendly method. Adsorption of 238U(VI) on AO/CNFs from aqueous solutions was significantly higher than that of 238U(VI) from seawater and groundwater; moreover, AO/CNFs displayed the highest effective selectivity for 238U(VI) compared to the other radionuclides. Adsorption of 238U(VI) onto AO/CNFs created inner-sphere complexes (e.g., U-C shells) as shown by X-ray absorption fine structure analysis, which was supported by surface complexation modeling. Three inner-sphere complexes gave excellent fits to pH-edge and isothermal adsorption of 238U(VI) on the AO/CNFs. These observations are crucial for the utilization of plasma-grafted, AO-based composites in the preconcentration and immobilization of lanthanides and actinides in environmental remediation.

New Insight into GO, Cadmium(II), Phosphate Interaction and Its Role in GO Colloidal Behavior.

This study establishes the relationship between the graphene oxide (GO) colloidal behavior and the co-adsorption of Cd(II) and phosphate (P(V)) on GO. Results reveal that the interactions among GO, Cd(II), and P(V) exhibit a significant dependence on solution chemistry and addition sequences and that these interactions subsequently affect the GO colloidal behavior. The GO aggregation is pH-dependent at pH < 4.0 and depends apparently on the binding ability of Cd(II) to GO at pH > 4.0. When the components were added simultaneously, the presence of P(V) enhances the GO binding capacity toward Cd(II), confirmed by theoretical calculation, resulting in the greater destabilizing influence of Cd(II) + P(V) on GO than Cd(II) at pH 3.0-9.5, while the formation of Cd3(PO4)2 precipitate leads to a lower destabilizing influence of Cd(II) + P(V) on GO than Cd(II) at pH > 9.5. Both pH and addition sequence affect the destabilizing ability of Cd(II) + P(V). These new insights are expected to provide valuable information not only for the application of GO as a potential adsorbent in multicomponent systems for heavy metal ion and oxyanion co-removal but also for the fate and risk assessment of GO after serving as heavy metal ion and oxyanion carrier.

Impact of Al2O3 on the aggregation and deposition of graphene oxide.

To assess the environmental behavior and impact of graphene oxide (GO) on living organisms more accurately, the aggregation of GO and its deposition on Al2O3 particles were systematically investigated using batch experiments across a wide range of solution chemistries. The results indicated that the aggregation of GO and its deposition on Al2O3 depended on the solution pH and the types and concentrations of electrolytes. MgCl2 and CaCl2 destabilized GO because of their effective charge screening and neutralization, and the presence of NaH2PO4 and poly(acrylic acid) (PAA) improved the stability of GO with the increase in pH values as a result of electrostatic interactions and steric repulsion. Specifically, the dissolution of Al2O3 contributed to GO aggregation at relatively low pH or high pH values. Results from this study provide critical information for predicting the fate of GO in aquatic-terrestrial transition zones, where aluminum (hydro)oxides are present.

Plasma-induced, N-doped, and reduced graphene oxide-incorporated NiCo-layered double hydroxide nanowires as a high-capacity redox mediator for sustainable decoupled water electrolysis.

Although the recent emergence of decoupled water electrolysis prevents typical H2/O2 mixing, the further development of decoupled water electrolysis has been confined by the lack of reliable redox mediator (RM) electrodes to support sustainable H2 production. As energy storage electrodes, layered double hydroxides (LDHs) possess inherently poor conductivity/stability, which can be improved by growing LDHs on graphene substrates in situ. The proper modification of the graphene surface structure can improve the electron transport and energy storage capacity of composite electrodes, while current methods are usually cumbersome and require high temperatures/chemical reagents. Therefore, in this study, dip coating was adopted to grow graphene oxide (GO) on nickel foam (NF). Then, the GO was reduced using nonthermal plasma (NTP) to reduced GO (rGO) in situ while simultaneously implementing N doping to obtain plasma-assisted N-doped rGO on NF (PNrGO/NF). The uniform conductive substrate ensured the subsequent growth of less-aggregated NiCo-LDH nanowires, which improved the conductivity and energy storage capacity (5.93 C/cm2 at 5 mA/cm2) of the NiCo-LDH@PNrGO/NF. For the decoupled system, the composite RM electrode exhibited a high buffering capacity for 1300 s during the decoupled H2/O2 evolution, and in the conventional coupled system, the necessary input voltage of 1.67 V was separated into two lower ones, 1.42/0.33 V for H2/O2 evolutions, respectively. Simultaneously, the RM possessed outstanding redox reversibility and structural stability during long-term cycling. This work could offer a feasible strategy for using NTP to synthesize excellent RM electrodes for application to decoupled water electrolysis.

Highly efficient enrichment of radionuclides on graphene oxide-supported polyaniline.

Graphene oxide-supported polyaniline (PANI@GO) composites were synthesized by chemical oxidation and were characterized by SEM, Raman and FT-IR spectroscopy, TGA, potentiometric titrations, and XPS. The characterization indicated that PANI can be grafted onto the surface of GO nanosheets successfully. The sorption of U(VI), Eu(III), Sr(II), and Cs(I) from aqueous solutions as a function of pH and initial concentration on the PANI@GO composites was investigated. The maximum sorption capacities of U(VI), Eu(III), Sr(II), and Cs(I) on the PANI@GO composites at pH 3.0 and T = 298 K calculated from the Langmuir model were 1.03, 1.65, 1.68, and 1.39 mmol·g(-1), respectively. According to the XPS analysis of the PANI@GO composites before and after Eu(III) desorption, nitrogen- and oxygen-containing functional groups on the surface of PANI@GO composites were responsible for radionuclide sorption, and that radionuclides can hardly be extracted from the nitrogen-containing functional groups. Therefore, the chemical affinity of radionuclides for nitrogen-containing functional groups is stronger than that for oxygen-containing functional groups. This paper focused on the application of PANI@GO composites as suitable materials for the preconcentration and removal of lanthanides and actinides from aqueous solutions in environmental pollution management in a wide range of acidic to alkaline conditions.

Volatile organic compounds degradation by nonthermal plasma: a review.

Volatile organic compounds (VOCs) have posed a severe threat on both ecosystem and human health which thus have gained much attention in recent years. Nonthermal plasma (NTP) as an alternative to traditional methods has been employed to degrade VOC in the atmosphere and wastewater for its high removal efficiency (up to 100%), mild operating conditions, and environmental friendliness. This review outlined the principles of NTP production and the applications on VOC removal in different kinds of reactors, like single/double dielectric barrier discharge, surface discharge, and gliding arc discharge reactors. The combination of NTP with catalysts/oxidants was also applied for VOC degradation to further promote the energy efficiency. Further, detailed explanations were given of the effect of various important factors including input/reactor/external conditions on VOC degradation performance. The reactive species (e.g., high-energy electrons, HO·, O·, N2+, Ar+, O3, H2O2) generated in NTP discharge process have played crucial roles in decomposing VOC molecules; therefore, their variation under different parameter conditions along with the reaction mechanisms involved in these NTP technologies was emphatically explained. Finally, a conclusion of the NTP technologies was presented, and special attention was paid to future challenges for NTP technologies in VOC treatment to stimulate the advances in this topic.

Efficient adsorption and reduction of Cr(VI) from aqueous solution by Santa Barbara Amorphous-15 (SBA-15) supported Fe/Ni bimetallic nanoparticles.

Nanoscale zero-valent iron (nZVI or Fe0) can rapidly reduce Cr(VI) contaminants in the water environment, but the agglomeration and passivation of the Fe0 system have adverse effects on its application. In this study, a novel mesoporous Santa Barbara Amorphous-15 supported Fe/Ni bimetallic composite (SBA-15@Fe/Ni) is proposed to remove Cr(VI). The proposed material can enhance the stability and removal capacity of the nZVI system. The results show that the unique six-way through-hole structure of SBA-15 provides a place for the dispersion of Fe0 particles. Meanwhile, SBA-15 effectively alleviates the accumulation of Fe0 particles. The removal efficiency of SBA-15@Fe/Ni is better than two single systems (SBA-15 and Fe/Ni). The removal efficiency of SBA-15@Fe/Ni towards Cr(VI) can reach 97.62% after 60 min at pH 4.0. SBA-15@Fe/Ni still maintains excellent performance in the presence of various competitive ions (Cl-, SO42-, CO32-, NO3-). At 298 K, the maximum removal capacity of SBA-15@Fe/Ni towards Cr(VI) is 180.99 mg/g. The possible removal process of SBA-15@Fe/Ni towards Cr(VI) is divided into the following steps: First, Cr(VI) is attracted into the vicinity of the SBA-15@Fe/Ni channel by the electrostatic attraction; Second, the reduction of Cr(VI) occurs after contacting with the Fe/Ni system, and its driving force mainly comes from nZVI and Fe(II); Furthermore, the introduction of Ni can promote Cr(VI) reduction through electron transfer and catalytic hydrogenation. In conclusion, adopting SBA-15@Fe/Ni to treat chromium contamination is an effective and promising approach.

High buffering capacity cobalt-doped nickel hydroxide electrode as redox mediator for flexible hydrogen evolution by two-step water electrolysis.

Two-step water electrolysis has been proposed to tackle the ticklish H2/O2 mixture problems in conventional alkaline water electrolysis recently. However, low buffering capacity of pure nickel hydroxide electrode as redox mediator limited practical application of two-step water electrolysis system. A high-capacity redox mediator (RM) is urgently needed to permit consecutive operation of two-step cycles and high-efficiency hydrogen evolution. Consequently, a high mass-loading cobalt-doped nickel hydroxide/active carbon cloth (NiCo-LDH/ACC) RM is synthesized via a facile electrochemical method. The proper Co doping can apparently enhance the conductivity and simultaneously remain the high-capacity of the electrode. Density functional theory results further confirms more negative values in redox potential of NiCo-LDH/ACC than Ni(OH)2/ACC on account of the charge redistribution induced by Co doping, which can prevent the parasitic O2 evolution on RM electrode during decoupled H2 evolution step. As a result, the NiCo-LDH/ACC combined the superiorities of high-capacity Ni(OH)2/ACC and high-conductivity Co(OH)2/ACC, and the NiCo-LDH/ACC with 4:1 ratio of Ni to Co presented a large specific capacitance of 33.52F/cm2 for reversible charge-discharge and high buffering capacity with two-step H2/O2 evolution duration of 1740 s at 10 mA/cm2. The necessary input voltage (2.00 V) of the whole water electrolysis was broken into two smaller ones, 1.41 and 0.38 V, for H2 and O2 production, respectively. NiCo-LDH/ACC provided a favorable electrode material for the practical application of two-step water electrolysis system.

Mechanisms and degradation pathways of doxycycline hydrochloride by Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres activated peroxymonosulfate.

Peroxymonosulfate (PMS) based advanced oxidation processes have gained widespread attention in refractory antibiotics treatment. In this study, Fe3O4 nanoparticles anchored nitrogen-doped porous carbon microspheres (Fe3O4/NCMS) were synthesized and applied to PMS heterogeneous activation for doxycycline hydrochloride (DOX-H) degradation. Benefitting from synergy effects of porous carbon structure, nitrogen doping, and fine dispersion of Fe3O4 nanoparticles, Fe3O4/NCMS showed excellent DOX-H degradation efficiency within 20 min via PMS activation. Further reaction mechanisms revealed that the reactive oxygen species including hydroxyl radicals (•OH) and singlet oxygen (1O2) played the dominant role for DOX-H degradation. Moreover, Fe(II)/Fe(III) redox cycle also participated in the radical generation, and nitrogen-doped carbonaceous structures served as the highly active centers for non-radical pathways. The possible degradation pathways and intermediate products accompanying DOX-H degradation were also analyzed in detail. This study provides key insights into the further development of heterogeneous metallic oxides-carbon catalysts for antibiotic-containing wastewater treatment.

Three-dimensional ordered macroporous molybdenum doped NiCoP honeycomb electrode for two-step water electrolysis.

Two-step alkaline water electrolysis is considered a safe and efficient method for producing hydrogen from renewable energy. Reversal of the current polarity in a bifunctional electrocatalyst used as a gas evolution electrode (GEE) in two-step water electrolysis can generate H2/O2 at different times and in different spaces. The design of a bifunctional electrocatalyst with high durability and excellent activity is imperative to achieving continuous, safe, and pure H2 generation via two-step alkaline water electrolysis. Here, we present for the first time a novel 3D Mo-doped NiCo phosphide honeycomb electrocatalyst that was grown on nickel foam (3D Mo-NiCoP/NF) and fabricated using polystyrene as a template. The electrocatalyst exhibited extremely low overpotentials in both the hydrogen evolution reaction (HER; 117 mV at 10 mA/cm2) and the oxygen evolution reaction (OER; 344 mV at 100 mA/cm2). As a bifunctional electrocatalyst for two-step alkaline water electrolysis, the device had a 1.784 V cell voltage at 10 mA/cm2, 95% decoupling efficiency, and ∼83% energy conversion efficiency. Taken together, the use of 3D Mo-NiCoP/NF as a GEE reduced the complexity and lowered the cost of the electrolyzer. The latter could be used to construct highly competitive water-splitting systems for continuous H2 production and green energy harvesting.

Nitrate removal under low carbon to nitrogen ratio by modified corn straw bioreactor: Optimization and possible mechanism.

ABSTRACTThe removal of nitrate (NO3--N) from water bodies under the conditions of poor nutrition and low carbon to nitrogen (C/N) ratio is a widespread problem. In this study, modified corn stalk (CS) was used to immobilize Burkholderia sp. CF6 with cellulose-degrading and denitrifying abilities. The optimal operating parameters of the bioreactor were explored. The results showed that under the hydraulic retention time (HRT) of 3 h and the C/N ratio of 2.0, the maximum nitrate removal efficiency was 96.75%. In addition, the organic substances in the bioreactor under different C/N ratios and HRT were analyzed by three-dimensional fluorescence excitation-emission mass spectrometry (3D-EEM), and it was found that the microorganisms have high metabolic activity. Scanning electron microscope (SEM) showed that the new material has excellent immobilization effects. Fourier transform infrared spectrometer (FTIR) showed that it has potential as a solid carbon source. Through high-throughput sequencing analysis, Burkholderia sp. CF6 was observed as the main bacteria present in the bioreactor. These research results showed that the use of waste corn stalks waste provides a theoretical basis for the advanced treatment of low C/N ratio wastewater.

Pd-doped HKUST-1 MOFs for enhanced hydrogen storage: effect of hydrogen spillover.

Extensive research has been devoted to developing metal nanoparticle (NP) doped porous materials with large hydrogen storage capacity and high hydrogen release pressure at ambient temperature. The ultra-sound assisted double-solvent approach (DSA) was applied for sample synthesis. In this study, tiny Pd NPs are confined into the pore space of HKUST-1, affording Pd@HKUST-1-DS with minimizing the aggregation of Pd NPs and subsequently the formation of Pd NPs on the external surface of HKUST-1. The experimental data reveal that the obtained Pd NP doped Pd@HKUST-1-DS possessed an outstanding hydrogen storage capacity of 3.68 wt% (and 1.63 wt%) at 77 K and 0.2 MPa H2 (and 298 K and 18 MPa H2), in comparison with pristine HKUST-1 and impregnated Pd/HKUST-1-IM. It is found that the storage capacity variation is not only ascribed to the different textural properties of materials but is also illustrated by the hydrogen spillover induced by different electron transport from Pd to the pores of MOFs (Pd@HKUST-1-DS > Pd/HKUST-1-IM), based on X-ray photoelectron spectroscopy and temperature desorption spectra. Pd@HKUST-1-DS, featuring high specific surface area, uniform Pd NP dispersion and strong interaction of Pd with hydrogen in the confined pore spaces of the support, displays the high hydrogen storage capacity. This work highlights the influence of spillover caused by Pd electron transport on the hydrogen storage capacity of metal NPs/MOFs, which is governed by both physical and chemical adsorption.