The versatility of nanocellulose, modification strategies, and its current progress in wastewater treatment and environmental remediation.

Deterioration in the environmental ecosystems through the depletion of nonrenewable resources and the burden of deleterious contaminants is considered a global concern. To this end, great interest has been shown in the use of renewable and environmentally-friendly reactive materials dually to promote environmental sustainability and cope with harmful contaminants. Among the different available options, the use of nanocellulose (NC) as an environmentally benign and renewable natural nanomaterial is an attractive candidate for environmental remediation owing to its miraculous physicochemical characteristics. This review discusses the intrinsic properties and the structural aspects of different types of NC, including cellulose nanofibrils (CNFs), cellulose nanocrystals (CNCs), and bacterial cellulose (BC) or bacterial nanocellulose (BNC). Also, the different modification strategies involving the functionalization or hybridization of NC by using different functional and reactive materials aimed at wastewater remediation have been elaborated. The modified or hybridized NC has been explored for its applications in the removal or degradation of aquatic contaminants through adsorption, filtration, coagulation, catalysis, photocatalysis, and pollutant sensing. This review highlights the role of NC in the modified composites and describes the underlying mechanisms involved in the removal of contaminants. The life-cycle assessment (LCA) of NC is discussed to unveil the hidden risks associated with its production to the final disposal. Moreover, the contribution of NC in the promotion of waste management at different stages has been described in the form of the five-Rs strategy. In summary, this review provides rational insights to develop NC-based environmentally-friendly reactive materials for the removal and degradation of hazardous aquatic contaminants.

Application of layered double hydroxide enriched with electron rich sulfide moieties (S2O42-) for efficient and selective removal of vanadium (V) from diverse aqueous medium.

The preparation of an adsorbent with highest efficiency, selectivity and stability is usually a challenging task. Herein, we prepared a thio functionalized layered double hydroxide (LDH) denoted as S2O4 LDH by intercalating a strong reducing agent (S2O42-) in the interlayers of trimetallic LDH and was applied to capture vanadium (V(V)) oxyanions from aqueous medium of diverse conditions. The successful preparation of the adsorbent was first confirmed using XRD, FTIR, EDX and CHS analyses. The results revealed that the modified LDH showed excellent performance at a wider pH range which can avoid the tedious work of adjusting pH in actual industrial wastewater treatment. The adsorption capacity was increased with temperature and obtained 379.55 mg/g at 323 K comparing to 112.3 mg/g at 293 K. The adsorption isotherm was better fitted to Langmuir model which suggested monolayer adsorption behavior. At lower temperature (293 K), the sorption kinetics were fitted to a pseudo-first order reaction model which implied physisorption reaction while at higher temperatures (303 and 323 K), the reaction order fitted to pseudo-second order reaction model which highlighted the chemisorption reaction mechanism. As confirmed using XRD, FTIR, EDX and XPS instrumental techniques, the dominant removal mechanism of V(V) involved ion-exchange and partial reduction reactions to nontoxic and less soluble V(IV) and V(III) species due to the low valent sulfur group and followed adsorption in S2O4 LDH. The prepared adsorbent showed very good selectivity towards V(V) in the presence of different co-existing ions both in synthetic wastewater and spiked real water samples. This novel adsorbent also exhibited high recyclability and obtained >90.0% removal of V(V) after four consecutive adsorption-desorption cycles due to the unique memory effect of the LDH. We believe that this strategy provides a new direction to find highly efficient and selective materials for capturing vanadium ions from wastewater of diverse conditions.

Biotemplate-Mediated Green Synthesis and Applications of Nanomaterials.

Green synthesis, an emerging field in bionanotechnology, refers to the utilization of non-toxic, biologically safe, and eco-friendly substances for the synthesis of desired materials. It provides both economic and environmental benefits along with simple, cost-effective, and reproducible synthesis approaches that result in the development of stable materials. The green synthesis approaches use living biotemplates, including plants and different microorganisms such as viruses, bacteria, fungi, algae, and actinomycetes. The various metabolites present in different parts of the plants, such as leaves, fruits, seeds, flower, and others, serve as the reducing and stabilizing agents. At the same time, the diverse surface chemistry of microorganisms enables them to convert different substrates into a variety of nanomaterials. This review briefly describes the concept of 'green synthesis' and provides an overview of controlled and green synthesis of nanomaterials using the plants and microbial cells as biotemplates. It also discusses the effect of different reaction conditions such as temperature, pH, reaction time, precursor concentration, and the post-synthesis processing of nanoparticles (NPs) on the material properties. It further describes the applications of different NPs in pharmaceutical and environment sectors by considering their diverse antimicrobial, anticancer, antioxidant, antiviral, antimalarial, reduction, and catalytic properties. Finally, it describes various future perspectives of nanomaterials to broaden the understanding of their synthesis mechanism and expand their applications to other fields.

Regulating the redox centers of Fe through the enrichment of Mo moiety for persulfate activation: A new strategy to achieve maximum persulfate utilization efficiency.

Persulfate Fe-based catalytic oxidation is considered as one of the most attractive strategy for the growing concerns of water pollution. However, the undesirable FeIII/FeII redox cycle restrict them from attending the sustainable activity during practical applications. This study was intended to develop a new strategy to regulate the redox cycles of FeIII/FeII by introducing the second redox center of MoS42- in the interlayers of Fe-based layered double hydroxide (FeMgAl-MoS4 LDH). Based on the first-order kinetic model, the fabricated FeMgAl-MoS4 catalyst was 10-100 fold more reactive than the bench marked peroxymonosulfate (PMS) activators including FeMgAl LDHs and other widely reported nano-catalysts such as Co3O4, Fe3O4, α-MnO2, CuO-Fe3O4 and Fe3O4. The enhanced catalytic activity of FeMgAl-MoS4 LDH was related to the continuous regeneration of active sites (FeII/MoIV), excellent PMS utilization efficiency and generation of abundant free radicals. Moreover, the FeMgAl-MoS4/PMS system shows an effective pH range from 3.0 to 7.0 and the degradation kinetics of parahydroxy benzoic acid (PHB) were not effected in the presence of huge amount of background electrolytes and natural organic matters. Based on the in-situ electron paramagnetic resonance spectroscopy (EPR), chemical scavengers, XPS analysis and gas chromatography couple with mass spectrometer (GC-MS), a degradation pathway based on dominant free radicals (•SO4- and •OH), passing through the redox cycles of FeIII/FeII and MoVI/MoIV was proposed for PMS activation. We believe that this strategy of regulating the redox center through MoS42- not only provides a base to prepare new materials with stable catalytic activity but also broaden the scope of Fe-based material for real application of contaminated water.

Non-radical PMS activation by the nanohybrid material with periodic confinement of reduced graphene oxide (rGO) and Cu hydroxides.

A new strategy was applied by periodic stacking of active sites of Cu and reduced graphene oxide (rGO) in the form of Cu-rGO LDH nanohybrid material. The experimental results revealed that newly prepared Cu-rGO LDH nanohybrid material was extremely reactive in PMS activation as evident from the degradation rate of 0.115 min-1, much higher than Mn-rGO LDH (0.071 min-1), Zn-rGO LDH (0.023 min-1) or other benchmarked material used during the degradation of bisphenol A (BPA). This excellent activity of Cu-rGO LDH nanohybrid was attributed to the better PMS utilization efficiency as compared to the other catalysts. Additionally, the characterization techniques disclosed that the layer by layer arrangement of active sites in the Cu-rGO LDH catalyst promotes interfacial electron mobility owing to the synergistic association between Cu in LDH and interlayered rGO. Based on the in-situ electron paramagnetic resonance spectroscopy (EPR) and chemical scavengers, singlet oxygen (1O2) was unveiled as dominant reactive species for pollutant removal, resulting from the recombination of superoxides (O2-) or reduction of active Cu centers. We believe that this novel Cu-rGO LDH/PMS system will open up a new avenue to design efficient metal-carbon nanohybrid catalysts for the degradation of emerging aquatic pollutants in a real application.

Tuning of Persulfate Activation from a Free Radical to a Nonradical Pathway through the Incorporation of Non-Redox Magnesium Oxide.

Nonradical-based advanced oxidation processes for pollutant removal have attracted much attention due to their inherent advantages. Herein we report that magnesium oxides (MgO) in CuOMgO/Fe3O4 not only enhanced the catalytic properties but also switched the free radical peroxymonosulfate (PMS)-activated process into the 1O2 based nonradical process. CuOMgO/Fe3O4 catalyst exhibited consistent performance in a wide pH range from 5.0 to 10.0, and the degradation kinetics were not inhibited by the common free radical scavengers, anions, or natural organic matter. Quantitative structure-activity relationships (QSARs) revealed the relationship between the degradation rate constant of 14 substituted phenols and their conventional descriptor variables (i.e., Hammett constants σ, σ-, σ+), half-wave oxidation potential (E1/2), and pKa values. QSARs together with the kinetic isotopic effect (KIE) recognized the electron transfer as the dominant oxidation process. Characterizations and DFT calculation indicated that the incorporated MgO alters the copper sites to highly oxidized metal centers, offering a more suitable platform for PMS to generate metastable copper intermediates. These highly oxidized metals centers of copper played the key role in producing O2•- after accepting an electron from another PMS molecule, and finally 1O2 as sole reactive species was generated from the direct oxidation of O2•- through thermodynamically feasible reactions.

Adsorptive purification of heavy metal contaminated wastewater with sewage sludge derived carbon-supported Mg(II) composite.

A rod-like SDBC-Mg(II) composite was synthesized and optimized in the conditions of 25% Mg(II) loading and 500 °C calcination temperature. As-prepared SDBC-25%Mg(II)-500 adsorbent attained equilibrium in 30 min, with an extraordinary capacity of 2931.76 mg g-1 (Pb(II)) and 861.11 mg g-1 (Cd(II)), revealing a promising adsorbent for the removal of such metals so far. The adsorption kinetics was well described by the pseudo-second-order model while the adsorption isotherm could be fitted by Redlich-Peterson model. Furthermore, SDBC-25%Mg(II)-500 has a high anti-interference and selectivity in the presence of competing ions/other environmental factors and, also effectively eliminates >99% of Pb2+, Cd2+, Ag+ and Cu2+ ions from pond water, lake water and tap water. The adsorption process demonstrated a synergetic adsorption mechanism comprised of ion exchange with Mg(II), coordination with surface and inner carboxylic or carbonyl functional groups and co-precipitations as metal silicates, which is responsible for its superb adsorption performance. Besides, surface carvings of Mg(II) and tunnels on the rods resulting from the sludge carbonization provided a high surface area (91.57 m2 g-1), extra sorption sites and room for easy pollutant diffusion which contributed to surface physical adsorption. Furthermore, this technique demonstrate an alternative pathway that will relieve the burdens of sewage sludge treatment process and turn this solid waste into highly efficient adsorbent for eliminating heavy metal ions from wastewater. This can be considered as a feasible waste resource utilization to meet with the requirement from both ecology and economy for auspicious applications in industries.

Facile synthesis of yolk shell Mn2O3@Mn5O8 as an effective catalyst for peroxymonosulfate activation.

Yolk shell Mn2O3@Mn5O8 was prepared through a facile synthetic procedure and was demonstrated to be a highly efficient and stable catalyst in peroxymonosulfate (PMS) activation for the catalytic degradation of organic contaminants. Mn2O3@Mn5O8 exhibits much improved activity compared with other classic manganese catalysts such as ε-MnO2, Mn2O3 and Mn3O4, and this performance was due to its yolk shell structure, mesoporous shell, well-defined interior voids, particular particle size and mixed valence states. The long-term stability and efficiency of Mn2O3@Mn5O8 was observed in activating PMS to generate sulfate radicals for the removal of various organic pollutants such as phenol, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DP) and 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous medium. The effects of the initial solution pH, influence of anions, catalyst stability and the temperature effect on 4-CP degradation were also investigated. Furthermore, electron paramagnetic resonance (EPR) spectroscopy and radical quenching tests were employed to investigate sulfate, hydroxyl, superoxide radicals and even 1O2 for organic degradation processes. Finally, a possible activation pathway of Mn2O3@Mn5O8/PMS was proposed that involved the inner-sphere interactions between the HSO5- and the catalyst surface, electron transfer from Mn species to PMS, and the generation of sulfate radicals. These findings provide new insights into PMS activation by using nano-particle catalysts of non-toxic metal oxides.

Fe-MoS4: An Effective and Stable LDH-Based Adsorbent for Selective Removal of Heavy Metals.

It has always been a serious challenge to design efficient, selective, and stable absorbents for heavy-metal removal. Herein, we design layered double hydroxide (LDH)-based Fe-MoS4, a highly efficient adsorbent, for selective removal of heavy metals. We initially synthesized FeMgAl-LDH and then enriched its protective layers with MoS42- anions as efficient binding sites for heavy metals. Various characterization tools, such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray, X-ray photoelectron spectroscopy (XPS), CHN analysis, and inductively coupled plasma analysis, were applied to confirm structural and compositional changes during the synthesis of Fe-MoS4 as final product. The prepared Fe-MoS4 offered excellent attraction for heavy metals, such as Hg2+, Ag+, Pb2+, and Cu2+, and displayed selectivity in the order Hg2+ ∼ Ag+ > Pb2+ > Cu2+ > Cr6+ > As3+ > Ni2+ ∼ Zn2+ ∼ Co2+. The immense capacities of Hg2+, Ag+, and Pb2+ (583, 565, and 346 mg/g, respectively), high distribution coefficient (Kd ∼ 107-108), and fast kinetics place Fe-MoS4 on the top of materials list known for removal of such metals. The sorption kinetics and isothermal studies conducted on Hg2+, Ag+, Pb2+, and Cu2+ suit well pseudo-second-order kinetics and Langmuir model, suggesting monolayer chemisorption mechanism through M-S linkages. XRD and FTIR studies suggested that adsorbed metals could result as coordinated complexes in LDH interlayer region. More interestingly, LDH structure offers protective space for MoS42- anions to avoid oxidation under ambient environments, as confirmed by XPS studies. These features provide Fe-MoS4 with enormous capacity, good reusability, and excellent selectivity even in the presence of huge concentration of common cations.