Preparation and Characterization of an Invasive Plant-Derived Biochar-Supported Nano-Sized Lanthanum Composite and Its Application in Phosphate Capture from Aqueous Media.

Invasive plants pose a great threat to natural ecosystems owing to their rapid propagation and spreading ability in nature. Herein, a typical invasive plant, Solidago canadensis, was chosen as a novel feedstock for the preparation of nano-sized lanthanum-loaded S. canadensis-derived biochar (SCBC-La), and its adsorption performance for phosphate removal was evaluated by batch adsorption experiment. The composite was characterized by multiple techniques. Effects of parameters, such as the initial concentration of phosphate, time, pH, coexisting ions, and ionic strength, were studied on the phosphate removal. Adsorption kinetics and isotherms showed that SCBC-La shows a faster adsorption rate at a low concentration and SCBC-La exhibits good La utilization efficiency than some of the reported La-modified adsorbents. Phosphate can be effectively removed over a relatively wide pH of 3-9 because of the high pH pzc of SCBC-La. Furthermore, the SCBC-La shows a strong anti-interference capability in terms of pH value, coexisting ions, and ionic strength, exhibiting a highly selective capacity for phosphate removal. Additionally, Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) measurements reveal that hydroxyl groups on the surface of SCBC-La were replaced by phosphate and manifest the reversible transformation between La(OH)3 and LaPO4. Considering its high adsorption capacity and excellent selectivity, SCBC-La is a promising material for preventing eutrophication. This work gives a new method of pollution control with waste treatment since the invasive plant (S. canadensis) is converted into biochar-based nanocomposite for effective removal of phosphate to mitigate eutrophication.

Titanium dioxide nanoparticles functionalized chitosan toward bio-based antibacterial adsorbent for enhanced phosphate capture.

Developing an eco-friendly, sustainable and antibacterial adsorbent is significant for actual water treatment. Herein, a bio-based antibacterial adsorbent based on titanium dioxide (TiO2) nanoparticles functionalized chitosan (CS) was prepared through an in-situ hydrolysis strategy using titanium oxysulfate as the source of TiO2. The as-obtained CS/TiO2 nanocomposite was characterized by a variety of analytical techniques. According to the Langmuir mode, the adsorption capacity of CS/TiO2 reached 23.64 mg P g-1, almost 8 times higher than that of CS. In addition, the normalized adsorption capacity (adsorption value per Ti) of CS/TiO2 was calculated to be 102.68 mg P g-1 Ti-1, much higher than pure TiO2 (60.11 mg P g-1 Ti-1). Moreover, CS/TiO2 exhibited a highly selective capacity for phosphate removal in the presence of competing anions, and showed high stability in a wide pH range of 3.0-8.0. When the phosphate concentration was 2.0 mg P L-1, the removal efficiency of phosphate reached 99.5 % and the residual concentration was only 10 µg P L-1, which meets the USEPA standards for eutrophication prevention and control. In addition, after treatment by CS/TiO2, the phosphate concentration of two sewage water samples decreased from 1.50 and 1.0 mg P L-1 to <0.10 mg P L-1, meeting the standard of level II water based on the Environmental Quality Standard of China (GB3838-2002). Ligand exchange and electrostatic interactions are mainly responsible for phosphate adsorption by CS/TiO2. Furthermore, the CS/TiO2 nanocomposites exhibited excellent antibacterial activity, which could avoid biofouling contamination caused by microorganisms. Benefiting from the above advantages, the as-designed CS/TiO2 nanocomposite has great potential as a bio-based antibacterial adsorbent for phosphate capture or removal from wastewater.

A Recyclable Magnetic Aminated Lignin Supported Zr-La Dual-Metal Hydroxide for Rapid Separation and Highly Efficient Sequestration of Phosphate.

The application of lignin-based adsorbents in the efficient removal of phosphate from wastewater has attracted much attention and been intensively studied in recent years. However, most currently reported lignin-based adsorbents are difficult to recover and recycle. Herein, we have developed a recyclable, nanostructured bio-adsorbent, poly(ethyleneimine) (PEI)-modified lignin (LG) integrated with Fe3O4 and Zr-La dual-metal hydroxide (LG-NH2@Fe3O4@Zr-La), by the Mannich reaction followed by the chemical coprecipitation method. Multilayer adsorption existed on the surface of LG-NH2@Fe3O4@Zr-La based on the isotherm fitting curve, and its adsorption capacity reached 57.8 mg P g-1, exhibiting a higher phosphate uptake than most reported metallic oxide-based composites. The adsorption process was dominated by inner-sphere complexation of ligand-exchange and electrostatic interactions. Moreover, LG-NH2@Fe3O4@Zr-La exhibited excellent selectivity against coexisting anions, and the adsorption was more efficient under acidic conditions. When the phosphate concentration was 2.0 mg P L-1, the removal efficiency of phosphate reached 99.5% and the residual concentration was only 10 µg P L-1, which meets the United States Environmental Protection Agency (USEPA) standard for eutrophication prevention. In addition, the LG-NH2@Fe3O4@Zr-La displayed excellent reusability, maintaining 91.8% of removal efficiency after five cycles. Importantly, owing to the magnetic properties of the loaded Fe3O4, the resulting composite could be separated within 30 s under an external magnetic field. Thus, the separable and recyclable biobased magnetic adsorbent developed in this work exhibited promising application in phosphate capture from real sewage. This research study provides a new perspective for lignin valorization in lignocellulose biorefineries and establishes an approach for developing an economical and efficient bio-adsorbent for phosphate removal from wastewater.

A magnetically recyclable lignin-based bio-adsorbent for efficient removal of Congo red from aqueous solution.

It has been always attractive to design a sustainable bio-derived adsorbent based on industrial waste lignin for removing organic dyes from water. However, existing adsorbent strategies often lead to the difficulties in adsorbent separation and recycling. Herein, we report a novel magnetically recyclable bio-adsorbent of Mg(OH)2/Fe3O4/PEI functionalized enzymatic lignin (EL) composite (EL-PEI@Fe3O4-Mg) for removing Congo red (CR) by Mannish reaction and hydrolysis-precipitation. The Mg(OH)2 and PEI functionalized EL on the surface act as active sites for the removal of CR, while the Fe3O4 allows for the easy separation under the help of a magnet. As-obtained EL-PEI@Fe3O4-Mg forms flower-like spheres and has a relatively lager surface area of 24.8 m2 g-1 which is 6 times that of EL. The EL-PEI@Fe3O4-Mg exhibits a relatively high CR adsorption capacity of 74.7 mg g-1 which is 15 times that of EL when initial concentration is around 100 mg L-1. And it can be easily separated from water by applying an external magnetic field. Moreover, EL-PEI@Fe3O4-Mg shows an excellent anti-interference capability according to the results of pH values and salt ions influences. Importantly, EL-PEI@Fe3O4-Mg possesses a good reusability and a removal efficiency of 92 % for CR remains after five consecutive cycles. It is illustrated that electrostatic attraction, π-π interaction and hydrogen binding are primary mechanisms for the removal of CR onto EL-PEI@Fe3O4-Mg. This work provides a novel sustainable strategy for the development of highly efficient, easy separable, recyclability bio-derived adsorbents for removing organic dyes, boosting the efficient utilization of industrial waste lignin.

A lignin-based epoxy/TiO2 hybrid nanoparticle for multifunctional bio-based epoxy with improved mechanical, UV absorption and antibacterial properties.

Lignin, as a natural polymer material, has the advantages of green safety, renewable, and pollution-free. It has a wide application prospect in the field of thermosetting. However, it has been attractive but a huge challenge to design high performance and high added-value lignin-based epoxy resin. Herein, lignin-based epoxy (LEP) was synthesized from moso bamboo-derived lignin, and then lignin-based epoxy/titanium dioxide (LEP/TiO2) hybrid nanoparticle was synthesized via liquid deposition method for modifying lignin-based epoxy resin to prepare multifunctional bio-based epoxy. The results show that the LEP/TiO2 hybrid nanoparticle exhibits a stable topological surface shape and good dispersion and uniformity. By adding 10 wt% LEP/TiO2 hybrid nanoparticles, the multifunctional bio-based epoxy exhibits good mechanical strength and toughness, and the tensile strength and fracture toughness reach 36 MPa and 1.26 MPa·m1/2, respectively. In addition, the thermal stability, UV absorption and antibacterial properties of the multifunctional bio-based epoxy are further improved. This study provides a facile and efficient method for the preparation of high-performance multifunctional bio-based epoxy composite and a novel solution for the utilization of lignin.

Preparation of TiO2/cellulose nanocomposites as antibacterial bio-adsorbents for effective phosphate removal from aqueous medium.

The design of environmentally benign bio-adsorbents for the removal of phosphate from aqueous medium was an economic and effective way for controlling eutrophication. Herein, we prepared three kinds of TiO2/cellulose (CE-Ti) nanocomposites by a facile hydrolysis-precipitation method, and used them as antibacterial bio-adsorbents for the removal of phosphate from aqueous medium. Multiple techniques including Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and thermogravimetric analysis (TGA) were employed to characterize the nanostructure and characteristics of the prepared CE-Ti nanocomposite. The adsorption capacity of the CE-Ti was 19.57 mg P g-1 according to the Langmuir model, which was 6 times higher than that of CE. Importantly, the bacterial inhibition zone of the CE-Ti was 2.88 mm (that of CE was 0 mm), indicating that CE-Ti had good antibacterial activity that could reduce the attachment of the microorganism to the surface of CE-Ti, which was suitable for long-term phosphate removal. Moreover, the CE-Ti had good adsorption selectivity and anti-interference capability, according to interfering ions and ion strength experiments. Furthermore, Ti4+ leakage tests suggested that CE-Ti was highly stable under acidic, neutral and alkali conditions. These results indicated that the CE-Ti nanocomposite could be utilized as a promising antibacterial bio-adsorbent for effective phosphate removal from aqueous medium.

Reusable Hyperbranched Polyethylenimine-Functionalized Ethyl Cellulose Film for the Removal of Phosphate with Easy Separation.

The design of a reusable film adsorbent with easy solid-liquid separation for the removal of phosphate is necessary and significant but remains hugely challenging. Herein, the hyperbranched polyethylenimine-functionalized ethyl cellulose (HPEI-EC) film was successfully synthesized by a one-step solution-casting method. The structure and elemental composition of the HPEI-EC film were characterized by Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The phosphate adsorption capacity of the HPEI-EC film was 15.53 mg g-1, which is 12 times higher than that of EC. Significantly, the elongation at break of the HPEI-EC film was 13.43%, which is higher than that of the EC film (8.9%), and the HPEI-EC film had a considerable tensile strength of 13.21 MPa. Such good mechanical properties of the HPEI-EC film bring about the advantage of the saturated HPEI-EC film, allowing it to be easily taken out using a pair of tweezers, which significantly reduces the operation time and saves the cost in the application process. Furthermore, the HPEI-EC film possessed good reusability, and 71.6% of the original adsorption capacity of phosphate was retained even after five cycles. Moreover, the electrostatic interaction between protonated the amine group (-NH3 +) and the phosphate ion (PO4 3-) is mainly responsible for the adsorption process. This study presents a low-cost and reusable film adsorbent for the effective removal of phosphate from water and provides an easy solid-liquid separation method for use in the adsorption field.

Colloidal CdS sensitized nano-ZnO/chitosan hydrogel with fast and efficient photocatalytic removal of congo red under solar light irradiation.

Colloidal CdS sensitized nano-ZnO/chitosan (CdS@n-ZnO/CS) hydrogel was prepared and characterized extensively by XRD, SEM-EDS, TEM, UV-Vis DRS, FT-IR and TGA. The photocatalytic activity of CdS@n-ZnO/CS was evaluated with the photodegradation of congo red (CR) as an organic pollutant under solar light irradiation. The influences of initial dye concentration, catalyst dosage, recycling runs, and radical scavenger on decolorization of CR by CdS@n-ZnO/CS were investigated. 95% of CR was removed in just 1 min for 5.0 mg L-1 and 94.34% of CR was removed in 30 min for 100 mg L-1. CdS@n-ZnO/CS exhibited an excellent and ultra-fast performance toward CR removal under solar light due to the synergistic effect of adsorption by chitosan and photocatalysis by ZnO and CdS in CdS@n-ZnO/CS hydrogel. Radical trapping control experiments indicated that h+ and O2- played the major role for CR decolorization. The high performance of CdS@n-ZnO/CS hydrogel was also demonstrated under natural solar light irradiation, suggesting that CdS@n-ZnO/CS hydrogel could be used in practical wastewater treatment.

Magnetic NiFe2O4/MWCNTs functionalized cellulose bioadsorbent with enhanced adsorption property and rapid separation.

Magnetic NiFe2O4 nanoparticles and multi-walled carbon nanotubes functionalized cellulose composite (m-NiFe2O4/MWCNTs@cellulose) as a magnetic bioadsorbent was prepared and used for effectively removing Congo Red (CR) from aqueous solution. The chemical and physical properties of the prepared m-NiFe2O4/MWCNTs@cellulose were characterized by XRD, TGA, FT-IR, VSM, SEM and TEM. Batch experiments were carried out to investigate the adsorption capacity and mechanisms. Effects of different adsorption parameters such as initial CR concentration, adsorbent dosage and temperature were studied. Results demonstrated that m-NiFe2O4/MWCNTs@cellulose had high adsorption capacity for CR from aqueous solution. The obtained experimental data fitted well with the pseudo-second-order equation and followed the Langmuir isotherm model with a maximum adsorption capacity of 95.70 mg g-1 for CR. The m-NiFe2O4/MWCNTs@cellulose with rapid magnetic separation and high adsorption capacity can be a promising and recyclable engineering biomaterials for purification and treatment of practical wastewater.

Cerium oxide nanoparticle functionalized lignin as a nano-biosorbent for efficient phosphate removal.

Removing excess phosphorus is a highly effective method to prevent eutrophication in contaminated water. However, the design and preparation of an efficient biosorbent for phosphate capture is still a great challenge. We fabricated a novel, and inexpensive nano-biosorbent, L-NH2@Ce, by loading cerium oxide nanoparticles (nano-CeO2) within the aminated lignin using a facile in situ precipitation approach for efficient phosphate removal. The as-designed nano-biosorbent L-NH2@Ce exhibited a BET surface area (S BET) of 89.8 m2 g-1, 3 times that of lignin, and a pore volume (V p) of 0.23 cm3 g-1. Owing to these results, the adsorption capacity of L-NH2@Ce increased by 14-fold to 27.86 mg g-1 compared with lignin (1.92 mg g-1). Moreover, the L-NH2@Ce can quickly reduce a high phosphate concentration of 10 ppm to well below the discharge standard of 0.5 ppm recommended by the World Health Organization (WHO) for drinking water. Importantly, a study of leaching tests indicated the negligible risk of Ce ion leakage during phosphate adsorption over the wide pH range of 4-9. Moreover, L-NH2@Ce exhibits good reusability and retains 90% of removal efficiency after two adsorption-desorption cycles. The environmentally benignity of the raw material, the simple preparation process, and the high stability and reusability makes L-NH2@Ce a promising nano-biosorbent for phosphate removal.

Combination of lignin and L-lactide towards grafted copolymers from lignocellulosic butanol residue.

A series of BBL-graft-poly (L-lactide) copolymers were synthesized via ring-opening polymerization (ROP) of L-lactide (L-LA) with a biobutanol lignin (BBL) initiator and a triazabicyclodecene (TBD) catalyst under free-solvent at 135 °C. By manipulating the mass ratio of BBL/LLA, BBL-g-PLLA copolymers with tunable number-average molecular weight (Mn) (2544-7033 g mol(-1)) were obtained. The chemical structure of PLLA chains was identifiable by FT-IR, (1)H NMR and (13)C NMR spectroscopies, in combination with UV-vis spectra to provide support for the existence of the BBL in the copolymer. This provided solid evidence for the successful synthesis of BBL-g-PLLA copolymer. The thermal properties and surface characterization of BBL-g-PLLA copolymers were different from those of linear PLLA. Furthermore, the BBL-g-PLLA copolymer film showed good absorption capacity in the UV region and high transparency in the visible light region, which was expected to find significant applications in UV-protective coating film.

Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue.

In this paper, a "graft from" Ring-Opening Polymerization (ROP) technique was used to synthesize a lignin-graft-poly (ɛ-caprolactone) copolymer (BBL-g-PCL) using biobutanol lignin (BBL) as raw material recovered from lignocellulosic butanol residue. Polymerizations were carried out with various mass ratios of BBL and CL monomer ([BBL]/([BBL]+[CL])=1.0%, 5.0%, 10%, 20% and 40% (w/w)) to obtain BBL-g-PCL copolymers with different molecular weights, ranging from 367 to 8163gmol(-1). The grafting efficiency was preliminary evidenced by the long-term stability of dissolution of BBL-g-PCL in toluene. FT-IR and NMR analysis provided the further evidences for successful formation of BBL-g-PCL copolymer. The thermal properties of BBL-g-PCL copolymers were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These results indicated that BBL-g-PCL copolymer had relatively good thermal stability. The static contact angle of BBL-g-PCL coating film reached to 80°. The surface functional groups and chemical composition of BBL-g-PCL copolymer was investigated in detail by X-ray photoelectron spectroscopy (XPS). The surface morphology of BBL-g-PCL copolymer was studied by Atomic force microscopy (AFM). Additionally, BBL-g-PCL coating film exhibited high absorption in the ultraviolet (UV) range, which could allow for applications in UV-blocking coatings, as well as the extents for the utilization of lignocellulosic butanol residue.

[Synthesis, characterization and electrocatalytic performance of Pd/CMK-3 for formic acid oxidation].

The synthesis of mesoporous carbons CMK-3 was implemented using SBA-15 samples as the hard templates and sucrose as the carbon source. Ordered mesoporous carbon CMK-3 supported palladium catalyst with a loading amount of 20% (Pd/CMK-3) was prepared by a complexing reduction method. XRD and TEM results showed that the p6mm hexagonal symmetric pore structures of CMK-3 were highly ordered and the Pd nanoparticles with the average size of 4. 2 nm and 4. 5 nm were well dispersed on CMK-3 and activated carbon (AC) surfaces respectively. Raman results revealed that CMK-3 presented higher graphitization and a higher electric conductivity than AC. The most probable pore size of CMK-3 was 4.5 nm, which is larger than that of AC (0.54 nm). The BET surface area of CMK-3 was 1 114 m2 x g(-1), which was also larger than that of AC(871 m2 x g(-1)). The mesoporous structure of CMK-3 was also observed. The Pd/CMK-3 catalyst exhibited more excellent initial electrocatalytic activity for formic acid oxidation than Pd/AC by cyclic voltammetry (CV). But the chronoamperometry (CA) demonstrated that the stability of the two catalysts were almost equal after 100 s polarization at 0.2 V (vs. SCE).

Adsorption of aromatic compounds on porous covalent triazine-based framework.

Covalent triazine-based frameworks (CTFs) are an emerging class of polymers whose adsorption properties of organic chemicals are not well understood. The main objective of this work was to evaluate combined effects of the functional groups of aromatic solutes and the triazine structure of a synthesized CTF on adsorption in aqueous solutions. Adsorption of the hydroxyl-, amino-, nitro-, and sulfonate-substituted monocyclic and bicyclic aromatic compounds was generally stronger than their non-substituted, nonpolar counterparts (benzene and naphthalene). When compared with Amberlite XAD-4 resin, one of the most common and widely used polymeric adsorbents, the CTF showed much stronger adsorption toward the polar and/or ionic compounds. To explain the adsorption enhancement of CTF, several specific, non-hydrophobic mechanisms were proposed, including hydrogen bonding (hydroxyl- and amino-substituted compounds), electrostatic attraction (anionized compounds), and π-π electron-donor-acceptor (EDA) interaction (nitroaromatic compounds) with the triazine structure of CTF. The hypothesized mechanisms were further supported by the observed pH dependence of adsorption. Resulting from size exclusion, adsorption of large-size dissolved humic acids on the homogeneous, nanopored (1.2 nm in size) CTF was negligible and did not affect adsorption of aromatic solutes. Additional advantages of fast adsorption/desorption kinetics and complete adsorption reversibility made CTF a superior adsorbent for aromatic compounds.