Titanium coated with 2-decenoic analogs reduces bacterial and fungal biofilms.

AIMS: Due to antibiotic tolerance of microbes within biofilm, non-antibiotic methods for prevention and treatment of implant-related infections are preferable. The goal of this work is to evaluate a facile loading strategy for medium-chain fatty-acid signaling molecules 2-heptycyclopropane-1-carboxylic acid (2CP), cis-2-decenoic acid (C2DA), and trans-2-decenoic acid, which all act as diffusible signaling factors (DSFs), onto titanium surfaces for comparison of their antimicrobial efficacy. METHODS AND RESULTS: Titanium coupons were drop-coated with 0.75 mg of DSF in ethanol and dried. Surface characteristics and the presence of DSF were confirmed with Fourier Transform infrared spectroscopy, x-ray photoelectron spectroscopy, and water contact angle. Antimicrobial assays analyzing biofilm and planktonic Staphylococcus aureus, Escherichia coli, or Candida albicans viability showed that planktonic growth was reduced after 24-h incubation but only sustained through 72 h for S. aureus and C. albicans. Biofilm formation on the titanium coupons was also reduced for all strains at the 24-h time point, but not through 72 h for E. coli. Although ∼60% of the loaded DSF was released within the first 2 days, enough remained on the surface after 4 days of elution to significantly inhibit E. coli and C. albicans biofilm. Cytocompatibility evaluations with a fibroblast cell line showed that none of the DSF-loaded groups decreased viability, while C2DA and 2CP increased viability by up to 50%. CONCLUSIONS: In this study, we found that DSF-loaded titanium coupons can inhibit planktonic microbes and prevent biofilm attachment, without toxicity to mammalian cells.

Single-Shot 3D Topography of Transmissive and Reflective Samples with a Dual-Mode Telecentric-Based Digital Holographic Microscope.

Common path DHM systems are the most robust DHM systems as they are based on self-interference and are thus less prone to external fluctuations. A common issue amongst these DHM systems is that the two replicas of the sample's information overlay due to self-interference, making them only suitable for imaging sparse samples. This overlay has restricted the use of common-path DHM systems in material science. The overlay can be overcome by limiting the sample's field of view to occupy only half of the imaging field of view or by using an optical spatial filter. In this work, we have implemented optical spatial filtering in a common-path DHM system using a Fresnel biprism. We have analyzed the optimal pinhole size by evaluating the frequency content of the reconstructed phase images of a star target. We have also measured the accuracy of the system and the sensitivity to noise for different pinhole sizes. Finally, we have proposed the first dual-mode common-path DHM system using a Fresnel biprism. The performance of the dual-model DHM system has been evaluated experimentally using transmissive and reflective microscopic samples.

Multilayer and Surface Immobilization of EDOT-Decorated Nanocapsules.

To assess the feasibility of utilizing reagent-loaded, porous polymeric nanocapsules (NCs) for chemical and biochemical sensor design, the surfaces of the NCs were decorated with 3,4-ethylenedioxythiophene (EDOT) moieties. The pores in the capsule wall allow unhindered bidirectional diffusion of molecules smaller than the programmed pore sizes, while larger molecules are either entrapped inside or blocked from entering the interior of the nanocapsules. Here, we investigate two electrochemical deposition methods to covalently attach acrylate-based porous nanocapsules with 3,4-ethylenedioxythiophene moieties on the nanocapsule surface, i.e., EDOT-decorated NCs to the surface of an existing PEDOT film: (1) galvanostatic or bilayer deposition with supporting EDOT in the deposition solution and (2) potentiostatic deposition without supporting EDOT in the deposition solution. The distribution of the covalently attached NCs in the PEDOT films was studied by variable angle FTIR-ATR and XPS depth profiling. The galvanostatic deposition of EDOT-decorated NCs over an existing PEDOT (tetrakis(pentafluorophenyl)borate) [PEDOT(TPFPhB)] film resulted in a bilayer structure, with an interface between the NC-free and NC-loaded layers, that could be traced with variable angle FTIR-ATR measurements. In contrast, the FTIR-ATR and XPS analyses of the films deposited potentiostatically from a solution without EDOT and containing only the EDOT-decorated NCs showed small amounts of NCs in the entire cross section of the films.

Characterization of graphene/pine wood biochar hybrids: Potential to remove aqueous Cu2.

Biochar-based hybrid composites containing added nano-sized phases are emerging adsorbents. Biochar, when functionalized with nanomaterials, can enhance pollutant removal when both the nanophase and the biochar surface act as adsorbents. Three different pine wood wastes (particle size < 0.5 mm, 10 g) were preblended with 1 wt% of three different graphenes in aqueous suspensions, designated as G1, G2, and G3. G1 (SBET, 8.1 m2/g) was prepared by sonicating graphite made from commercial synthetic graphite powder (particle size 7-11 µm). G2 (312.0 m2/g) and G3 (712.0 m2/g) were purchased commercial graphene nanoplatelets (100 mg in 100 mL deionized water). These three pine wood-graphene mixtures were pyrolyzed at 600 °C for 1 h to generate three graphene-biochar adsorbents, GPBC-1, GPBC-2, and GPBC-3 containing 4.4, 4.9, and 5.0 wt% of G1, G2, and G3 respectively. Aqueous Cu2+ adsorption capacities were 10.6 mg/g (GPBC-1), 4.7 mg/g (GPBC-2), and 5.5 mg/g (GPBC-3) versus 7.2 mg/g for raw pine wood biochar (PBC) (0.05 g adsorbent dose, Cu2+ 75 mg/L, 25 mL, pH 6, 24 h, 25 ± 0.5 °C). Increased graphene surface areas did not result in adsorption increases. GPBC-1, containing the lowest nanophase surface area with the highest Cu2+ capacity, was chosen to evaluate its Cu2+ adsorption characteristics further. Results from XPS showed that the surface concentration of oxygenated functional groups on the GPBC-1 is greater than that on the PBC, possibly contributing to its greater Cu2+ removal versus PBC. GPBC-1 and PBC uptake of Cu2+ followed the pseudo-second-order kinetic model. Langmuir maximum adsorption capacities and BET surface areas were 18.4 mg/g, 484.0 m2/g (GPBC-1) and 9.2 mg/g, 378.0 m2/g (PBC). This corresponds to 3.8 × 10-2 versus 2.4 × 10-2 mg/m2 of Cu2+ removed on GPBC-1 (58% more Cu2+ per m2) versus PBC. Cu2+ adsorption on both these adsorbents was spontaneous and endothermic.

Biochar-supported polyaniline hybrid for aqueous chromium and nitrate adsorption.

Biochar adsorbents can remove environmental pollutants and the remediation of Cr(VI) and nitrate are considered. Cr(VI) is a proven carcinogen causing serious health issues in humans and nitrate induced eutrophication causes negative effect on aquatic systems around the world. Douglas fir biochar (DFBC), synthesized by fast pyrolysis during syn gas production, was treated with aniline. Then, a polyaniline biochar (PANIBC) composite containing 47 wt% PANI was prepared by precipitating PANI on DFBC surfaces by oxidative chemical polymerization of aniline in 2M HCl. PANIBC exhibited a point of zero charge (PZC) of 3.0 and 8.2 m2/g BET (N2) surface area. This modified biochar was characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM) morphology and surface elements, and oxidation states by X-ray photoelectron spectroscopy (XPS). PANIBC exhibited positive surface charge below pH 3, making it an outstanding adsorbent, for Cr(VI) removal. Cr(VI) and nitrate removal mechanisms are presented based on XPS analysis. DFBC and PANIBC Cr(VI) and nitrate adsorption data were fitted to Langmuir and Freundlich isotherm models with maximum Langmuir adsorption capacities of 150 mg/g and 72 mg/g, respectively. Cr(VI) and nitrate removal at pH 2 and 6 were evaluated by reducing the amount of PANI (9 wt%) dispersed on to DFBC. Adsorption capacities verses temperature studies revealed that both Cr(VI) and nitrate adsorption are endothermic and thermodynamically favored. Regeneration studies were conducted on both DFBC and PANIBC using 0.1M NaOH and PANIBC exhibited excellent sorption capacities for Cr(VI) and nitrate in lake water samples and in the presence of competitive ions.

Synthesis and Characterization of Cu(II) and Mixed-Valence Cu(I)Cu(II) Clusters Supported by Pyridylamide Ligands.

A group of copper complexes supported by polydentate pyridylamide ligands H2bpda and H2ppda were synthesized and characterized. The two Cu(II) dimers [CuII2(Hbpda)2(ClO4)2] (1) and [CuII2(ppda)2(DMF)2] (2) were constructed by using neutral ligands to react with Cu(II) salts. Although the dimers showed similar structural features, the second-sphere interactions affect the structures differently. With the application of Et3N, the tetranuclear cluster (HNEt3)[CuII4(bpda)2(µ3-OH)2(ClO4)(DMF)3](ClO4)2 (3) and hexanuclear cluster (HNEt3)2[CuII6(ppda)6(H2O)2(CH3OH)2](ClO4)2 (4) were prepared under similar reaction conditions. The symmetrical and unsymmetrical arrangement of the ligand donors in ligands H2bpda and H2ppda led to the dramatic conformation difference of the two Cu(II) complexes. As part of our effort to explore mixed-valence copper chemistry, the triple-decker pentanuclear cluster [CuII3CuI2(bpda)3(µ3-O)] (5) was prepared. XPS examination demonstrated the localized mixed-valence properties of complex 5. Magnetic studies of the clusters with EPR evidence showed either weak ferromagnetic or antiferromagnetic interactions among copper centers. Due to the trigonal-planar conformation of the trinuclear Cu(II) motif with the µ3-O center, complex 5 exhibits geometric spin frustration and engages in antisymmetric exchange interactions. DFT calculations were also performed to better interpret spectroscopic evidence and understand the electronic structures, especially the mixed-valence nature of complex 5.

Removal of Arsenic(III) from water using magnetite precipitated onto Douglas fir biochar.

Magnetic Fe3O4/Douglas fir biochar composites (MBC) were prepared with a 29.2% wt. Fe3O4 loading and used to treat As(III)-contaminated water. Toxicity of As(III) (inorganic) is significantly greater than As(V) and more difficult to remove from water. Removal efficiency was optimized verses pH, contact time and initial concentration. Column sorption and regeneration were also studied. Adsorption kinetics data best fitted the pseudo second order model (R2 > 0.99). Adsorption was analyzed with three isotherm models at 20, 25 and 40 °C. The Sips isotherm showed the best fit at 25 °C with a 5.49 mg/g adsorption capacity, which is comparable with other adsorbents. MBC gave faster kinetics (~1-1.5 h) at pH 7 and ambient temperature than previous adsorbents. The Gibbs free energy (ΔG) of this spontaneous As(III) adsorption was -35 kJ/mol and ΔH = 70 kJ/mol was endothermic. Experiments were performed on industrial and laboratory wastewater samples in the presence of other co-existing contaminants (pharmaceutical residues, heavy metals ions and oxi-anions). The composite reduced the arsenic concentrations below the WHO's safe limit of 0.2 mg/L for waste water discharge. X-ray photoelectron spectroscopy (XPS) studies found As(III) and less toxic As(V) on Fe3O4 surfaces indicating adsorbed (or adsorbing) As(III) oxidation occurred upon contact with O2 and possibly dissolved Fe(III) or upon drying under oxic conditions. Under anoxic conditions magnetite to maghemite transformation drives the oxidation. A pH-dependent surface chemisorption mechanism was proposed governing adsorption aided by XPS studies vs pH.

PEDOT(PSS) as Solid Contact for Ion-Selective Electrodes: The Influence of the PEDOT(PSS) Film Thickness on the Equilibration Times.

To understand the rate determining processes during the equilibration of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate-based (PEDOT(PSS)-based) solid contact (SC) ion-selective electrodes (ISEs), the surfaces of Pt, Au, and GC electrodes were coated with 0.1, 1.0, 2.0, and 4.0 µm thick galvanostatically deposited PEDOT(PSS) films. Next, potential vs time transients were recorded with these electrodes, with and without an additional potassium ion-selective membrane (ISM) coating, following their first contact with 0.1 M KCl solutions. The transients were significantly different when the multilayered sensor structures were assembled on Au or GC compared to Pt. The differences in the rate of equilibration were interpreted as a consequence of differences in the hydrophilicity of PEDOT(PSS) in contact with the substrate electrode surfaces based on X-ray photoelectron spectroscopy (XPS) and synchrotron radiation-XPS (SR-XPS) analysis of 10-100 nm thick PEDOT(PSS) films. The influence of the layer thickness of the electrochemically deposited PEDOT(PSS)-films on the hydrophilicity of these films has been documented by contact angle measurements over PEDOT(PSS)-coated Au, GC, and Pt electrode surfaces. This study demonstrates that it is possible to minimize the equilibration (conditioning) time of SC ISEs with aqueous solutions before usage by optimizing the thickness of the SC layer with a controlled ISM thickness. PEDOT(PSS)-coated Au and GC electrodes exhibit a significant negative potential drift during their equilibration in an aqueous solution. By coating the PEDOT(PSS) surface with an ISM, the negative potential drift is compensated by a positive potential drift related to the hydration of the ISM and activity changes at the PEDOT(PSS)|ISM interface. The potential drifts related to activity changes in the ISM have been determined by a novel adaptation of the "sandwich membrane" method.

Synthesis and Characterization of Copper Complexes with CuICuI, Cu1.5Cu1.5m and CuIICuII Core Structures Supported by a Flexible Dipyridylamide Ligand.

A series of copper complexes supported by a simple dipyridylamide ligand (H2pcp) were isolated and characterized. Treatment of H2pcp with NaH and copper(I) salts led to the formation of [Cu2(2pcp)2] (1a) and {Na[(Cu2(2pcp)2)2]PF6}n (1b). The X-ray crystal structures of both complexes feature CuICuI cores with close Cu···Cu interactions. Electrochemical studies of 1a showed a reversible one-electron oxidation wave in CH2Cl2. On the basis of the work on 1a, we began studying the mixed-valence copper species supported by this ligand. The reaction of H2pcp with Cu(OAc)2 and CuCl in different stoichiometries yielded [Cu2(2pcp)2Cl] (2) and [Cu3(2pcp)2Cl2] (3). X-ray crystallography and spectroscopic characterization suggested delocalized Cu1.5Cu1.5 core structures of both compounds. These results further inspired us to explore the coordination properties of H2pcp toward CuII ions. The complexes [HNEt3][Cu2(2pcp)3(ClO4)](ClO4) (4a), [Cu2(2pcp)3(NO3)] (4b), and [Cu2(2pcp)3(H2O)]BF4 (4c) featuring dinuclear CuIICuII cores were prepared and characterized by X-ray crystallography and spectroscopic methods. Structural analysis of these complexes implied that the accommodation of CuICuI, Cu1.5Cu1.5, and CuIICuII is attributed to the structural flexibility of the ligand H2pcp. Complexes 1a, 2, 3, and 4a were examined by X-ray photoelectron spectroscopy, which confirmed the oxidation state assignments. Computational studies were also performed to provide insight into the electronic structures of these complexes.

Phase diagram of a three-dimensional antiferromagnet with random magnetic anisotropy.

Three-dimensional antiferromagnets with random magnetic anisotropy (RMA) that have been experimentally studied to date have competing two-dimensional and three-dimensional exchange interactions which can obscure the authentic effects of RMA. The magnetic phase diagram of Fe_{x}Ni_{1-x}F_{2} epitaxial thin films with true random single-ion anisotropy was deduced from magnetometry and neutron scattering measurements and analyzed using mean-field theory. Regions with uniaxial, oblique, and easy-plane anisotropies were identified. A RMA-induced glass region was discovered where a Griffiths-like breakdown of long-range spin order occurs.

Utilization of shea butter waste-derived hierarchical activated carbon for high-performance supercapacitor applications.

In this work, carbonization and subsequent activation procedures were adopted to synthesize waste shea butter shells into oxygen-rich interconnected porous activated carbon (SAC_x, x is the mass ratio of KOH used for activation). The SAC_1.5 electrode material showed outstanding electrochemical performance with high specific capacitance (286.6 F/g) and improved rate capability, owing to various synergistic effects originating from a high specific surface area (1233.5 m2/g) and O-rich content. The SAC_1.5-based symmetric device delivered an impressive specific capacitance of 91.6 F/g with a high energy density of 12.7 Wh/kg at 0.5 A/g. The device recorded 99.9 % capacitance retention after 10,000 charge-discharge cycles. The symmetric supercapacitor device successfully lit an LED bulb for more than 1 h, signifying the potential of bio-waste as an efficient carbon precursor for electrode material in practical supercapacitors. This work offers an efficient, affordable, and environmentally friendly strategy for potential renewable energy storage devices.

Bimetallic Co-Fe sulfide and phosphide as efficient electrode materials for overall water splitting and supercapacitor.

The major center of attraction in renewable energy technology is the designing of an efficient material for both electrocatalytic and supercapacitor (SC) applications. Herein, we report the simple hydrothermal method to synthesize cobalt-iron-based nanocomposites followed by sulfurization and phosphorization. The crystallinity of nanocomposites has been confirmed using X-ray diffraction, where crystalline nature improves from as-prepared to sulfurized to phosphorized. The as-synthesized CoFe-nanocomposite requires 263 mV overpotential for oxygen evolution reaction (OER) to reach a current density of 10 mA/cm2 whereas the phosphorized requires 240 mV to reach 10 mA/cm2. The hydrogen evolution reaction (HER) for CoFe-nanocomposite exhibits 208 mV overpotential at 10 mA/cm2. Moreover, the results improved after phosphorization showing 186 mV to reach 10 mA/cm2. The specific capacitance (Csp) of as-synthesized nanocomposite is 120 F/g at 1 A/g, along with a power density of 3752 W/kg and a maximum energy density of 4.3 Wh/kg. Furthermore, the phosphorized nanocomposite shows the best performance by exhibiting 252 F/g at 1 A/g and the highest power and energy density of 4.2 kW/kg and 10.1 Wh/kg. This shows that the results get improved more than twice. The 97% capacitance retention after 5000 cycles shows cyclic stability of phosphorized CoFe. Our research thus offers cost-effective and highly efficient material for energy production and storage applications.

Optimum iron-pyrophosphate electronic coupling to improve electrochemical water splitting and charge storage.

Tuning the electronic properties of transition metals using pyrophosphate (P2O7) ligand moieties can be a promising approach to improving the electrochemical performance of water electrolyzers and supercapacitors, although such a material's configuration is rarely exposed. Herein, we grow NiP2O7, CoP2O7, and FeP2O7 nanoparticles on conductive Ni-foam using a hydrothermal procedure. The results indicated that, among all the prepared samples, FeP2O7 exhibited outstanding oxygen evolution reaction and hydrogen evolution reaction with the least overpotential of 220 and 241 mV to draw a current density of 10 mA/cm2. Theoretical studies indicate that the optimal electronic coupling of the Fe site with pyrophosphate enhances the overall electronic properties of FeP2O7, thereby enhancing its electrochemical performance in water splitting. Further investigation of these materials found that NiP2O7 had the highest specific capacitance and remarkable cycle stability due to its high crystallinity as compared to FeP2O7, having a higher percentage composition of Ni on the Ni-foam, which allows more Ni to convert into its oxidation states and come back to its original oxidation state during supercapacitor testing. This work shows how to use pyrophosphate moieties to fabricate non-noble metal-based electrode materials to achieve good performance in electrocatalytic splitting water and supercapacitors.

Efficient aqueous molybdenum removal using commercial Douglas fir biochar and its iron oxide hybrids.

Molybdenum (Mo) is a naturally-occurring trace element in drinking water. Most commonly, molybdate anions (MoO42-) are in well water and breast milk. In addition, it is used in medical image testing. Recently, the EPA classified Mo as a potential contaminant, as exposure can lead to health effects such as gout, hyperuricemia, and even lung cancer. We have assessed the sorptive removal of aqueous molybdate using Douglas fir biochar (DFBC) and a hybrid DFBC/Fe3O4 composite containing chemically-coprecipitated iron oxide (Fe3O4). Adsorption was studied at various: pH values, equilibrium times (5 min-24 h), initial Mo concentrations (2.5-1000 mg/L), and temperatures (5, 25, and 40 °C) using batch sorption and fixed-bed column equilibrium methods. Langmuir capacities for DFBC and DFBC/Fe3O4 (at pH 3, 2 hrs equilibrium) were within 459.3-487.9 mg/g and 288-572 mg/g, respectively. These adsorbents and their Mo-laden counterparts were characterized by elemental analysis, BET, PZC, SEM, TEM, EDS, XRD, and XPS. MoO42- adsorption on DFBC is thought to be governed primarily via electrostatic attraction. Adsorption by DFBC/Fe3O4 is primarily governed by chemisorption onto magnetite surface hydroxyl groups, while electrostatics prevail in the DFBC-exposed phase. Stoichiometric precipitation of iron molybdates triggered by iron dissolution was also considered. The data suggest that DFBC and DFBC/Fe3O4 are promising candidates for molybdate sorption.

Iron/titanium oxide-biochar (Fe2TiO5/BC): A versatile adsorbent/photocatalyst for aqueous Cr(VI), Pb2+, F- and methylene blue.

This is the first report of the metal Fe-Ti oxide/biochar (Fe2TiO5/BC) composite for simultaneous removal of aqueous Pb2+, Cr6+, F- and methylene blue (MB). Primary Fe2TiO5 nano particles and aggregates were dispersed on a high surface area Douglas fir BC (∼700 m2/g) by a simple chemical co-precipitation method using FeCl3 and TiO(acac)2 salts treated by base and heated to 80 °C. This was followed by calcination at 500 °C. This method previously was used without BC to make the neat mixed oxide Fe2TiO5, exhibiting a lower energy band gap than TiO2. Adsorption of Cr(VI), Pb(II), fluoride, and MB on Fe2TiO5/BC was studied as a function of pH, equilibrium time, initial adsorbate concentration, and temperature. Adsorption isotherm studies were conducted at 5, 25, and 45 ℃ and kinetics for all four adsorbates followed the pseudo second order model. Maximum Langmuir adsorption capacities for Pb2+, Cr6+, F- and MB at their initial pH values were 141 (pH 2), 200 (pH 5), 36 (pH 6) and 229 (pH 6) mg/g at 45 ℃ and 114, 180, 26 and 210 mg/g at 25 ℃, respectively. MB was removed from the water on Fe2TiO5/BC by synergistic adsorption and photocatalytic degradation at pH 3 and 6 under UV (365 nm) light irradiation. Cr6+, Pb2+, F-, and MB each exhibited excellent removal capacities in the presence of eight different competitive ions in simulated water samples. The removal mechanisms on Fe2TiO5/BC and various competitive ion interactions were proposed. Some iron ion leaching at pH 3 catalyzed Photo-Fenton destruction of MB. Fe2TiO5, BC, and Fe2TiO5/BC bandgaps were studied to help understand photocatalysis of MB and to advance supported metal oxide photodegradation using smaller energy band gaps than the larger bandgap of TiO2 for water treatment. A long range goal is to photocatalytically destroy some sorbates with adsorbents to avoid the need for regeneration steps.

Batch and fixed bed sorption of low to moderate concentrations of aqueous per- and poly-fluoroalkyl substances (PFAS) on Douglas fir biochar and its Fe3O4 hybrids.

Per- and poly-fluoroalkyl substances (PFAS) can cause deleterious effects at low concentrations (70 ng/L). Their remediation is challenging. Aqueous µg/L levels of PFOS, PFOS, PFOSA, PFBS, GenX, PFHxS, PFPeA, PFHxA, and PFHpA (abbreviations defined in Table 1) multi-component adsorption (pH dependence, kinetics, isotherms, fixed-bed adsorption, regeneration, complex matrix) was studied on commercial Douglas fir biochar (BC) and its Fe3O4-containing BC. BC is a waste product when syn-gas is produced in a large scale from wet Douglas fir wood fed to gasification at 900-1000 °C and held for 1-20 s. This generates a relatively high surface area (∼700 m2/g) and large pore volume (∼0.25 cm3/g) biochar. Treatment of BC with FeCl3/FeSO4 and NaOH to chemically precipitate Fe3O4 onto BC. BC and its magnetic Fe3O4/BC analogue rapidly adsorbed (20-45 min equilibrium time) significant amounts of PFOS (∼14.6 mg/g) and PFOA (∼652 mg/g) at natural waters' pH range (6-8). Adsorption from µg/L concentrations has produced remediated aqueous PFAS concentrations of ∼50 ng/L or below the detection limits, which is closing in on EPA advisory limits. Column capacities of PFOS were 215.3 mg/g on BC and 51.9 mg/g Fe3O4/BC vs 53.0 mg/g and 21.8 mg/g, respectively, for PFOA. Hydrophobic and electrostatic interactions are thought to drive this sorption. Successful stripping regeneration by methanol was achieved. Thus, hydrophobic Douglas fir biochar produced by fast high temperature pyrolysis and its Fe3O4/BC analogue are adsorbent candidates for PFAS remediation from the dilute PFAS concentrations often found in polluted environments. Small Fe3O4/BC particles can be magnetically removed from batch treatments avoiding filtration.

KOH-activated high surface area Douglas Fir biochar for adsorbing aqueous Cr(VI), Pb(II) and Cd(II).

Biochar has become a popular research topic in sustainable chemistry for use both in agriculture and pollution abatement. To enhance aqueous Cr(VI), Pb(II) and Cd(II) removal efficiency, high surface area (535 m2/g) byproduct Douglas fir biochar (DFBC) from commercial syn-gas production obtained by fast pyrolysis (900-1000 °C, 1-10 s), was subjected to a KOH activation. KOH-activated biochar (KOHBC) underwent a remarkable surface area increase to 1049 m2/g and a three-fold increase in pore volume (BET analysis). Batch sorption studies on KOHBC verses pH revealed that the highest chromium, lead and cadmium removal capacities occurred at pH 2.0, 5.0 and 6.0, respectively. KOHBC exhibited much higher adsorption capacities than unactivated DFBC. Heavy metal loadings onto KOHBC were characterized by scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Sorption of Cr(VI), Pb(II) and Cd(II) all followed pseudo-second order kinetics and the Langmuir adsorption model. The highest Langmuir adsorption capacities at the respective pH's of maximum adsorption were 140.0 mg g-1 Pb(II), 127.2 mg g-1 Cr(VI) and 29.0 mg g-1 Cd(II). Metal ions spiked into natural and laboratory waste water systems exhibited high sorption capacities. Desorption studies carried out using 0.1 M HCl revealed that Pb(II) adsorption onto the KOHBC surface is reversible. Portions of Cd(II) and Cr(VI) adsorbed strongly onto KOHBC were unable to be desorbed by 0.1 M HCl and 0.1 M NaOH.

High capacity aqueous phosphate reclamation using Fe/Mg-layered double hydroxide (LDH) dispersed on biochar.

Phosphate is a primary plant nutrient, serving integral role in environmental stability. Excessive phosphate in water causes eutrophication; hence, phosphate ions need to be harvested from soil nutrient levels and water and used efficiently. Fe-Mg (1:2) layered double hydroxides (LDH) were chemically co-precipitated and widely dispersed on a cheap, commercial Douglas fir biochar (695 m2/g surface area and 0.26 cm3/g pore volume) byproduct from syn gas production. This hybrid multiphase LDH dispersed on biochar (LDHBC) robustly adsorbed (~5h equilibrium) phosphate from aqueous solutions in exceptional sorption capacities and no pH dependence between pH 1-11. High phosphate Langmuir sorption capacities were found for both LDH (154 to 241 mg/g) and LDH-modified biochar (117 to 1589 mg/g). LDHBC was able to provide excellent sorption performance in the presence of nine competitive anion contaminants (CO32-, AsO43-, SeO42-, NO3-, Cr2O72-, Cl-, F-, SO42-, and MoO42-) and also upon remediating natural eutrophic water samples. Regeneration was demonstrated by stripping with aqueous 1 M NaOH. No dramatic performance drop was observed over 3 sorption-stripping cycles for low concentrations (5 ppm). The adsorbents and phosphate-laden adsorbents were characterized using Elemental analysis, BET, PZC, TGA, DSC, XRD, SEM, TEM, and XPS. The primary sorption mechanism is ion-exchange from low to moderate concentrations (10-500 ppm). Chemisorption and stoichiometric phosphate compound formation were also considered at higher phosphate concentrations (>500 ppm) and at 40 °C. This work advances the state of the art for environmentally friendly phosphate reclamation. These phosphate-laden adsorbents also have potential to be used as a slow-release phosphate fertilizer.

Household arsenic contaminated water treatment employing iron oxide/bamboo biochar composite: An approach to technology transfer.

Commercialization of novel adsorbents technology for providing safe drinking water must consider scale-up methodological approaches to bridge the gap between laboratory and industrial applications. These imply complex matrix analysis and large-scale experiment designs. Arsenic concentrations up to 200-fold higher (2000 µg/L) than the WHO safe drinking limit (10 µg/L) have been reported in Latin American drinking waters. In this work, biochar was developed from a single, readily available, and taxonomically identified woody bamboo species, Guadua chacoensis. Raw biochar (BC) from slow pyrolysis (700 °C for 1 h) and its analog containing chemically precipitated Fe3O4 nanoparticles (BC-Fe) were produced. BC-Fe performed well in fixed-bed column sorption. Predicted model capacities ranged from 8.2 to 7.5 mg/g and were not affected by pH 5-9 shift. The effect of competing matrix chemicals including sulfate, phosphate, nitrate, chloride, acetate, dichromate, carbonate, fluoride, selenate, and molybdate ions (each at 0.01 mM, 0.1 mM and 1 mM) was evaluated. Fe3O4 enhanced the adsorption of arsenate as well as phosphate, molybdate, dichromate and selenate. With the exception of nitrate, individually competing ions at low concentration (0.01 mM) did not significantly inhibit As(V) sorption onto BC-Fe. The presence of ten different ions in low concentrations (0.01 mM) did not exert much influence and BC-Fe's preference for arsenate, and removal remained above 90%. The batch and column BC and BC-Fe adsorption capacities and their ability to provide safe drinking water were evaluated using a naturally contaminated tap water (165 ± 5 µg/L As). A 960 mL volume (203.8 Bed Volumes) of As-free drinking water was collected from a 1 g BC-Fe fixed bed. Adsorbent regeneration was attempted with (NH4)2SO4, KOH, or K3PO4 (1 M) strippers. Potassium phosphate performed the best for BC-Fe regeneration. Safe disposal options for the exhausted adsorbents are proposed. Adsorbents and their As-laden analogues (from single and multi-component mixtures) were characterized using high resolution XPS and possible competitive interactions and adsorption pathways and attractive interactions were proposed including electrostatic attractions, hydrogen bonding and weak chemisorption to BC phenolics. Stoichiometric precipitation of metal (Mg, Ca and Fe) oxyanion (phosphate, molybdate, selenate and chromate) insoluble compounds is considered. The use of a packed BC-Fe cartridge to provide As-free drinking water is presented for potential commercial use. BC-Fe is an environmentally friendly and potentially cost-effective adsorbent to provide arsenic-free household water.

Assessing South American Guadua chacoensis bamboo biochar and Fe3O4 nanoparticle dispersed analogues for aqueous arsenic(V) remediation.

Discarded bamboo culms of Guadua chacoensis were used for biochar remediation of aqueous As(V). Raw biochar (BC), activated biochar (BCA), raw Fe3O4 nanoparticle-covered biochar (BC-Fe), and activated biochar covered with Fe3O4 nanoparticles (BCA-Fe) were prepared, characterized and tested for As(V) aqueous adsorption. The goal is to develop an economic, viable, and sustainable adsorbent to provide safe arsenic-free water. Adsorbents were characterized using scanning electron microscopy (SEM) and energy dispersive analysis by X-ray (SEM-EDX), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (TEM-EDS), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller surface area measurements (SBET), point of zero charge determinations (PZC), and elemental analysis. Activation with KOH increased the O/C ratio and the surface area of BC from 6.7 m2/g to 1239.7 m2/g (BCA). As(V) sorption equilibrium was achieved within <2 h for all four adsorbents and kinetics followed the pseudo-second-order model. At a 10 mg/L initial As(V) concentration, BC-Fe achieved a 100% removal (5 mg/g) over a pH 5 to 9 window. Sorption was endothermic on all four adsorbents and the capacities rose with the increasing temperature. Langmuir capacities at 40 °C for BC, BCA, BC-Fe, and BCA-Fe were 256, 217, 457, and 868 mg/g, respectively, and capacities were compared with other sorbents. Breakthrough fixed-bed column sorption was carried out for BC and BC-Fe producing 6.6 mg/g and 13.9 mg/g bed capacities, respectively. Potassium phosphate was a better As stripping agent than sodium bicarbonate. Performance of the adsorbents in an As(V)-spiked natural water and a naturally As(V)-contaminated domestic water were assessed. Robust arsenate sequestration occurred generating As-safe water (As <0.01 mg/L), despite the presence of competing ions. Stoichiometric precipitation of iron-arsenate complexes triggered by iron dissolution was also established.