Selective Gold Precipitation by a Tertiary Diamide Driven by Thermodynamic Control.

The simple diamide ligand L was previously shown to selectively precipitate gold from acidic solutions typical of e-waste leach streams, with precipitation of gallium, iron, tin, and platinum possible under more forcing conditions. Herein, we report direct competition experiments to afford the order of selectivity. Thermal analysis indicates that the gold-, gallium-, and iron-containing precipitates present as the most thermodynamically stable structures at room temperature, while the tin-containing structure does not. Computational modeling established that the precipitation process is thermodynamically driven, with ion exchange calculations matching the observed experimental selectivity ordering. Calculations also show that the stretched ligand conformation seen in the X-ray crystal structure of the gold-containing precipitate is more strained than in the structures of the other metal precipitates, indicating that intermolecular interactions likely dictate the selectivity ordering. This was confirmed through a combination of Hirshfeld, noncovalent interaction (NCI), and quantum theory of atoms in molecules (QTAIM) analyses, which highlight favorable halogen···halogen contacts between metalates and pseudo-anagostic C-H···metal interactions in the crystal structure of the gold-containing precipitate.

Synergistic sono-adsorption and adsorption-enhanced sonochemical degradation of dyes in water by additive manufactured PVDF-based materials.

The present study proposes the first mechanistic model accounting for the most meaningful physico-chemical phenomena taking place in liquid phase adsorption processes under ultrasound. Initially, this study was aimed at developing an easy-to-make and easy-to-recover piezocatalyst for the degradation of RhB in water by combining the high piezocatalytical performance of BaTiO3 with a compatible piezoelectric support such as PVDF, manufactured by a customised additive manufacturing - direct ink writing system with in-situ poling. However, initial results showed that the resulting PVDF-BaTiO3 composite slabs performed worse than BaTiO3 piezocatalysts on their own, and that poling did not have any effect on their performance (82% RhB removal after 2 h when using either poled or unpoled PVDF-BaTiO3 composite slabs compared to 92% RhB removal after 2 h in presence of BaTiO3 piezocatalysts). Further investigation with pure PVDF materials demonstrated that, instead of piezocatalysis, synergistic ultrasound-assisted adsorption and sonochemical degradation were taking place, enabling the removal of >95% of the dye within 40 min of ultrasound treatment in the presence of 4 g L-1 of additive manufactured PVDF slabs. The results of this study and their evaluation with the mechanistic model proposed for liquid phase adsorption under ultrasound suggest that the adsorption of RhB on additive manufactured PVDF slabs was enhanced by the structure, higher specific surface ratio and higher volume of mesopores achieved through the 3D-printing process, as well as the minimisation of film resistance to mass transport due to ultrasound. Moreover, adsorption on additive manufactured PVDF enhanced the sonochemical degradation of the dye due to its high concentration in the adsorbed phase. This study demonstrates that adsorption processes, especially in the presence of PVDF materials, may be significantly more important in piezocatalysis than what has been reported to date, to the point that the synergistic combination of sono-adsorption and sonochemical degradation in presence of additive-manufactured PVDF slabs may be enough to achieve high removal rates of dyes in water.

Selective bacterial separation of critical metals: towards a sustainable method for recycling lithium ion batteries.

The large scale recycling of lithium ion batteries (LIBs) is essential to satisfy global demands for the raw materials required to implement this technology as part of a clean energy strategy. However, despite what is rapidly becoming a critical need, an efficient and sustainable recycling process for LIBs has yet to be developed. Biological reactions occur with great selectivity under mild conditions, offering new avenues for the implementation of more environmentally sustainable processes. Here, we demonstrate a sequential process employing two bacterial species to recover Mn, Co and Ni, from vehicular LIBs through the biosynthesis of metallic nanoparticles, whilst Li remains within the leachate. Moreover the feasibility of Mn recovery from polymetallic solutions was demonstrated at semi-pilot scale in a 30 L bioreactor. Additionally, to provide insight into the biological process occurring, we investigated selectivity between Co and Ni using proteomics to identify the biological response and confirm the potential of a bio-based method to separate these two essential metals. Our approach determines the principles and first steps of a practical bio-separation and recovery system, underlining the relevance of harnessing biological specificity for recycling and up-cycling critical materials.

Investigating the hydration of C3A in the presence of the potentially toxic element chromium-a route to remediation?

Pollution by hexavalent chromium is a growing, global problem. Its presence in public water systems is often the result of industrial activities, both past and present. In this study, tricalcium aluminate (C3A, Ca3Al2O6) is added to solutions of varying concentrations of potassium chromate (K2CrO4) and samples of both the solid and liquid are taken at various time intervals to monitor the removal of chromium from the solutions. Solution concentrations of 0.2 M, 0.1 M, 0.02 M, and 0.01 M are used, and the chromium concentration is found to reduce in all cases. For the 0.02 M solution the chromium concentration is reduced from 1040 ppm to 3.1 ppm in 1 week, and the chromium concentration of the 0.01 M solution is reduced from 520 ppm to 0.26 ppm in only one day of reaction with the C3A. The chromium removed from solution is identified in the solid products, which were fully characterised as being a mixture of ettringite (Ca6[Al(OH)6]2(CrO4)3·26H2O) and monochromate (Ca4[Al(OH)6]2CrO4·8H2O) phases from analysis of Powder X-ray Diffraction and Fourier Transform Infrared Spectroscopy data. The work presented here is a proof of concept study to investigate C3A as a potential material for the removal of hexavalent chromium from solution. The results from this study are initial steps towards development of this as a technology for hexavalent chromium remediation.

Synthesis and spectroscopic identification of nickel and cobalt layered hydroxides and hydroxynitrates.

The formation of different nickel and cobalt layered hydroxide phases by a variety of solution and solid-state synthesis methods has been investigated. Initially, preparative methods were refined to generate single-phase products from metal(II) nitrate hexahydrate starting materials which were then characterised by powder X-ray diffraction, vibrational spectroscopy and thermogravimetric analysis. As well as the brucite type ß-M(OH)2 and the hydrotalcite-like [M(OH)2-x(H2O)x]x+ alpha-phases (where M = Ni, Co), two different hydroxynitrate phases were isolated with the generic formula M(OH)2-x(NO3)x with x = 0.67 and 1.0 (where M = Ni, Co). The reduction of symmetry of the nitrate anion from D3h to C2v allows the alpha-phases to be distinguished from the two different layered hydroxynitrate phases by both infrared and Raman spectroscopy through the loss of symmetry and concomitant splitting of the degenerate bands. The symmetric N-O stretch enables the two hydroxynitrate phases to be distinguished from one another through the sharp absorption bands at ca. 1000 cm-1 (x = 0.67) and ca. 1050 cm-1 (x = 1.0). The thermogravimetric analysis data of the phases showed key differences between the layered hydroxides, with anhydrous phases having singular weight losses over short temperature ranges and hydrated phases having multiple losses over more extended temperature ranges.

Locating hydrogen positions in the autunite mineral metatorbernite [Cu(UO2)2(PO4)2·8H2O]: a combined approach using neutron powder diffraction and computational modelling.

Metatorbernite [Cu(UO2)2(PO4)2·8H2O] is a promising remediation material for environmental uranium contamination. Previous X-ray diffraction studies have been unable to definitively locate hydrogen positions within metatorbernite, which are key to determining the hydrogen-bond network that helps to stabilize the structure. Here, hydrogen positions have been determined using a combination of neutron powder diffraction and the computational modelling technique ab initio random structure searching (AIRSS). Atomic coordinates determined through Rietveld analysis of neutron powder diffraction data are in excellent agreement with the minimum energy configuration predicted by AIRSS; thus, simulations confirm that our proposed model likely represents the global minimum configuration. Two groups of water molecules exist within the metatorbernite structure: free water and copper-coordinating water. Free water molecules are held within the structure by hydrogen bonding only, whilst the coordinating water molecules bond to copper in the equatorial positions to produce a 4 + 2 Jahn-Teller octahedra. The successful agreement between neutron powder diffraction data and AIRSS suggests that this combined approach has excellent potential for the study of other (trans)uranium materials in which hydrogen bonding plays a key role in phase stability.

Nitrogen Doping and Carbon Coating Affects Substrate Selectivity of TiO2 Photocatalytic Organic Pollutant Degradation.

A series of carbon-coated, nitrogen-doped titanium dioxide photocatalysts was produced and characterized. N-doped TiO2 powder samples were prepared using a sol-gel method and subsequently used for making doped-TiO2 thin films on glass substrates. Carbon layers were coated on the films by a thermal decomposition method using catechol. Diffuse reflectance spectra and Mott-Schottky analyses of the samples proved that nitrogen doping and carbon coating can slightly lower the band gap of TiO2 , broaden its absorption to visible light and enhance its n-type character. According to photocatalytic tests against model contaminants, carbon-coated nitrogen-doped TiO2 films have better performance than simple TiO2 on the degradation of Rhodamine B dye molecules, but are poorly effective for degrading 4-chlorophenol molecules. Several possible explanations are proposed for this result, supported by scavenging experiments. This reveals the importance of a broad substrate scope when assessing new photocatalytic materials for water treatment, something which is often overlooked in many literature studies.

Reply to comments on "Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent" by Pap et al. [Water research 173 (2020) 115573].

This letter is in response to the comments of Dr Hu and Dr Zhang on "Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent" (Pap et al., 2020). We thank Dr Hu and Dr Zhang for their interest and comments, and having reflected, we wish to provide some clarification.

Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent.

Phosphorous (P) recovery from wastewater will become increasingly vital in the future as terrestrial rock phosphate deposits are expended. Effective management of P as a critical resource will require new techniques to recover P from wastewater, ideally in a form that can be used in agriculture as fertiliser. In this study, batch and fixed-bed column conditions were tested using a novel KOH deacetylated calcite-chitosan based adsorbent (CCM) for P removal from aqueous solutions and wastewater effluents. The unique characteristics of this adsorbent as a phosphate adsorbent were the result of rich surface functionality (amine and sulphur functional groups of the chitosan and proteins) and the CaCO3 content (providing donor ligands; and additionally beneficial if the material were used as fertiliser, buffering soil acidification caused by nitrogen application). The maximum P adsorption capacity was determined to be 21.36 mgP/g (at 22 °C) and the endodermic process reached equilibrium after 120 min. The experimental data was best described using a Langmuir isotherm and a pseudo-second order kinetic model. The diffusion kinetic analysis highlighted the importance of both film and intraparticle mass-transport. Material characterisation suggested that the adsorption process involved interactions between P and functional groups (mostly -NH3+) due to electrostatic interaction on the chitosan chain or involved ligand exchange with CO32-. Analysis of materials using X-Ray Powder Diffraction (XRPD) and Thermogravimetric Analysis (TGA) indicated a microprecipitation-type mechanism may occur through the formation of hydroxylapatite (Ca5(PO4)3(OH)). Desorption studies demonstrated that the P-laden CCM (derived from crab carapace) had the potential to be reused in soil amendment as a slow-release P fertiliser. The effects of different operating parameters were explored in a fixed-bed column, and the experimental data fitted well to the Clark model (R2 = 0.99). The CCM also showed excellent P adsorption potential from secondary and final wastewater effluent in dynamic conditions, even at low P concentrations. Finally, a scale-up approach with cost analysis was used to evaluate the price and parameters needed for a potential large-scale P recovery system using this adsorbent.

Synthesis optimisation and characterisation of chitosan-calcite adsorbent from fishery-food waste for phosphorus removal.

Here, Box-Behnken design (BBD) approaches were utilised to optimise synthesis methodology for the chitosan-calcite rich adsorbent (CCM) made from fishery-food waste material (crab carapace), using low-temperature activation and potassium hydroxide (KOH). The effect of activation temperature, activation time and impregnation ratio was studied. The final adsorbent material was evaluated for its phosphorus (P) removal efficiency from liquid phase. Results showed that impregnation ratio was the most significant individual factor as this acted to increase surface deacetylation of the chitin (to chitosan) and increased the number of amine groups (-NH2) in the chitosan chain. P removal efficiency approached 75.89% (at initial P concentration of 20 mg/L) under optimised experimental conditions, i.e. where the impregnation ratio for KOH:carapace (g/g) was 1:1, the activation temperature was 105 °C and the activation time was 150 min. Predicted responses were in good agreement with the experimental data. Additionally, the pristine and CCM material were further analysed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), Brunauer-Emmett-Teller technique (BET), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal gravimetric analysis (TGA). Characterisation showed enhancements in surface chemistry (introducing positively charged amine groups), textural properties and thermal stability of the CCM.

Solid solution formation in the metatorbernite-metazeunerite system (Cu(UO2)2(PO4)2- x(AsO4) x. nH2O) and their stability under conditions of variable temperature.

Mineral phases which can be thought of as members of a metatorbernite-metazeunerite solid solution (Cu(UO2)2(PO4)2- x(AsO4) x.8H2O have been identified in radioactive samples from spoil heaps at the uranium mine site in South Terras, Cornwall (grid reference SW935523). A complete solid solution (0 < x < 2) was synthesized by precipitation from solution using uranium (VI) nitrate and copper (II) chloride and phosphoric acid/arsenic acid in the appropriate molar proportions. Refined unit cell parameters determined by Pawley fitting of powder X-ray diffraction data showed a linear variation in the a unit cell parameter according to Vegard's Law, allowing the composition of the natural mineral phases found at South Terras to be determined from measurement of their unit cell parameters. High-resolution variable-temperature synchrotron powder X-ray diffraction studies were carried out at the Diamond Light Source on three members of this solid solution ( x = 0, 1, 2) and showed different structural behaviour as a function of composition and temperature. Metatorbenite ( x = 0) retains its tetragonal symmetry at low temperatures and dehydrates to an amorphous phase at 473 K, whereas metazeunrite ( x = 2) transforms to an orthorhombic phase at low temperatures, regains its tetragonal symmetry on heating to 323 K and undergoes a further transition to an, as yet, unidentified phase at 473 K. This article is part of the theme issue 'Fifty years of synchrotron science: achievements and opportunities'.

Synthesis of Gold Nanoparticles Using the Interface of an Emulsion Droplet.

A facile and rapid method for synthesizing single crystal gold spherical or platelet (nonspherical) particles is reported. The reaction takes place at the interface of two immiscible liquids where the reducing agent decamethylferrocene (DmFc) was initially added to hexane and gold chloride (AuCl4-) to an aqueous phase. The reaction is spontaneous at room temperature, leading to the creation of Au nanoparticles (AuNP). A flow focusing microfluidic chip was used to create emulsion droplets, allowing the same reaction to take place within a series of microreactors. The technique allows the number of droplets, their diameter, and even the concentration of reactants in both phases to be controlled. The size and shape of the AuNP are dependent upon the concentration of the reactants and the size of the droplets. By tuning the reaction parameters, the synthesized nanoparticles vary from nanometer to micrometer sized spheres or platelets. The surfactant used to stabilize the emulsion was also shown to influence the particle shape. Finally, the addition of other nanoparticles within the droplet allows for core@shell particles to be readily formed, and we believe this could be a versatile platform for the large scale production of core@shell particles.

Electrochromic and colorimetric properties of nickel(II) oxide thin films prepared by aerosol-assisted chemical vapor deposition.

Aerosol-assisted chemical vapor deposition (AACVD) was used for the first time in the preparation of thin-film electrochromic nickel(II) oxide (NiO). The as-deposited films were cubic NiO, with an octahedral-like grain structure, and an optical band gap that decreased from 3.61 to 3.48 eV on increase in film thickness (in the range 500-1000 nm). On oxidative voltammetric cycling in aqueous KOH (0.1 mol dm(-3)) electrolyte, the morphology gradually changed to an open porous NiO structure. The electrochromic properties of the films were investigated as a function of film thickness, following 50, 100, and 500 conditioning oxidative voltammetric cycles in aqueous KOH (0.1 mol dm(-3)). Light modulation of the films increased with the number of conditioning cycles. The maximum coloration efficiency (CE) for the NiO (transmissive light green, the "bleached" state) to NiOOH (deep brown, the colored state) electrochromic process was found to be 56.3 cm(2) C(-1) (at 450 nm) for films prepared by AACVD for 15 min followed by 100 "bleached"-to-colored conditioning oxidative voltammetric cycles. Electrochromic response times were <10 s and generally longer for the coloration than the bleaching process. The films showed good stability when tested for up to 10 000 color/bleach cycles. Using the CIE (Commission Internationale de l'Eclairage) system of colorimetry the color stimuli of the electrochromic NiO films and the changes that take place on reversibly oxidatively switching to the NiOOH form were calculated from in situ visible spectra recorded under electrochemical control. Reversible changes in the hue and saturation occur on oxidation of the NiO (transmissive light green) form to the NiOOH (deep brown) form, as shown by the track of the CIE 1931 xy chromaticity coordinates. As the NiO film is oxidized, a sharp decrease in luminance was observed. CIELAB L*a*b* coordinates were also used to quantify the electrochromic color states. A combination of a low L* and positive a* and b* values quantified the perceived deep brown colored state.

Li(+) ion conductivity in rock salt-structured nickel-doped Li(3)NbO(4).

Two mechanisms of doping Li(3)NbO(4), which has an ordered, rock salt superstructure, have been established. In the "stoichiometric mechanism", the overall cation-to-anion ratio is maintained at 1:1 by means of the substitution 3Li(+) + Nb(5+) --> 4Ni(2+). In the "vacancy mechanism", Li(+) ion vacancies are created by means of the substitution 2Li(+) --> Ni(2+). Solid solution ranges have been determined for both mechanisms and a partial phase diagram constructed for the stoichiometric join. On the vacancy join, the substitution mechanism has been confirmed by powder neutron diffraction; associated with lithium vacancy creation, a dramatic increase in Li(+) ion conductivity occurs with increasing Ni content, reaching a value of 5 x 10(-4) Omega(-1) cm(-1) at 300 degrees C for composition x= 0.1 in the formula Li(3-2x)Ni(x)NbO(4). This is the first example of high Li(+) ion conductivity in complex oxides with rock salt-related structures.