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  1. Abstract

    The separation of tellurium from cadmium telluride is examined using a unique combination of mild, anhydrous chlorination and complexation of the subsequent tellurium tetrachloride with 3,5‐di‐tert‐butylcatecholate ligands (dtbc). The resulting tellurium complex, Te(dtbc)2, is isolated in moderate yield and features a 103to 104reduction in cadmium content, as provided by XRF and ICP‐MS analysis. Similar results were obtained from zinc telluride. A significant separation between Te, Se, and S was observed after treating a complex mixture of metal chalcogenides with this protocol. These three tunable steps can be applied for future applications of CdTe photovoltaic waste.

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  2. Abstract

    The recognition and separation of anions attracts attention from chemists, materials scientists, and engineers. Employing exo‐binding of artificial macrocycles to selectively recognize anions remains a challenge in supramolecular chemistry. We report the instantaneous co‐crystallization and concomitant co‐precipitation between [PtCl6]2−dianions and cucurbit[6]uril, which relies on the selective recognition of these dianions through noncovalent bonding interactions on the outer surface of cucurbit[6]uril. The selective [PtCl6]2−dianion recognition is driven by weak [Pt−Cl⋅⋅⋅H−C] hydrogen bonding and [Pt−Cl⋅⋅⋅C=O] ion–dipole interactions. The synthetic protocol is highly selective. Recognition is not observed in combinations between cucurbit[6]uril and six other Pt‐ and Pd‐ or Rh‐based chloride anions. We also demonstrated that cucurbit[6]uril is able to separate selectively [PtCl6]2−dianions from a mixture of [PtCl6]2−, [PdCl4]2−, and [RhCl6]3−anions. This protocol could be exploited to recover platinum from spent vehicular three‐way catalytic converters and other platinum‐bearing metal waste.

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  3. Abstract Developing an eco-friendly, efficient, and highly selective gold-recovery technology is urgently needed in order to maintain sustainable environments and improve the utilization of resources. Here we report an additive-induced gold recovery paradigm based on precisely controlling the reciprocal transformation and instantaneous assembly of the second-sphere coordinated adducts formed between β-cyclodextrin and tetrabromoaurate anions. The additives initiate a rapid assembly process by co-occupying the binding cavity of β-cyclodextrin along with the tetrabromoaurate anions, leading to the formation of supramolecular polymers that precipitate from aqueous solutions as cocrystals. The efficiency of gold recovery reaches 99.8% when dibutyl carbitol is deployed as the additive. This cocrystallization is highly selective for square-planar tetrabromoaurate anions. In a laboratory-scale gold-recovery protocol, over 94% of gold in electronic waste was recovered at gold concentrations as low as 9.3 ppm. This simple protocol constitutes a promising paradigm for the sustainable recovery of gold, featuring reduced energy consumption, low cost inputs, and the avoidance of environmental pollution. 
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    Free, publicly-accessible full text available December 1, 2024
  4. The separation and purification of niobium and tantalum, which co-occur in natural sources, is difficult due to their similar physical and chemical properties. The current industrial method for separating Ta/Nb mixtures uses an energy-intensive process with caustic and toxic conditions. It is of interest to develop alternative, fundamental methodologies for the purification of these technologically important metals that improve upon their environmental impact. Herein, we introduce new Ta/Nb imido compounds: M( t BuN)(TriNOx) (1-M) bound by the TriNOx 3− ligand and demonstrate a fundamental, proof-of-concept Ta/Nb separation based on differences in the imido reactivities. Despite the nearly identical structures of 1-M, density functional theory (DFT)-computed electronic structures of 1-M indicate enhanced basic character of the imido group in 1-Ta as compared to 1-Nb. Accordingly, the rate of CO 2 insertion into the MN imido bond of 1-Ta to form a carbamate complex (2-Ta) was selective compared to the analogous, unobserved reaction with 1-Nb. Differences in solubility between the imido and carbamate complexes allowed for separation of the carbamate complex, and led to an efficient Ta/Nb separation ( S Ta/Nb = 404 ± 150) dependent on the kinetic differences in nucleophilicities between the imido moieties in 1-Ta and 1-Nb. 
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  5. We investigate a spin-boson inspired model of electron transfer, where the diabatic coupling is given by a position-dependent phase, e iWx . We consider both equilibrium and nonequilibrium initial conditions. We show that, for this model, all equilibrium results are completely invariant to the sign of W (to infinite order). However, the nonequilibrium results do depend on the sign of W, suggesting that photo-induced electron transfer dynamics with spin–orbit coupling can exhibit electronic spin polarization (at least for some time). 
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  6. Increasing lanthanide demand to support clean energy goals drives the need to develop more efficient approaches to separate adjacent lanthanides. Most approaches for lanthanide separations are not very selective and are based on small differences in lanthanide ionic radii. Concentrated potassium carbonate media has shown some potential to enable oxidation of praseodymium (Pr) and terbium (Tb) to their tetravalent states, which could ultimately enable a separation based on differences in oxidation states, but very little is known regarding the system’s chemistry. This work completes a detailed examination of cerium (Ce) redox chemistry in concentrated carbonate media to support the development of Pr and Tb oxidation studies. The half-wave potential (E 1/2 ) of the Ce(III)/(IV) redox couple is evaluated under various solution conditions and computational modeling of carbonate coordination environments is discussed. Cyclic voltammetry shows higher carbonate concentrations and temperatures can lower the potential required to oxidize Ce(III) by 54 mV (3.5 to 5.5 M) and 39 mV (from 10 °C to 70 °C). Chronoabsorptometry shows Ce(III) and Ce(IV) carbonate complexes are chemically stable and reversible. Computational modelling suggests the most likely coordination environment for the Ce(IV) complex is Ce(CO 3 ) 4 (OH) 5− which is less entropically favorable than the lowest energy Ce(III) complex, Ce(CO 3 ) 4 5− . 
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  7. Optical spectroscopy is a powerful characterization tool with applications ranging from fundamental studies to real-time process monitoring. However, it can be difficult to apply to complex samples that contain interfering analytes which are common in processing streams. Multivariate (chemometric) analysis has been examined for providing selectivity and accuracy to the analysis of optical spectra and expanding its potential applications. Here we will discuss chemometric modeling with an in-depth comparison to more simplistic analysis approaches and outline how chemometric modeling works while exploring the limits on modeling accuracy. Understanding the limitations of the chemometric model can provide better analytical assessment regarding the accuracy and precision of the analytical result. This will be explored in the context of UV–Vis absorbance of neodymium (Nd 3+ ) in the presence of interferents, erbium (Er 3+ ) and copper (Cu 2+ ) under conditions simulating the liquid–liquid extraction approach used to recycle plutonium (Pu) and uranium (U) in used nuclear fuel worldwide. The selected chemometric model, partial least squares regression, accurately quantifies Nd 3+ with a low percentage error in the presence of interfering analytes and even under conditions that the training set does not describe. 
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  8. Sensors are routinely developed for specific applications, but multipurpose sensors are challenging, due to stability and poor functional design. We report organic materials that operate in solution and gas phase. They show a strong response behaviour to at least three types of environmental changes: pH, amine and metal ion binding/detection. We have confirmed and validated our findings using various analytical and computational methods. We found that the changes in polarity of the solvent and pH not only red shift the tail of the absorption spectra, but also extend the peak optical absorption of these structures by up to 100 nm, with consequential effects on the optical gap and colour changes of the materials. Acid–base response has been studied by spectrophotometric titrations with trifluoroacetic acid (TFA) and triethyl amine (TEA). The experiments show excellent reversibility with greater sensitivity to base than acid for all compounds. Analysis into metal sensing using Zn( ii ) and Cu( ii ) ions as analytes show that the materials can successfully bind the cations forming stable complexes. Moreover, a strong suppression of signal with copper gives an operative modality to detect the copper ion as low as 2.5 × 10 −6 M. The formation of the metal complexes was also confirmed by growing crystals using a slow diffusion method; subsequent single crystal X-ray analysis reveals the ratio of ligand to metal to be 2 to 1. To test sensitivity towards various amine vapours, paper-based sensors have been fabricated. The sensors show a detection capability at 1 ppm of amine concentration. We have employed CIE L * a * b * colour space as the evaluation method, this provides numeric comparison of the samples from different series and allows comparison of small colour differences, which are generally undetectable by the human-eye. It shows that the CIE L * a * b * method can assess both sensitivity to a particular class of analytes and a specificity response to individual amines in this subclass offering an inexpensive and versatile methodology. 
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