Structured LDH/Bentonite Composites for Chromium Removal and Recovery from Aqueous Solutions.

This study focuses on chromium removal through adsorption and ion exchange using structured calcined layered double hydroxide (LDH) (MgAl)-bentonite composites. Firstly, the powders were structured into granulates to study the effect on Cr sorption kinetics to circumvent the limitations of working with powders in real-life applications. Secondly, the regeneration of the structured composites was optimized to enable multi-cycling operation, which is the key for their applicability beyond laboratory scale. Firstly, the LDH/bentonite ratio was optimized to obtain the best performance for the removal of Cr3+ and Cr6+ species. In powder form, the calcined adsorbent containing 80 wt% LDH and 20 wt% bentonite performed best with an adsorption capacity of 48 and 40 mg/g for Cr3+ and Cr6+, respectively. The desorption was optimized by studying the effect of the NaCl concentration and pH, with a 2 M NaCl solution without pH modification being optimal. The kinetic data of the adsorption and desorption steps were modelled, revealing a pseudo-second order model for both. This was also demonstrated using XRD and Raman measurements after the Cr3+ and Cr6+ adsorption tests, indicating successful uptake and revealing the adsorption mechanism. Finally, five consecutive adsorption-desorption cycles were performed, each showing nearly 100% adsorption and desorption.

Self-Induced and Progressive Photo-Oxidation of Organophosphonic Acid Grafted Titanium Dioxide.

While synthesis-properties-performance correlations are being studied for organophosphonic acid grafted TiO2 , their stability and the impact of the exposure conditions on possible changes in the interfacial surface chemistry remain unexplored. Here, the impact of different ageing conditions on the evolution of the surface properties of propyl- and 3-aminopropylphosphonic acid grafted mesoporous TiO2 over a period of 2 years is reported, using solid-state 31 P and 13 C NMR, ToF-SIMS and EPR as main techniques. In humid conditions under ambient light exposure, PA grafted TiO2 surfaces initiate and facilitate photo-induced oxidative reactions, resulting in the formation of phosphate species and degradation of the grafted organic group with a loss of carbon content ranging from 40 to 60 wt %. By revealing its mechanism, solutions were provided to prevent degradation. This work provides valuable insights for the broad community in choosing optimal exposure/storage conditions that extend the lifetime and improve the materials' performance, positively impacting sustainability.

Amino-Alkylphosphonate-Grafted TiO2: How the Alkyl Chain Length Impacts the Surface Properties and the Adsorption Efficiency for Pd.

Amino-alkylphosphonic acid-grafted TiO2 materials are of increasing interest in a variety of applications such as metal sorption, heterogeneous catalysis, CO2 capture, and enzyme immobilization. To date, systematic insights into the synthesis-properties-performance correlation are missing for such materials, albeit giving important know-how towards their applicability and limitations. In this work, the impact of the chain length and modification conditions (concentration and temperature) of amino-alkylphosphonic acid-grafted TiO2 on the surface properties and adsorption performance of palladium is studied. Via grafting with aminomethyl-, 3-aminopropyl-, and 6-aminohexylphosphonic acid, combined with the spectroscopic techniques (DRIFT, 31P NMR, XPS) and zeta potential measurements, differences in surface properties between the C1, C3, and C6 chains are revealed. The modification degree decreases with increasing chain length under the same synthesis conditions, indicative of folded grafted groups that sterically shield an increasing area of binding sites with increasing chain length. Next, all techniques confirm the different surface interactions of a C1 chain compared to a C3 or C6 chain. This is in line with palladium adsorption experiments, where only for a C1 chain, the adsorption efficiency is affected by the precursor concentration used for modification. The absence of a straightforward correlation between the number of free NH2 groups and the adsorption capacity for the different chain lengths indicates that other chain-length-specific surface interactions are controlling the adsorption performance. The increasing pH stability in the order of C1 < C3 < C6 can possibly be associated to a higher fraction of inaccessible hydrophilic sites due to the presence of folded structures. Lastly, the comparison of adsorption performance and pH stability with 3-aminopropyl(triethoxysilane)-grafted TiO2 reveals the applicability of both grafting methods depending on the envisaged pH during sorption.

Selective Pd recovery from acidic leachates by 3-mercaptopropylphosphonic acid grafted TiO2: does surface coverage correlate to performance?

Modification of metal oxides with organophosphonic acids (PAs) provides the ability to control and tailor the surface properties. The metal oxide phosphonic acid bond (M-O-P) is known to be stable under harsh conditions, making PAs a promising candidate for the recovery of metals from complex acidic leachates. The thiol functional group is an excellent regenerable scavenging group for these applications. However, the research on organophosphonic acid grafting with thiol groups is very limited. In this study, four different metal sorbent materials were designed with different thiol surface coverages. An aqueous-based grafting of 3-mercaptopropylphosphonic acid (3MPPA) on mesoporous TiO2 was employed. Surface grafted thiol groups could be obtained in the range from 0.9 to 1.9 groups per nm2. The different obtained surface properties were studied and correlated to the Pd adsorption performance. High Pd/S adsorption efficiencies were achieved, indicating the presence of readily available sorption sites. A large difference in their selectivity towards Pd removal from a spend automotive catalyst leachate was observed due to the co-adsorption of Fe on the titania support. The highest surface coverage showed the highest selectivity (K d: 530 mL g-1) and adsorption capacity (Q max: 0.32 mmol g-1) towards Pd, while strongly reducing the co-adsorption of Fe on remaining TiO2 sites.

Silanization of 3D-Printed Silica Fibers and Monoliths.

Surface functionalization of complex three-dimensional (3D) porous architectures has not been widely investigated despite their potential in different application domains. In this work, silanization was performed in silica 3D-printed porous structures, and the homogeneity of functional groups within the architecture was investigated by comparing the extent of the functionalization in the walls and core of the monolith. A silica ink was used for direct ink writing (DIW) to shape fibers and monoliths with different architectures and stacking designs. The surfaces of the fibers and monoliths were functionalized with 3-aminopropyl(triethoxysilane) (APTES) using different reaction conditions. The nature of the functional groups on the surface and the presence of RSiO1.5 bonds were identified by solid-state 13C-NMR, 29Si-NMR, and by ξ-potential measurements. Elemental analysis was used to quantify the concentration of bonded APTES in the core and walls of the monolith. The availability and hydrolytic stability of the introduced amine group on fibers were evaluated using the adsorption of PdCl42- ions within the pH range of 2-5. The study found that geometries with interfiber distances above 250 µm are homogeneously functionalized with amine groups. As the interfiber distance of the monolith decreases, a significantly lower density of amine groups is detected in the core of the monolith. The determination of the homogeneity of 3D-printed monoliths makes this work relevant as it provides the limits of functionalization carried out in stirred batch reactors for geometrically defined structures produced from a 3D-printing process.

Granulation and calcination of alum sludge for the development of a phosphorus adsorbent: From lab scale to pilot scale.

Alum sludge, an Al-oxyhydroxide rich waste product from water treatment practices, has the potential to be valorized as a P adsorbent material. However, several challenges currently prevent its application as an adsorbent in industrial setting, i.e. a limited P adsorption capacity due to saturation by organic matter and a fine nature resulting in percolation problems in adsorption bed setups. In this study, granulation and subsequent calcination of alum sludge were proposed to overcome these issues and to improve the P adsorption properties of alum-based adsorbent (ABA) materials. The effect of calcination temperature on the physicochemical properties of granular material was examined using X-ray diffraction, mass-spectroscopy coupled thermogravimetric analysis, Fourier-transform infrared spectrometry and specific surface area analysis, combined with density and crushing strength measurements. The ABA material obtained at 550 °C showed superior P adsorption properties and, therefore, this material was selected for further P adsorption testing and characterization (scanning electron microscopy and sieving). Batch P adsorption tests showed that this material had a maximum P adsorption capacity of 7.27 mg-P g-1. Kinetic adsorption tests determined the effect of the solid-to-liquid ratio and the granule particle size on the P removal. Finally, the performance of the ABA-550 material was tested in a pilot-scale adsorption setup, using a surface water stream (0.47 mg-P L-1) at a flow rate of 200 L h-1. During the test, the P removal efficiency always exceeded 86%, while the material maintained its structural stability. The results of this study illustrate the potential of granulated/calcined ABA materials for P adsorption, paving the way for the industrial application of this novel, sustainable P removal technology.

Recovery of cobalt from dilute aqueous solutions using activated carbon-alginate composite spheres impregnated with Cyanex 272.

A novel adsorbent was designed for selective recovery of cobalt(ii) from synthetic binary cobalt(ii)-nickel(ii) and cobalt(ii)-manganese(ii) solutions, a synthetic multi-element solution and a real aqueous waste stream from the petrochemical sector. The adsorbent consisted of shaped activated carbon-alginate spheres impregnated with Cyanex 272. The synthesis was followed by characterisation using SEM, infrared spectroscopy, BET analysis and elemental analysis. Good selectivity for cobalt(ii) over nickel(ii) could be achieved during adsorption, while this was not the case for cobalt(ii) over manganese(ii). Cobalt(ii) and manganese(ii) were therefore fully adsorbed and stripped using a dilute sulphuric acid solution. The adsorbent was shown to be reusable in a column setup. Finally, the adsorbent material was used for the purification of a real aqueous waste stream from the petrochemical sector.

Solute-solvent interactions in cryosolutions: a study of halothane-ammonia complexes.

The formation of C-H···N bonded complexes of halothane with ammonia has been studied using infrared and Raman spectroscopy of solutions in the liquid rare gases argon, krypton and xenon, of supersonic jet expansions and of room temperature vapor phase mixtures. For the solutions and for the vapor phase experiments, the formation of complexes with 1:1 and 1:2 stoichiometry was observed. The complexation enthalpy for the 1:1 complex was determined to be -20 (1) kJ mol(-1) in the vapor phase, -17.0 (5) kJ mol(-1) in liquid xenon and -17.3 (6) kJ mol(-1) in liquid krypton. For the 1:2 complex in liquid xenon, the complexation enthalpy was determined to be -31.5 (12) kJ mol(-1). Using the complexation enthalpies for the vapor phase and for the solutions in liquid xenon and krypton, a critical assessment is made of the Monte Carlo Free Energy Perturbation approach to model solvent influences on the thermodynamical properties of the cryosolutions. The influences of temperature and solvent on the complexation shifts of the halothane C-H stretching mode are discussed.

On the weakly C-H···π hydrogen bonded complexes of sevoflurane and benzene.

A vibrational assignment of the anaesthetic sevoflurane, (CF(3))(2)CHOCH(2)F, is proposed and its interaction with the aromatic model compound benzene is studied using vibrational spectroscopy of supersonic jet expansions and of cryosolutions in liquid xenon. Ab initio calculations, at the MP2/cc-pVDZ and MP2/aug-cc-pVDZ levels, predict two isomers for the 1 : 1 complex, one in which the near-cis, gauche conformer of sevoflurane is hydrogen bonded through its isopropyl-hydrogen atom, the other in which the same conformer is bonded through a bifurcated hydrogen bond with the fluoromethyl hydrogen atoms. From the experiments it is shown that the two isomers are formed, however with a strong population dominance of the isopropyl-bonded species, both in the jet and liquid phase spectra. The experimental complexation enthalpy in liquid xenon, ΔH(o)(LXe), of this species equals -10.9(2) kJ mol(-1), as derived from the temperature dependent behaviour of the cryosolution spectra. Theoretical complexation enthalpies in liquid xenon were obtained by combining the complete basis set extrapolated complexation energies at the MP2/aug-cc-pVXZ (X = D,T) level with corrections derived from statistical thermodynamics and Monte Carlo Free Energy Perturbation calculations, resulting in a complexation enthalpy of -11.2(3) kJ mol(-1) for the isopropyl-bonded complex, in very good agreement with the experimental value, and of -11.4(4) kJ mol(-1), for the fluoromethyl-bonded complex. The Monte Carlo calculations show that the solvation entropy of the isopropyl-bonded species is considerably higher than that of the fluoromethyl-bonded complex, which assists in explaining its dominance in the liquid phase spectra.

The complexes of halothane with benzene: the temperature dependent direction of the complexation shift of the aliphatic C-H stretching.

The formation of C-H...π bonded complexes of halothane with benzene(-d(6)) has been studied using infrared and Raman spectroscopy of solutions in liquid krypton, in supersonic jet expansions and in room temperature vapour phase. The formation of complexes with 1 ∶ 1 and 2 ∶ 1 stoichiometry was observed. The complexation enthalpy in liquid krypton for the 1 ∶ 1 complex was determined to be -9.8(2) kJ mol(-1) and the enthalpy for the addition of a second halothane molecule to the 1 ∶ 1 complex was determined at -7.0(3) kJ mol(-1). The stretching mode of the halothane C-H bond involved in the formation of the complex in the jets was observed to blue shift by 7.7(10) cm(-1). In contrast, for the solutions of liquid krypton and the room temperature measurements a small red shift was observed. Supported by ab initio calculations and Monte Carlo simulations, this shift was explained by the differences in thermal populations of the van der Waals vibrations of the complex in the different experiments.

C-H bonds with a positive dipole gradient can form blue-shifting hydrogen bonds: the complex of halothane with methyl fluoride.

The complex of halothane (CF(3)CBrClH) with ([D(3)])methyl fluoride is investigated theoretically by means of ab initio calculations at the MP2/6-311++G(d,p) level and experimentally by infrared spectroscopy of solutions in liquid krypton. The complexation energy is calculated to be -12.5 kJ mol(-1). The dipole moment of halothane monomer as a function of the C-H stretching coordinate is calculated with different methodologies and the value of (partial differential(mu)/partial differential(Q(1)))0 is found to be positive. In the spectra, formation of a 1:1 complex is observed. The standard complexation enthalpy is measured to be -8.4(2) kJ mol(-1). The C-H stretching vibration of halothane shows a blueshift of +15.4 cm(-1) on complexation, and its infrared intensity ratio epsilon(complex)/epsilon(monomer) is found to be 1.39(7). The frequency shift is analyzed by a Morokuma analysis, and the infrared intensities are rationalized by using a model which includes the mechanical and electrical anharmonicity of the C-H stretching vibration.

Intermolecular interactions between halothane and dimethyl ether: a cryosolution infrared and Ab initio study.

The complex of halothane (CHClBrCF(3)) and dimethyl ether has been investigated experimentally in solutions of liquid krypton using infrared spectroscopy and theoretically using ab initio calculations at the MP2/6-311++G(d,p) level. The formation of a 1:1 complex was experimentally detected. The most stable ab initio geometry found is the one in which the C--H bond of halothane interacts with the oxygen atom of dimethyl ether. The complexes in which the chlorine or the bromine atom of halothane interacts with the oxygen atom of the ether were found to be local energy minima and were less stable by 14.5 and 9.3 kJ mol(-1), respectively, than the global minimum. The formation of a single complex species was observed in the infrared spectra; the standard complexation enthalpy of this complex was determined to be -12.3(8) kJ mol(-1). Analysis of the observed complexation shifts supports the identification of the complex as the hydrogen-bonded species. The C--H stretching vibration of halothane was found to show a redshift upon complexation of 19(2) cm(-1). The infrared intensity ratios epsilon(complex)/epsilon(monomer) for the fundamental and its first overtone were measured to be 6.5(1) and 0.31(1). The frequency shift was analyzed using Morokuma-type analysis, and the infrared intensity ratios were rationalized using a model including the mechanical and electric anharmonicity of the C--H stretching fundamental.