Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis.

A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts "Eco-MgZnOx" is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign thermal treatment of leaves rich in Zn, and without any further chemical treatment. The elemental composition and structure of Eco-MgZnOx were characterized by MP-AES, XRPD, HRTEM, and STEM-EDX techniques. These analyses revealed a natural richness in two unusual and valuable mixed zinc-magnesium and iron-magnesium oxides. The ecocatalysts were employed in this study to demonstrate their potential use in hydrophosphonylation of aldehydes, leading to various α-hydroxyphosphonate derivatives, which are critical building blocks in the modern chemical industry. Computational chemistry was performed to help discriminate the role of some of the constituents of the mixed oxide ecocatalysts. High conversions, broad substrate scope, mild reaction conditions, and easy purification of the final products together with simplicity of the preparation of the ecocatalysts are the major advantages of the presented protocol. Additionally, Eco-MgZnOx-P could be recovered and reused for up to five times.

New biomaterials for Ni biosorption turned into catalysts for Suzuki-Miyaura cross coupling of aryl iodides in green conditions.

In parallel with increasing Ni production and utilisation, Ni pollution in the soil-water continuum has become an alarming and global problem. Solutions for removing Ni from industrial effluents have been widely investigated and biosorption has emerged as an efficient, cost-effective, scalable and sustainable alternative for water treatment. However, the biosorption capacity is limited by the chemical composition of the biomaterial and the Ni-enriched biomaterials are rarely valorised. In this work, the biosorption capacity of three abundant biomaterials with different chemical properties - water hyacinth, coffee grounds and pinecones - was studied before and after functionalization, and reached a maximum biosorption capacity of 51 mg g-1 of Ni(ii). A bioinspired functionalization approach was investigated introducing carboxylate moieties and was conducted in green conditions. The Ni-enriched biomaterials were valorised by transformation into catalysts, which were characterised by MP-AES and XRPD. Their characterisation revealed a structure similar to nickel formate, and hence the Eco-Ni(HCOO)2 catalysts were tested in Suzuki-Miyaura reactions. Several aryl iodides were successfully cross-coupled to phenylboronic acids using Eco-Ni(HCOO)2 without any ligand, a mild and green base in a mixture of green solvents.

Morphological and chemical dynamics upon electrochemical cyclic sodiation of electrochromic tungsten oxide coatings extracted by in situ ellipsometry.

The sodiation-desodiation process of sputtered amorphous electrochromic tungsten oxide coatings in an aqueous-based medium was simultaneously monitored over 99 cycles by cyclic voltammetry and in situ spectroscopic ellipsometry. This allowed extracting the evolution of optical and geometrical parameters upon cycling. The resulting electrochemical coloring-bleaching process was dynamically fitted in the 1.8-2.8 eV optical range with a four-phase model including a constrained spline parametrization of the dielectric function. This allows real time access to thickness, surface roughness, and dielectric function of ${{\rm Na}_x}\!{{\rm WO}_3}$NaxWO3. The temporal evolution of the latter in the fully colored state was used to highlight the porosity extent of the probed coating of opened morphology. The designed spectroelectrochemical approach was applied to map the temporal evolution of the $\rm Na$Na content (${x}$x in ${{\rm Na}_x}\!{{\rm WO}_3}$NaxWO3) during and between cycles, taking into account the intricate interplay between charge density, thickness, and electrolyte uptake.

Coloration mechanism of electrochromic NaxWO3 thin films.

The coloration mechanism of tungsten trioxide (WO3) upon insertion of alkali ions is still under debate after several decades of research. This Letter provides new insights into the reversible insertion and coloration mechanisms of Na+ ions in WO3 thin films sputter-deposited on ITO/glass substrates. A unique model based on a constrained spline approach was developed and applied to draw out ε1+iε2from spectroscopic ellipsometry data from 0.6 to 4.8 eV, whatever the state of the electrochromic active layer, i.e., as-deposited, colored, or bleached. It is shown that electrochemically intercalated sodium-tungsten trioxide, NaxWO3(x=0.1,0.2,0.35), exhibits an absorption band centered at ca. 1.14 eV in ε2 governing the coloration mechanism.

In Situ Synchrotron Powder Diffraction Study of Cd Intercalation into Chevrel Phases: Crystal Structure and Kinetic Effect.

Chevrel phases are molybdenum chalcogenides of formula M xMo6X8 (where M is a cation and X is a chalcogen) that present a complex and captivating intercalation chemistry that has drawn the interest of the solid-state chemistry community since their discovery. This property has a huge potential for applied science and device development for energy storage and pollutant removal and detection, but a deeper knowledge of the intercalation processes and chemistry is still necessary. In the present work, the intercalation of Cd2+ in aqueous solution has been studied, taking advantage of the complementarity of electrochemical characterization and synchrotron powder diffraction acquired during an in situ combined experiment. During the experiment, industrially adequate electrochemical conditions (room temperature and reduced process time) were applied, allowing a better understanding of the intercalation processes. The intercalated phases obtained by electrochemistry have been characterized ex situ, and for the first time the structures of Cd2Mo6X8 (X = S, Se) have been determined. Unexpectedly, Cd2Mo6Se8 presents a trigonal crystal structure with only cavity 2 occupied, which has not been encountered before for Chevrel phases.

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation.

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix "Tordis" (Salix schwerinii × Salix viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

Electroleaching and electrodeposition of zinc in a single-cell process for the treatment of solid waste.

This work deals with zinc beneficiation of industrial solid waste by an electrochemical technique combining electroleaching and electrodeposition in a single-cell process. This technique is based on leaching of the solid waste by the protons generated at the anode and migration of the resulting ions toward the cathode where deposition takes place. A laboratory cell was built for testing the method. It consisted of three compartments, two electrode compartments and a solid waste chamber placed between these. Catholyte and anolyte were sulphuric/sulphate solutions at optimised concentrations. Experiments were first carried out using a zinc solution and an inert matrix in the central compartment, then using a synthetic waste prepared by dispersing zinc oxide in silicon dioxide. Best performance was obtained with treatment duration of 6h, at 4.5Adm(-2) and with catholyte circulation. In this case, a 97% of zinc oxide lixiviation and 75% of zinc-plated were achieved.