Single-Atom (Iron-Based) Catalysts: Synthesis and Applications.

Supported single-metal atom catalysts (SACs) are constituted of isolated active metal centers, which are heterogenized on inert supports such as graphene, porous carbon, and metal oxides. Their thermal stability, electronic properties, and catalytic activities can be controlled via interactions between the single-metal atom center and neighboring heteroatoms such as nitrogen, oxygen, and sulfur. Due to the atomic dispersion of the active catalytic centers, the amount of metal required for catalysis can be decreased, thus offering new possibilities to control the selectivity of a given transformation as well as to improve catalyst turnover frequencies and turnover numbers. This review aims to comprehensively summarize the synthesis of Fe-SACs with a focus on anchoring single atoms (SA) on carbon/graphene supports. The characterization of these advanced materials using various spectroscopic techniques and their applications in diverse research areas are described. When applicable, mechanistic investigations conducted to understand the specific behavior of Fe-SACs-based catalysts are highlighted, including the use of theoretical models.

Designing Materials for Aqueous Catalysis: Ionic Liquid Gel and Silica Sphere Entrapped Iron-TAML Catalysts for Oxidative Degradation of Dyes.

Materials have been developed that encapsulate a homogeneous catalyst and enable it to operate as a heterogeneous catalyst in water. A hydrophobic ionic liquid within the material was used to dissolve Fe-TAML and keep it from leaching into the aqueous phase. One-pot processes were used to entrap Fe-TAML in basic ionic liquid gels, and ionic liquid gel spheres structured via a modified Stöber synthesis forming SiO2 particles of uniform size. Catalytic activity was demonstrated via the oxidative degradation of dyes. Fe-TAML entrapped in a basic ionic liquid gel exhibited consistent activity in five recycles. This discovery of heterogenized H2O2 activators prepared by sol-gel and Stöber processes opens new possibilities for the creation of engineered catalytic materials for water purification.

Cellulose modification for sustainable polymers: overcoming problems of solubility and processing.

Two new water-soluble cellulose derivatives were prepared by a two-step transformation with 1,3-propane sultone, followed by either maleic or succinic anhydride, thereby converting cellulose into a more easily processable form. It was found that the solubility was dependent on both the degree of substitution and the chemical properties of the substituents. The water-soluble cellulose has a molecular weight greater than 100 000 g mol-1 and both the morphology and molecular weight can be tuned by varying the reaction conditions. Furthermore, the flexible, two-step nature of the process allows for expansion of this methodology in order to prepare cellulose analogues for different applications.

Improved Electrochemical Hydrogen Peroxide Detection Using a Nickel(II) Phthalimide-Substituted Porphyrazine Combined with Various Carbon Nanomaterials.

A metal-free porphyrazine derivative with peripheral phthalimide substituents was metallated with a nickel(II) ion. The purity of the nickel macrocycle was confirmed using HPLC, and characterized by MS, UV-VIS, and 1D (1H, 13C) and 2D (1H-13C HSQC, 1H-13C HMBC, 1H-1H COSY) NMR techniques. The novel porphyrazine was combined with various carbon nanomaterials, such as carbon nanotubes-single walled (SWCNTs) and multi-walled (MWCNTs), and electrochemically reduced graphene oxide (rGO), to create hybrid electroactive electrode materials. The carbon nanomaterials' effect on the electrocatalytic properties of nickel(II) cations was compared. As a result, an extensive electrochemical characterization of the synthesized metallated porphyrazine derivative on various carbon nanostructures was carried out using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). An electrode modified with carbon nanomaterials GC/MWCNTs, GC/SWCNTs, or GC/rGO, respectively, was shown to have a lower overpotential than a bare glassy carbon electrode (GC), allowing for the measurement of hydrogen peroxide in neutral conditions (pH 7.4). It was shown that among the tested carbon nanomaterials, the modified electrode GC/MWCNTs/Pz3 exhibited the best electrocatalytic properties in the direction of hydrogen peroxide oxidation/reduction. The prepared sensor was determined to enable a linear response to H2O2 in concentrations ranging between 20-1200 µM with the detection limit of 18.57 µM and sensitivity of 14.18 µA mM-1 cm-2. As a result of this research, the sensors produced here may find use in biomedical and environmental applications.