Alkoxide Research Articles

Spontaneous Generation of Alkoxide Radical from Alcohols on Microdroplets Surface.

Water microdroplets have been demonstrated to exhibit extraordinary chemical behaviors, including the abilities to accelerate chemical reactions by several orders of magnitude and to trigger reactions that cannot occur in bulk water. One of the most striking examples is the spontaneous generation of hydroxyl radical from hydroxide ions. Alcohols and alkoxide ions, being structurally similar to water and hydroxide ions, might exhibit similar behavior on microdroplets. Here, we report the spontaneous generation of alkoxide radicals from alcohols (RCH2OH) in aqueous microdroplets through quantum chemical calculations, quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations, ab initio MD simulations, and mass spectrometry. Our results show that an electric field (EF) on the order of 10-1 V/Å and partial solvation at the air-water interface jointly promote the dissociation of RCH2OH into RCH2O- and H3O+ ions. QM/MM MD simulations indicate that RCH2O- can be ionized to produce RCH2O⋅ radicals on the microdroplet surface. Furthermore, partial solvation and the EF collaboratively catalyze the isomerization of the RCH2O⋅ radical into a more stable tautomer, R⋅CHOH. This study highlights the molecular mechanisms underlying the widespread generation of radicals at the microdroplet surface and provides insights into the importance of fundamental alcohol chemistry in the atmosphere.

Spontaneous Generation of Alkoxide Radical from Alcohols on Microdroplets Surface

AbstractWater microdroplets have been demonstrated to exhibit extraordinary chemical behaviors, including the abilities to accelerate chemical reactions by several orders of magnitude and to trigger reactions that cannot occur in bulk water. One of the most striking examples is the spontaneous generation of hydroxyl radical from hydroxide ions. Alcohols and alkoxide ions, being structurally similar to water and hydroxide ions, might exhibit similar behavior on microdroplets. Here, we report the spontaneous generation of alkoxide radicals from alcohols (RCH2OH) in aqueous microdroplets through quantum chemical calculations, quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations, ab initio MD simulations, and mass spectrometry. Our results show that an electric field (EF) on the order of 10−1 V/Å and partial solvation at the air‐water interface jointly promote the dissociation of RCH2OH into RCH2O− and H3O+ ions. QM/MM MD simulations indicate that RCH2O− can be ionized to produce RCH2O⋅ radicals on the microdroplet surface. Furthermore, partial solvation and the EF collaboratively catalyze the isomerization of the RCH2O⋅ radical into a more stable tautomer, R⋅CHOH. This study highlights the molecular mechanisms underlying the widespread generation of radicals at the microdroplet surface and provides insights into the importance of fundamental alcohol chemistry in the atmosphere.

Co-Catalyzed Suzuki-Miyaura Coupling of Organoboronic Acids and Alkynyl Chlorides Using Potassium Bicarbonate as Base.

Organoboronic acids, some of the most common and widely used organoboron compounds, have not yet been used in the cobalt-catalyzed cross coupling reactions, despite cobalt demonstrating good reactivity with zinc reagents, Grignard reagents, and metal organoborates that are formed by n-butyl lithium or alkaline metal alkoxide salts and organoboron esters. Herein, a highly efficient and practical cobalt-catalyzed coupling reaction of aryl/alkenyl boronic acids and alkynyl chloride under mild reaction conditions is reported. The advantages of the organoboronic acids, along with a broad functional group compatibility and the reaction's tolerance to moisture and air, enable this reaction to be a synthetically useful protocol for the construction of a C(sp2)-C(sp) bond. Lastly, the synthesis of two natural products and a key intermediate of roxadustat was effectively accomplished using the methodology to construct the critical alkynyl-aryl bond.

Novel sol-gel derived layered double oxides and layered double oxide/γ-Al2O3 with tunable selectivity as promising adsorbents for L-lactate uptake from the myoblast culture medium

Cultured meat production, a biotechnological solution for global protein demand and sustainability, faces economic challenges due to the high demand for cell culture medium. Contamination with cell metabolites, particularly L-lactate, impedes myoblast proliferation in high-density suspension culture. Eliminating L-lactate is crucial for reusing the medium and overcoming economic barriers in mass myoblast culture. Retaining essential nutrients like D-glucose, amino acids, and vitamins after L-lactate removal is imperative for sustained myoblast growth. This study proposes a sustainable and economically feasible adsorption technique utilizing novel sol-gel derived Mg-Al layered double oxides and Mg-Al layered double oxide/γ-Al2O3 with tunable selectivity as a promising tool for L-lactate uptake from the myoblast medium. In an aqueous solution, L-lactate uptake and selectivity over D-glucose were enhanced with the decrease in total Mg/Al ratio and crystallinity, increase in Al2O3 dispersion in adsorbent, specific surface area, and porosity. The latter was achieved successfully by metal alkoxide sol-gel method employing an organic structure-directing agent, where LDO/amorphous alumina nanohybrid with Mg/Al = 1.23 was successfully prepared in mixed methanol-ethanol solution in a relatively short time. A simple mixture of Mg-Al LDO with Mg/Al = 2 and nano-γ-Al2O3 prepared by a sustainable and economically feasible co-precipitation method was found to have comparable efficiency and selectivity to a costly sol-gel derived material. In myoblast medium, lower total Mg/Al was associated with higher cytocompatibility, pH-stability, and selectivity, while surface properties of materials did not play a significant role. Nano-γ-Al2O3 was identified as the most promising material for selective L-lactate uptake from the myoblast culture medium. Thus, further optimization of the medium treatment process with nano-γ-Al2O3 can realize cost-effective high-density myoblast culture with circular use of the medium – a novel sustainable process in the biotechnology field.

Computational Studies of Nucleophilic Substitution at Nitrogen Center: Reactions of NH2Cl with HO-, CH3O- and C2H5O.

The atomic-level mechanisms of the nucleophilic substitution reactions at the nitrogen center (SN2@N) were investigated for the reactions of chloramine (NH2Cl) with the alkoxide ions (RO-, where R=H, CH3, and C2H5) using DFT and MP2 methods. The computed potential energy profiles for the SN2@N pathways involving the back-side attack of the nucleophiles show the typical double-well potential with submerged barriers similar to the SN2 reactions at the carbon center (SN2@C). However, the pre-reaction and post-reaction complexes are, respectively, the N-H⋅⋅⋅O and N-H⋅⋅⋅Cl hydrogen-bonded intermediates, which are different from those generally seen in SN2@C reactions. The SN2@N pathways involving front-side attack of the nucleophiles have high-energy barriers. The potential energy surfaces (PESs) along the proton-transfer pathways were flat. In addition to the proton-transfer and SN2 pathways, we also observed a new path for the methoxide and ethoxide nucleophiles where a hydride-transfer from the nucleophile to chloramine resulted in the products Cl-+R'CHO+NH3, (R'=H, CH3), and was the most exoergic. A comparison of the energetics obtained used different DFT and MP2 methods with that of the benchmark coupled-cluster methods reveals that CAM-B3LYP best describes the PESs.

Synthesis of alternating polyesters using a dual catalytic system of alkali metal alkoxides and crown ether

In this study, a dual catalytic system that merges crown ether with alkali metal alkoxides (AMA) is utilized in the ring-opening alternating polymerization (ROAP) of phthalic anhydride (PA) and propylene oxide (PO). This method streamlines the production of polyesters characterized by a fully alternating sequence, a modifiable molar mass (achieving up to 59.3 kg mol−1), and a narrow molar mass distribution (ÐM < 1.26). Analysis of various commercially available AMAs, notably sodium ethoxide (EtONa), sodium methoxide, and lithium ethoxide, in tandem with crown ethers (15-crown-5 and 18-crown-6), underscores the superior catalytic efficacy of the EtONa and 18-crown-6 pairing. This heightened efficiency is attributed to the coordination of crown ether with alkali metal ions, thereby boosting the nucleophilicity of terminal alkoxide anions. The methodology has been successfully deployed in the ROAP of PA, norbornene anhydride, and multiple epoxides, while also simplifying the creation of aliphatic–aromatic block polyesters from a mixture of PA, PO, and lactide. This strategy presents a straightforward approach to polyester production, thus making significant contributions to the evolution of polyester synthesis technology.

Metal alkoxides as models for metal oxides—the concept revisited

Sol-Gel synthesis of metal oxides constitutes a tremendously exciting domain of inorganic chemistry, where molecular and supramolecular science meet the physical chemistry and materials science. Structure and reactivity, especially surface complexation of biologically important molecules on the surface of metal oxide nanoparticles can efficiently be traced through structural studies of metal oxo-paperbags—the product of partial hydrolysis of alkoxide precursors. Paperbag is a recently proposed term to denote oligonuclear complexes not featuring intrinsic metal-metal bonding and thus not qualified to be called “clusters”. Another important insight, provided recently by the studies of heterometallic species, is dealing with visualization of bonding modes of single atom catalysts on metal oxide substrates and reveals possible coordination environments of heteroatoms on doping. The studies of large paperbag aggregates can contribute to understanding of factors influencing the bandgap and photocatalytic activity of related oxides. The use of these species directly as photo or electro catalysts is rather debatable, however, in the view of high reactivity of these alkoxide intermediates, easily transforming them into metal oxide nanoparticles on hydrolysis or thermolysis.Graphical

Structural connectivity and bioactivity in sol–gel silicate glass design

Bioactive glasses (BGs) bond with bone by forming hydroxy carbonate apatite (HCA) upon reaction in physiological fluid, a phenomenon known as bioactivity. BGs structural network connectivity determines their bioactivity. Sol–gel BGs are synthesized through the hydrolysis and condensation of metal alkoxide precursors in the presence of a catalyst, in aqueous environments. Several sol–gel synthesis parameters directly impact BG network connectivity: pH (i.e. acid or basic catalysis), water to alkoxide ratio (Rw), alkoxide type and presence of dopant ions. However, the relationship between bioactivity and these parameters remains surprisingly unexplored.This study highlights the relationship between synthesis pH, Rw, network connectivity and bioactivity in silica-based sol-gel BGs and BGs doped with titanium (Ti) ions (TiBGs), the latter selected for their known ability to enhance network connectivity. BGs and TiBGs are synthesized with various Rw values under acidic and basic conditions, and their bioactivity is assessed in simulated body fluid for 7 days.Increasing Rw decreases network connectivity and increases bioactivity of BGs with high network connectivity, as observed for base-catalyzed BGs and for both acid and base catalyzed TiBGs, but not in BGs with lower connectivity as evidenced in acid-catalyzed BGs. Basic catalysis of TiBGs prevents crystalline TiO2 domain formation, which was instead consistently observed in TiBGs synthesized under acidic catalysis.These findings help the design of BGs for applications where ion release needs to be enhanced even in the presence of dopants that slow down HCA formation, and of BGs with specific properties, e.g. TiO2-containing BGs with potential bactericidal activity. Statement of significanceBioactive glasses (BGs) bond with bone by dissolving and forming hydroxycarbonate apatite (HCA) on their surface, offering applications in medicine and dentistry. BG's network connectivity influences its dissolution rate, and hence HCA formation. While solution-gelation (sol-gel) is commonly used for BG production, the effect of sol gel synthesis parameters on HCA formation remains unexplored. We studied the relationship between synthesis parameters (water-to-alkoxide ratio (Rw), catalyst, and dopant ions, particularly titanium), BG network connectivity, and HCA formation. We find that increasing Rw with any catalyst enhances HCA formation, particularly in glasses with high network connectivity. This understanding allows tailoring BG synthesis for different applications, e.g. those requiring doping with ions that increase network connectivity and fills a crucial gap in BG literature.

Excited State Bond Homolysis of Vanadium(V) Photocatalysts for Alkoxy Radical Generation.

Advancements in photocatalysis have transformed synthetic organic chemistry, using light as a powerful tool to drive selective chemical transformations. Recent approaches have focused on metal-halide ligand-to-metal charge transfer (LMCT) photoactivated bond homolysis reactions leveraged by earth-abundant elements to generate valuable synthons for radical-mediated cross-coupling reactions. Of recent utility, oxovanadium(V) LMCT photocatalysts exhibit selective alkoxy radical generation from aliphatic alcohols upon blue light (UVA) irradiation under mild conditions. The selective photochemical liberation of alkoxy radicals is valuable for applying late-stage fragmentation approaches in organic synthesis and depolymerization strategies for nonbiodegradable polymers. Steady-state and time-resolved spectroscopy were used to assign the electronic structure of three well-defined V(V) photocatalysts in their ground and excited states. We assign the excited state for this transformation at earth-abundant vanadium(V), interrogating the electronic structure using static UV-visible absorption, ultrafast transient absorption, and electron paramagnetic resonance spectroscopy coupled to computational approaches. These findings afford assignments of the short-lived excited state intermediates that dictate selective homolytic bond cleavage in metal alkoxides, illustrating the valuable insight gleaned from fundamental investigations of the molecular photochemistry responsible for light-escalated chemical transformations.

A REVIEW OF THE SOL-GEL PROCESS AND ITS APPLICATION

The sol-gel process has been very useful to produce nanomaterials using different precursors since the early days. Precursors like metal alkoxide or organic/inorganic hybrids are dissolved in alcohol or water and converted into gel after alcoholysis or hydrolysis. The low temperature and low cost of the sol-gel technique make it more convenient than other methods. In comparison to other method, it has good control over the homogeneity of the particles. This process is very much used in ceramics, composites, thin film coating, and other industrial purposes. This review is a study about the process and application of sol-gel-derived materials. The historical point of view of this process is also explained in this review.

Metal alkoxides: A new type of reversible anode materials for stable and high-rate lithium-ion batteries

Metal-organic compounds have attracted significant attention for lithium-ion battery (LIB) anodes. However, their practical application is severely hindered by the poor structural stability and sluggish Li+ reaction kinetics. Herein, we proposed a new type of metal–organic compound, metal alkoxides, for high-performance LIBs. A series of metal-alkoxide/graphene composites with different transition metal centers and alkoxide anions are prepared to investigate the structural stability, Li-storage ability, and Li+ diffusion kinetics. The results reveal that the metal centers and alkoxide anions have significant influence on the structural stability, molar mass, and electronic structures, which are highly related to the Li-storage performance. Among them, Co-EG/rGO (EG represents the ethylene glycol anion) delivers the best performance involving high specific capacity (975 mAh g−1 at 0.2 A g−1), excellent rate capability (400.8 mAh g−1 at 10 A g−1), and stable cycling performance (86.8 % capacity retention after 600 cycles) due to its stable structure, smaller molar mass, and favorable electronic structure. Moreover, the Li-storage mechanism and solid electrolyte interphase (SEI) evolution of the Co-EG/rGO electrode are studied in detail through multiple ex-situ/in-situ characterizations. This work provides a new type of metal alkoxide anode material for high-rate and long-life LIBs toward practical energy applications.

Revitalizing CO2 photoreduction: Fine-tuning electronic synergy in ultrathin g-C3N4 with amorphous (CoFeNiMnCu)S2 high-entropy sulfide nanoparticles for enhanced sustainability

Sustainability is a key issue in developing stable and efficient catalysts for solar-catalyzed CO2 conversion. The concept of structural stabilization by quenching the Gibbs free energy, which is achieved by increasing the configurational entropy level of the system, introduced high-entropy materials. However, because alloying immiscible multimetallic atoms into a unit system is still an arduous process, the potential of high-entropy materials has not yet been fully exploited. Surprisingly, although metal sulfide photocatalysts have an enviable reputation for CO2 photoreduction (CO2-PR) owing to their optical/electronic merits and more negative redox potential than other materials, the capability of high-entropy metal sulfides has been completely disregarded. Herein, an adaptable, self-templating metal alkoxide appropriately addresses the immiscibility of metallic constituents by the well-blended metal ions with polyalcohol in the metal glycerate. Consequently, (CoFeNiMnCu)S2 high-entropy metal sulfide nanoparticles (HEMS-Nps) were grown in situ on crossed ultrathin g-C3N4 (UCN) monolayers during the sulfidation of the metal glycerate. The as-synthesized HEMS-Np has a crystalline–amorphous structure, which is conducive to the acceleration of charge transfer to/from reaction sites, and a convincing orientation for CO2 adsorption. These features are combined with synergistic electronic multimetallic interactions, facilitating a heterogeneous valence electron distribution and atomic disorder. The CO2-PR power of the (CoFeNiMnCu)S2@UCN nanostructure was noticeable in realizing added-value products in both the liquid–solid (1063 µmol/g h of syngas and 250 µmol/g h of methane) and gas–solid phases (1883 µmol/cm2 h of syngas and 321 µmol/cm2 h of methane). To prove its utility, long-term and corresponding time-equivalent cycling experiments were conducted, demonstrating a highly stable system that endured for a long time. Overall, this approach simultaneously exploits the advantages of sulfide-based materials and high-entropy materials in stable structures to generate sustainable CO2-PR materials.

Cationic Bis(hydrosilane)-Coinage-Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer-Sphere C=O Hydrosilylation Not Involving Metal Hydrides.

The preparation of cationic bis(hydrosilane)-coinage-metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF 4] is described. Unlike previously reported hydrosilane-stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate (ortho-silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X-ray diffraction analysis, revealing that both Si-H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer-sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether.

Cationic Bis(hydrosilane)−Coinage Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer‐Sphere C=O Hydrosilylation Not Involving Metal Hydrides

The preparation of cationic bis(hydrosilane)–coinage‐metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF4] is described. Unlike previously reported hydrosilane‐stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate ortho‐(silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X‐ray diffraction analysis, revealing that both Si–H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer‐sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether.

Ag Nanoparticles Deposited onto BaTiO3 Aerogel for Highly Efficient Photodegradation.

Given the increasingly severe environmental problems caused by water pollution, the degradation of organic dyes can be effectively achieved through the utilization of photocatalysis. In this work, metal alkoxides and a combination of alcohol/hydrophobic solvents are employed to prepare BaTiO3 aerogels via a liquid-phase and template-free synthetic route. The preparation process of the aerogels solely entails facile agitation and supercritical drying, eliminating the need for additional heat treatment. The binary solvent of ethanol and toluene is identified as the optimal choice, resulting in a significantly enhanced surface area (up to 223 m2/g) and an abundant pore structure of BaTiO3 aerogels compared to that of the BaTiO3 nanoparticles. Thus, the removal efficiency of the BaTiO3 aerogel sample for MO is nearly twice as high as that of the BaTiO3 nanoparticles sample. Noble metal Ag nanoparticles' deposition onto the BaTiO3 aerogel surface is further achieved via the photochemical deposition method, which enhances the capture of photogenerated electrons, thereby ensuring an elevated level of photocatalytic efficiency. As a result, Ag nanoparticles deposited on BaTiO3 aerogel can degrade MO completely after 40 min of illumination, while the corresponding aerogel before modification can only remove 80% of MO after 60 min. The present work not only complements the preparatory investigation of intricate aerogels but also offers a fresh perspective for the development of diverse perovskite aerogels with broad applications.

Molecular synthesis strategies for binary MO2 (M = V, Sn, Ti, Zr, Hf) high-entropy oxides as superior catalysts for enhanced oxygen evolution

Entropy stabilized multi-cation oxides are of significant interest in heterogeneous catalysis due to higher number of active sites, when compared to simple binary oxides, which reduces the overpotential for catalytic transformations. To control the enthalpy of mixing and suppress potential phase segregation, the use of molecular metal alkoxides for chemical cross-linking of different metal centers shows promise in creating homogenous high entropy chemical preceramic networks. Herein, we report on a high-entropy MO2 phase (M = V, Sn, Ti, Zr, Hf), synthesized by cross-linking partially hydrolyzed metal iso-propoxides [M(OH)n(OiPr)4-n]x. The amorphous xerogels calcined at 700 °C, 900 °C and 1250 °C revealed the formation of a single crystalline phase [(V, Sn, Ti, Zr, Hf)O2] that was verified by powder X-ray diffraction analysis, whereas the chemical composition was investigated by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy. The HEO exhibited superior catalytic activity in oxygen evolution reaction with an overpotential of 312.7 mV and an electrochemically active surface area of 0.625 F cm−2. Furthermore, the chronopotentiometry measurements confirmed a high stability (> 90 h) for the HEO samples.

Ag-Incorporated Cr-Doped BaTiO3 Aerogel toward Enhanced Photocatalytic Degradation of Methyl Orange.

A novel Cr-doped BaTiO3 aerogel was successfully synthesized using a co-gelation technique that involves two metallic alkoxides and a supercritical drying method. This freshly prepared aerogel has a high specific surface area of over 100 m2/g and exhibits improved responsiveness to the simulated sunlight spectrum. Methyl orange (MO) was chosen as the simulated pollutant, and the results reveal that the Cr-doped BaTiO3 aerogel, when modified with the noble metal silver (Ag), achieves a pollutant removal rate approximately 3.2 times higher than that of the commercially available P25, reaching up to 92% within 60 min. The excellent photocatalytic performance of the Ag-modified Cr-doped BaTiO3 aerogel can be primarily attributed to its extensive specific surface area and three-dimensional porous architecture. Furthermore, the incorporation of Ag nanoparticles effectively suppresses the recombination of photo-generated electrons and holes. Stability and reusability tests have confirmed the reliability of the Ag-modified Cr-doped BaTiO3 aerogel. Therefore, this material emerges as a highly promising candidate for the treatment of textile wastewater.

Rational design of boron-doped NiCo-glycerate spheres with covered nanosheets for high performance supercapacitors

Nowadays, the restricted availability of fossil fuels longs for the more efficient energy storage devices. Due to the high reactivity, metal alkoxides are thought to be viable potential electrode materials for the energy storage field. In this work, the B-doped NiCo-glycerate (NiCo–B-glycerate) with sphere@nanosheet structure is obtained through a straightforward method for supercapacitors. The B doping and 2D nanosheets covering on the sphere surface have an effect on the creation of defective sites, adjustment of the electronic properties, and reduction the charge transfer distance. The NiCo–B-glycerate electrode provides an ultrahigh specific capacitance of 2036 F g−1 at the current density of 1 A g−1 while maintaining a good rate performance of 74.6 % at current density of 30 A g−1. Moreover, an asymmetric supercapacitor is successfully assembled based on the NiCo–B-glycerate, showing a high energy density of 58.3 Wh kg−1 at a power density of 0.8 kW kg−1. This study might encourage the development of metal alkoxides for application in energy storage field.

Enhancing the stereoselectivity of Me2GaOR(NHC) species in the ring-opening polymerization of rac-lactide, with the help of the chelation effect.

Using dialkylgallium alkoxides with N-hetrocyclic carbenes (Me2GaOR(NHC)) for the ring-opening polymerization of rac-lactide, we have demonstrated the effect of the chelate interaction between the growing PLA chain and gallium on the stereoselectivity of dialkylgallium alkoxide propagating species - Me2Ga(OPLA)(NHC). In order to do so, we have conducted the structure-activity studies of both Me2Ga(OCH2CH2OMe)(NHC) (NHC = SIMes (1) and IMes (2)) and Me2Ga(OCH(Me)CO2Me)(NHC) (NHC = SIMes (3) and IMes (4)), the latter mimicking active species in the ROP of lactide with growing PLA chain. Based on VT NMR and FTIR spectroscopy, the effect of toluene, CH2Cl2 and THF on the structure of 3 and 4 have been demonstrated, especially with regard to the interaction of methyl lactate ligand with gallium. In a combination with the latter, the studies on the activity of 1 and 2 in the ROP of rac-LA, in different solvents, and at temperatures between -40 °C and 40 °C, have shown the extent of the chelation effect on the isoselectivity of Me2Ga(OPLA)(NHC) in the ROP of rac-LA, which varied between P m of 0.75 and 0.89 depending on the polymerization conditions. Both the latter, and the contribution resulting from the structure of Me2Ga(OPLA)(NHC) (P m = 0.75) have been decisive for the total isoselectivity observed under specific conditions. Our finding represents the first evidence demonstrating that the chelation effect, resulting from the weak interaction between the growing PLA chain and the metal centre, can be responsible for the enhancement of stereoselectivity in the ROP of rac-LA with metal alkoxide propagating species. It should remain of interest, especially in the case of metal based catalysts, which are able to carry out the stereoselective polymerization of rac-LA at mild conditions, under which the chelation effect can manifest itself.

Me-N-C Electrocatalyst Foams for the Oxygen Reduction Reaction in PEFCs

Polymer electrolyte fuel cells (PEFCs) will perform the crucial role of energy conversion when society shifts towards the hydrogen economy. However, to perform the the oxygen reduction reaction (ORR) efficiently, a finely dispersed platinum catalyst on a carbon black support is generally utilised. Platinum is an expensive critical raw material (CRM) and is thus susceptible to future shocks, such as bottlenecks in supply or volatile prices. As such it is imperative to investigate alternative platinum-free electrocatalysts.Over the past decade we have developed platinum-free Fe-N-C electrocatalysts with unique properties and microstructure. The basis for our catalysts is a nitrogen-doped carbon foam, which is obtained by thermal decomposition of metal alkoxides. The materials are exceptional in this field due to their unusually large macropores which aid gas diffusion, the very large surface area due to high microporosity, and the fact that the nitrogen content can be systematically varied.Using these electrocatalysts we have with achieved high activity and excellent durability in both acid and alkaline media. One of the advantages of this materials system is that it can be applied as a model catalyst to independently study the effect of different parameters on the catalytic activity. As such we have made important insights into the synthesis mechanisms of Fe-N-C electrocatalysts using techniques such as in situ X-ray absorption spectroscopy (XAS) and in situ X-ray photoelectron spectroscopy (XPS).Furthermore, whilst most research into platinum-free catalysts focusses on iron-containing materials, iron is known to cause degradation in the microporous layer and membrane due to the generation of peroxide-related radicals. As such, a new generation of Me-N-C electrocatalysts are being developed, in which Fe is replaced with e.g., Co or Sn. Here we will discuss the performance of these interesting new Fe-free electrocatalysts.This work was supported by JSPS KAKENHI Grant Number 19H02558.1. Mufundirwa, M. Ismail, G. F. Harrington, B. Smid, K. Sasaki, M. Pourkashanian, A. Hayashi, S. M. Lyth, Nanotechnology 31 (22), 225401 (2020)2. Mufundirwa, B. Smid, G. Harrington, B. V. Cunning, K. Sasaki, and S. M. Lyth, Journal of Power Sources, 375, 244-254 (2018)3. Zitolo, N. Ranjbar-Sahraie, T. Mineva, J. Li, Q. Jia, S. Stamatin, P. Krtil, S. M. Lyth, G. Harrington, S. Mukerjee, E. Fonda, F. Jaouen, Nature Communications, 8, 959 (2017)4. Liu, T. Daio, A. Mufundirwa, B. Cunning, K. Sasaki, S. M. Lyth, Electrochimica Acta, 220, 554-561 (2016)5. Liu, S. Yu, T. Daio, M. Ismail, K. Sasaki, and S. M. Lyth, Journal of the Electrochemical Society, 163 (9), F1049-F1054 (2016)6. Liu, T. Daio, K. Sasaki, S. M. Lyth, Journal of the Electrochemical Society, 161 (9), F838-F844 (2014)7. Liu, T. Daio, D. Orejon, K. Sasaki, S. M. Lyth, Journal of the Electrochemical Society 161 (4), F544-F550 (2014)8. S. M. Lyth*, Y. Nabae, N. M. Islam, T. Hayakawa, S. Kuroki, M. Kakimoto, S. Miyata, eJournal of Surface Science and Nanotechnology, 10, 29-32 (2012)