Oxidation State Research Articles

Isomeric chlorination of conjugated thiophene side chain based on quinoxaline to design high-performance electrochromic polymers

The isomeric chlorination of the conjugated side chain is an effective method to improve the photoelectronic properties of polymers, but has not been well investigated in electrochromic performance. Herein, two new D-A-D type isomeric monomers, EQx-α-Cl and EQx-β-Cl, based on 2,3-bis(5-chloro-4-(2-ethylhexyl)thioph-en-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-α-Cl) and 2,3-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-β-Cl) as the acceptor units by the isomeric chlorination of the different position of the conjugated thiophene side chain were designed and synthesized. Then their D-A-D type polymers (PEQx-α-Cl and PEQx-β-Cl) were synthesized by electrochemical polymerization. EQx-α-Cl not only exhibits slight red-shifted absorption onset and much stronger absorption with molar extinction coefficient of 1.16 × 105 M−1 cm−1 but also shows lower onset oxidation potential (Eonset) of 0.65 V compared with those of EQx-β-Cl (7.26 × 104 M−1 cm−1 and 0.73 V). And PEQx-α-Cl displayed yellow green at neutral state and dark green at oxidation state, respectively, and showed much better electrochemical stability and electrochromic performance including the higher optical contrast 37.7 % and the CE value of 319 cm2 C−1 at 890 nm in comparison with PEQx-β-Cl, which was beneficial to design the electrochromic materials toward adaptive camouflage application. These results demonstrated that the isomeric chlorination strategy of conjugated side chain is a promising approach which may open up a new horizon for designing and synthesizing the high-performance electrochromic polymers.

Engineering a Cu-Pd Paddle-Wheel Metal-Organic Framework for Selective CO2 Electroreduction.

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO2 to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu-Pd paddle wheel dimers within Cu-based metal-organic frameworks (MOFs), [Cu3-xPdx(BTC)2] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu3(BTC)2], HKUST-1), the Cu-Pd MOF shifts CO2 electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu-Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO2 reduction using molecular catalysts.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels

AbstractPhotocatalytic CO2 reduction serves as an important technology for value‐added solar fuel production, however, it is generally limited by interfacial charge transport. To address this limitation, a two‐dimensional/two‐dimensional (2D/2D) p‐n heterojunction CuS‐Bi2WO6 (CS‐BWO) with highly connected and matched interfacial lattices was designed in this work via a two‐step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p‐n heterojunction combination promoted the electron transfer from the Cu to Bi sites, leading to the coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in the BWO nanosheets facilitated the adsorption and activation of CO2, and the generation of high‐coverage key intermediate b‐CO32−, while CuS (CS) acted as a broad light‐harvesting material to provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p‐n heterojunction CS‐BWO exhibited average CO and CH4 yields of 33.9 and 16.4 μmol g−1 h−1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS‐BWO samples. This work provided an innovative design strategy for developing high‐activity heterojunction photocatalyst for converting CO2 into value‐added solar fuels.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels.

Photocatalytic CO2 reduction serves as an important technology for value-added solar fuel production, however, it is generally limited by interfacial charge transport. To address this limitation, a two-dimensional/two-dimensional (2D/2D) p-n heterojunction CuS-Bi2WO6 (CS-BWO) with highly connected and matched interfacial lattices was designed in this work via a two-step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p-n heterojunction combination promoted the electron transfer from the Cu to Bi sites, leading to the coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in the BWO nanosheets facilitated the adsorption and activation of CO2, and the generation of high-coverage key intermediate b-CO3 2-, while CuS (CS) acted as a broad light-harvesting material to provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p-n heterojunction CS-BWO exhibited average CO and CH4 yields of 33.9 and 16.4 μmol g-1 h-1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS-BWO samples. This work provided an innovative design strategy for developing high-activity heterojunction photocatalyst for converting CO2 into value-added solar fuels.

Synthesis and Mechanistic Study of Naphthalimide Derivative Formation via Cu-Mediated Ullmann-Type Reactions.

Cu-mediated Ullmann-type coupling reactions are fundamental to organic synthesis, garnering significant academic and industrial interest since their inception. Optimizing reaction parameters, particularly temperature control, is crucial for maximizing efficiency while maintaining high yields. Bidentate ligands, such as amino acids, have demonstrated potential in facilitating these reactions at lower temperatures (<100 °C). This study explores the Cu-catalyzed Ullmann-type coupling of naphthalimide derivatives with amino acid substitutions. Naphthalimide dyes, known for their diverse applications in bioimaging, solar cells, medicine, and sensors, were selected for their potent anticancer properties. The synthesized compounds were characterized by using 1H NMR, ESI-MS, and melting point analyses. Compounds with significant steric hindrance exhibited lower yields, leading to the development of a novel catalytic system employing l-carnosine as a bidentate ligand, which significantly improved yields. Mechanistic insights, derived from density functional theory calculations, identified "L-complex 3" as the most stable and reactive intermediate during oxidative addition to aryl halides. The oxidative addition transition state "OX1-TS" was found to be the most favorable, with a relatively low energy barrier of 6.13 kcal/mol, suggesting that this step, despite being the rate-limiting stage, is energetically accessible. In contrast, reductive elimination was facilitated by a Cu(III) penta-coordinated intermediate, with a barrier of just 8.34 kcal/mol, making it a more straightforward process. Theoretical findings aligned closely with experimental data, reinforcing the oxidative addition/reductive elimination pathway as the operative mechanism for this reaction.

The Analysis of Electron Densities: From Basics to Emergent Applications.

The electron density determines all properties of a system of nuclei and electrons. It is both computable and observable. Its topology allows gaining insight into the mechanisms of bonding and other phenomena in a way that is complementary to and beyond that available from the molecular orbital picture and the formal oxidation state (FOS) formalism. The ability to derive mechanistic insight from electron density is also important with methods where orbitals are not available, such as orbital-free density functional theory (OF-DFT). While density topology-based analyses such as QTAIM (quantum theory of atoms-in-molecules) have been widely used, novel, vector-based techniques recently emerged such as next-generation (NG) QTAIM. Density-dependent quantities are also actively used in machine learning (ML)-based methods, in particular, for ML DFT functional development, including machine-learnt kinetic energy functionals. We review QTAIM and its recent extensions such as NG-QTAIM and localization-delocalization matrices (LDM) and their uses in the analysis of bonding, conformations, mechanisms of redox reactions excitations, as well as ultrafast phenomena. We review recent research showing that direct density analysis can circumvent certain pitfalls of the FOS formalism, in particular in the description of anionic redox, and of the widely used (spherically) projected density of states analysis. We discuss uses of density-based quantities for the construction of DFT functionals and prospects of applications of analyses of density topology to get mechanistic insight with OF-DFT and recently developed time-dependent OF-DFT.

Effect of La concentration on phase formation, local structure and optical properties of Sr1-xLaxTiO3 nanoparticles

The objective of this paper is to give information about phase formation, local structure and optical characteristics measured of the Sr1-xLaxTiO3 (x = 0–0.10; SLTO) nanoparticles. These nanoparticles have been synthesized by microwave-assisted sol-gel auto combustion method. Experimentally, the structural information was gathered by using the X-ray diffractometer and showed a pure phase with cubic perovskite structure of all samples. As well, the crystallite size and particle size of the SLTO samples decreased as the La doping content increased. The micro-strain (varying between 0.63×10−3 and 1.48×10−3) produced in the samples through Williamson-hall plot. The optical properties were determined using UV–Vis spectrophotometer. The band gap (Eg) was determined for all samples to be 4.10 eV. The study of local structure was performed by utilizing the synchrotron radiation X-ray absorption near edge structure (XANES) technique. The analyses XANES spectra clearly showed that the oxidation state of Sr, La and Ti ions are +2, +3 and + 4, respectively. The clear agreement between measured and calculated XANES spectra was the strongest evidence of La atoms occupies A-site (Sr) in SrTiO3 structure.

Development of CuFe2O4 microspheres/carbon sheets composite materials as a sensitive electrochemical sensorfor determination of bisphenol A.

A composite material based on CuFe-ZIF-derived CuFe2O4 nano-microspheres grown in situ and well-ordered on carbon sheets (CS) was prepared and applied for highly effective determination of bisphenol A (BPA). The composite material possessed inherently high redox activity due to the presence of both Cu and Fe ions with various oxidation states (Cu²⁺/Cu⁺ and Fe³⁺/Fe²⁺), high specific surface area, uniform distribution of Cu and Fe ions, and a robust framework imparted by its precursor CuFe-ZIF. Thisled to increased active sites for electrochemical reactions, improved electron transfer efficiency, and structural integrity during electrochemical cycling. Furthermore, combining CS with CuFe2O4 not only provided a large surface area to support well-ordered CuFe₂O₄ nano-microspheres without aggregation, but also enhanced the conductivity and mechanical stability of the CuFe₂O₄/CS composite. This results in synergistic effects that enhanced the overall performance of the composite material. In addition, both copper and iron are relatively non-toxic and abundant, making CuFe₂O₄/CS safe and cost-effective for large-scale applications. Consequently, the CuFe2O4/CS-modified electrode shows highly efficient electrochemical sensing properties with a wider detection range of 0.009-168 µM and lower detection limit of 0.0027 µM (S/N = 3) compared withmost reported BPA sensors. It also hasanoptimized current at pH 7 which is convenient for real world applications. This CuFe2O4/CS modified electrode as a highly sensitive electrochemical platform can be applied to monitor BPA concentrations in bottled water with good recovery (97.2-102.2%).

Biofabrication and Characterisation of Ni‐Doped SnO2 Nanoparticles With Enhanced Cytotoxicity, Antioxidant, Antimicrobial and Photocatalytic Activities

ABSTRACTThe present work focuses on Annona muricata leaf extract–mediated green synthesis of pure and nickel‐doped tin oxide nanoparticles for 3%, 5% and 7% concentrations. The properties of the obtained nanoparticles were investigated through XRD, FTIR, XPS, HRTEM–SAED, SEM–EDX and UV–visible spectroscopy techniques. The XRD pattern reveals all samples have tetragonal structures with high crystallinity. The Sn–O stretching vibration has been confirmed through FTIR spectra. The XPS results demonstrate that Sn0.93Ni0.07O2 nanoparticles have Sn3d, Ni2p and O1s oxidation states. EDX spectra contain Ni, Sn and O elements, which indicate the purity of the samples. UV–visible absorption spectrum shows decreases in optical energy bandgap with increases in nickel dopant concentration. The samples exhibit notable antibacterial activity against P. aeruginosa and S. aureus. Also, Sn0.93Ni0.07O2 nanoparticle has higher antifungal activity against A. niger than against C. albicans. Moreover, SnO2 nanoparticles have considerable antioxidant activity in DPPH scavenging compared to Sn0.93Ni0.07O2 nanoparticles. Furthermore, SnO2 nanoparticles have a better cytotoxic effect for L929 normal fibroblast cell lines with an LD50 value of 146.42 μg/mL. Additionally, the photocatalytic activity of SnO2 and Sn0.93Ni0.07O2 nanoparticles was done against methylene blue dye under direct sunlight irradiation. Overall, environmentally friendly synthetic pure and Ni‐doped SnO2 nanoparticles can be used in wastewater filter technologies as well as in medical aids due to their better cytotoxic, antioxidant and antimicrobial effects.

Effect of vitamin C injections on exercise muscular performance and biochemical parameters in Trichinella spiralis-infected mice.

Trichinella spiralis is a worldwide intestinal nematode that can parasitize the striated muscles of its hosts at the larval stage. This study aims to evaluate potential of vitamin C for treating trichinellosis-related pathological problems in the infected muscles of mice. Thirty CD1 male Albino mice were divided into three groups (10 mice per group). Negative and positive control groups (0.9% NaCl) and the infected vitamin C group (10 mg/kg body weight). Two weeks post-infection, each group was intraperitoneally injected daily for two weeks with Vitamin C or saline. The performance of the muscles was assessed both before and after the treatment. After dissection, constant parts of striated muscles were removed for further assays. The scoring of the histological changes of infected muscles was carried out. In addition to muscle malondialdehyde levels, superoxide dismutase and catalase activities were measured for the oxidative and antioxidant states. Creatine kinase and aspartate aminotransferase were also measured in tissues to reflect the degree of muscular damage. Vitamin C enhances the weakness of the muscular performance resulting from the infection. Vitamin C was able to repair some of the histological lesions that resulted from the infection. Trichinellosis caused severe changes in the biochemical markers in positive control animals. Muscle damage biomarkers and, besides, oxidative and antioxidant conditions were greatly ameliorated in infected vitamin C animals. Summing up, vitamin C can be used as a complementary drug due to its efficiency in improving pathogenesis following a trichinellosis infection. The supplement also must be tested in the intestinal stage of infection after showing promising results in the muscular stage.

Regulating the Spin‐State of Cobalt in Three‐Dimensional Covalent Organic Frameworks for High‐Performance Sodium‐Iodine Rechargeable Batteries

AbstractAlthough the catalytic activity is heavily reliant on the electronic structure of the catalyst, understanding the impact of electron spin regulation on electrocatalytic performance is still rarely investigated. This work presents a novel approach involving the single‐atom coordination of cobalt (Co) within metalloporphyrin‐based three‐dimensional covalent organic frameworks (3D‐COFs) to facilitate the catalytic conversion for sodium‐iodine batteries. The spin state of Co is modulated by altering the oxidation state of the porphyrin‐centered Co, achieving optimal catalysis for iodine reduction. Experimental results demonstrate that CoII and CoIII are incorporated into the 3D‐COFs, exhibiting spin ground states of S=1/2 and S=0, respectively. The low spin state of CoIII is favorable to hybridize with the sp 3d orbitals of I3−, thus facilitating the conversion of I3− to I−. Density‐functional theory (DFT) calculations further reveal that the presence of CoIII enhances iodide adsorption and accelerates the formation of NaI in 3D‐COFs‐CoIII, thereby promoting its rapid kinetic behaviors. Notably, the I2@3D‐COFs‐CoIII cathode achieves a high reversible capacity of 227.7 mAh g−1 after 200 cycles at 0.5 C and demonstrates exceptional cyclic stability, exceeding 2000 cycles at 10 C with a minor capacity fading rate of less than one 0.01 % per cycle.

High‐Throughput Screening of Dual‐Atom Catalysts for Methane Combustion: A Combined Density Functional Theory and Machine‐Learning Study

AbstractCeria‐supported precious metal catalysts have undergone extensive investigation for the catalytic methane combustion. However, it remains a significant challenge to achieve both highly synergistic oxidation activity and efficient atom utilization remains a challenge for commonly used supported nanoparticles and single‐atom catalysts. Dual‐atom catalysts (DACs) emerges as a frontier of advanced catalysts, presenting unique catalytic properties that benefit from the synergy of neighboring metal sites. In this study, 361 ceria‐supported DACs (M1M2/CeO2) encompassing combinations of 19 transition metals are systematically explored. Using high‐throughput density functional theory calculations, the structures, stability as well as activity of M1M2/CeO2 are assessed. Notably, Au1Ga1/CeO2 is identified as a promising DAC exhibiting high activity for methane total oxidation, substantiated by comprehensive DFT‐calculated reaction pathways. Furthermore, employing six machine‐learning algorithms, the structure‐properties relationship is explored within ceria‐based DACs and highlight the importance of oxidation states and atomic radii of doped metals as the descriptors. The trained model by computational dataset exhibits high accuracy and predict a more active Mn1Au1/CeO2 than those screened using only DFT datasets. The high‐throughput strategy demonstrated in this work not only provides insights into the rational design of methane oxidation catalysts, but also paves the way for exploring DACs for diverse applications.

Regulating the Spin-State of Cobalt in Three-Dimensional Covalent Organic Frameworks for High-Performance Sodium-Iodine Rechargeable Batteries.

Although the catalytic activity is heavily reliant on the electronic structure of the catalyst, understanding the impact of electron spin regulation on electrocatalytic performance is still rarely investigated. This work presents a novel approach involving the single-atom coordination of cobalt (Co) within metalloporphyrin-based three-dimensional covalent organic frameworks (3D-COFs) to facilitate the catalytic conversion for sodium-iodine batteries. The spin state of Co is modulated by altering the oxidation state of the porphyrin-centered Co, achieving optimal catalysis for iodine reduction. Experimental results demonstrate that CoII and CoIII are incorporated into the 3D-COFs, exhibiting spin ground states of S=1/2 and S=0, respectively. The low spin state of CoIII is favorable to hybridize with the sp 3d orbitals of I3 -, thus facilitating the conversion of I3 - to I-. Density-functional theory (DFT) calculations further reveal that the presence of CoIII enhances iodide adsorption and accelerates the formation of NaI in 3D-COFs-CoIII, thereby promoting its rapid kinetic behaviors. Notably, the I2@3D-COFs-CoIII cathode achieves a high reversible capacity of 227.7 mAh g-1 after 200 cycles at 0.5 C and demonstrates exceptional cyclic stability, exceeding 2000 cycles at 10 C with a minor capacity fading rate of less than one 0.01 % per cycle.

Exploring fine-aerosol episodes in urban Seoul during the cold season of the 2021 SIJAQ campaign: Measurement evidences of heterogeneous reactions on black carbon particles

Significant PM2.5 pollution has been prevalent on a regional scale in East Asia including a megacity Seoul in South Korea. Here, we explore fine-aerosol episodes occurred in Seoul during the Satellite Integrated Joint monitoring of Air Quality (SIJAQ) campaign from October to November of the 2021, focusing on experimental evidences of heterogeneous reactions to form secondary aerosol under a highly oxidized atmospheric condition.At this urban site in Seoul, vehicle exhaust was the clear source of fresh emissions, leading to a high level of NO and small refractory black carbon (rBC) particles (mass median diameter of 162 nm ± 16 nm) in the morning time. The hourly mass concentration of PM2.5 ranged from 5.3 μg m−3 to 146.1 μg m−3, averaging at 24.5 ± 22.2 μg m−3. During the campaign, the most intense episode, EP3 (November 18–21), recorded an average PM2.5 concentration of 72.5 ± 38.2 μg m−3, peaking at 146.1 μg m−3, was characterized by relatively higher temperature (∼12 °C) and relative humidity (67 %) on average thoroughly governed by continental migratory high and westerly winds. While the average NO3− concentration was 27.7 μg m−3, four times the whole campaign's average, EP3 was highlighted by a high morning NO2/NOx ratio and significantly elevated daytime and nighttime Ox (O3+NO2) concentrations compared to non-episode days. Throughout the entire campaign, NOz surrogate (NO2(CL)-NO2(T)), Ox, and Fmoderate + thick (the combined number fractions of moderately and thickly coated-rBC particles) tended to increase with the PM2.5 concentration. During the daytime, as PM2.5 increased, Fmoderate + thick showed a monotonic increase, accompanied by RH rising from 54 ± 16% to 63 ± 11%. In contrast, at nighttime of humid condition with RH often exceeding 70% the enhancement of Fmoderate + thick was more sensitive to condensable gas levels than RH. Given that high levels of PM2.5 (>60 μg m−3) were observed only during EP3, enhanced levels of NOz surrogate, Ox, Fmoderate + thick, and RH were evident characteristics of EP3. Such chemical and meteorological conditions suggest that the chemically enhanced oxidation state was evident during EP3, which promoted the formation of secondary aerosols on primary particles including rBC, especially under conditions of elevated RH. Considering the recent trend of increasing number of vehicles and rising atmospheric O3 concentrations in East Asia, future studies should be well designed to investigate the detailed mechanisms involved in heterogeneous reactions that lead to the formation of secondary aerosols.

Catalytic Ammonia Synthesis by Supported Molybdenum Nitride: Insight into the Support Effect

AbstractThe influence of the support on the performance of Mo nitrides has been investigated in ammonia synthesis and decomposition. A series of Mo–N catalysts supported on different materials, namely SiO2 (commercial, SBA‐15), Al2O3, and CeO2, were prepared. The results indicated that, despite the high dispersion of Mo species in all catalysts, large disparities in the activity for ammonia synthesis exist. Initial rates of ∼1208, ∼481, and ∼372 µmol gactive phase−1 h−1 are obtained over 10‐Mo–N/SBA‐15, 10‐Mo–N/SiO2, and 10‐Mo–N/Al2O3 respectively. However, no catalytic activity was registered when Mo species were supported on CeO2. Furthermore, 10‐Mo–N/Al2O3 deactivated after few hours of reaction. The surface composition was studied by means of XPS to probe the origin of the catalytic activity differences, and the results indicated that a range of various oxidation states of Mo was detected depending on the support. The difference in catalytic behavior could not be solely explained by the differences in Mo–N species concentrations. In situ EPR analysis exhibited that the mechanism of MoO3 nitridation could differ depending on the support, leading to the formation of different Mo–N species. The effect of support was, however, not as severe in ammonia decomposition as it was the case of ammonia synthesis.

Bridging Carbonyl and Carbyne Complexes of Weak-Field Iron: Electronic Structure and Iron-Carbon Bonding.

Carbon monoxide inhibited forms of nitrogenases have carbonyl (CO) and carbide (C4-) bridges, which are common in synthetic iron complexes with strong-field ligand environments but rare in iron sites with weak-field ligand environments analogous to the enzyme. Here, we explore the fundamental bonding description of bridging CO in high-spin iron systems. We describe the isolation of several diiron carbonyls and related species, and elucidate their electronic structures, magnetic coupling, and characteristic structural and vibrational parameters. These high-spin iron complexes exhibit equivalent π-backbonding abilities to low-spin iron complexes. Sequential reduction and silylation of a formally diiron(I) bridging CO complex ultimately gives a formally diiron(IV) bridging carbyne complex. Despite the large range of formal oxidation states across this series, X-ray absorption spectroscopy and density functional theory calculations indicate that the electron density at the iron sites does not change. Thus, the [Fe(μ-CO)]2 core undergoes redox changes at the bridging carbonyls rather than the metal centers, rendering the metal's formal oxidation state misleading. The ability of the Fe2C2 core to easily shift charge between the metals and the ligands has implications for nitrogenases, and for other multinuclear systems for redox catalysis.

Basics and Advances of Manganese-Based Cathode Materials for Aqueous Zinc-Ion Batteries.

It is greatly crucial to develop low-cost energy storage candidates with high safety and stability to replace alkali metal systems for a sustainable future. Recently, aqueous zinc-ion batteries (ZIBs) have received tremendous interest owing to their low cost, high safety, wide oxidation states, and sophisticated fabrication process. Nanostructured manganese (Mn)-based oxides in different polymorphs are the potential cathode materials for the widespread application of ZIBs. However, Mn-based oxide materials suffer from several drawbacks, such as low electronic/ionic conductivity and poor cycling performance. To overcome these issues, various structural modification strategies have been adopted to enhance their electrochemical activity, including phase/defect engineering, doping with foreign atoms (e.g., metal and/or nonmetal atoms), and coupling with carbon materials or conducting polymers. Herein, this review targets to summarize the advantages and disadvantages of the above-mentioned strategies to improve the electrochemical performance of the cathodic part of ZIBs. The challenges and suggestions for the development of manganese oxides for ZIBs are put forward.

Unveiling the Structural Effects in Hybrid Copper Phosphonate Frameworks for Selective Electrocatalytic CO2 Reduction Reaction.

Electrochemical CO2 reduction holds tremendous promise for transforming carbon dioxide into several value-added energy feedstocks and utilizing renewable energy sources. Herein, we have developed two novel copper-based organophosphonates for selective electrocatalytic conversion of CO2 to CH3OH conversion. The two-dimensional layer structure of Cu3[(Hhedp)2(C4H4N2)].2H2O (I) and the three-dimensional Cu3[(H3hedp)2(C4H4N2)4(SO4)].2H2O (II) have been isolated as single crystals via a hydrothermal strategy. Compound I consists of Cu2+ oxidation states exclusively, while compound II has Cu1+ oxidation states in a network wherein a Cu2+-phosphonate template is embedded inside the framework. Depending on mixed valent oxidation states, compound II exhibits high selectivity compared to compound I for the electrocatalytic reduction of CO2 to CH3OH (C1) as the primary product and CH3COOH (C2) as the secondary product. Notably, product selectivity is enhanced as the Faradaic efficiency (FE) of the competing hydrogen evolution reaction (HER) is significantly reduced in compound II relative to that of I, particularly at higher applied reduction potentials. The optimal ratio of Cu1+ active sites in compound II plays a pivotal role in enhancing methanol selectivity, stabilizing critical intermediates, and maintaining ideal reduction potentials as a noble-metal free electrocatalyst. Moreover, the optical band gap and the Mott-Schottky measurements further suggest the title Cu-phosphonate materials could be promising and effective photocatalysts.

Mechanistic Interrogation of Photochemical Nickel-Catalyzed Tetrahydrofuran Arylation Leveraging Enantioinduction Data.

This manuscript details the development of an asymmetric variant for the Ni-photoredox α-arylation of tetrahydrofuran (THF), which was originally reported in a racemic fashion by Doyle and Molander. Leveraging the enantioselectivity data that we obtained, a complex mechanistic scenario different from those originally proposed is uncovered. Specifically, an unexpected dependence of the product enantiomeric ratio was observed on both the halide identity (aryl chloride vs bromide substrates) and the Ni source. Stoichiometric experiments and time course analyses of the evolution of product enantioselectivity with time revealed a different initial behavior for reactions carried out with Ni(II) and Ni(0) precatalysts that later converge into a common mechanism. For studying the predominant pathway, this paper describes a rare example of the syntheses of chiral bisoxazoline Ni(II) aryl halide complexes, which proved essential for probing enantioselectivity via stochiometric experiments. These experiments identify the Ni(II) aryl halide complex as the primary species involved in the key THF radical trapping event. A multivariate linear regression model is presented that further validates the dominant mechanism and delineates structure-selectivity relationships between ligand properties and enantioselectivity. EPR analysis of Ni(0)/aryl halide mixtures highlights the fast access to a variety of Ni complexes in 0, +1, and +2 oxidation states that are proposed to be responsible for the initial divergence in mechanism observed when using Ni(0) precatalysts. More broadly, beyond advancing the mechanistic understanding of this THF arylation protocol, this work underscores the potential of leveraging enantioselectivity data to unravel intricate mechanistic manifolds within Ni-photoredox catalysis.

Redox-Tunable Ring Expansion Enabled By A Single-Component Electrophilic Nitrogen Atom Synthon.

Controllable installation of a single nitrogen atom is central to many major goals in skeletal editing, with progress often gated by the availability of an appropriate N-atom source. Here we introduce a novel reagent, termed DNIBX, based on dibenzoazabicycloheptadiene (dbabh), which allows the electrophilic installation of dbabh to organic substrates. When indanone β-ketoesters are aminated by DNIBX, the resulting products undergo divergent ring expansions depending on the mode of activation, producing heterocycles in differing oxidation states under thermal and photochemical conditions. The mechanism of each transformation is discussed, and the different reactivity modes of the indanone-dbabh adducts are compared to other nitrogenous precursors.