Lower Oxidation States Research Articles

SBA-15 Type Mesoporous Silica Modified with Vanadium as a Catalyst for Oxidative and Extractive Oxidative Desulfurization Processes.

One of the current challenges is the reduction of sulfur emitted into the atmosphere, usually in the form of sulfur oxides generated by fossil fuel combustion. To achieve this goal, the sulfur content should be reduced in fuel. In this context, vanadium-containing materials based on SBA-15 mesoporous silica supports and two different sources of vanadium were prepared, characterized, and applied as catalysts for oxidative desulfurization (CODS) and extractive oxidative desulfurization processes (ECODSs). The novelty of this work was the comparative study of vanadium-containing materials in two desulfurization systems. The properties of the catalysts, the concentration and state of vanadium species, and their role in the catalytic process were examined by low-temperature nitrogen physisorption, XRD, UV-Vis, XPS, and chemisorption of pyridine combined with FTIR spectroscopy. The catalytic performance of the material prepared using ammonium metavanadate was superior to that of the catalyst obtained using vanadium(IV) oxide sulfate, which was explained by a higher concentration of vanadium species on the surface of the support and their lower oxidation state in the former. Both types of catalysts showed high activity and stability in the ECODS process.

Phosphorous-doped nickel-cobalt bimetallic molybdate/three-dimensional hierarchical porous carbon for high-efficiency solid-state supercapacitors

The limited electrical conductivity and insufficient quantity of electrochemically active sites in transition-metal oxides impede their extensive utilization in high-performance supercapacitors. Herein, we present a successful synthesis of phosphorus-doped NixCo1-xMoO4 (P-NCMO) on three-dimensional hierarchical porous carbon (HPC) derived from enzymatically hydrolyzed lignin through a co-precipitation pathway and subsequent phosphorylation process. The electrochemical performance was improved by optimizing the content of P doping. Additionally, the incorporation of phosphorus into P-NCMO led to a decrease in Co-O bonding energy and facilitated the formation of molybdenum species with lower oxidation states, thereby enhancing surface redox chemistry and improving electrochemical performance. As a result, the optimized HPC/P-NCMO-2 electrode exhibits a high specific capacity of 1003 C g−1 at a current density of 1 A g−1, and it maintains 89.87 % of its initial capacity after 10,000 cycles at a current density of 1 A g−1. The optimized HPC/P-NCMO-2 assembled as the positive electrode and activated carbon as the negative electrode in an asymmetric supercapacitor delivers a high energy density of 94.7 Wh kg−1 at a power density of 800 W kg−1, while maintaining excellent cycle life.

Towards a Mechanistic Understanding of Transition-Metal Dissolution Phenomenon in Lithium-Ion Batteries

Dissolution of transition metals (TMs) from the layered NMC-type cathodes (LiNixMnyCozO2) occurs during cycling of lithium-ion full cells and is known to accelerate their capacity fade. This is because the dissolved metals migrate to the graphite anode and deposit there, where they accelerate irreversible active-lithium loss to reductive side reactions. The dissolution is known to get aggravated by cycling the cells to a greater upper cut-off voltage (UCV), where larger amounts of metals are typically found to be accumulated at the anode after long term cycling. At higher UCV oxygen loss from the cathode lattice also gets accelerated causing changes in the layered crystal structure at the surface level to a rock-salt and spinel mixture which has a very high impedance for Li-ion transport. Several other phenomena get accelerated as well, such as proton generation, and solvent decomposition etc. However, a complete mechanistic understanding of the how these phenomena impact the TM dissolution is lacking. For example, it is unclear whether the dissolution can occur in the charged state when the metals are in the oxidized state despite the presence of large number of acidic species, especially since most of the dissolved metal species typically detected in the electrolyte are in lower oxidation state. In this study, this question was targeted by aging the full graphite//NMC cells via long potentiostatic holds at UCV with/without any discharge steps, and recording the dissolved metals deposited at the graphite after aging. It is shown that a much greater amounts are deposited at the anode when discharge steps are included. Atomic structural changes from TM dissolution at the cathode surface corresponding to the two aging protocols in the charged/discharged state will also be presented.This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy (DOE) through Cathode-Electrolyte Interphase (CEI) Consortium. Part of the measurements was performed at the Center for Nanophase Materials Sciences (CNMS), which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences.

Applicability of Non-PGM Bi-Functional Electrocatalyst in a Scaled-up Anion Exchange Membrane Water Electrolysis

While non-precious metal catalyst materials are crucial for AEMWE systems, catalyst substances possessing both adequate hydrogen molecule adsorption ability and suitable electrical conductivity and hydrophilicity are still in the developmental stage.Ni-Mo alloy metals are known as those that have appropriate hydrogen molecule adsorption binding energy, making them excellent electrochemical catalysts for the cathode. However, they suffer from a high content of oxide, which hampers electrical conductivity, and the formation of a high oxidation state of Ni molecules, making hydrogen molecule detachment challenging.On the other hand, Ni-Fe alloys are recognized for their excellent -OOH group adsorption ability and high electrical conductivity, and that has a low oxidation state Ni phase for high hydrogen desorption ability.Therefore, in this study, we aimed to synthesize NiMoFe-based alloy catalysts to enhance the hydrogen evolution reaction (HER) activity of Ni-Mo group catalysts while simultaneously increasing the oxygen evolution reaction (OER) activity. Using a hydrothermal synthesis method for NiMoFe catalysts we employed a high-temperature thermal reduction process to minimize the oxide layer that has poor conductivity.Evaluation of the catalyst activity through half-cell experiments demonstrated low overpotentials in both Overall water electrolysis reactions. Furthermore, an MEA-type experiment was conducted to evaluate the applicability of single-cell.Furthermore, Stability tests confirmed a stable voltage.Finally, when compared to the combination of precious metal catalysts, this exhibited superior performance. Therefore, this study suggests that non-noble catalysts could serve as a crucial stepping stone, surpassing PGM metal catalysts in alkaline media.

Understanding Ligand Effects on Bielectronic Transitions: Chemo‐ and Electroreduction of Rhodium Bis(Diphosphine) Complexes to Low Oxidation States

AbstractRhodium complexes in the −I and 0 oxidation states are of great potential interest in catalytic applications. In contrast to their rhodium +I congeners, however, the structural and electronic parameters governing their access and stability are far less understood. Herein, we investigate the two‐electron reduction of a parameterized series of bis(diphosphine) Rh complexes [Rh(dxpy)2]NTf2 (x=P‐substituent, y=alkanediyl bridging P atoms). Through (electro)reductions from the RhI parents, Rh−I d10‐complexes were obtained and characterized spectroscopically, including 103Rh NMR data. The reductive steps convolute with structural rearrangements from square planar to tetrahedral coordination. We found that the extent of these reorganisations defines whether the first E0(RhI/0) and second E0(Rh0/−I) reduction potentials are normally ordered, leading to monoelectronic stepwise transitions, or inverted, giving bielectronic events. Reductionist approaches based on Hammett parameters or the P−Rh‐P bite angles provide only partial correlations with the redox potentials. However, we identified the C−O stretch of analogue diphosphine complexes as an expedient computational parameter that enables these correlations through both electronic and geometric features, even in a predictive manner. Gaining control over two‐electron reduction behaviors through rationalized ligand effects has potential impact beyond Rh complexes, for molecular and enzymatic metal sites commonly exhibiting bielectronic transitions.

Understanding Ligand Effects on Bielectronic Transitions: Chemo- and Electroreduction of Rhodium Bis(Diphosphine) Complexes to Low Oxidation States.

Rhodium complexes in the -I and 0 oxidation states are of great potential interest in catalytic applications. In contrast to their rhodium +I congeners, however, the structural and electronic parameters governing their access and stability are far less understood. Herein, we investigate the two-electron reduction of a parameterized series of bis(diphosphine) Rh complexes [Rh(dxpy)2]NTf2 (x=P-substituent, y=alkanediyl bridging P atoms). Through (electro)reductions from the RhI parents, Rh-I d10-complexes were obtained and characterized spectroscopically, including 103Rh NMR data. The reductive steps convolute with structural rearrangements from square planar to tetrahedral coordination. We found that the extent of these reorganisations defines whether the first E0(RhI/0) and second E0(Rh0/-I) reduction potentials are normally ordered, leading to monoelectronic stepwise transitions, or inverted, giving bielectronic events. Reductionist approaches based on Hammett parameters or the P-Rh-P bite angles provide only partial correlations with the redox potentials. However, we identified the C-O stretch of analogue diphosphine complexes as an expedient computational parameter that enables these correlations through both electronic and geometric features, even in a predictive manner. Gaining control over two-electron reduction behaviors through rationalized ligand effects has potential impact beyond Rh complexes, for molecular and enzymatic metal sites commonly exhibiting bielectronic transitions.

Influence of support properties on the activity of 2Cr-Fe/MgO-MO2 catalysts (M = Ce, Zr, CeZr and Si) for the dehydrogenation of n-octane with CO2

The influence of the support on catalytic activity and stability of supported 2Cr-Fe bimetallic catalysts for the CO2-assisted dehydrogenation (DH) of n-octane has been investigated. Four MgO modified supports viz; MgO-CeO2 (MgCe), MgO-ZrO2 (MgZr), MgO-CeO2-ZrO2 (MgCeZr) and MgO-SiO2 (MgSi) were synthesized by the sol-gel combustion technique. The supported catalysts were in turn prepared by vacuum impregnation and thereafter tested for the CO2-assisted DH of n-octane. The catalysts were characterized by inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray diffraction (XRD), N2-physisorption, Raman spectroscopy, transmission electron microscopy (TEM), electron dispersive x-ray (EDX), temperature programmed desorption of CO2 (CO2-TPD), temperature programmed reduction and oxidation (H2-TPR and CO2-TPO), electron paramagnetic resonance (EPR) and thermal gravimetric analysis (TGA) techniques. Raman results showed that the CrOx is stabilized as mono- and/or polynuclear Cr(VI) species over the 2Cr-Fe/MgCe catalyst, which are reduced to lower oxidation state species during the DH reaction. The 2Cr-Fe/MgZr, 2Cr-Fe/MgCeZr and 2Cr-Fe/MgSi catalysts stabilized the CrOx as polymerized species, forming the more active Cr-O-Fe polymer units on the catalysts’ surface. XRD, TEM and EDX results showed that the ZrO2-containing supports have smaller particles and stabilized the active metal oxides in a more dispersed amorphous state. The CO2-TPO of the pre-reduced catalysts and EPR of the used catalysts indicated that the 2Cr-Fe/MgCeZr undergoes significant re-oxidation by CO2 during the catalytic process. The 2Cr-Fe/MgCe was the least active, while the 2Cr-Fe/MgZr catalyst showed the best performance and stability over three regeneration cycles. Selectivity to C8 products (octenes and aromatics) was found to strongly depend on the surface basicity of the catalysts. Deactivation of the catalysts was found to follow first order kinetics and coke deposition was identified as the major cause.

Improved Characterization of Soil Organic Matter by Integrating FT-ICR MS, Liquid Chromatography Tandem Mass Spectrometry, and Molecular Networking: A Case Study of Root Litter Decay under Drought Conditions.

Understanding of how soil organic matter (SOM) chemistry is altered in a changing climate has advanced considerably; however, most SOM components remain unidentified, impeding the ability to characterize a major fraction of organic matter and predict what types of molecules, and from which sources, will persist in soil. We present a novel approach to better characterize SOM extracts by integrating information from three types of analyses, and we deploy this method to characterize decaying root-detritus soil microcosms subjected to either drought or normal conditions. To observe broad differences in composition, we employed direct infusion Fourier-transform ion cyclotron resonance mass spectrometry (DI-FT-ICR MS). We complemented this with liquid chromatography tandem mass spectrometry (LC-MS/MS) to identify components by library matching. Since libraries contain only a small fraction of SOM components, we also used fragment spectral cosine similarity scores to relate unknowns and library matches through molecular networks. This integrated approach allowed us to corroborate DI-FT-ICR MS molecular formulas using library matches, which included fungal metabolites and related polyphenolic compounds. We also inferred structures of unknowns from molecular networks and improved LC-MS/MS annotation rates from ∼5 to 35% by considering DI-FT-ICR MS molecular formula assignments. Under drought conditions, we found greater relative amounts of lignin-like vs condensed aromatic polyphenol formulas and lower average nominal oxidation state of carbon, suggesting reduced decomposition of SOM and/or microbes under stress. Our integrated approach provides a framework for enhanced annotation of SOM components that is more comprehensive than performing individual data analyses in parallel.

Revisited Synthesis of Trispyrazolylborate Aluminum Halides Suban Kundu, Raju Chambenahalli, Alex P. Andrews and Ajay Venugopal*

Tris(3,5‐dimethylpyrazolyl)borate aluminum dihalides TpMe2AlX2 (X=Cl, Br and I) can be potential precursors for preparing highly electrophilic dications as well as low oxidation state aluminum compounds. However, the coordinative unsaturation in TpMe2AlX2 makes them susceptible to rearrangement to [Tp2Al][AlX4]. In this work, we revisited the synthesis of TpMe2AlX2 by isolating the solvent‐stabilized tris(3,5‐dimethylpyrazolyl)borate aluminum dihalides TpMe2AlX2(L) (X=Cl, Br; L = THF, HPMA). Efforts to isolate TpMe2All2 resulted in the ring opening of THF revealing the mediation of a highly reactive cationic aluminum species. The monocationic, [TpMe2AlCl(THF)2][B{C6H3(CF3)2}4] was prepared from TpMe2AlCl2(THF) via silver salt metathesis. Attempts to prepare the dicationic species [TpMe2Al(THF)3]2+ resulted in the instantaneous ring‐opening polymerization of THF.

Molecular features of uranium-binding natural organic matter in a riparian wetland determined by ultrahigh resolution mass spectrometry

Tims Branch riparian wetland located in South Carolina, USA has immobilized 94 % of the U released >50 years ago from a nuclear fuel fabrication facility. Sediment organic matter (OM) has been shown to play an important role in immobilizing U. Yet, uranium-OM-mineral interactions at the molecular scale have never been investigated at ambient concentrations. The objectives of this study were to extract, purify, and concentrate U-bound sediment OM along the stream water pathway and perform molecular characterization using Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). Out of 9614 identified formulas, 715 contained U. These U-containing formulas were enriched with Fe, N, and/or S compared to the total OM. Lignin-like and protein-like molecules accounted for 40 % and 19 % of the U-containing formulas, respectively. Phosphorus-containing formulas were found to exert an insignificant influence on complexing U. U-containing formulas in the ‘mobile’ (groundwater extractable) OM fraction had lower (reduced) nominal oxidation states of carbon (NOSC); and less aromatic moieties than OM recovered from the ‘immobile’ (sodium pyrophosphate extractable) OM fraction. U-containing formulas in the redox interfacial zones (stream banks) compared to those in nearby up-slope zones tended to have smaller molecular weights; lower NOSC; higher contents of COO and/or CONO functional groups; and higher abundance of Fe-containing formulas. Fe was present in 38 % of the U-containing formulas but only 20 % of the total OM formulas. It is postulated that Fe played an important role in stabilizing the structure of sedimentary OM, especially U-containing compounds. The identification for the first time of hundreds of Fe-U-OM formulas demonstrates the complexity of such system is much greater than commonly believed and numerically predicting U binding behavior in OM-rich systems may require greater use of statistical or artificial intelligence approaches rather than deterministic approaches limited to measuring metal complexation with well-defined individual analogue organic ligands.

Enhanced nitrogen electroreduction to ammonia activities on Sb2S3 electrocatalyst by sulfur defects coupled with carbon doping

Exploiting effective, robust while cheap catalysts for the nitrogen reduction reaction (NRR) is of great significance in the scalability and renewability of electrochemical NH3 synthesis. Herein, a synergetic strategy of C dopants and S vacancies was employed into Sb2S3 (marked as C-Sb2S3-x) to boost the electrochemical NRR performance. The induced effects of C dopants and S vacancies of Sb2S3 on the physical and electrochemical behaviors were throughly investigated. Experiments verify that, the content of low oxidation state in Sb species are remarkably enhanced after introducing C dopants and S vacancies, this facilitate the enhanced electric conductivity and NRR activities of C-Sb2S3-x, together with the encouraged reaction kinetics. The prepared C-Sb2S3-x delivered an optimized NH3 yield rate of 47.2 μg h−1 mg−1cat. at −0.6 V along with a high Faradaic efficiency value of 6.4 % at −0.5 V in acid, outperforming than those of Sb2S3 and most disclosed sulfid NRR electrocatalysts. Density functional theory calculations validate that, cooperation of C doping and S vacancy could achieve the elevated NH3 yield rate, Faradaic efficiency as well as competitive stability. This approach puts forward an effective strategy for transition metal compounds to be more suitable for efficient electrocatalysis.

Atomic-Layer IrOx Enabling Ligand Effect Boosts Water Oxidation Electrocatalysis.

An in situ formed IrOx (x ≤ 2) layer driven by anodic bias serves as the essential active site of Ir-based materials for oxygen evolution reaction (OER) electrocatalysis. Once being confined to atomic thickness, such an IrOx layer possesses both a favorable ligand effect and maximized active Ir sites with a lower O-coordination number. However, limited by a poor understanding of surface reconstruction dynamics, obtaining atomic layers of IrOx remains experimentally challenging. Herein, we report an idea of material design using intermetallic IrVMn nanoparticles to induce in situ formation of an ultrathin IrOx layer (O-IrVMn/IrOx) to enable the ligand effect for achieving superior OER electrocatalysis. Theoretical calculations predict that a strong electronic interaction originating from an orderly atomic arrangement can effectively hamper the excessive leaching of transition metals, minimizing vacancies for oxygen coordination. Linear X-ray absorption near edge spectra analysis, extended X-ray absorption fine structure fitting outcomes, and X-ray photoelectron spectroscopy collectively confirm that Ir is present in lower oxidation states in O-IrVMn/IrOx due to the presence of unsaturated O-coordination. Consequently, the O-IrVMn/IrOx delivers excellent acidic OER performances with an overpotential of only 279 mV at 10 mA cm-2 and a high mass activity of 2.3 A mg-1 at 1.53 V (vs RHE), exceeding most Ir-based catalysts reported. Moreover, O-IrVMn/IrOx also showed excellent catalytic stability with only 0.05 at. % Ir dissolution under electrochemical oxidation, much lower than that of disordered D-IrVMn/IrOx (0.20 at. %). Density functional theory calculations unravel that the intensified ligand effect optimizes the adsorption energies of multiple intermediates involved in the OER and stabilizes the as-formed catalytic IrOx layer.

Solid solutions in disulfide systems Re(IV)S<sub>2</sub>–Ti(IV)S<sub>2</sub>, Re(IV)S<sub>2</sub>–Mo(IV)S<sub>2</sub>, and Re(IV)S<sub>2</sub>–W(IV)S<sub>2</sub>

Objectives. Chalcogenides of transition elements with low oxidation states, as well as their substituted derivatives, remain a poorly studied class of chemical compounds. Rhenium disulfide has many distinctive features and great application potential as a new twodimensional semiconductor. This is due to its unusual structure and unique anisotropic properties. The presence of weak interlayer bonding and a unique distorted octahedral (1T) structure suggests the possibility of creating new phases on its basis. The aim of this work is to obtain and study phases in systems Re(IV)S2–Ti(IV)S2, Re(IV)S2–Mo(IV)S2, and Re(IV)S2–W(IV)S2.Methods. The samples were obtained by high-temperature solid-phase ampoule synthesis in a vacuum. The study was carried out using X-ray phase analysis and X-ray photoelectron spectroscopy.Results. The regions of existence of solid solutions, intercalates and two-phase regions in the resulting systems were established.Diffraction patterns were obtained for the new phases and the crystal lattice parameters were calculated. Based on data relating to the binding energies of core electrons with the nucleus, the study showed the valence states of the elements after synthesis. The study also confirmed that all phases obtained as a result of synthesis contain transition elements in the oxidation state (IV).Conclusions. Intercalated solid solutions are formed in areas rich in rhenium, while in areas close to titanium and molybdenum disulfides, intercalated phases are attained. In the ReS2–WS2 system there is a region of solid solutions, including 30, 50, and 70 mol % rhenium disulfide. Their structure is a polymorphic modification of the structure of the original components. The presence of rhenium, molybdenum, and tungsten in these phases in the oxidation state (+IV) was confirmed. The data obtained on phase formation in dichalcogenide systems can be practically used in the creation of materials with unique electronic, magnetic, and optical properties with a wide range of applications.

Selenium-induced anion vacancy and active site migration stimulating remarkable sulfide Na-Ion storage

Heterojunctions and controllable anionic vacancies are perceived to be powerful means of ameliorating the performance of sodium-ion batteries assignable to their unique physical and chemical properties. However, the mechanism by which heterojunction and vacancy structures affect sodium-ion battery storage remains to be systemically explored. In this study, the Se doped CoS2@CoS1.035@Carbon (Se-CoS2@CoS1.035@C) heterostructure with anion vacancy was synthesized by a one-step calcination. These heterostructures with lower metal oxidation states and anionic vacancies exhibit exceptional Na+ storage performance (554.3 mA h g−1 after 1500 cycles at 5.0 A g−1). Both electrochemical tests and theoretical calculations demonstrate excellent pseudocapacitive behavior and enhanced Na+ adsorption during discharge because of anionic vacancies and Se doping. Additionally, introducing weaker Co-Se bonds and extending Co-S and Co-Se bonds reduce binding energies, which effectively accelerates the conversion reaction. Our findings provide a feasible way to rationally design and facilely prepare heterostructured anode materials with rich anionic vacancies for sodium-ion batteries.

Reaction of hydrogen peroxide with amorphous Ti–O surfaces

Amorphous Ti–O thin films were synthesized by reactive magnetron sputtering and their affinity to H2O2 was studied electrochemically. They exhibit a pronounced affinity to H2O2, with TiO0.6 outperforming TiO1.5 and TiO2. Cathodic currents in the range of −211 μA/cm2 suggest that TiO0.6 is highly electroactive to H2O2. Molecular dynamics simulations based on density functional theory revealed rapid dissociation of H2O2 into OH on Ti–O surfaces, leading to diffusion of OH, facilitating both oxidation and reduction processes. These OH groups predominantly dock onto bridge and atop sites, oxidizing the surfaces. Notably, stronger interactions observed for lower oxidation states give rise to higher cathodic currents. Additionally, the ability of amorphous Ti–O thin films to generate free H atoms implies a possible reduction mechanism, likely leading to the desorption of H2O. Hence, amorphous TiO0.6 is more suitable for detection and monitoring of H2O2 than higher oxidation states in their crystalline forms, e.g., rutile TiO2, known as a benchmark for such applications.

Enhanced electrochemical performance of partially amorphous La0.6Sr0.4CoO3-δ oxygen electrode materials for low-temperature solid oxide cells operating at 400 °C

This work evaluates partially amorphous La0.6Sr0.4CoO3-δ (LSC) as a potential oxygen electrode for low-temperature solid oxide cells. LSC was deposited using the spin-coating technique onto Ce0.8Gd0.2O2-δ (CGO) substrates. The optimal oxygen electrode thickness was determined as 500 nm. The electrochemical impedance spectroscopy (EIS) study showed a significant improvement in oxygen reduction/oxidation reaction kinetics when annealing temperatures below 600 °C. The lowest value of the polarisation resistance was observed for the sample annealed at 400 °C, followed by a temperature of 500 °C. EIS measurements at different pO2 content were performed at levels between 0.5 % and 20 %. A comprehensive equivalent circuit analysis was carried out for an explanation of the limiting factors of the catalytic reaction. X-ray absorption fine structure analysis allowed for the identification of differences between crystalline LSC and its partially amorphous form. X-ray absorption near-edge spectroscopy analysis indicated that cobalt adopts a lower oxidation state for the partially amorphous form. Moreover, extended X-ray absorption fine structure analysis indicated the decreased of cobalt oxidation state in partially amorphous LSC. It can be assumed that the increased activity of LSC at temperatures below the crystallization may be due to increased defects and oxygen vacancies in the material.

Two-step annealing synthesis of MOF-derived Cr-Co-Ru metallic oxides for improving the oxygen evolution reaction in acidic water splitting

The development of acid-sensitive OER (Oxygen Evolution Reaction) electrocatalysts based on ruthenium oxides is a crucial step toward achieving large-scale hydrogen production in low-cost Proton Exchange Membrane (PEM) electrolyzers. However, a major challenge in this field is to overcome the tendency of ruthenium-based metal oxide dissolving in acidic environments, which affects long-term stability. In this study, we employed MIL-88B(Cr) as a precursor and used a two-step annealing method to prepare trimetallic metal oxides Cr0.5CoxRu0.5-xO2-δ. Detailed experimental measurements demonstrate that the introduction of Co reduced the volume of individual catalyst crystallites without disrupting the rutile crystal structure and inherent activity of CrO2@RuO2. Simultaneously, Co and Cr doping lowered the oxidation state of Ru within the catalyst system. Lower oxidation states of Ru are more stable during the OER reaction, ensuring the stability of this catalyst to be at least 100 hours. Furthermore, Co incorporation raises the energy required for oxygen vacancy formation, reduced the involvement of lattice oxygen, and enhanced the catalyst's activity. The catalyst Cr0.5Co0.17Ru0.33O2-δ with the best performance exhibited the overpotential of only 224 mV at 10 mA cm-2 in 0.5 M H2SO4. This study offers a viable strategy for developing highly active and stable catalysts in acidic media by controlling the electronic structure of RuO2.

Synthesis and Characterization of Bulky 1,3-Diamidopropane Complexes of Group 2 Metals (Be-Sr).

Reaction of lithium 1,3-diamidopropane Li2(TripNCN) (TripNCN=[{(Trip)NCH2}2CH2]2-, Trip=2,4,6-triisopropylphenyl) with BeBr2(OEt2)2 gave the diamido beryllium complex, [(TripNCN)Be(OEt2)]. Deprotonation reactions between the bulkier 1,3-diaminopropane (TCHPNCN)H2 (TCHPNCN=[{(TCHP)NCH2}2CH2]2-, TCHP=2,4,6-tricyclohexylphenyl) and magnesium alkyls afforded the adduct complexes [(TCHPNCN)Mg(OEt2)] and [(TCHPNCN)Mg(THF)2], depending on the reaction conditions employed. Treating [(TCHPNCN)Mg(THF)2] with the N-heterocyclic carbene :C{(MeNCMe)2} (TMC) gave [(TCHPNCN)Mg(TMC)2] via substitution of the THF ligands. Reactions of (ArNCN)H2 (Ar=Trip or TCHP) with Mg{CH2(SiMe3)}2, in the absence of Lewis bases, yielded the N-bridged dimers [{(ArNCN)Mg}2]. Salt metathesis reactions between alkali metal salts M2(TCHPNCN) (M=Li or K) and CaI2 or SrI2 led to the THF adduct compounds [(TCHPNCN)Ca(THF)3] and [(TCHPNCN)Sr(THF)4], the differing number of THF ligands in which is a result of the different sizes of the metals involved. The described complexes hold potential as precursors to kinetically protected, low oxidation state group 2 metal species.

Atomically dispersed Zn-NxCy sites on N-doped carbon for catalytic transfer hydrogenation of ethyl levulinate into γ-valerolactone

Catalytic transfer hydrogenation (CTH) of biomass-derived carbonyl compounds provides a viable strategy to synthesize high value-added chemicals and biofuels, for which the development of efficient catalysts still remains a formidable challenge. Here, we report a Zn-based single-atom catalyst (Zn/NC-950), prepared by pyrolysis of ZIF-8 at 950 °C, for the CTH of ethyl levulinate to γ-valerolactone (GVL). This catalyst exhibited excellent performance, affording a GVL selectivity of 95.3 % at an ethyl levulinate conversion of 100 %, using isopropanol as the hydrogen source at 200 °C and autogenous pressure. The structural characterization and theoretical calculation demonstrate that such extraordinary efficacy of the Zn/NC-950 catalyst is attributed to the dual Zn-N3C1 and Zn-N2C2 sites of low Zn oxidation states, which work synergistically to generate the active hydrogen species and activate the carbonyl bonds, respectively. This work provides a rationale for the precise design of the non-noble metal single-atom catalysts efficient for the biomass valorization.

Antimony-Doped Wide Bandgap Molybdenum Trioxide with Enhanced Localized Surface Plasmon Resonance for Nitrogen Photofixation.

Plasmonic metal oxides are promising photocatalysts for the artificial photosynthesis of green ammonia due to localized surface plasmon resonance (LSPR) enhanced photoconversion and rich surface oxygen vacancies improved chemisorption and activation of dinitrogen molecules. However, these oxygen vacancies are unstable during the photocatalytic process and could be oxidized by photogenerated holes, leading to the vanishing of the LSPR. Here, we fabricated antimony-doped molybdenum trioxide nanosheets with stable plasmonic absorption extending into the near-infrared (NIR) range, even after harsh treatment in oxidative atmospheric conditions at high temperatures. For undoped plasmonic MoO3-x nanosheets, the LSPR originates from the abundant oxygen vacancies that vanish after heat treatment at high temperatures in air, leading to the disappearance of the LSPR absorption. Sb doping does not significantly increase the concentration of oxygen vacancies while donating more free electrons because Sb can keep a lower oxidation state. Heat treatment diminished the oxygen vacancies while not affecting the low oxidation state of Sb. As a result, heat-treated Sb-doped MoO3-x nanosheets still show strong LSPR absorption in the NIR range. Both experimental results and theoretical calculations demonstrated that add-on states close to the Fermi level are formed due to the Sb doping and high concentration of oxygen vacancies. The prepared samples were used for photocatalytic nitrogen reduction and showed an LSPR-dependent photocatalytic performance. The present work has provided an effective strategy to stabilize the LSPR of plasmonic semiconductor photocatalysts.