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At least 739 records · Page 41

Rapid photooxidation and removal of As(III) from drinking water using Fe-Mn composite oxide

Fe-Mn composite oxide (FMO) is widely applied to the oxidation and removal of As(III) from water. However, As(III) can directly reduce manganese oxides, decreasing the oxidation capacity or reusability and thereby greatly limiting the applicability of FMO. Here, the oxidation capacity and reusability of FMO for As(III) were efficiently improved by light radiation, and the effect of typical coexisting ions (SO 4 2– and Ca 2+ ) on the removal of As(III) was also studied. O 2 •– produced from excited manganese oxide and ligand-to-metal charge transfer in iron oxide-As(III) complex enhanced As(III) oxidation and removal under light radiation. At an initial As(III) concentration of 1000 μg L –1 , the total As concentration was respectively decreased to 11.5, 1.5 and 4.4 μg L –1 under darkness, UV light and sunlight at 180 min, and could be reduced to below the guideline limitation of drinking water (10 μg L –1 ) within 40 and 60 min under UV light and sunlight, respectively. SO 4 2– exhibited negligible effect on As removal efficiency because FMO had obviously lower adsorption capacity and selectivity for SO 4 2– than for As(V). The adsorption of coexisting Ca 2+ on manganese oxide decreased the negative charge on the FMO surface, thereby improving As(III) adsorption and oxidation. FMO exhibited excellent reusability, and a total As removal efficiency of 99.1% was still maintained after five cycles of an adsorption-desorption process under UV light. Finally, this work elucidates the photochemical oxidation and removal mechanism of FMO for As(III), and proposes a low-cost and efficient method for the detoxification of As(III)-contaminated drinking water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale Tracking of the High-Temperature Spin-State Transition in LaCoO 3

The high-temperature spin and electronic transitions in LaCoO 3 have recently been leveraged to create neuromorphic (brain-inspired) devices. While these devices have shown the potential for impactful functionality in next-generation computing systems, the nanoscale dynamics of the spin and electronic transitions that underlie their operation are not well understood. Inhomogeneities related to interfaces, electrode contacts, strain, and crystal defects can all affect device performance, making nanoscale characterization of the transitions essential for producing consistent and reliable devices. Here, we demonstrate the first nanoscale in situ measurement of the spin transition in LaCoO 3 at device-relevant temperatures (25–325 °C) over length scales of tens of nanometers using STEM-EELS. This measurement is enabled by an Al 2 O 3 coating, which prevents unwanted reduction of the LaCoO 3 specimen at high temperature and vacuum. The detailed understanding of LaCoO 3 transition dynamics enabled by such measurements will be crucial for optimizing LaCoO 3 -based neuromorphic devices and increasing reliability for real-world application.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The crystal structure of feitknechtite (β-MnOOH) and a new MnOOH polymorph

Studies suggest that feitknechtite (β-MnOOH) is a prevalent, and perhaps necessary, intermediate phase during the synthesis of birnessite-like phases, the abiotic oxidation of Mn2+, and the transformation of biogenic hexagonal phyllomanganates to more complex Mn oxides in laboratory and natural systems. Researchers have generally described feitknechtite as consisting of pyrochroite-like (or cadmium iodide-like) Mn-O octahedral layers, but a detailed crystal structure has not been reported. For this work, we used TEM/SAED and powder XRD and Rietveld refinements to derive the unit cell and, for the first time, report a complete structure description for feitknechtite (β-MnOOH). Rietveld refinements were also completed for three natural feitknechtite/hausmannite samples, and time-resolved synchrotron XRD experiments were used to follow the thermal transformation of feitknechtite to hausmannite. Additionally, we identified and report the structure for a second, and perhaps novel, MnOOH polymorph (proposed designation ε-MnOOH), mixed with the synthetic feitknechtite, that is similar to β-MnOOH but with a different layer stacking.

58 GEOSCIENCES↗

Magnetite-sulfide-metal complexes in the Allende meteorite

A model of liquid immiscibility is presented that seemingly accounts for the sulfide-oxide-metal complexes that are present in olivine-rich chondrules in the Allende meteorite. The four major assemblages that are identified are: (1) magnetite + Ni-Fe metal; (2) magnetite + troilite + Ni-Fe metal; (3) magnetite + troilite + pentlandite + Ni-Fe metal; and (4) troilite + or - pentlandite. Specific attention is focused on oxide-metal associations and experimental data confirm earlier suggestions that magnetite results from the oxidation of an initially high-Fe-content metal alloy. Oxidation decreases the modal abundance of the Fe metal and this is accompanied by substantial increases in Ni contents which reach a maximum of approximately 70 wt % Ni. The proposed oxidation mechanism is entirely consistent with condensation of Fe-metal + olivine (Fa5) that subsequently reequilibrated at lower temperatures. Although the sulfide constituents could also have formed by the reaction of Fe-Ni metal + gaseous H2S, sulfide immiscibility under increased conditions of partial O2 pressure is the preferred process.

Haggerty, S. E.↗

Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H 2 and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Towards this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under DRM reaction conditions. In conclusion, the fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active sites formation from easily synthesized metal oxide solid solutions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLC reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4 ). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4 , from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bimetallic oxamato complexes synthesized into mesoporous matrix as precursor to tunable nanosized oxide

Highlights: • The bimetallic oxamato complexes as single-source precursor. • We prepared into a porous silica glass tunable nanosized oxide powders. • X-ray diffraction shows the formation of CeO{sub 2}/CuO and spinel cobaltite. • The different number of IDC allows control of the nanoparticle size. - Abstract: The bimetallic complexes were employed to prepare into a porous silica glass tunable nanosized oxide powders through the single source precursor (SSP) method. These materials were prepared by first anchoring of [Cu(opba)]{sup 2−} [opba = ortho-phenylenebis(oxamato)], second by reaction in situ with second metal [Co(II) or Ce(III)] and followed by a thermal treatment. The different number of impregnation–decomposition cycles (IDC) allows control of the nanoparticle size. X-ray diffraction shows the formation of mixture CeO{sub 2}–CuO and spinel copper cobaltite. Raman spectroscopy confirmed the formation of such phases. Transmission electron microscopy images revealed that spinel cobaltite particles (8 IDC) present a mean size of about 9 nm, whereas for the CeO{sub 2}–CuO phase the particle diameters are 4 nm (2 IDC) and 8 nm (6 IDC). For CeO{sub 2}–CuO the diffuse reflectance spectroscopy indicates a consistent red shift in band gap from 3.41 to 2.87 eV with increasing of particle size due to quantum confinement effect.

36 MATERIALS SCIENCE↗

Resolving the Valence of Iron Oxides by Resonant Photoemission Spectroscopy

Precisely determining the oxidation states of metal cations within variable-valence transition metal oxides remains a significant challenge, yet it is crucial for understanding and predicting the properties of these technologically important materials. Iron oxides, in particular, exhibit a remarkable diversity of electronic structures due to the variable valence states of iron (Fe 2+ and Fe 3+ ). A quantitative analysis using conventional X-ray photoelectron spectroscopy (XPS) is challenging because of the strong overlap of the Fe 2p XPS peaks from different oxidation states. Here, in this study, we show how this problem can be resolved using Resonant Photoemission Spectroscopy (ResPES), which unambiguously distinguishes Fe oxidation states and spectroscopically estimates the composition ratio of Fe cation valence states in the complex Fe oxides. We demonstrate this in the model case of a FeO 2 monolayer film on Pt(111), showing that the FeO 2 film consists of an equal mixture of Fe 2+ and Fe 3+ cations, yielding an average valence of +2.5, contrary to the +3 valence proposed based on density functional theory (DFT).

Chen, Hao [Lawrence Berkeley National Laboratory (↗

Lithium-Ion Battery Materials as Tunable, “Redox Non-Innocent” Catalyst Supports

The development of general strategies for the electronic tuning of a catalyst’s active site is an ongoing challenge in heterogeneous catalysis. To this end, herein, we describe the application of Li-ion battery cathode and anode materials as redox non-innocent catalyst supports that can be continuously modulated as a function of lithium intercalation. A zero-valent nickel complex was oxidatively grafted onto the surface of lithium manganese oxide (Li x Mn 2 O 4 ) to yield isolated Ni2+ occupying the vacant interstitial octahedral site in the Li diffusion channel on the surface and subsurface of the spinel structure (Ni/Li x Mn 2 O 4 ). Additionally, the activity of Ni/Li x Mn 2 O 4 for olefin hydrogenation, as a representative probe reaction, was found to increase monotonically as a function of support reductive lithiation. Simulation of Ni/Li x Mn 2 O 4 reveals the dramatic impact of surface redox states on the viability of the homolytic oxidative addition mechanism for H 2 activation. Catalyst control through support lithiation was extended to an organotantalum complex on Li x TiO 2 , demonstrating the generality of this phenomenon.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sliding durability of two carbide-oxide candidate high temperature fiber seal materials in air to 900 C

A test program to determine the friction and wear properties of two complex carbide oxide ceramic fibers for high temperature sliding seal applications is described. The fibers are based on Si, C, O, and Ti or Si, C, N, and O ceramic systems. Pin on disk tests using ceramic fiber covered pins and Inconel 718 disks, were conducted in air from 25 to 900 C to evaluate potential seal materials. This testing procedure was used in a previous study of oxide ceramic fibers which were found to exhibit wear behavior based predominantly on their mechanical properties. Like the oxide fibers tested previously, these carbide oxide ceramic fibers, show an increase in friction and wear with increased test temperature. At room temperature, the wear behavior seems to be based upon mechanical properties, namely tensile strength. At 500 and especially 900 C, the fibers wear by both mechanical fracture and by oxidative type wear. Based upon post test microscopic and x ray analyses, interaction between the fiber constituents and elements transferred from the counterface, namely Ni and Cr, may have occurred enhancing the tribochemical wear process. These results are interpreted.

Dellacorte, Christopher↗

Immobilization of “Capping Arene” Cobalt(II) Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation

We report the synthesis, characterization, and electrocatalytic water oxidation activity of two cobalt complexes, (6-FP)Co(NO 3 ) 2 (1) (6-FP = 8,8'-(1,2-phenylene)diquinoline) and (5-FP)Co(NO 3 ) 2 (2) (5-FP = 1,2-bis(N-7-azaindolyl)benzene), containing "capping arene" bidentate ligands with nitrogen atom donors. The cobalt complexes 1 and 2 were supported on ordered mesoporous carbon (OMC) by π-π stacking, resulting in heterogenized cobalt materials 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, respectively, and studied for electrocatalytic water oxidation. We find that 6-FP-Co-OMC-1 exhibits an overpotential of 355 mV for a current density of 10 mA cm -2 and a turnover frequency (TOF) of ~0.53 s -1 at an overpotential of 400 mV at pH 14. 6-FP-Co-OMC-1 exhibits activity that is ~1.6 times that of 5-FP-Co-OMC-2, which gives a TOF of 0.32 s -1 at 400 mV overpotential. The structural stability of the single-atom Co site was demonstrated for 6-FP-Co-OMC-1 using X-ray absorption spectroscopy for the molecular complex supported on OMC, but slow degradation in catalyst activity can be attributed to eventual formation of Co oxide clusters. DFT computations of electrocatalytic water oxidation using the molecular complexes as models provide a description of the catalytic mechanism. These studies reveal that the mechanism for O-O bond formation involves an intermediate Co IV oxo complex that undergoes an intramolecular reductive O-O coupling to form a Co II -OOH species. Further, the calculations predict that the molecular 6-FP-Co structure is more active for electrocatalytic water oxidation than 5-FP-Co, which is consistent with experimental studies of 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, highlighting the possibility that the ligand structure influences the catalytic activity of the supported molecular catalysts.

25 ENERGY STORAGE↗

Structural, thermal and electrical conductivity characteristics of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm) complex perovskites as anode materials for solid oxide fuel cell

The Ti and Mn replaced complex perovskites, Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (Ln: La, Nd and Sm), were reported as potential anode materials for high temperature-operating solid oxide fuel cells (HT-SOFCs). For the present research study, synthesis, crystallographic, thermal and electrical conductivity properties of Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} complex perovskites were investigated using X-ray diffraction (XRD), Rietveld method, thermogravimetric analysis (TGA) and electrical conductivity to apply these oxide materials for the HT-SOFC anode materials. XRD results showed that Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems synthesized as single phases did not react with 8 mol% yttria stabilized zirconia (8YSZ) and 10 mol% Gd-doped cerium oxide (CGO91) up to 1500 °C and did not decompose under dry 3.9% hydrogen at 850 °C. The crystal structures of La{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (LSTM), Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (NSTM) and Sm{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} (SSTM) showed orthorhombic symmetry with the space group Pbnm and SSTM showed a more distorted structure. Thermogravimetric analysis (TGA) proved weight gains in these three sample occurred under oxidizing conditions and weight loss under reducing conditions. Electrical conductivity values of NSTM were higher than those of LSTM and SSTM under oxidizing and reducing conditions. - Graphical abstract: The B-site cations (Ti/Mn) are surrounded by regular octahedra of oxygen in Nd{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}(NSTM). These octahedra are linked together in a corner sharing three dimensional framework, while Nd/Sr ion occupies 12-coordinated A-site between these octahedra. The Ti/Mn–O{sub 6} octahedra are elongated along the c-axis. The crystal structure distortion was due to the smaller ionic radius of the A-site cations, which force the (Ti/Mn)–O{sub 6} octahedra to tilt in order to optimize the A–O bond distances. The same structural symmetry was found when the samples were reduced in 3.9% H{sub 2} in Ar at 900 °C for 12 h. - Highlights: • Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d} oxide systems do not react with 8YSZ and CGO91. • LSTM, NSTM and SSTM show orthorhombic symmetry with the space group Pbnm. • LSTM shows relatively lower onset temperature in Ln{sub 0.5}Sr{sub 0.5}Ti{sub 0.5}Mn{sub 0.5}O{sub 3±d}. • Electrical conductivity values of NSTM are higher than those of LSTM and SSTM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roles of surface Mn(III) and MgOH + /CaOH + complexation in photochemically assisted Mn 2+ oxidation and Todorokite formation

Todorokite, a Mn oxide phase commonly found in seafloor Mn nodules, is one of the most abundant Mn oxides in nature and has wide applications in environmental engineering, including heavy metal remediation, contaminant adsorption for water purification, and catalysis for organic pollutant degradation. However, traditional abiotic formation of todorokite reported to date typically requires high temperature, pressure, and pH outside circumneutral conditions, or involves several days of phase transformations from precursor phases. In this study, we demonstrate rapid todorokite formation within 6 h via photochemically assisted oxidation of Mn 2+ (aq) in the presence of Mg 2+ or Ca 2+ , notably at ambient temperature and pressure. The concentrations of aqueous MgOH + and CaOH + , as well as the pH (initial 9 or 6), had significant collective influences on the crystalline phases of the formed Mn oxide solids. The proportions of the Mn oxidation states (IV, III, and II) and the extent of Mn(III) surface complexation with MgOH + or CaOH + controlled the crystalline phases (todorokite, feitknechtite, and birnessite) and the extent of cation incorporation into the resulting Mn oxide solids. Specifically, the oxidation state of Mn influenced the crystallization of different Mn oxide phases, and the formed Mn(III) complexed with MgOH + or CaOH + facilitated the formation of todorokite, along with cation incorporation. X-ray pair distribution function analysis revealed that incorporated Mg species were located at the inside corner sites of the 5 × 3 MnO 6 octahedral tunnel structure of todorokite, suggesting complexation between MgOH + and Mn(III) at the corners of the tunnel. Furthermore, this study provides novel insights into the elusive formation of todorokite and its potential for applications in advanced water treatment and environmental remediation.

Abiotic Mn2+ oxidation↗

Comparison of the photochemical properties of phthalocyanine and hemiporphyrazine Zn(II) complexes

In DMF (dimethylformamide) solutions containing concentrations of (NEt 4 )Br (Et = ethyl) between 0.001 and 0.05 M both zinc phthalocyanine (Pc) and hemiporphyrazine (Hp) complexes are dissolved and form species [Zn(Hp)(Br)] – , and [Zn(Pc)(Br)] – . The increase in formation of the hemiporphyrazine bromide adduct is revealed by a linear dependence of the UV–Vis absorption spectrum on the Br – concentration whereas, over the same concentration range, absorption measurements indicate the formation of the phthalocyanine bromide adduct in solution. The x-ray and molecular structure of [NEt 4 ][Zn(Pc)(Br)](H 2 O) 0.33 has been determined showing the coordination of the Br – to the metal center. Photo-induced processes of the Zn complexes were investigated with deaerated solutions in a time scale t ≥10 ns. The 355 nm flash irradiation of [Zn(Hp)(Br)] – produced transient spectra which showed a bathochromic shift of the absorption maximum from 460 nm to 440 nm and an increase of the spectrum rate of decay with increasing Br – concentrations. The initial spectrum is attributed to the (nπ*–LLCT Br→Hp )[Zn(Hp)(Br)] – excited state which reacts with H-atom donors forming a radical [Zn(Hp-H)(Br)] •– . On the other hand, a transient spectrum, λ max ~600 nm, grows in a time t ≤0.6 µs when [Zn(Pc)(Br)] – is flash irradiated at 355 nm. The photoreactions of these complexes with SCN – and 2-propanol (IPA) were studied. Despite of the apparent similarity between both complexes, IPA was photo-oxidized by both complexes although by different mechanisms, an electron transfer with [Zn(Pc)(Br)] – and an H atom abstraction with [Zn(Hp)(Br)] – . Finally, the photo-oxidation of SCN– by [Zn(Pc)(Br)] – but not by [Zn(Hp)(Br)] – makes a remarkable difference between the photochemistries of these complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT and new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗