Rod-Like Nanostructured Cu-Co Spinel with Rich Oxygen Vacancies for Efficient Electrocatalytic Dechlorination.

Dichloromethane (CH2Cl2) hydrodechlorination to methane (CH4) is a promising approach to remove the halogenated contaminants and generate clean energy. In this work, rod-like nanostructured CuCo2O4 spinels with rich oxygen vacancies are designed for highly efficient electrochemical reduction dechlorination of dichloromethane. Microscopy characterizations revealed that the special rod-like nanostructure and rich oxygen vacancies can efficiently enhance surface area, electronic/ionic transport, and expose more active sites. The experimental tests demonstrated that CuCo2O4-3 with rod-like nanostructures outperformed other morphology of CuCo2O4 spinel nanostructures in catalytic activity and product selectivity. The highest methane production of 148.84 µmol in 4 h with a Faradaic efficiency of 21.61% at -2.94 V (vs SCE) is shown. Furthermore, the density function theory proved oxygen vacancies significantly decreased the energy barrier to promote the catalyst in the reaction and Ov-Cu was the main active site in dichloromethane hydrodechlorination. This work explores a promising way to synthesize the highly efficient electrocatalysts, which may be an effective catalyst for dichloromethane hydrodechlorination to methane.

Effect of Cu-Doped Co-Mn Spinel for Boosting Low-Temperature NO Reduction by CO: Exploring the Structural Properties, Performance, and Mechanisms.

Cobalt-manganese spinel catalysts performed unsatisfactory activity at low-temperature and narrow reaction temperature window, which greatly limited the application in NO reduction by CO. Herein, we synthesize a series of Cu-doped CoMn2O4 catalysts and apply to NO reduction by CO. The Cu0.3Co0.7Mn2O4 exhibited superior catalytic performance, reaching 100% NO conversion and 80% N2 selectivity at 250 °C. Detailed structural analysis showed that the introduced Cu replaces some Co in tetrahedral coordination to induce a strong synergistic effect between different metals. This endows the catalyst with the promotion of both electron transfer and oxygen vacancy generation on the catalyst surface. Importantly, the reaction mechanism and pathway were further revealed by in situ diffusion Fourier transform infrared spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results indicated that the cycle of oxygen vacancy mainly determines the catalytic activity of NO reduction by CO. Notably, Cu doping significantly lowered the energy barrier of the rate-determining step (*CO + O → *Ov + CO2), facilitating the desorption of the CO2 and exposing the active sites for efficient NO reduction with CO. This work offers an effective way for designing the catalyst in NO reduction by CO and provides a reference for exploring the catalytic mechanism of the reaction.

Cubic CuFe2O4 Spinel with Octahedral Fe Active Sites for Electrochemical Dechlorination of 1,2-Dichloroethane.

CuFe2O4 spinel has been considered as a promising catalyst for the electrochemical reaction, while the nature of the crystal phase on its intrinsic activity and the kind of active site need to be further explored. Herein, the crystal phase-dependent catalytic behavior and the main active sites of CuFe2O4 spinel for electrochemical dechlorination of 1,2-dichloroethane are carefully studied based on the combination of experiments and theoretical calculations. Cubic and tetragonal CuFe2O4 are successfully prepared by a facile sol-gel method combined with high temperature calcination. Impressively, CuFe2O4 with the cubic phase shows a higher activity and ethylene selectivity compared to CuFe2O4 with the tetragonal phase, suggesting a significant facilitation of electrocatalytic performance by the cubic crystal structure. Moreover, the octahedral Fe atom on the surface of cubic CuFe2O4(311) is the active site responsible to produce ethylene with the energy barrier of 0.40 eV. This work demonstrates the significance of crystal phase engineering for the optimization of electrocatalytic performance and offers an efficient strategy for the development of advanced electrocatalysts.

Rational Design of Carbon-Based Porous Aerogels with Nitrogen Defects and Dedicated Interfacial Structures toward Highly Efficient CO2 Greenhouse Gas Capture and Separation.

CO2 capture from flowing flue gases through adsorption technology is essential to reduce the emission of CO2 to the atmosphere. The rational design of highly efficient carbon-based absorbents with interfacial structures containing interconnected porous structures and abundant adsorption sites might be one of the promising strategies. Here, we report the synthesis of nitrogen-doped carbon aerogels (NCAs) via prepolymerized phenol-melamine-formaldehyde organic aerogels (PMF) by controlling the addition amount of ZnCl2 and the precursor M/P ratio. It has been revealed that NCAs with a higher specific surface area and interconnected porous structures contain a large amount of pyridinic nitrogen and pyrrolic nitrogen. These would act as the intrinsic adsorption sites for highly effective CO2 capture and further improve the CO2/N2 separation efficiencies. Among the prepared samples, NCA-1-2 with a high micropore surface area and high nitrogen content exhibits a high CO2 adsorption capacity (4.30 mmol g-1 at 0 °C and 1 bar) and CO2/N2 selectivity (36.5 at 25 °C, IAST). Under typical flue gas conditions (25 °C and 1.01 bar), equilibrium gas adsorption analysis and dynamic breakthrough measurement associated with a high adsorption capacity of 2.65 mmol g-1 at 25 °C and 1.01 bar and 0.81 mmol g-1 at 25 °C and 0.15 bar. This rationally designed N-doped carbon aerogel with specific interfacial structures and high CO2 adsorption capacity, high selectivity, and adsorption performance remained pretty stable after multiple uses.

Facile Tailoring of the Electronic Structure and the d-Band Center of Copper-Doped Cobaltate for Efficient Nitrate Electrochemical Hydrogenation.

Electrocatalytic nitrate reduction is an effective strategy to eliminate nitrate's environmental impact and produce high-value-added ammonia products. However, most of the current reports focus on preparation strategies of catalysts, with poor exploration of the mechanism. In this work, we fabricated a binding-free Cu-doped Co3O4 electrode (Cu-Co3O4) to reveal the structure-activity relationship. Cu-Co3O4 exhibited a maximum Faradaic efficiency of ammonia of up to 86.5% at -0.6 V vs reversible hydrogen electrode in a neutral electrolyte, with the corresponding yield rate of 36.71 mmol h-1 g-1. In situ electrochemical Raman spectroscopy confirmed that the structure of Cu-Co3O4 exhibits excellent stability and durability. Theoretical analysis revealed that the interaction between Cu and Co induces the d-band center position of the mono-metal oxide to shift toward the center to optimize the nitrate reduction intermediate hydrodeoxygenation free-energy change, especially of *NOx (x = 1, 2, and 3). These results offer guidelines for the electrochemical reduction of nitrate with transition metal oxide electrocatalysts.

Electroreductive CO coupling of benzaldehyde over SACs Au-NiMn2O4 spinel synergetic composites.

Electroreductive CO coupling provides a prospective strategy for biomass derivative upgrading via reducing the number of oxygen-containing functional groups and increasing their molecular weight. However, exploring superior electrocatalysts with effective reactivity and high selectivity for target products are still a challenge. In this work, single atom Au surface derived NiMn2O4 (SACs Au-NiMn2O4) spinel synergetic composites were fabricated by a versatile adsorption-deposition method and applied in electroreductive self-coupling of benzaldehyde to dibenzyl ether. The SACs Au-NiMn2O4 spinel synergetic composites enhanced electroreductive coupling of benzaldehyde, significantly improved the yield and selectivity of dibenzyl ether. Systematic characterizations and density functional theory calculation revealed that atomically dispersed Au occupied surface Ni2+ vacancies, which played a dominated role in CO coupling of benzaldehyde. Detailed calculation results showed that benzaldehyde preferred to adsorb on Ni octa-hedral sites of NiMn2O4 spinel synergetic structure, single atom Au surficial derivation over NiMn2O4 further reduced the adsorption energy (Eads) of benzaldehyde on SACs Au-NiMn2O4, thus the CO coupling of benzaldehyde to dibenzyl ether was promoted. Moreover, single atom Au surficial derivation lowered the energy barrier of rate-determining step, facilitated the formation of dibenzyl ether species. Our work also paves an avenue for rational design single atom materials using spinel as support.

Functionalized Activated Carbon for Competing Adsorption of Volatile Organic Compounds and Water.

The interfacial interaction of activated carbon with volatile organic compounds (VOCs) is seriously affected by water vapor. Therefore, it is vital to enhance the hydrophobic performance of activated carbon for expanding its application in industrial and environmental fields. Herein, a series of hydrophobic activated carbon was fabricated by tailored mixed siloxane and applied in dynamic competitive adsorption at 0, 50, and 90% humidity. Simultaneously, the diffusion molecular models and multicomponent adsorption experiments were used to study the adsorption and diffusion mechanisms. The hydrophobicity of activated carbon was significantly improved by loading of mixed siloxane, in which the equilibrium water absorption decreased from 21.9 to 7.2% and the contact angles increased by 70.10°. Meanwhile, dynamic competitive adsorption at different humidities indicated that the siloxane-functionalized activated carbons (SACs) showed much better competitive adsorption performances for VOCs than original activated carbon, which was further confirmed by the theoretical calculations of adsorption energy. In addition, a remarkable adsorption selectivity and reusability could be demonstrated to VOCs with different polarities on SACs. This study not only provides a new strategy for the hydrophobic modification of activated carbon materials but also offers theoretical guidance for the treatment of gas streams with significant water contents.

Novel Two-Dimensional AgInS2/SnS2/RGO Dual Heterojunctions: High Spatial Charge and Toxicity Evaluation.

A single semiconductor employed into photo(electro)catalysis is not sufficient for charge carrier separation. Designing a multiple heterojunction system is a practical method for photo(electro)catalysis. Herein, novel two-dimensional AgInS2/SnS2/RGO (AISR) photocatalysts with multiple junctions were prepared by a simple hydrothermal method. The synthesized AISR heterojunctions showed superior photoelectrochemical performance and photocatalytic degradation of norfloxacin, with a high degradation rate reaching 95%. More importantly, the toxicity of photocatalytic products decreased within the reaction process. High spatial separation efficiency of photogenerated electron-hole pairs was evidenced by optical and photoelectrochemical characterizations. Furthermore, a laser flash photolysis technique was carried on investigating the lifetime of the charge carrier of the fabricated dual heterostructures. In addition, sulfur and oxygen vacancies existed in AISR heterojunctions could largely constrain the recombination of electron-hole pairs. Density functional theory calculations were carried out to analyze the mechanism of photoinduced interfacial redox reactions, showing that reduced graphene oxide and AgInS2 act as electron and hole trappers in the photocatalytic reaction, respectively. Due to the interfacial electric field formed from AISR dual heterojunctions, the effective spatial charge separation and transfer contributed to the boosting photo(electro)catalytic performance.

A Porous Nano-Micro-Composite as a High-Performance Bi-Functional Air Electrode with Remarkable Stability for Rechargeable Zinc-Air Batteries.

The development of bi-functional electrocatalyst with high catalytic activity and stable performance for both oxygen evolution/reduction reactions (OER/ORR) in aqueous alkaline solution is key to realize practical application of zinc-air batteries (ZABs). In this study, we reported a new porous nano-micro-composite as a bi-functional electrocatalyst for ZABs, devised by the in situ growth of metal-organic framework (MOF) nanocrystals onto the micrometer-sized Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF) perovskite oxide. Upon carbonization, MOF was converted to porous nitrogen-doped carbon nanocages and ultrafine cobalt oxides and CoN4 nanoparticles dispersing inside the carbon nanocages, which further anchored on the surface of BSCF oxide. We homogeneously dispersed BSCF perovskite particles in the surfactant; subsequently, ZIF-67 nanocrystals were grown onto the BSCF particles. In this way, leaching of metallic or organic species in MOFs and the aggregation of BSCF were effectively suppressed, thus maximizing the number of active sites for improving OER. The BSCF in turn acted as catalyst to promote the graphitization of carbon during pyrolysis, as well as to optimize the transition metal-to-carbon ratio, thus enhancing the ORR catalytic activity. A ZAB fabricated from such air electrode showed outstanding performance with a potential gap of only 0.83 V at 5 mA cm-2 for OER/ORR. Notably, no obvious performance degradation was observed for the continuous charge-discharge operation for 1800 cycles over an extended period of 300 h.

Functionalized nitrogen-doped carbon dot-modified yolk-shell ZnFe2O4 nanospheres with highly efficient light harvesting and superior catalytic activity.

Volatile organic compounds (VOCs), as hazardous gaseous pollutants, have attracted much attention due to their potential threat to both human health and the environment. Accordingly, photocatalysis technology is seen as a promising technology to control low concentration VOCs due to its mild operation conditions, low energy consumption, and mineralization ability. However, there are some issues with photocatalysts, such as low light utility and fast photogenerated carrier recombination, which need to be addressed for practical applications. In this work, novel nitrogen-doped carbon dot (NCD)-modified ZnFe2O4 yolk-shell nanostructure photocatalysts were fabricated for the first time. The yolk-shell structure of ZnFe2O4 efficiently shortened the photogenerated carrier migration path and enhanced light scattering in its void, while the decorated NCDs accelerated the charge transfer from the bulk to the surface. A series of characterizations was conducted to investigate the crystal structure, elemental status, optical properties, and photocatalytic performance of the obtained composite photocatalysts. The NCD-modified ZnFe2O4 yolk-shell photocatalysts exhibited both a wide spectral absorbance and low carrier recombination, resulting in high photocatalytic activity and degradation ability towards gaseous o-dichlorobenzene. Density functional theory (DFT) calculations further revealed that the NCDs effectively promoted charge transfer and weakened the recombination of photo-generated electron-hole pairs. Additionally, in situ Fourier transform infrared (FTIR) spectroscopy was performed to investigate the degradation path in the photocatalytic process, and an electron paramagnetic resonance (EPR) radical trapping experiment was conducted to unveil the reactive oxygen species involved in the system. Combining the results obtained, the synergistic effect in the enhancement of photocatalysis between NCDs and yolk-shell ZnFe2O4 was schematically proposed.

Rational design and synthesis of highly oriented copper-zinc ferrite QDs/titania NAE nano-heterojunction composites with novel photoelectrochemical and photoelectrocatalytic behaviors.

This work reported that novel highly oriented and vertically aligned stoichiometric copper- and zinc-based ferrites, i.e., Cu0.5Zn0.5Fe2O4 quantum dots (QDs) anchored with TiO2 nanotube array electrode (NAE) composites, with n-n nano-heterojunctions and highly effective simulated solar light harvesting could be successfully achieved via electrochemical anodization followed by a vacuum-assisted impregnation strategy. It has been observed that Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE composites exhibit distinctly enhanced visible light photoelectrocatalytic (PEC) performance toward the degradation of typical pollutants including sulfamethoxazole (SMX) and methylene blue (MB) as compared to that of pristine TiO2 NAEs, which can be attributed to the synergistic effect of heterostructures with strong interfacial interaction and abundant 1D nanotube array structures to facilitate efficient spatial charge separation and interfacial transfers. The cocatalyst-anchoring of ternary oxides with derived spinel crystal structures onto nanotube arrays forming novel nanocomposites have obviously achieved remarkably enhanced photoelectrochemical (PE) conversion efficiencies, up to a dedicated value of 3.75%, under visible light irradiation as compared to that of 0.88% for aligned standalone TiO2 NAEs. Transient absorption spectroscopy quantitatively indicated long-lived photo-holes with lifetimes exceeding 72.23 µs generated among Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAE nanocomposites. Electron spinning resonance (ESR) demonstrated that more ˙O2- species derived from molecular uptake played the predominant role in the PEC oxidations of SMX and MB species. Moreover, the binding energy of the onset edge (Evf) and Fermi level (Ef) of Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs indicated that Cu0.5Zn0.5Fe2O4 QDs modification could considerably enhance the visible light harvesting and adsorption properties of TiO2 NTs. Furthermore, Cu0.5Zn0.5Fe2O4 QDs/TiO2 NAEs achieved up to 50% PEC degradation efficiency and 52.4% COD removal with regard to practical textile wastewater when irradiated by simulated sunlight. This work has provided new insights into the molecular tailing and coupling of multiple spinels with TiO2 NTs possessing remarkable visible light harvesting and sensitization characteristics, which would offer a prospective strategy toward designing highly efficient and easily recyclable photocatalytic materials for environmental remediation and solar energy utilizations and conversions both simultaneously and standalone.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba2Bi0.1Sc0.2Co1.7O6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g-1 was achieved, and a high capacitance of 780 F g-1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g-1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba2Bi0.1Sc0.2Co1.7O6-δ reaches up to 2549.4 F cm-3 based on the dense construction and high tap density (3.2 g cm-3). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg-1 at the power density of 787 W kg-1 in this study.

Submicron sized water-stable metal organic framework (bio-MOF-11) for catalytic degradation of pharmaceuticals and personal care products.

Water-stable and active metal organic frameworks (MOFs) are important materials for mitigation of water contaminants via adsorption and catalytic reactions. In this study, a highly water-stable Co-based MOF, namely bio-MOF-11-Co, was synthesized by a simplified benign method. Moreover, it was used as a catalyst in successful activation of peroxymonsulfate for catalytic degradation of sulfachloropyradazine (SCP) and para-hydroxybenzoic acid (p-HBA) as representatives of pharmaceuticals and personal care products, respectively. The bio-MOF-11-Co showed rapid degradation of both p-HBA and SCP and could be reused multiple times without losing the activity by simply water washing. The effects of catalyst and PMS loadings as well as temperature were further studied, showing that high catalyst and PMS loadings as well as temperature produced faster kinetic degradation of p-HBA and SCP. The generation of highly reactive and HO radicals during the degradation was investigated by quenching tests and electron paramagnetic resonance. A plausible degradation mechanism was proposed based on the functionalities in the bio-MOF-11-Co. The availability of electron rich nucleobase adenine reinforced the reaction kinetics by electron donation along with cobalt atoms in the bio-MOF-11-Co structure.

Adsorptive removal of antibiotic sulfonamide by UiO-66 and ZIF-67 for wastewater treatment.

Adsorptive removal of a toxic sulfonamide antibiotic, sulfachloropyradazine (SCP), from aqueous solution was studied on several metal organic frameworks, UiO-66 and ZIF-67, for the first time. UiO-66 exhibited a much higher adsorption capacity than ZIF-67, fast kinetics, and easy regeneration for reuse, demonstrating as a promising adsorbent in wastewater treatment processes. The batch adsorption shows an adsorption capacity of SCP at 417mg/g on UiO-66. The kinetic adsorption of SCP on UiO-66 reached equilibrium just in 10min and the kinetics fits accurately with a pseudo 2nd order model. A plausible mechanism was proposed based on pH effect, pKa value of the adsorbate and Zeta potential of UiO-66. The high adsorption is mainly contributed to hydrophobicity and π-π interactions along with electrostatic interactions. Thermodynamic studies show the spontaneous adsorption and exothermic process. The easy regeneration and high adsorption capacity confirms structural stability of the robust UiO-66 in wastewater treatment processes, making it suitable for a large scale application.

Oxygen Vacancies in Shape Controlled Cu2O/Reduced Graphene Oxide/In2O3 Hybrid for Promoted Photocatalytic Water Oxidation and Degradation of Environmental Pollutants.

A novel shape controlled Cu2O/reduced graphene oxide/In2O3 (Cu2O/RGO/In2O3) hybrid with abundant oxygen vacancies was prepared by a facile, surfactant-free method. The hybrid photocatalyst exhibits an increased photocatalytic activity in water oxidation and degradation of environmental pollutants (methylene blue and Cr6+ solutions) compared with pure In2O3 and Cu2O materials. The presence of oxygen vacancies in Cu2O/RGO/In2O3 and the formation of heterojunction between In2O3 and Cu2O induce extra diffusive electronic states above the valence band (VB) edge and reduce the band gap of the hybrid consequently. Besides, the increased activity of Cu2O/RGO/In2O3 hybrid is also attributed to the alignment of band edge, a process that is assisted by different Fermi levels between In2O3 and Cu2O, as well as the charge transfer and distribution onto the graphene sheets, which causes the downshift of VB of In2O3 and the significant increase in its oxidation potential. Additionally, a built-in electric field is generated on the interface of n-type In2O3 and p-type Cu2O, suppressing the recombination of photoinduced electron-hole pairs and allowing the photogenerated electrons and holes to participate in the reduction and oxidation reactions for oxidizing water molecules and pollutants more efficiently.

Metal-free hybrids of graphitic carbon nitride and nanodiamonds for photoelectrochemical and photocatalytic applications.

Graphitic carbon nitride (g-C3N4) has been considered as a metal-free, cost-effective, eco-friendly and efficient catalyst for various photoelectrochemical applications. However, compared to conventional metal-based photocatalysts, its photocatalytic activity is still low because of the low mobility of carriers restricted by the polymer nature. Herein, a series of hybrids of g-C3N4 (GCN) and nanodiamonds (NDs) were synthesized using a solvothermal method. The photoelectrochemical performance and photocatalytic efficiency of the GCN/NDs were investigated by means of the generation of photocurrent and photodegradation of methylene blue (MB) solutions under UV-visible light irradiations. In this study, the sample of GCN/ND-33% derived from 0.1g GCN and 0.05g NDs displayed the highest photocatalytic activity and the strongest photocurrent density. The mechanism of enhanced photoelectrochemical and photocatalytic performances was also discussed.

One-pot synthesis of binary metal organic frameworks (HKUST-1 and UiO-66) for enhanced adsorptive removal of water contaminants.

In this study, binary metal organic frameworks (MOFs) with HKUST-1 and UiO-66 have been synthesized in a one-pot process. The synthesized MOFs were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption, and thermogravimetric analysis (TGA). The meso-porosity and thermal stability of the binary MOFs were higher than those of single HKUST-1 or UiO-66. The synthesized MOF hybrids were then tested for adsorptive removal of methylene blue (MB) from wastewater in terms of kinetic and isothermal adsorption as compared to a commercially available activated carbon (AC). All the synthesized MOFs showed significant removal of MB under a wide range of pH. The adsorption capacities of HKUST-1 are higher than UiO-66 and commercial AC while the binary MOFs presented an even higher adsorption capacity than single MOFs. This is the first time that binary HKUST-1 and UiO-66 MOFs have been successfully synthesized and demonstrated enhanced adsorptive removal of contaminants.

Flower-like Cobalt Hydroxide/Oxide on Graphitic Carbon Nitride for Visible-Light-Driven Water Oxidation.

Direct water oxidation via photocatalysis is a four-electron and multiple-proton process which requires high extra energy input to produce free dioxygen gas, making it exacting, especially under visible light irradiation. To improve the oxygen evolution reaction rates (OERs) and utilize more visible light, flower-like cobalt hydroxide/oxide (Fw-Co(OH)2/Fw-Co3O4) photocatalysts were prepared and loaded onto graphitic carbon nitride (g-C3N4) by a facile coating method in this work. Influenced by the unique three-dimensional morphologies, the synthesized Fw-Co(OH)2 or Fw-Co3O4/g-C3N4 hybrids reveal favorable combination and synergism reflected by the modified photoelectric activities and the improved OER performances. Attributed to its prominent hydrotalcite structure, Fw-Co(OH)2 shows better cocatalytic activity for g-C3N4 modification compared with that of Fw-Co3O4. Specifically, 7 wt % Fw-Co(OH)2/g-C3N4 photocatalyst exhibits photocurrent density 4 times higher and OER performance 5 times better than pristine g-C3N4. This work unambiguously promotes the application of sustainable g-C3N4 in water oxidation.

Design of Perovskite Oxides as Anion-Intercalation-Type Electrodes for Supercapacitors: Cation Leaching Effect.

Oxygen ions can be exploited as a charge carrier to effectively realize a new type of anion-intercalation supercapacitor. In this study, to get some useful guidelines for future materials development, we comparatively studied SrCoO3-δ (SC), Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF), and Co3O4 as electrodes in supercapacitors with aqueous alkaline electrolyte. The effect of interaction between the electrode materials with the alkaline solution was focused on the structure and specific surface area of the electrode material, and ultimately the electrochemical performance was emphasized. Both BSCF and SC were found to experience cation leaching in alkaline solution, resulting in an increase in the specific surface area of the material, but overleaching caused the damage of perovskite structure of BSCF. Barium leaching was more serious than strontium, and the cation leaching was component dependent. Although high initial capacitance was achieved for BSCF, it was not a good candidate as intercalation-type electrode for supercapacitor because of poor cycling stability from serious Ba(2+) and Sr(2+) leaching. Instead, SC was a favorable electrode candidate for practical use in supercapacitors due to its high capacity and proper cation leaching capacity, which brought beneficial effect on cycling stability. It is suggested that cation leaching effect should be seriously considered in the development of new perovskite materials as electrodes for supercapacitors.

Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater.

The increasing concerns on toxicity of sulfonamide antibiotics in water require a prompt action to establish efficient wastewater treatment processes for their removal. In this study, adsorptive removal of a model sulfonamide antibiotic, sulfachloropyridazine (SCP), from wastewater is presented for the first time using a metal organic framework (MOF). A high surface area and thermally stable MOF, HKUST-1, was synthesized by a facile method. Batch adsorption studies were systematically carried out using HKUST-1. The high surface area and unsaturated metal sites resulted in a significant adsorption capacity with faster kinetics. Most of the SCP was removed in 15min and the kinetic data were best fitted with the pseudo second order model. Moreover, isothermal data were best fitted with the Langmuir model. The thermodynamic results showed that the adsorption is a spontaneous and endothermic process. The adsorption capacity of HKUST-1 is 384mg/g at 298K which is the highest compared to most of the materials for the antibiotics. The high adsorption capacity is attributed mainly to π-π stacking, hydrogen bonding and electrostatic interactions.