Electron-exchange processes on simple columns of kel-f supporting tetrachlorohydroquinone

The preparation of simple electron-exchange columns is reported. An organic porous material (Kel-F powder) is used to support a water-insoluble redox reagent. Of the organic compounds tested, tetrachlorohydroquinone was best. Very stable columns were obtained with a sufficiently high redox capacity (1.59 $\text{meq}\text{g}$ dry material) and a satisfactory reaction rate.The following oxidation reactions were carried out: Fe²⁺→Fe³⁺, Cu⁺→Cu²⁺, Sn²⁺→Sn⁴⁺, I^-→I,ascorbic acid → dehydroascorbic acid, as well as the following reduction reactions: Fe³⁺→Fe²⁺, I→I^-, Ce⁴⁺→Ce³⁺, V⁵⁺→V⁴⁺, Cr⁶⁺→Cr³⁺. The effect of hydrogen ion concentration on the redox reactions was also studied.The Kel-F-tetrachlorohydroquinone columns can be used for indirect titration of redox systems and for selective oxidations or reductions, e.g. Fe³⁺ in presence of Fe²⁺ and vice versa, Cr⁶⁺ in presence of Fe³⁺, Ce⁴⁺ in presence of Ce³⁺, ascorbic acid in the presence of glucose, and Sn²⁺ in presence of Sn⁴⁺ or Fe²⁺.     

Hollow Nanotube Ru/Cu2+1O Supported on Copper Foam as a Bifunctional Catalyst for Overall Water Splitting

Hydrogen energy is considered as one of the ideal clean energies for solving the energy shortage and environmental issues, and developing highly efficient electrocatalysts for overall water splitting to produce hydrogen is still a huge challenge. Herein, for the first time, Ru-doped Cu₂₊₁O vertically arranged nanotube arrays in situ grown on Cu foam (Ru/Cu₂₊₁O NT/CuF) are reported and further investigated for their catalytic properties for overall water splitting. The Ru/Cu₂₊₁O NT/CuF presents ultrahigh catalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline conditions, and it exhibits a small overpotential of 32 mV at 10 mA cm⁻² in the HER, and only needs 210 mV overpotential to achieve a current density of 10 mA cm⁻² in the OER. Importantly, the alkaline electrolyzer using Ru/Cu₂₊₁O NT/CuF as a bifunctional electrocatalyst only needs 1.53 V voltage to deliver a current density of 10 mA cm⁻², which is much lower than the benchmark of IrO₂(+)/Pt(−) counterpart (1.64 V at 10 mA cm⁻²). The excellent performance of the Ru/Cu₂₊₁O NT/CuF catalyst is attributed to its high conductive substrate and special Ru-doped nanotube structure, which provides a high electrochemical active surface area and 3D gas diffusion channel.     

Wurtzite CuGaS2 with an In-Situ-Formed CuO Layer Photocatalyzes CO2 Conversion to Ethylene with High Selectivity

We present surface reconstruction-induced C−C coupling whereby CO₂ is converted into ethylene. The wurtzite phase of CuGaS_2. undergoes in situ surface reconstruction, leading to the formation of a thin CuO layer over the pristine catalyst, which facilitates selective conversion of CO₂ to ethylene (C₂H₄). Upon illumination, the catalyst efficiently converts CO₂ to C₂H₄ with 75.1 % selectivity (92.7 % selectivity in terms of R_electron) and a 20.6 μmol g⁻¹ h⁻¹ evolution rate. Subsequent spectroscopic and microscopic studies supported by theoretical analysis revealed operando-generated Cu²⁺, with the assistance of existing Cu⁺, functioning as an anchor for the generated *CO and thereby facilitating C−C coupling. This study demonstrates strain-induced in situ surface reconstruction leading to heterojunction formation, which finetunes the oxidation state of Cu and modulates the CO₂ reduction reaction pathway to selective formation of ethylene.     

Unraveling the reversible formation of defective Ce3+ sites in the UiO-66(Ce) material: a multi-technique study

Ce³⁺ presence and formation in Ce-based UiO-66 Metal-Organic Framework (MOF) still presents a debated evaluation between the employed characterization techniques. In this work, we have prepared a defective UiO-66(Ce) and investigated the nature of Ce³⁺ sites on the CeO_x clusters. Laboratory techniques (EPR, XPS, UV–Vis and FTIR spectroscopy) were compared with operando Ce M₅-edge NEXAFS to study Ce³⁺ accessibility. All the employed techniques presented different degrees of accessibility or reliability (e.g., sample damage or not sufficient sensitivity). Among the obtained results, EPR, UV–Vis and NEXAFS spectroscopies unraveled Ce⁴⁺→Ce³⁺ conversion during the sample dehydration. The MOF structure was not damaged by neither water loss nor the beam, directly relating Ce oxidation state to the water content, opening a new route to both synthesis of stable and active MOFs and non-invasive characterization strategies. Finally, laboratory measurements considerations were exploited for studying Ce³⁺ formation in Zr-doped UiO-66(Ce) samples.     

Naked-eye detection of Cu (II) and Fe (III) based on a Schiff Base Ruthenium complex with nicotinohydrazide

A cyclometalated ruthenium (II) complex 1 [(Ru (Phen)₂(Pbznh)]⁺ PF₆⁻ (Phen = 1,10-phenanthroline and Pbznh = N-(4-(pyridine-2-yl)benzylidene) nicotinohydrazide) with nicotinohydrazide as a functional group was synthesized and characterized. Changes of its absorption spectra and color induced by Cu²⁺ and Fe³⁺ were systematic investigated. The results demonstrated that complex 1 could be served as a colorimetric probe to fast, selective and sensitive detection of Cu²⁺ and Fe³⁺ both in acetonitrile and filter paper based strips. Upon addition of Cu²⁺ and Fe³⁺ to solution of probe 1 , solution color changed from pink to colorless and light yellow respectively, and their corresponding detection limit were calculated to be 3.26 × 10⁻⁸ M and 3.12 × 10⁻⁷ M. Moreover, color of test papers with 1 changed from pink to colorless/yellow when Cu²⁺/Fe³⁺ were dropwise added. Therefore, it can be used as a desirable ‘naked-eye’ indicator candidate for Cu²⁺ and Fe³⁺.     

Construction of Cu-Ce interface for boosting toluene oxidation: Study of Cu-Ce interaction and intermediates identified by in situ DRIFTS

A facile hydrothermal method was applied to gain stably and highly efficient CuO-CeO₂ (denoted as Cu1Ce2) catalyst for toluene oxidation. The changes of surface and inter properties on Cu1Ce2 were investigated comparing with pure CeO₂ and pure CuO. The formation of Cu-Ce interface promotes the electron transfer between Cu and Ce through Cu²⁺ + Ce³⁺ ↔ Cu⁺ + Ce⁴⁺ and leads to high redox properties and mobility of oxygen species. Thus, the Cu1Ce2 catalyst makes up the shortcoming of CeO₂ and CuO and achieved high catalytic performance with T₅₀ = 234 °C and T₉₉ = 250 °C (the temperature at which 50% and 90% C₇H₈ conversion is obtained, respectively) for toluene oxidation. Different reaction steps and intermediates for toluene oxidation over Cu1Ce2, CeO₂ and CuO were detected by in situ DRIFTS, the fast benzyl species conversion and preferential transformation of benzoates into carbonates through C=C breaking over Cu1Ce2 should accelerate the reaction.     

Catalysis of photoelectrochemical reactions: II. Catalytic behaviors of Ir needles deposited on n-TiO2 electrode

The competitive photo-oxidation of Ce³⁺ on the surface of n-TiO₂ electrode before and after deposition of porous Ir-needles was studied by using rotating ring-disc electrode with interchangeable disc. It was found that highly dispersed porous layer composed of Ir needles could catalyse the photo-oxidation of Ce³⁺. Basic postulates of catalyst of photoelectrochemical reactions were discussed.     

Imaging of Oxygen Diffusion in Individual Platinum/Ce2Zr2Ox Catalyst Particles During Oxygen Storage and Release

The spatial distribution of Ce³⁺ and Ce⁴⁺ in each particle of Ce₂Zr₂O_x in a three‐way conversion catalyst system was successfully imaged during an oxygen storage/release cycle by scanning X‐ray absorption fine structure (XAFS) using hard X‐ray nanobeams. For the first time, nano‐XAFS imaging visualized and identified the modes of non‐uniform oxygen diffusion from the interface of Pt catalyst and Ce₂Zr₂O_x support and the active parts in individual catalyst particles.     

Enhancing Photoactivity of TiO2(B)/Anatase Core–Shell Nanofibers by Selectively Doping Cerium Ions into the TiO2(B) Core

Cerium ions (Ce³⁺⁾ can be selectively doped into the TiO₂(B) core of TiO₂(B)/anatase core–shell nanofibers by means of a simple one‐pot hydrothermal treatment of a starting material of hydrogen trititanate (H₂Ti₃O₇) nanofibers. These Ce³⁺ ions (≈0.202 nm) are located on the (110) lattice planes of the TiO₂(B) core in tunnels (width≈0.297 nm). The introduction of Ce³⁺ ions reduces the defects of the TiO₂(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce³⁺/Ce⁴⁺ couple (E°(Ce³⁺/Ce⁴⁺)=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO₂(B). Therefore, once the Ce³⁺‐doped nanofibers are irradiated by UV light, the doped Ce³⁺ ions—in close vicinity to the interface between the TiO₂(B) core and anatase nanoshell—can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge‐separation mechanism accelerates dye degradation and alcohol oxidation processes. The one‐pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co^2+/3+ and Cu^+/2+ ions. The doping substantially improves the photocatalytic activity of the mixed‐phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn²⁺, Ca²⁺, or Mg²⁺, does not enhance the photoactivity of the mixed‐phase nanofibers as the ions could not trap the photogenerated holes.     

Diffusion of Cu2+ catalysts from Cu-metal polymer or Cu-oxide/polymer interfaces into isotactic polypropylene

Diffusion coefficients of Cu²⁺ in the form of its carboxylate have been measured in isotactic polypropylene as a function of temperature (90–128°C) and extent of preoxidation. Diffusion take place from the metal catalyst/polymer interface into the bulk polymer. The diffusion is dependent on the extent of preoxidation and temperature but not on the type of catalyst (Cu, CuO, CuO_0.67). Analysis of polymer sections for Cu²⁺ ions was carried out with a selective Cu²⁺ electrode. Diffusion in isotactic polypropylene is about 1000 times faster than in lowdensity polyethylene. The carboxylate anion appears to have about 7 C-atoms for diffusion in isotactic polypropylene compared with 29 C-atoms for low-density polyethylene.     

Cu–Ce substituted cobalt nano ferrite - Structural,morphological, and magnetic behavior prepared by sol-gel auto-combustion

Sol-gel auto-combustion synthesized Co_1-xCu_xFe_2-yCe_yO₄ (x = 0.0, 0.25, 0.5 and 0.75; y = 0.0, 0.03, 0.06, and 0.09), Cu–Ce substituted Co ferrite nanopowders. Investigations have been done on how Cu–Ce substitution affects the structural and magnetic characteristics. The Cu–Ce substitution variation effect on structural and magnetic properties is studied with X-ray diffraction (XRD), Field effect scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and Vibrating sample magnetometer (VSM). The XRD was used to identify the crystal phase, and the role of Cu–Ce substituted for Co indicates how it formed. There is no change in the crystal structure, and no additional characteristic peak linked to Cu²⁺ and Ce³⁺ ions substitution was found in the XRD. The powder was sintered at 1100 °C. The crystallite sizes were found in between 33 and 62 nm. Increasing the Cu–Ce content decreases the lattice constant and is found between 8.4044 and 8.3309 Å. The FESEM images were used to analyze the nanostructural properties. The range of 110–128 nm is the value of average grain size. Two vibrational bands can be seen in FTIR spectra at about 600 cm⁻¹ (v₁) and 400 cm⁻¹ (v₂). They are attributed to the spinel lattices A and B sites, respectively. The tetrahedral site has a greater vibrational frequency of 566.09 cm^−1, while the octahedral site has a lower vibrational frequency of 420.09 cm⁻¹. FTIR spectra show the tetrahedral stretching peaks shifting towards lower frequencies with increasing Cu²⁺ and Ce³⁺ ions content. At ambient temperature, the magnetic properties of Cu–Ce substituted cobalt ferrites revealed a strong hysteresis loop. There was a decrease in magnetic saturation and an increase in coercivity.     

Synthesis,Structure, and Photoluminescence Properties of Novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+ Phosphors for White‐Light‐Emitting Diodes

A series of novel KBaSc₂(PO₄)₃:Ce³⁺/Eu²⁺/Tb³⁺phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce³⁺‐ and Eu²⁺‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc₂(PO₄)₃:Eu²⁺ and KBaSc₂(PO₄)₃:Ce³⁺ phosphors with Tb³⁺ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu²⁺ and Tb³⁺ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu²⁺→Tb³⁺ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc₂(PO₄)₃:Eu²⁺,Tb³⁺ and KBaSc₂(PO₄)₃:Ce³⁺,Tb³⁺ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.     

Selective CO2 Reduction to Ethylene Mediated by Adaptive Small-molecule Engineering of Copper-based Electrocatalysts

Electrochemical CO₂ reduction reaction (CO₂RR) over Cu catalysts exhibits enormous potential for efficiently converting CO₂ to ethylene (C₂H₄). However, achieving high C₂H₄ selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO₂RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu-based material to a pathway that facilitates CO₂ reduction to C₂H₄ products. An excellent Faraday efficiency (FE) of 63.6 % on C₂H₄ with a current density of 497.2 mA cm⁻² in flow cell was achieved, about 6.5 times higher than the pristine Cu catalyst which mainly produce CH₄. The in situ X-ray absorption spectroscopy and Raman studies reveal that the hydroxyl group in TA stabilizes Cu^δ+ during the CO₂RR. Furthermore, theoretical calculations demonstrate that the Cu^δ+/Cu⁰ interfaces lower the activation energy barrier for *CO dimerization, and hydroxyl species stabilize the *COH intermediate via hydrogen bonding, thereby promoting C₂H₄ production. Such molecule engineering modulated electronic structure provides a promising strategy to achieve highly selective CO₂ reduction to value-added chemicals.     

Determination of Cu2+ in Drinking Water Based on Electrochemiluminescence of Ru(phen)32+ and Cyclam

A convenient and simple electrochemiluminescence (ECL) method was employed to detect trace amounts of Cu²⁺ in drinking water. This method is based on the inhibitory effect of Cu²⁺ on the ECL of Ru(phen)₃²⁺ and 1,4,8,11‐tetraazacyclotetradecane (cyclam) system. ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of cyclam because of the ECL reaction between them. The ECL intensity of Ru(phen)₃²⁺/cyclam system rapidy decreased with the addition Cu²⁺ because of the formation of chelate complex [Cu(cyclam)]²⁺. Good linear response (R ²=0.9948) was obtained at Cu²⁺ concentration of 1.0×10⁻⁹−1.0×10⁻⁵ mol ⋅ L⁻¹ at glassy carbon electrode in 0.1 mol ⋅ L⁻¹ phosphate buffer (pH 9.0). Observed detection limit of 4.8×10⁻¹⁰ mol ⋅ L⁻¹ satisfied the maximum contaminant level goal (MCLG) for Cu²⁺ set by the US Environmental Protection Agency (US EPA). Applicability of the proposed method was verified by the good reproducibility and stability of the method when applied to determine Cu²⁺ in tap water and simulated wastewater. Thus, a novel ECL detection method was developed for Cu²⁺ detection.     

Synthesis and optical studies of novel Eu2+ and Ce3+ doped BaMg8Al18Si18O72 phosphors

Novel Eu²⁺ and Ce³⁺ activated BaMg₈Al₁₈Si₁₈O₇₂ phosphors was prepared by combustion method and their PL characteristics were investigated. The result shows that all samples can be excited efficiently by near UV excitation under 334 nm and 316 nm. The emission was observed for BaMg₈Al₁₈Si₁₈O₇₂:Eu²⁺ phosphor at 437 nm corresponding to d → f transition, under 334 nm broad-band excitation, whereas BaMg₈Al₁₈Si₁₈O₇₂:Ce³⁺ phosphor shows emission band at 376 nm under 316 nm excitation. Phase purity of the phosphor was checked with the help of XRD pattern. SEM analysis shows the external morphology of the combustion synthesized phosphor.     

Electrochemical Detection of Acetaminophen with Silicon Nanowires

Acetaminophen (APAP) is an antipyretic, analgesic agent, the overdose of which during medical treatment poses a risk for liver failure. Hence, it is important to develop methods to monitor physiological APAP levels to avoid poisoning. Here, we report an efficient, selective electrochemical APAP sensor made from depositing silicon nanowires (SiNWs) onto glassy carbon electrodes (GCEs). Electrocatalytic activity of the SiNW/GCE sensors was monitored under varying pH and concentrations of APAP using cyclic voltammetry (CV) and chronoamperometry (CA). CV of the SiNWs at 0.5 to 13 mmol dm⁻³ APAP concentrations was used to determine the oxidation and reduction potentials of APAP. The selective detection of APAP was then demonstrated using CA at +0.568 V vs Ag/AgCl, where APAP is fully oxidized, in the 0.01 to 3 mmol dm⁻³ concentration range with potentially‐interfering analytes. The SiNW sensor has the ability to detect APAP well within the detection limits for APAP toxicity, showing promise as a practical biosensor.     

Catalytic NO Reduction by NO Pre-Adsorbed RhCeO2NO− Clusters

A fundamental understanding on the dynamically structural evolution of catalysts induced by reactant gases under working conditions is challenging but pivotal in catalyst design. Herein, in combination with state-of-the-art mass spectrometry for cluster reactions, cryogenic photoelectron imaging spectroscopy, and quantum-chemical calculations, we identified that NO adsorption on rhodium-cerium bimetallic oxide cluster RhCeO₂⁻ can create a Ce³⁺ ion in product RhCeO₂NO⁻ that serves as the starting point to trigger the catalysis of NO reduction by CO. Theoretical calculations substantiated that the reduction of another two NO molecules into N₂O takes place exclusively on the Ce³⁺ ion while Rh behaves like a promoter to buffer electrons and cooperates with Ce³⁺ to drive NO reduction. Our finding demonstrates the importance of NO in regulating the catalytic behavior of Rh under reaction conditions and provides much-needed insights into the essence of NO reduction over Rh/CeO₂, one of the most efficient components in three-way catalysts for NO_x removal.     

Emergence of a Lanthanide Chalcogenide as an Ideal Scintillator for a Flexible X-ray Detector

The development of high-performance X-ray detectors requires scintillators with fast decay time, high light yield, stability, and X-ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS₄ : 1 % Ce³⁺ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS₄ : 1 % Ce³⁺ demonstrates a remarkably low detection limit of 43.13 nGy_air s⁻¹ and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS₄ : 1 % Ce³⁺ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide-based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X-ray imaging capacity of LaCsSiS₄ : 1 % Ce³⁺, we fabricated a flexible X-ray detector that achieved a high spatial resolution of 8.2 lp mm⁻¹. This work highlights the potential of lanthanide chalcogenide as a promising candidate for high-performance scintillators.     

A Highly Sensitive and Selective Fluorescence Chemosensor for Cu2+ and Zn2+ Based on Solvent Effect

A novel fluorescence chemosensor 1 based on (R)‐binaphthyl‐salen can exhibit highly sensitive and selective recognition responses toward Cu²⁺ by "turn‐off" fluorescence quench type in THF/H₂O, and Zn²⁺ by "turn‐on" fluorescence enhancement type in CHCl₃/CH₃CN, respectively, suggesting that solvents can dramatically affect the responsive properties of salen‐based chemosensor. In addition, Cu²⁺ can lead to the most pronounced changes of CD spectra without the influence of solvents, which indicates this kind chemosensor can also be used as a sole Cu²⁺ probe based on CD spectra.