Active Metal Research Articles

Reuse and Recovery of Water from Industrial Textile Dyeing Effluent Using High-Performance Electrodes Continuous Flow Electrocoagulation Reactor

The dye effluents released from the textile and printing industries contain strong colorants, inorganic salts, and other toxic compounds. The conventional coagulation technique of dye effluent treatment is plagued with issues of low removal rate of color, generation of large quantities of sludge, and toxic end-products. Recently electrocoagulation technique gained immense attention due to its high efficiency. This technique involves the dissolution of the sacrificial anodes to provide an active metal hydroxide as a strong coagulant that destabilizes the pollutants and removes them by precipitation or flocculation. This study is about the efficiency of the electrocoagulation process using titanium coated - aluminum and mild steel electrodes to treat industrial dye wastewater. Effects of parameters such as current density & initial dye concentration were investigated. It was observed that, for the same current density, electrode consumption was higher with TiO2/Al electrode than with mild steel electrode, resulting in more color removal efficiency (CRE) using TiO2/Al electrode. The settling rate of the flocs was higher in the rector having TiO2/Al electrode at the 100 mL with current density (2.5 mL.min-1 to 5.3 mL.min-1), while in the reactor with mild steel electrode, the settling rate was very less. The results showed that dye removal was 95.11% and 92.1% for mild steel and titanium-coated electrodes, respectively. It was observed that 50 % of Aluminum was removed from the treated effluent after the final stage of filtration. Based on the multicriteria analysis to identify the optimum operational parameters to be applied at the field level, it was observed that maximum CRE may be obtained with TiO2/Al electrode and the applied current of 1 Amps with a flow rate of 100 mL.min-1. It can be concluded that electrocoagulation is a highly efficient and the fastest method to treat dye effluents from industries.

Synthesis of bentonite-supported Ni, La, and Ca catalysts for hydrogen production through steam reforming of acetic acid

In this study, the production of hydrogen-rich gas through the steam reforming of acetic acid using bentonite-supported catalysts was investigated. Bentonite was treated by washing and calcination. Bentonite-supported Ni, Ca, La, Ni–La, and Ni–Ca catalysts with different active metal loadings of 10 and 30 wt% were synthesized using the wet impregnation method. The catalysts were characterized using XRD, XRF, SEM, EDS, BET, FT-IR, NH3-TPD, and Raman. The activity tests of the catalysts were carried out in a continuous flow tubular reactor at various temperatures (500, 600, 700, and 800 °C). Product gas composition was determined by gas chromatography (μ-GC). The effect of bentonite treatment, active metal type, and bimetallic combinations (Ni/Bent, Ni/Bent*, La/Bent, Ca/Bent, Ni–La/Bent, and Ni–Ca/Bent) were studied. The highest hydrogen yield obtained without a catalyst was 8.61% at 700 °C. This yield increased to 74.5% at 600 °C with 30 wt% Ni–La/Bentonite, and to 42.6% with 30 wt% Ni/Bentonite catalysts, respectively. The experimental results show that bentonite has a suitable catalytic activity on its own and is a promising support material for the steam reforming of acetic acid.

One-step synthesis of Pt@(CrMnFeCoNi)3O4 high entropy oxide catalysts through flame spray pyrolysis

High entropy oxides (HEOs) show great prospects in catalysis owing to their widely tunable component structures and ease of combination with active metals. However, the development of HEO catalysts is limited by the lack of efficient synthesis methods due to the difficulty of homogeneously mixing at least five elements. In this work, flame spray pyrolysis (FSP) is successfully employed to synthesize (CrMnFeCoNi)3O4 HEO with a single phase spinel structure in one step, which is verified by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and energy-dispersive X-ray spectroscopy (EDS). Taking CO catalytic oxidation as a probe reaction, the Pt@(CrMnFeCoNi)3O4 HEO catalyst synthesized by FSP in one step is compared with the catalyst whose Pt is impregnated on (CrMnFeCoNi)3O4 HEO support. The FSP-made catalysts have a higher catalytic reaction rate and better redox ability, which lowers the temperature of complete CO conversion by nearly 100 °C. Furthermore, it can be observed that the flame parameters can be optimized to modify the particle size and oxygen vacancies of the HEO nanoparticles, thus enhancing the catalytic performances. This work demonstrates that FSP is an effective method for the one-step synthesis of HEO catalysts with excellent catalytic performance, providing a new perspective for the synthesis of HEO-based materials.

Co and F co-doping to augmenting the electrochemical performance of P2-type sodium lithium manganese oxide for sodium ion battery

P2-type sodium lithium manganese oxide is recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, its practical application has been hindered by poor cycling performance and limited rate capacity. In this study, we successfully co-doped cobalt (Co) and fluorine (F) into P2-type sodium lithium manganese oxide, resulting in the enhanced material CoF-NLM, which significantly improves its electrochemical performance. The CoF-NLM material exhibits several advantageous characteristics: (i) a notable increase in lattice constant and lattice cell volume, which facilitates the intercalation and deintercalation of sodium ions within its bulk structure; (ii) an enhanced surface morphology that promotes better contact between the electrode and the electrolyte; and (iii) an increased Mn3+/Mn4+ ratio, which enhances the number of active transition metal centers available for electrochemical reactions. As a result, the CoF-NLM sample demonstrates exceptional electrochemical performance, boasting a specific capacity of 135.51 mAh/g at a current density of 8 mA g−1 and maintaining an impressive 92.69 % capacity retention after 100 cycles. This study conclusively demonstrates that ion doping is a highly effective strategy for enhancing the electrochemical performance of cathode electrode materials in SIBs; paving the way for the development of high-energy, high-power SIBs that can meet the demands of next-generation energy storage applications.

Cerium-optimized platinum-free high-entropy alloy nanoclusters for enhanced ampere-level sustainable hydrogen generation

The incorporation of rare earth (RE) elements into high-entropy alloys (HEAs) as electrocatalysts for hydrogen evolution reaction (HER) shows great potential in addressing the energy crisis. Here, we successfully synthesized cerium (Ce)-tailored PdCeMoCuRu HEA with chemical homogeneity and stability using a facile wet-chemical synthesis strategy. The obtained PdCeMoCuRu HEA provides abundant active metal sites, resulting in superior HER performance compared to state-of-the-art Pt/C. It only requires 12.8 mV to achieve a current density of 10 mA cm−2, which is nearly half that required for Pt/C (24.8 mV). Importantly, it exhibits excellent electrocatalytic durability for 100 hours even under a high current density of 1.0 A cm−2 at the ampere level. Density functional theory (DFT) calculations confirm that the introduction of Ce can modify the electronic configuration and generate synergistic effects around Pd, Cu, and Ru active sites. This work establishes a novel approach for designing efficient RE-tailored HEA electrocatalysts.

Modulating the electronic structure of PdCoP nanonetworks alloy for efficient electro-catalysis of methanol oxidation

Modulating the d-orbital electronic structure of active metals by doping heteroatoms is efficient for the electro-catalysis of methanol oxidation reaction (MOR). However, precise doping hybrid atoms into the lattices of alloy catalysts remains challenging. Herein, the selected doping of electron-rich P atoms at the active site of Pd was achieved by hydrothermal reduction. We found that P atoms prefer to bond Pd atoms, thus tuning the electronic structure of active sites in PdCoP alloy. Consequently, the tailored PdCoP catalyst exhibited remarkable mass activity of 2.13 A mgPd−1 towards MOR, which surpasses most reported Pd-based alloy nanocatalysts. Theoretical calculations revealed that the tailored d-band center of Pd in PdCoP catalyst exhibited moderate adsorption of CO and OH intermediates, thus maximizing the MOR performance. The current work highlights the fabrication of P-doped Pd-based catalysts for realizing high MOR, which can be further extended to other energy-related applications.

Dry Reforming of Methane to Syngas Mediated by Rhodium-Cobalt Oxide Cluster Anions Rh2CoO.

Dry reforming of methane (DRM) to syngas is an important route to co-convert CH4 and CO2. However, the highly endothermic nature of DRM induces the thermocatalysis to commonly operate at high temperatures that inevitably causes coke deposition through pyrolysis of methane. Herein, benefiting from the mass spectrometric experiments complemented with quantum chemical calculations, we have discovered that the bimetallic oxide cluster Rh2CoO- can mediate the co-conversion of CH4 and CO2 at room temperature giving rise to two free H2 molecules and two adsorbed CO molecules (COads). The only elementary step requiring the input of external energy (e.g., high temperature) is desorption of COads from the reaction intermediate Rh2CoOC2O2-. The doping effect of Co has also been clarified that the Co could tune the charge distribution and orbital energy of the active metal Rh, enabling the enhancement of cluster reactivity toward C-H activation, which is essential to facilitating the DRM to syngas. This work not only underlines the importance of temperature control over elementary steps in practical thermocatalysis but also identifies a promising active species containing the late 3d transition metal to drive DRM to syngas. The findings could provide novel insights into design of bimetallic catalysts for co-conversion of CH4 and CO2 at low temperatures.

Scaling Up Stability: Navigating from Lab Insights to Robust Oxygen Evolution Electrocatalysts for Industrial Water Electrolysis

AbstractIn the pursuit of sustainable hydrogen production via water electrolysis, paramount importance of electrocatalyst stability emerges as a defining factor for long‐term industrial viability. A thorough understanding and enhancement of stability not only ensure extended catalyst lifetimes but also pave the way for consistent and efficient hydrogen generation. This review focuses on the pivotal role of stability in determining the practical viability of oxygen evolution electrocatalysts (OECs) for large‐scale applications in water electrolysis for hydrogen production. The paper explores the pivotal role of stability over initial activity, citing examples and hypothetical scenarios. First, figures of merits for stability evaluation of the electrocatalyst are explained along with the available benchmarking protocols for stability evaluation. Further, the text delves into various strategies that can enhance the stability of the electrocatalyst which include self‐healing/regeneration pathway, oxygen evolution reaction (OER) mechanism optimization to achieve highly stable OER and stabilization of active metals atoms within the electrocatalyst to inhibit dissolution as a way forward for industrial application. The interplay of stability, activity, and cost is also explained to suit the industrial application of the electrocatalyst. Lastly, it outlines challenges, prospects, and future directions, presenting a guide for advancing OECs in the hydrogen generation landscape.

Thermal and cyclic performance of aluminum alloy composite phase change microcapsules for high-temperature thermal energy storage

Al alloys are suitable for high-temperature applications such as solar thermal power generation and industrial heat utilization. However, addressing the challenges of high-temperature corrosion and material failure in Al alloys is of paramount importance. In practical industrial applications, there is a need to develop encapsulation techniques applicable to a wider range of Al alloy types and phase change temperature ranges, exploring the universality of the technology and the diversity of application scenarios. In this study, a dual encapsulation was conducted on binary and ternary Al alloys (including Al-Ni, Al-Mg, Al-Si-Mg, and Al-Mg-Zn). Aiming at thermal energy storage, four composite phase change microcapsules (CPCM) were successfully prepared and subjected to material characterization, thermal performance analysis, and thermal cyclic tests in air environments. After 2000 thermal cycles, no cracks were observed on the surface of the four CPCMs, and the microstructure remained intact. The components of the CPCMs maintained good chemical compatibility. Among the four types of CPCMs, the Al-Si-Mg CPCMs exhibited the best thermal cyclic stability, with a latent heat reduction rate of 19.5 % after 2000 cycles. The experimental results indicated that the dual encapsulation strategy was effective for various types of Al alloy PCMs, thereby expanding the application of Al alloys in high-temperature thermal storage. Furthermore, Al alloys with more regular morphology and lower active metal content exhibited better thermal performance and cyclic capability, making them more suitable candidates for high-temperature thermal storage applications.

Cu0·1In0·01/S-1 catalysts with high efficiency towards methanol steam reforming

Cu0·1/S-1, Cu0·1Zn0·01/S-1, Cu0.1Inx/S-1 (x = 0.01, 0.03, 0.05) and Cu0·1Ce0·01/S-1 were successfully prepared with S-1 as the carrier material and applied to methanol steam reforming (MSR) reaction. To further explore its chemical and physical properties, XRD, BET, SEM-EDS, ICP, FTIR, H2-TPR, NH3-TPD, CO2-TPD, and Raman were used to characterize the synthetic S-1 zeolite catalysts. The measured physicochemical properties revealed that utilizing S-1 zeolite as the carrier effectively altered the size of the metal particles, enhancing their dispersion and reduction characteristics. Compared with five different types of S-1 zeolite catalysts, the Cu0·1In0·01/S-1 catalyst has a large specific surface area and pore size. It exhibited superior active metal dispersion, with the lowest reduction temperature for the active metal CuO. The catalyst also showed a high Lewis acid content on its surface, forming the In-Lewis acid site. Consequently, the Cu0·1In0·01/S-1 catalyst exhibits exceptional performance in methanol steam reforming for hydrogen production reactions. It exhibited the best performance with a methanol conversion rate of 100%, H2 selectivity of 100% under the conditions of 1 MPa, 250 °C, the S/C molar ratio of 2.5, and the WHSV of 0.5 h−1, which outperforms most of the reported catalysts in methanol steam reforming.© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Rational design of titanium-doped Y zeolite for hydrodenitrogenation of aromatic N-heterocyclic compounds

Ti modified Y zeolites with different Ti content were synthesized by in-situ hydrothermal crystallization method and used as the support of hydrodenitrogenation (HDN) catalyst. The forms of Ti species in the zeolites and the effect of Ti incorporation on the active metal states of the corresponding catalysts were investigated by XRD, UV–Vis DRS, XPS, HAADF-STEM, ICP-OES, Py-FTIR, H2-TPR, HRTEM, and DFT calculation. The results show that the incorporation of in-situ Ti species into Y zeolite led to a decrease in the Brønsted acid sites (BAS) /Lewis acid sites (LAS) value of the corresponding catalyst, but effectively enhanced the stacking layer number of the WS2 active phase by weakening the interaction between the active metals and the supports, which is manifested in the improvement of the hydrogenolysis activity and the decrease of the hydrogenation activity of the catalyst. When the hydrogenolysis activity and hydrogenation activity in the catalyst match to a certain extent, that is, the BAS/LAS value and the stacking layer number of the active phase reach an appropriate value, the HDN catalyst exhibited the highest catalytic activity. The NiW/Y-0.1Ti catalyst with suitable amount of BAS and stacking layer number of active phase showed the maximum kHDN values (11.7 × 10-4 mol·g−1·h−1 and 3.9 × 10-4 mol·g−1·h−1) and TOFs (1.91 h−1 and 1.04 h−1) of quinoline and indole HDN.

Wood-derived continuously oriented channels coupled with tunable built-in electric fields for efficient oxygen evolution

Interface engineering has emerged as a promising strategy for efficiently enhancing catalytic performance. Herein, we present a built-in electric field (BEF) strategy to assemble Co9S8/Ni3S2 heterojunctions confined in S-doped carbon matrix (SC) and anchored S-doped carbide wood framework (SCW). Leveraging BEF, Co-S-Ni charge transfer channels and the superior mass transfer properties inherent in wood’s unique structure, (Co9S8/Ni3S2)@SC/SCW exhibits a low overpotential of 220 mV at 50 mA cm−2, and remarkable stability. The experimental characterizations and theoretical simulation indicate that the constructed BEF can induce the directional transfer of electrons from Co9S8 to Ni3S2, which is beneficial for the adsorption of OH- owing to the electrostatic interaction, thereby promotes the formation of the highly active amorphous metal hydroxide oxides at lower OER potentials. This work provides a new perspective for exploring the design of energy storage and conversion catalysts based on renewable wood substrates.

Accelerated structural transformation of metal-organic frameworks via interfacial engineering for efficient oxygen evolution reaction

Most metal-organic frameworks (MOFs) undergo structural transformations during the oxygen evolution reaction (OER), prompting the development of more catalytically active metal oxyhydroxides. However, one of the biggest challenges still is managing the MOF reconstruction process. Here, we present an interface engineering strategy to encourage MOFs to structurally change into metal oxyhydroxides, which are more active in the OER process. By meticulous design, the NiSe/CoFc′ (CoFc-MOF, Fc′ = 1,1′-ferrocenecarboxylic acid) heterojunction was successfully constructed, exhibiting remarkable interface coupling effects. This characteristic not only facilitates efficient electron transfer from CoFc′ to NiSe, and accelerates the structural transformation process of CoFc′, but also activates more catalytic active sites. Compared to pure CoFc′, NiSe/CoFc′ exhibits enhanced structural transformation capability, occurring in a shorter time and at a lower voltage, with more catalytic sites being activated. Furthermore, the transformed NiSe/CoFc′ displays suprior catalytic activity with an overpotential of 227 mV at a current density of 100 mA cm−2, surpassing the single-component CoFc′. And the Faradaic efficiency of NiSe/CoFc′ is near to 99.6%. This approach offers a noval avenue for the levelheaded plan of non-precious metal electrocatalysts for water electrolysis, enabling the control of structural conversion through interface engineering.

Catalytic property and synergistic effect of the multi-active sites Pd/PdO/Er2O3/Cu2O/PdCu3 formed in situ on the surface of the tri-organometallic Pd(II)/Er(III)/Cu(II) film

Explaining the formation and synergistic effect in multi-active sites is a vital factor in designing a highly efficient catalyst. In this study, a series of new graphene oxide(GO) supported arylimine Pd(II), Pd(II)/Er(III), and Pd(II)/Cu(II), Pd(II)/Er(III)/Cu(II) (GO@A-Pchmba-Pd, GO@A-Pchmba-Pd0.1Er0.9, GO@A-Pchmba-Pd0.1Cu0.9, GO@A-Pchmba-Pd0.1Er0.4Cu0.5) catalytic films were fabricated using self-assembly. Among these catalysts, GO@A-Pchmba-Pd0.1Er0.4Cu0.5 exhibited the highest activity (TOF = 145,506 h−1) in Suzuki cross-coupling reaction with a good compatibility, but poor recycling stability. The catalytic film acted not only as a "reservoir" to supply the active sites, but "stabilizer" to stabilize the active species, which provided a research platform to gain deep insight into the truly active center. The synergistic effect in the truly active center containing Pd/PdO/Cu2O/Er2O3/PdCu3 was described as that: the electron transferred from GO to Pd/Er/Cu via ligand, and then the electron transferred from erbium to palladium or its oxide, or from erbium to copper or cuprous oxide and then to palladium, resulting in enhancing the more electronegative Pd and further promoting the activity. The aggregation of the active metals, the loss of the active metals, residues absorbed on the surface, some destroyed organometallic in film, and the reduced average pore size were the crucial reasons for the deactivation and instability.

Promoting metal oxides–zeolite electron interaction on MnCeOx/HY catalyst for boosting nitrogen oxides reduction

The MnOx-CeO2 metal oxides are considered as promising alternative catalysts for selective catalytic reduction with NH3 (NH3-SCR) to remove NOx due to its excellent low temperature performance. However, their strong oxidative ability can lead to NH3 over-oxidation, narrowing the active temperature range and reducing N2 selectivity. Moreover, their weak surface acidity hampers medium to high-temperature activity and alkali metal resistance. Hence, in this study, MnCeOx metal oxides were coupled with HY zeolite to create MnCeOx/HY, demonstrating excellent NH3-SCR performance. The high dispersion of metal oxides on the zeolite surface and their close integration promoted strong electron interaction, effectively reducing oxygen vacancies and surface adsorbed oxygen concentrations. Consequently, the oxidative ability of active metal oxides was appropriately weakened, suppressing undesirable side reactions. MnCeOx/HY also notably suppressed NO adsorption and nitrate formation, promoting the catalytic reaction solely through the E-R mechanism and enhancing N2 selectivity. The abundant strong acid sites on the zeolite surface facilitates NH3 adsorption at moderate to high temperatures, notably expanding the active temperature window. Furthermore, the acid sites of HY zeolite serve as sacrificial sites, preferentially reacting with alkali metals, thus exhibiting excellent resistance to alkali metal poisoning on MnCeOx/HY. Combining with the DFT results, the structure-activity relationships in this study also reveal the importance of the effective synergy between acid sites and redox sites for optimal catalytic performance, offering valuable insights into the development of highly active and alkali-resistant denitrification catalysts.

Calculation of the Rate Constants of Vacuum Residue Hydrogenation Reactions in the Presence of a Chrysotile/NiTi Nanocatalyst

The paper presents the results of an investigation into the kinetics of catalytic hydrogenation of vacuum residue at temperatures of 380, 400 and 420 °C and different durations, ranging from 30 to 70 min, using a nanocatalyst containing the active metals nickel and titanium supported on chrysotile. It was found that the yield of oils from 30 to 50 wt.% and tars from 12 to 18 wt.% increased with increasing temperatures and reaction times. A slight increase in the proportion of solids in the range of 2.0 to 6.0 wt.% is explained by the activity of the nanocatalyst used. In the study of the kinetics of vacuum residue hydrogenation, using the nanocatalyst developed by the authors, we were able to achieve a low yield of solids with a short contact time as well as a high yield of low-molecular-weight compounds such as oils and tars. To determine the kinetic parameters (rate constants and activation energies), Simpson’s integral method and a random search engine optimization method were used. High values of rate constants are characteristic of reactions in the formation of oils k1, tars k2 and asphaltenes k3 in the temperature range of 380–420 °C. The high values of the rate constants k1, k2 and k3 in the catalytic hydrogenation of the vacuum residue indicate the high reaction rate and activity of the nanocatalyst used. With an increase in temperature from 380 to 420 °C, the rate constant of the formation of gas products from vacuum residue and the conversion of asphaltenes into oils significantly increase, which indicates the accumulation of low-molecular-weight compounds in oils. The activation energy for reactions leading to the formation of oils, tars, asphaltenes, gas and solid products was 75.7, 124.8, 40.7, 205.4 and 57.2 kJ/mol, respectively. These data indicate that the processes of vacuum residue hydrogenation with the formation of oils and asphaltenes require the lowest energy inputs. Reducing the process temperature to increase the selectivity of the vacuum residue hydrogenation process when using the prepared nanocatalyst is recommended. The formation of oils at the initial stage plays a key role in the technology of the heavy hydrocarbon feedstock (HHF) hydrogenation process. Perhaps the resulting oils can serve as an additional solvent for high-molecular-weight products such as asphaltenes, as evidenced by the low activation energy of the process.

Enhanced CO2 Reduction on a Cu-Decorated Single-Atom Catalyst via an Inverse Sandwich M-Graphene-Cu Structure.

The highly active and selective electrochemical CO2 reduction reaction (CO2RR) can be exploited to produce valuable chemicals and fuels and is also crucial for achieving clean energy goals and environmental remediation. Decorated single-atom catalysts (D-SACs), which feature synergistic interactions between the active metal site (M) and an axially decorated ligand, have been extensively explored for the CO2RR. Very recently, novel double-atom catalysts (DACs) featuring inverse sandwich structures were theoretically proposed and identified as promising CO2RR electrocatalysts. However, the experimental synthesis of DACs remains a challenge. To facilitate the fabrication and to realize the potential of these novel DACs, we designed a D-SAC system, denoted as M1@gra+Cuslab. This system features a graphene layer with a vacancy-anchored SAC, all stacked on a Cu(111) surface, thereby embodying a Cu slab-supported inverse sandwich M-graphene-Cu structure. Using density functional theory calculations, we evaluated the stability, selectivity, and activity of 27 M1@gra+Cuslab systems (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, or Au) and showed five M1@gra+Cuslab (M = Co, Ni, Cu, Rh, or Pd) systems exhibit optimal characteristics for the CO2RR and can potentially outperform their SAC and DAC counterparts. This study offers a new strategy for developing highly efficient CO2RR D-SACs with an inverse sandwich structural moiety.

Hydrogen Production from Methanol Steam Reforming over Fe-Modified Cu/CeO2 Catalysts.

Fe-modified Cu catalysts with CeO2 support, prepared by the impregnation method, were subjected to physicochemical analysis and catalytic tests in the steam reforming of methanol (SRM). Physicochemical studies of the catalysts were carried out using the XRF, TEM, STEM-EDS, XRD, TPR and nitrogen adsorption/desorption methods. XRD, TEM studies and catalytic tests of the catalysts were carried out at two reduction temperatures, 260 °C and 400 °C, to determine the relationship between the form and oxidation state of the active phase of the catalysts and the catalytic properties of these systems in the SRM. Additionally, the catalysts after the reaction were analysed for the changes in the structure and morphology using TEM methods. The presented results show that the composition of the catalysts, morphology, structure, form and oxidation state of the Cu and Fe active metals in the catalysts and the reaction temperature significantly impact their activity, selectivity and stability in the SRM process. The gradual deactivation of the studied catalysts under SRM conditions could result from the forming of carbon deposits and/or the gradual oxidation of the copper and iron phases under the reaction conditions.

Luminescent photon-upconversion nanoparticles with advanced functionalization for smart sensing and imaging.

Photon-upconversion nanoparticles (UCNP) have already been established as labels for affinity assays in analog and digital formats. Here, advanced, or smart, systems based on UCNPs coated with active shells, fluorescent dyes, and metal and semiconductor nanoparticles participating in energy transfer reactions are reviewed. In addition, switching elements can be embedded in such assemblies and provide temporal and spatial control of action, which is important for intracellular imaging and monitoring activities. Demonstration and critical comments on representative approaches demonstrating the progress in the use of such UCNPs in bioanalytical assays, imaging, and monitoring of target molecules in cells are reported, including particular examples in the field of cancer theranostics.

Electronic and Structural Properties of Thin Iron Oxide Films on CeO2.

Modification of CeO2 (ceria) with 3d transition metals, particularly iron, has been proven to significantly enhance its catalytic efficiency in oxidation or combustion reactions. Although this phenomenon is widely reported, the nature of the iron-ceria interaction responsible for this improvement remains debated. To address this issue, we prepared well-defined model FeOx/CeO2(111) catalytic systems and studied their structure and interfacial electronic properties using photoelectron spectroscopy, scanning tunneling microscopy, and low-energy electron diffraction, coupled with density functional theory (DFT) calculations. Our results show that under ultrahigh vacuum conditions, Fe deposition leads to the formation of small FeOx clusters on the ceria surface. Subsequent annealing results in the growth of large amorphous FeOx particles and a 2D FeOx layer. Annealing in an oxygen-rich atmosphere further oxidizes iron up to the Fe3+ state and improves the crystallinity of both the 2D layer and the 3D particles. Our DFT calculations indicate that the 2D FeOx layer interacts strongly with the ceria surface, exhibiting structural corrugations and transferred electrons between Fe2+/Fe3+ and Ce4+/Ce3+ redox pairs. The novel 2D FeOx/CeO2(111) phase may explain the enhancement of the catalytic properties of CeO2 by iron. Moreover, the corrugated 2D FeOx layer can serve as a template for the ordered nucleation of other catalytically active metals, in which the redox properties of the 2D FeOx/CeO2(111) system are exploited to modulate the charge of the supported metals.