Diffuse Reflectance Research Articles

Modulating Ti coordination environment in Ti-containing materials by sulfation for synergizing with Au sites to facilitate propylene epoxidation

Modulating the coordination environment of Ti sites in Ti-containing materials to synergize with Au sites is a crucial issue to boost the process of propylene epoxidation with H2 and O2 to produce propylene oxide (i.e., HOPO), but still remains a great challenge. Herein, we report a facile strategy to tailor the coordination states and electronic properties of Ti sites. The sulfur-decorated Ti-SiO2 (i.e., Ti sites anchored onto silica) with moderate sulfur loading (Ti-SiO2-S-M) can synergize well with Au sites for the HOPO process with high activity, propylene oxide (PO) selectivity, and H2 efficiency, which are superior to those achieved on the referenced Ti-SiO2 synergizing with Au sites. Multiple characterizations, in-situ diffuse reflectance infrared Fourier transform spectroscopy of propylene and PO, PO conversion experiment, and kinetics behaviors demonstrate that the superior advantages of Ti-SiO2-S-M against Ti-SiO2 result from the increased Ti binding energy, improved hydrophobicity, and weakened acidity, which simultaneously facilitate the adsorption of propylene and promote the desorption of PO. This insight reported here could guide the rational design and optimization of Ti-containing materials to synergize with Au catalysts for propylene epoxidation.

Ultramarine blue containing paint layers: Further study of the photo-catalytic degradation of binding media

Photo-catalytic degradation of a linseed oil binder by natural ultramarine (Lapis Lazuli or Lazurite) and Sodalite in paint layers was studied. Both pigments degrade the binder under xenon arc exposure, leading to erosion of the binder at the surface, increased roughness, light scattering and desaturation of the color. Both pigments behave similarly to synthetic ultramarine blue studied earlier. The results for Sodalite provide further proof that the zeolitic nature of the aluminosilicate cage causes the catalytic degradation and that the enclathrated polysulfur radical anions S2-. and S3-. trapped inside the cage are not responsible for the catalytic action. Relatively stable synthetic binders are less affected by the presence of synthetic ultramarine blue. The paints were aged in a xenon arc apparatus using a simulated indoor environment (radiation > ca. 320 nm). The samples were analyzed using diffuse reflectance spectroscopy in the UV–vis and short wavelength infrared (SWIR) ranges, Raman spectroscopy, field-emission gun scanning electron microscopy (FEG-SEM) and FTIR.

Layered Perovskite La2Ti2O7 Nanostructures for Photocatalytic Degradation of Congo Red Dye Pollutant

AbstractIn photocatalytic innovation, there has been a lot of interest in creating broad spectral responsive photocatalysts to get superior catalytic performance. In this study, we synthesized highly visible‐light responsive La2Ti2O7 perovskite photocatalysts by the probe ultrasonication procedure followed by high‐temperature calcination. Such materials are characterized using UV‐vis diffuse reflectance spectra, powder X‐ray diffraction, X‐ray photoelectron spectroscopy, and scanning electron microscopy to illustrate the optical absorption activities, crystalline properties, chemical composition, and microscopic features. La2Ti2O7 extends optical absorption towards the visible light spectrum and narrows the band gap. The photocatalytic efficacy of the resulting La2Ti2O7 nanostructures was investigated by performing photocatalytic degradation of persistent Congo red (CR) dye while subjected to visible photon illumination using three Osram 150 W tungsten halogen lamp ((λ≥400 nm), 5000 lm nominal luminous flux, 80,600 lx radiation intensity. With effective efficiency, the optimum degradation of the 10 ppm CR dye with a percentage of 95.9 was achieved after 90 min during exposure to the La2Ti2O7 perovskite with a catalyst dosage of 30 mg/100 mL at pH 6. Consequently, La2Ti2O7 nanostructures alone depicted 19.8 % adsorption efficiency for CR dye. In addition, OH⋅ and holes were important in degrading CR dye, which included many different reaction pathways. The treated solution can also demonstrate the environment's safety for accepting water. In summary, under natural visible light irradiation, the synthesized La2Ti2O7 showed enormous promise for eliminating different organic contaminants using photocatalytic methodology.

Synthesis and Characterization of TiO2 Thin Films Modified with Anderson-Type Polyoxometalates (Ni, Co, and Fe)

In this work, TiO2 and Anderson-type polyoxometalates (Ni, Co, and Fe) thin-film composites were fabricated. The composites were characterized by FTIR and Raman spectroscopy, diffuse reflectance, and scanning electronic microscopy. The methylene blue (MB) photocatalytic degradation on the composites under UV irradiation was studied. Spectroscopic results verified the modification of TiO2 thin films. Optical and morphological properties changed after TiO2 modification. The largest change in the optical band gap was observed for the FePOM/TiO2 system, which reported a value of 3.05 eV. The POM/TiO2 systems were more efficient in methylene blue (MB) adsorption than bare TiO2. Furthermore, the modified films were more efficient than bare TiO2 during MB photodegradation tests. The NiPOM/TiO2 and the CoPOM/TiO2 were the most efficient in the MB adsorption, reaching ~20%. The NiPOM/TiO2 and the CoPOM/TiO2 composites were the most efficient in the photodegradation process, reaching ~50% of MB removal. The stability tests indicated that composite films were moderately stable after the three performed reusability cycles. Thus, these results suggest that POM modification of TiO2 can improve the adsorption and photodegradation capacity of semiconductors.

Understanding the Environmental Sensitivity of Copper‐Metal Oxides Interactions in Cu/ZnO and Cu/Al2O3 Catalysts

AbstractTernary Cu/ZnO/Al2O3 catalysts are one of the most important industrial catalysts and show excellent activity in methanol reforming reaction. However, it is challenging to elucidate the metal support interactions, which critically influence the catalyst structure and performance, due to their environmentally sensitive nature. This study examines the interactions between Cu and Al2O3 and ZnO, after reductive treatments of the Cu/Al2O3 and Cu/ZnO model catalysts with varying temperatures and hydrogen concentration. A combination of Brunner‐Emmet‐Teller (BET) measurements, X‐ray diffraction (XRD), N2O titration, diffuse reflectance infrared Fourier transformations spectroscopy (DRIFTS) and high‐resolution transmission electron microscopy (HRTEM) provided comprehensive insights into the structural evolution of the catalysts.

Application of nano-TiO2 and micro-ZnO on cementitious surfaces for self-cleaning façades by spray coating and dip coating: A comparative study

Building façades are constantly exposed to atmospheric pollution and various external agents that can degrade their aesthetic qualities and introduce degradation patterns that affect the durability and performance of the materials. Façades with self-cleaning properties are important in the modern construction industry and the conservation of historic buildings, as they reduce costs and allow the preservation of original surfaces without the need for invasive interventions that could compromise cultural heritage. This study does a comparative analysis of the application of photocatalytic coatings composed of aqueous dispersions of titanium dioxide nanoparticles (TiO₂) and zinc oxide microparticles (ZnO) on cementitious substrates for use on façades by two functionalisation methods: spray coating and dip coating. A comprehensive characterisation was carried out using techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), and diffuse reflectance spectroscopy (DRS) to assess the morphology, crystal structure and light absorption properties of the photocatalyst particles while Energy Dispersive Spectroscopy (EDS) and scanning electron microscopy (SEM) were employed to evaluate the substrate. The self-cleaning performance was evaluated by monitoring the degradation of Rhodamine B (RhB) dye under simulated sunlight. Spectrophotometric analysis was used to assess the colour coordinates using a standard colour system (CIELAB colour space). The results showed that the photocatalytic coatings improved the surfaces' self-cleaning properties while maintaining the substrate's original aesthetics. Spray-applied micro-ZnO-based coatings showed the most significant effectiveness in terms of self-cleaning.

Physical and enhanced photocatalytic MO dye degradation behaviour of Zn doped β-Ga2O3 microrods

This work explored the effects of Zn doping on the structural, micrographic, optical and photocatalytic behaviour of gallium oxide (β-Ga2O3) microrods. The X-ray diffractogram (XRD) and Raman spectral analyses confirmed the monoclinic structure of β-Ga2O3, with a shift to lower angles in the XRD pattern indicating Zn incorporation into the Ga2O3 lattice. The Scanning electron microscopy (SEM) images revealed a rod-like shape, with the diameter decreasing from 604 nm to 573 nm with Zn doping. Further analysis using TEM, HR-TEM, SAED, EDX, and elemental mapping confirmed the shape, crystallinity, crystal structure, and elemental distribution. The interplanar spacings were measured as 0.4 and 0.2 nm, corresponding to the (002) and (−311) planes of β-Ga2O3. UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS) showed a slight shift in the absorption edge, while photoluminescence (PL) analysis demonstrated strong UV and weak visible light emission. Photocatalytic results revealed a high efficiency of dye degradation,(i.e) 98 % (20 ppm) and 89 % (30 ppm) against methyl orange (MO) dye aqueous solution over 150 min, with a rate constant of 0.02/min and 0.01/min, respectively for 1.5 wt% Zn doping. This suggests that the Zn-doped material holds promise as a photocatalyst for wastewater treatment applications.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NOx removal reactions through the inter-particle diffusion of intermediate species, their subsequent reaction mechanism on acid sites is still unclear and requires investigation. In this study, the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions, which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species. Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NOx with NH3 (NH3-SCR) reaction demonstrate that the Lewis acid sites over MnOx are more active for NO reduction but have lower selectivity to N2 than Brønsted acids sites. Brønsted acid sites primarily produce N2, whereas Lewis acid sites primarily produce N2O, contributing to unfavorable N2 selectivity. The Brønsted acid sites present in Y zeolite, which are stronger than those on MnOx, accelerate the NH3-SCR reaction in which the nitrite/nitrate species diffused from the MnOx particles rapidly convert into the N2. Therefore, it is important to design the catalyst so that the activated NO species formed in MnOx diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnOx particle. For the physically mixed H-MnOx+H-Y sample, the abundant Brønsted/Lewis acid sites in H-MnOx give rise to significant consumption of activated NO species before their inter-particle diffusion, thereby hindering the enhancement of the synergistic effects. Furthermore, we found that the intercalated K+ in K-MnOx has an unexpected favorable role in the NO reduction rate, probably owing to faster diffusion of the activated NO species on K-MnOx than H-MnOx. This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO2, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement

Relationship between the activity for photocatalytic H2O overall splitting (HOS) and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram, and specially the d10 electronic configuration in valley bottom exhibits inert activity, which seriously fetters the development of catalytic materials with great potentials. Herein, In d10 electronic configuration of In2O3 was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band (In ɛ5p) and descended O 2p-band (O ɛ2p) centers as efficient active sites for chemisorption to *OH and *H during forward HOS, respectively, along with a declined In 4d-band center (In ɛ4d) to inhibit its backward reaction. A stable STH efficiency of 2.23% under AM 1.5 G irradiation at 65 °C has been obtained over the activated d10 electronic configuration with a lowered activation energy for H2 evolution, verified by femtosecond transient absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics. These findings devote to activating d10 electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS, which expands the exploration of high-efficiency catalytic materials.

“Investigating impact of Ni-Cd substitution on structural magnetic and optical properties of nanosize Al ferrites”

Ferrites are among the most extensively studied materials, specifically due to their amazing and diverse characteristics. Therefore, we synthesized NixCd1-xAlyFe2-yO4 (NCAF) ferrites using a microwave auto-combustion process, with x varying from 0.0 to 1.0 and y set at 0.1. We conducted a meticulous characterization of their structural, surface morphological, magnetic, molecular vibrational and optical properties. X-ray diffraction confirms the lattice parameter and a single-phase spinel structure. Rietveld refined XRD patterns identified the Fd-3m space group cubic spinel phase. HR-TEM examination shows pseudo-spherical particles with an average size of 40–45 nm. Surface topography exhibits tiny, spherical microstructures. The lognormal histogram showed an average particle size of 56.6 nm–124.8 nm, decreasing with nickel concentration. At a nickel concentration (x) of 0.6, saturation magnetization (Ms) increases and then decreases at 1.0. FTIR confirms no organic phase and spinel development. Absorption measurements determined the band gap energy, which Tauc plot revealed to be 2.5870–2.1657 eV. We used the Kubelka-Munk function to find the band gap energy in the UV–Vis diffuse reflectance spectra (DRS), which was between 2.0027 and 1.6817 eV.

Synthesis, Structure, and Properties of Dion–Jacobson Double‐Layered Perovskites A′SmNb2O7 (A′ = Rb, K, Na, Li, H)

Dion‐Jacobson‐type layered perovskite compounds A′SmNb2O7 (A′ = Rb, K, Na, Li, H) were synthesized using solid‐state and ion‐exchange methods. While the parent solid‐state product RbSmNb2O7, has previously been studied, the ion‐exchanged compounds were obtained and studied for the first time. The phase and chemical purity of the compounds were confirmed by X‐ray diffraction (XRD) and energy‐dispersive X‐ray spectroscopy (EDX). The crystal structures of RbSmNb2O7 (I2cm, a=0.54356(1) nm, b=0.53935(1) nm, c=2.1891(5) nm), KSmNb2O7 (I2cm, a=0.53660(7) nm, b=0.54481(6) nm, c=2.1527(1) nm) and LiSmNb2O7 (B2cm, a=0.54546(4) nm, b=0.53567(4) nm, c=2.04582(5) nm) were refined using the Rietveld method. Polyhedral distortions in these structures have been studied in detail. The thermal behavior of the compounds has been determined using differential thermal analysis (DTA), revealing that A′ = Na, Li and H compounds are metastable hydrates, while A′ = Rb and K compounds are stable. The optical band gap, valence band edge, and conduction band edge potentials of the compounds obtained were calculated using diffuse reflection spectroscopy data. A photocatalytic experiment was performed on the degradation of methylene blue under ultraviolet light. All of the samples obtained showed some activity in the reaction of dye photooxidation.

Adaptive slicing in powder bed fusion of metals using a laser beam—Investigation on productivity, laser absorption, geometrical accuracy, and thermal conditions

Powder bed fusion of metals using a laser beam (PBF-LB/M acc. to DIN EN ISO/ASTM 52900) has reached market maturity. In addition to developing new materials and enabling new applications, the industry focuses on increasing productivity and reducing costs. In this context, increasing the layer thickness can increase productivity but often leads to a deterioration of surface quality and part density. Using variable layer thicknesses depending on the manufactured geometry is well-known from filament-based material extrusion processes and is called adaptive slicing. This study investigates the manufacturing aspects of adaptive slicing using AlSi10Mg. Laser beam reflectance of the different powder layer thicknesses is quantified using diffuse reflectance infrared Fourier transform spectroscopy. The process window is identified and analyzed, focusing on the achievable productivity and required energy input. Furthermore, the suitability of layer thicknesses and processing parameters is analyzed by measuring the dimensional accuracy and process stability of overhanging structures. Heat input, heat dissipation, and potential heat-up are investigated and compared to conventional processes using part-scale thermal simulations. In this study, parameters are developed for layer thicknesses of 120 μm with an almost threefold increase in productivity in nonoverhanging structures with a part density above 99.7%. Further, adaptive slicing can increase productivity in PBF-LB/M while decreasing the impact on part quality. Future work will focus on automated algorithms to optimize and automize adaptive slicing.

Reversible multimode modulations in photochromic transparent Eu3+doped K0.5Na0.5NbO3 based ceramics

Rare-earth doped transparent photochromic materials have attracted extensive attention in applications of optical information storage and optical switching, in which the high transparency and large fluorescence modulation ratio are required. In this work, 0.94 (K0.5Na0.5)NbO3-0.06 (Sr0.5Ba0.5) (Zn1/3Bi2/3)O3: x wt% Eu2O3 ceramics (KNN-SBZB: xEu) with x=0.1, 0.2, 0.3, 0.4 were prepared by traditional high temperature solid state sintering reaction method. High transmittance (T) was achieved due to the small grain size (less than 110 nm) and the highly symmetrical phase structure. High optical transmittance of 69.27 % at 780 nm and 78.24 % at 1100 nm were obtained in the KNN-SBZB: 0.3Eu ceramic, while large luminescence intensity modulation ratio (∆RL) ∼94.9 %, transmittance (∆RT) ∼5.76 % and diffuse reflectivity (∆ABS) ∼12.59 % were achieved in KNN-SBZB: 0.2Eu ceramic (T ∼62.92 % at 780 nm). Additionally, both the transmittance modulation and luminescence intensity modulation of KNN-SBZB: xEu ceramics show good stability after 10 cycles.

Anodic Synthesis of Highly Ordered TiO2 Nanotube Arrays: Role of Electrolyte Composition on the Structural, Morphological, Optical, and Photo-electrochemical Properties

The fluoride species present in two different anodizing electrolytes were used to produce TiO2 nanotube arrays (TiO2 NTAs) by simultaneous anodic reaction and chemical dissolution. In this investigation, two different electrolytes were used for the preparation; [Eth-TiO2 NAs: 95 ml ethylene glycol+0.5% NH4F+5 ml DI water] and [Gly-TiO2 NAs: 75 ml glycerine+0.5% NH4F+25 ml DI water]. The effects of the prepared electrolytes used in the synthesis of TiO2 nanotube arrays on structural element composition, morphology, and optical properties are the focus of this study and are characterized by X-ray diffraction (XRD), scanning electron microscopy field emission (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and UV-vis diffusion reflection spectroscopy (DRS), respectively. The photoelectrochemical properties of TiO2 NTAs prepared in different electrolytes were investigated. The photoelectrochemical performance of TiO2 NTAs in Na2SO3 (0.1 M) and Na2S (0.1) was examined under the light of 100 mW/cm2 from a xenon lamp. Comparing the photoelectrochemical (PEC) results of both electrolytes, we find that Eth-TiO2 NTAs contribute a wide surface area resulting in an enhanced PEC response. TiO2 NTs, which were prepared with Eth-TiO2 NTAs, exhibited the highest photocurrent density, 0.326 mA cm–2, and photoconversion efficiency (0.22%).

Synthesis of tin selenide nanoparticles using Polygonum avicular extract decorated on graphitic carbon nitride for enhancing photodegradation of amoxicillin trihydrate and photoproduction of hydrogen peroxide

In this research, tin selenide nanoparticles (SnSe-NPs) were synthesized using Polygonum avicular extract via the hydrothermal method and decorated on graphitic carbon nitride (g-C3N4) by the simple sonicated method to produce SnSe/g-C3N4 composites. The characterization and properties of the SnSe/g-C3N4 composites, as compared to pristine SnSe and g-C3N4, were determined by Fourier-transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscope, transmission electron microscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, ultraviolet–visible diffuse reflectance spectroscopy, Mott-Schottky, and electrochemical impedance spectroscopy. As a result, the SnSe-NPs possessed the rod-like shape and after the decoration onto the g-C3N4 sheet surface, it reduced the bandgap energy of the g-C3N4 from 2.58 downward 1.43 eV. Besides, the photoactivities of the 10-SnSe/g-C3N4 catalyst were investigated via both sides of amoxicillin trihydrate (AMXT) photodegradation and hydrogen peroxide (H2O2) photoproduction, in which the results were achieved 87.84 % AMXT and 85.48 μM H2O2, respectively, under visible light. Furthermore, the photodegradation was consistent with the pseudo-first-order kinetics and it performed the highest photodegradation at pH ∼5, while the importance of isopropyl alcohol as a trapping agent and •O2− radicals was affirmed in the H2O2 photoproduction. Moreover, the photoproduction of H2O2 was remained after 4 cycles achieved at 62.70 % in the final cycle, which demonstrated the stability and reusability of the 10-SnSe/g-C3N4. These aforementioned results demonstrate that the SnSe/g-C3N4 material is a promising candidate for addressing environmental pollution and energy scarcity issues.

Cation rearrangement at tetrahedral sites in the Cu/ZnAl2O4 spinel enhancing CO2 hydrogenation to methanol

Cu/ZnAl2O4 spinel is a promising catalyst for CO2-to-methanol due to its dual-site H2 activation. However, controlling surface properties and metal-support interactions (MSI) through the coordination environment of spinel cations remains underexplored. Herein, the occupancy of Zn2+ and Al3+ cations in Cu/ZnAl2O4 spinel is fine-tuned by manipulating the calcination atmosphere. More disordered structures (AlO4 and ZnO6) observed on the CZA-Ar catalyst benefit the creation of oxygen vacancies and surface hydroxyl groups, which facilitate the formation of highly dispersed small-sized Cu species. This enhances MSI and hydrogen spillover effects, thereby boosting CO2 conversion and the space-time yield (STY) of methanol. High-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the crucial formate intermediates form at tetrahedral sites in ZnAl2O4 spinel, with more Al-HCOO- species observed on the CZA-Ar catalyst due to the formation of AlO4. This work advances the understanding of spinel catalysts in CO2 hydrogenation to methanol.

A MOF@MOF S-scheme Heterojunction with Lewis Acid-Base Sites Synergistically Boosts Cocatalyst-Free CO2 Cycloaddition.

The photocatalytic cycloaddition reaction between CO2 and epoxide is one of the most promising green routes for CO2 utilization, for which high performance photocatalysts are intensely desired. Herein, we have constructed an S-scheme heterojunction of MIL-125@ZIF-67 modified by amino groups, which achieves a cyclic carbonate yield of as high as 99 % without employing any co-catalyst, outperforming the previously reported photocatalysts. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ electron paramagnetic resonance (EPR) spectroscopy reveal the important role of photogenerated electron migration from Lewis acid (Co) sites to the O atom of epoxide in triggering its ring-opening (the rate-determining step of CO2 cycloaddition reaction) under the assistance of photogenerated hole. Synergistically and concurrently, the Lewis base (amino groups) sites activate CO2 to CO2*, facilitating the following CO2 cycloaddition. Such a synergistic effect provides a most favorable approach to design efficient heterogeneous photocatalysts with dual/multiple-active sites for CO2 cycloaddition reaction.

Energy trapping to substitutional and charge compensation defects in persistent luminescent BaAl2O4:Tb3+

The holistic approach of the photoluminescence (PL), thermoluminescence (TL), and persistent luminescence properties at room temperature of BaAl2O4:Tb3+ were investigated in detail using a wide range of techniques. Materials were obtained using a solution combustion synthesis. The x-ray powder diffraction patterns of nondoped and Tb3+ doped BaAl2O4 indicated the hexagonal phase, and a Tb4O7 solid solution was observed at 4 and 5 mol% Tb doped aluminate. X-ray photoelectron spectroscopy revealed that Ba occupied one site and that Tb ions occupied this site as Tb3+ as well as TbIV. PL emission in blue, green, and red was observed under an excitation at 228 nm, that originated from the interconfigurational 4f8–4f75d1 transitions of Tb3+. Time-of-flight secondary ion mass spectroscopy, UV–vis diffuse reflectance, and PL revealed the presence of a Cr3+ impurity. The 0.5 mol% Tb3+ doped BaAl2O4 exhibited a strong TL band at 354, 437 and 598 K, which were attributed to the traps formed by Tb3+ doping and subsequent O2− charge compensation. A persistent luminescence mechanism was constructed for the Tb3+ doped BaAl2O4. After the energy was stored in thermally liberated Tb3+ in the Ba2+ substitution sites and charge compensation defects, the Tb3+ was the source of the continuous luminescence.

Electronic effect in bromide-modified noble metal catalysts promotes highly stable and selective hydrogenation

Halides with strong affiliation to metals are traditionally viewed as positions in heterogeneous catalysis. This study introduces a method to enhance the selective hydrogenation performance of noble metal nanoparticle catalysts (Pd, Pt, and Rh hosted on N-doped carbon, SiO2, and Al2O3) by gas-phase bromination with 1-bromooctane. Brominated Pd catalysts, particularly those supported on N-doped carbon, show significant improvements in total butene selectivity and stability in butadiene hydrogenation reactions, displaying >97.5 % selectivity to total butenes at complete conversion with 50 h stable performance even at excessive H2 (H2:butadiene = 50) and a high temperature of 473 K. Comprehensive characterizations coupled with density functional theory calculations reveal that bromide species enhance selective hydrogenation by preferentially adsorbing at stepped Pd sites, altering reaction kinetics and preventing over-hydrogenation. Bromination influences reactant and intermediate adsorption, leading to increased competitive adsorption compared to pristine catalysts. Chemisorption studies on butadiene and 1-butene support altered kinetic behaviors post-bromination. X-ray photoelectron spectroscopy analysis demonstrate an increase in surface Pdδ+ species, owing to the electron-pulling character of nearby adsorbed bromide. In situ diffuse reflection infrared Fourier transform spectroscopy with CO probe molecules confirms Br species adsorption at unsaturated Pd sites. Overall, the study provides an effective approach to tuning the electronic properties of metal catalysts and highlights the positive impact of bromination on improving the hydrogenation performance.