Lasers Research Articles

Unraveling the Mechanism of Hydrogen Atom Transfer by a Nickel-Hypochlorite Species and the Influence of Electronic Effects.

The oxidation of hydrocarbons is an important chemical transformation with relevance to biology and industry. Ni-catalyzed transformations are more scarce compared to Mn or Fe but have gained attention in recent years, affording efficient oxidations. Understanding the mechanism of action of these catalysts, including the detection and characterization of the active nickel-oxygen species, is of interest to design better catalysts. In this work, we undertake a theoretical study to unravel the mechanism of formation of the previously reported [Ni(OCl)(HL)]+ (H2) and how it activates C-H bonds. We disclose that the active species is indeed compound [Ni(O)(HL)]+, formed after homolytic cleavage of the O-Cl bond in H2 assisted by a chlorine radical. [Ni(O)(HL)]+ mediates C-H activation through an asynchronous concerted mechanism, in which the transition state is given by hydrogen atom transfer. Moreover, the electronic tuning of the ligand has a very modest impact on the stability and reactivity of the corresponding X2 species. Effective oxidation state analysis reveals an intriguing electronic structure of H2 and [Ni(O)(HL)]+, in which both the macrocycic HL ligand and the OCl and O ligands behave as redox noninnocent. Such redox activity leads to a fully ambiguous oxidation state assignation.

Magnesium-promoted rapid self-reconstruction of NiFe-based electrocatalysts toward efficient oxygen evolution

The acceleration of active sites formation through surface reconstruction is widely acknowledged as the crucial factor in developing high-performance oxygen evolution reaction (OER) catalysts for water splitting. Herein, a simple one-step corrosion method and magnesium (Mg)-promoted strategy are reported to facilitate the NiFe-based catalysts with enhanced OER performance. The Mg is introduced in NiFe materials to preparate a “pre-catalyst” Mg-Ni/Fe2O3. In-situ Raman shows that Mg doping would accelerate the self-reconstruction of Ni/Fe2O3 to form active NiOOH species during OER. In-situ infrared indicates that Mg doping benefits the formation of *OOH. Theoretical analysis further confirms that Mg doping can optimize the adsorption of oxygen intermediates with fast evolution, accelerating the OER kinetics. Accordingly, the Mg-Ni/Fe2O3 catalyst exhibits excellent OER performance with overpotential of 168 mV at 10 mA cm−2. The anion exchange membrane water electrolyzer achieved 200 mA cm−2 at voltage of 1.53 V, demonstrating excellent stability over 500 h. This work demonstrates the potential of Mg-promoted strategy in regulating the activity of transition metal-based OER electrocatalysts.

Crystal Facets-Activity Correlation for Oxygen Evolution Reaction in Compositional Complex Alloys.

Compositional complex alloys, including high and medium-entropy alloys (HEAs/MEAs) have displayed significant potential as efficient electrocatalysts for the oxygen evolution reaction (OER), but their structure-activity relationship remains unclear. In particular, the basic question of which crystal facets are more active, especially considering the surface reconstructions, has yet to be answered. This study demonstrates that the lowest index {100} facets of FeCoNiCr MEAs exhibit the highest activity. The underlying mechanism associated with the {100} facet's low in-plane density, making it easier to surface reconstruction and form amorphous structures containing the true active species is uncovered. These results are validated by experiments on single crystals and polycrystal MEAs, as well as DFT calculations. The discoveries contribute to a fundamental comprehension of MEAs in electrocatalysis and offer physics-based strategies for developing electrocatalysts.

Complex and highly saturated soundscapes in restored oak woodlands reflect avian richness and abundance.

Temperate woodlands are biodiverse natural communities threatened by land use change and fire suppression. Excluding historic disturbance regimes of periodic groundfires from woodlands causes degradation, resulting from changes in the plant community and subsequent biodiversity loss. Restoration, through prescribed fire and tree thinning, can reverse biodiversity losses, however, because the diversity of woodland species spans many taxa, efficiently quantifying biodiversity can be challenging. We assessed whether soundscapes in an eastern North American woodland reflect biodiversity changes during restoration measured in a concurrent multitrophic field study. In five restored and five degraded woodland sites in Wisconsin, USA, we sampled vegetation, measured arthropod biomass, conducted bird surveys, and recorded soundscapes for five days of every 15-day period from May to August 2022. We calculated two complementary acoustic indices: Soundscape Saturation, which focuses on all acoustically active species, and Acoustic Complexity Index (ACI), which was developed to study vocalizing birds. We used generalized additive models to predict both indices based on Julian date, time of day, and level of habitat degradation. We found that restored woodlands had higher arthropod biomass, and higher richness and abundance of breeding birds. Additionally, soundscapes in restored sites had higher mean Soundscape Saturation and higher mean ACI. Restored woodland acoustic indices exhibited greater magnitudes of daily and seasonal peaks. We conclude that woodland restoration results in higher soundscape saturation and complexity, due to greater richness and abundance of vocalizing animals. This bioacoustic signature of restoration offers a promising monitoring tool for efficiently documenting differences in woodland biodiversity.

Carbonate radicals mediated catalytic degradation of antibiotics over earth-abundant BaCO3-based system: Performance, mechanism and calculation

The semiconductor-insulator heterostructure, characterized by outstanding economic-efficiency and catalytic activity, represents a promising photocatalyst for practical pollutants degradation. However, achieving energy band matching between semiconductors and insulators remains a challenge. In this study, we meticulously designed and synthesized a band-matched semiconductor-insulator photocatalysts (AgI-BaCO3), leveraging the in-situ nucleation of ultrafine AgI nanoparticles on BaCO3 surface. The finely crafted heterostructure notably enhanced degradation efficiency of tetracycline over both pure AgI and BaCO3, demonstrating a remarkable pseudo-first-order kinetic rate constant that surpassed them by 27.2 and 33.5 times, respectively. The density functional theory calculations uncovered that the intense covalent interaction between AgI and BaCO3 established a specific channel for interfacial charge carriers. The generated CO3·- radicals as the main active species markedly expedited the removal of antibiotics. Furthermore, the catalysts demonstrated robust activity in real wastewater and surface water. This work supplies a novel reference for constructing insulator-based photocatalysts and elucidates its potential application in actual aquatic environments.

W single-atom mediated singlet oxygen formation on carbon nitride for powerful photocatalytic abatement of organic pollutants

Active single-atom W anchoring on graphitic carbon nitride (g-C3N4) with interplanar four-coordination with N was achieved via a microwave hydrothermal process followed by thermal polymerization. The optimal monoatomic W incorporated g-C3N4 (W-CN) catalyst exhibited a high photocatalytic activity toward a wide range of pharmaceutical and personal care products (PPCPs). The anchoring of W single atom narrowed the energy-band, negatively shifted the conduction band of g-C3N4, and promoted the charge transfer and photogenerated carrier separation. Moreover, W single-atom intercalation obviously favored the formation of singlet oxygen (1O2), as validated by the active species capture test and density functional theory (DFT) calculation, which played an important role in the photocatalytic degradation of PPCPs. The treatment of actual wastewater, toxicity assessment and hemp-pea-growth experiments further showed that the W-CN photocatalyst could effectively degrade the organic pollutants and reduce their poisonousness in the water environment. This work offers a facile route to obtain reactive g-C3N4 with single-metal active sites and some insights into its activity enhancement for the abatement of organic pollutant-containing wastewater.

Enhanced photocatalytic performance of NiFe2O4/ZnIn2S4 p-n heterojunction for efficient degradation of tetracycline

The persistent release of tetracycline into the environment significantly endangers both ecosystems and human health. Zinc indium sulfide (ZnIn2S4) capable to degrade tetracycline pollutants under visible light irradiation has attracted extensive attentions and great effort has been devoted to augment its catalytic efficacy. In this work, we synthesized a p-n heterojunction, NiFe2O4/ZnIn2S4, to enhance the carrier migration rate and explained the intrinsic mechanism by density functional theory. When the heterojunction was formed, carriers traversed from the n-type NiFe2O4 to the p-type ZnIn2S4, instigating the emergence of a built-in electric field to facilitate the separation of carriers. 2 %-NiFe2O4/ZnIn2S4 exhibited excellent photocatalytic efficiency in tetracycline (TC) degradation and total organic carbon (TOC) removal. Compared to pure ZnIn2S4 and NiFe2O4, the TC degradation rates of 2 %-NiFe2O4/ZnIn2S4 were 2.0 times and 16.9 times higher, respectively. Additionally, 2 %-NiFe2O4/ZnIn2S4 had a saturation magnetization intensity of 3.05 emu/g, allowing for rapid recovery of the catalyst under a magnetic field. Superoxide radicals (O2−) and holes (h+) were the primary active species driving the degradation process. Furthermore, potential reaction pathways of tetracycline in this photocatalytic process were determined and bioconcentration factor and developmental toxicity of the intermediate products were accessed. This work held great potential for wastewater treatment and provided a pathway for the development of magnetic recyclable photocatalysts.

Synthesis of 2,4,6‐Triaryl‐1,3,5‐triazines via the Cyclotrimerization of Benzonitriles with Catalytic Systems Composed of Titanium Chlorido Complexes and Magnesium

The catalytic activity of low‐valent transition metals for the cyclotrimerization of nitriles has rarely been investigated to date. Here, we report on the cyclotrimerization of benzonitrile (PhCN) and its derivatives using catalytic systems composed of magnesium and bis(indolyl)TiCl2 (bis(indolyl) = di(3‐methylindol‐2‐yl)phenylmethane), Cp2TiCl2 (Cp = η5‐C5H5), (CGC)TiCl2 (CGC = Me2Si(Me4C5)(tBuN)), TiCl4(thf)2 (thf = tetrahydrofuran), Cp*TiCl3 (Cp* = η5‐Me5C5), or CpTiCl3, which can be expected to generate coordinatively unsaturated Ti(II) complexes as the catalytically active species. All the investigated catalytic systems were active for the cyclotrimerization of PhCN. Notably, even the simple catalytic precursor (TiCl4(thf)2) mediated the cyclotrimerization of PhCN as well as p‐ and m‐tolunitriles. Moreover, these reactions can be carried out on the gram scale and the cyclotrimerized products can be isolated via recrystallization of the reaction mixture from hot toluene. The findings of this study suggest that low‐valent titanium species have the potential to serve as catalysts for the cyclotrimerization of PhCN and its derivatives. During this study, we also found that 2,4,6‐tri(p‐tolyl)‐1,3,5‐triazine, which is obtained from the cyclotrimerization of p‐tolunitrile, exhibits fluorescent properties in both the solid state and in solution.

Construction of a BiOCl/Bi2O2CO3 S-Scheme Heterojunction Photocatalyst via Sharing [Bi2O2]2+ Slabs with Enhanced Photocatalytic H2O2 Production Performance.

The construction of a close contact interface is key to enhancing the photocatalytic activity in heterojunctions. In the work, the BiOCl/Bi2O2CO3 of sharing [Bi2O2]2+ slabs S-scheme heterojunction was prepared by a HCl in situ etching method. The optimal composite photocatalyst could accomplish sizable productivity of H2O2 to 2562.95 μmol g-1 h-1 under simulated solar irradiation, higher than that of primitive Bi2O2CO3 and BiOCl. Moreover, the synthesized catalysts showed good stability. The band structures of BiOCl and Bi2O2CO3 were determined, confirming the formation of BiOCl/Bi2O2CO3 S-scheme heterojunction The BiOCl/Bi2O2CO3, which obviously improved the separation efficiency of photoinduced carriers and effectively enhanced the redox ability of the photocatalyst. In addition, density functional theory (DFT) calculations were utilized to analyze the electron transfer properties and the constitution of the built-in electric field at the interface of BiOCl and Bi2O2CO3. The photocatalytic reaction process was further researched by electron paramagnetic resonance (EPR), indicating the active species in the photocatalytic production of hydrogen peroxide. Eventually, a feasible S-scheme electron transfer mechanism on the BiOCl/Bi2O2CO3 heterojunction during the photocatalytic H2O2 production process was proposed and discussed. This work provides a reliable strategy for the fine design of the S-scheme heterojunction.

A Combination of Remote Sensing Datasets for Coastal Marine Habitat Mapping Using Random Forest Algorithm in Pistolet Bay, Canada

Marine ecosystems serve as vital indicators of biodiversity, providing habitats for diverse flora and fauna. Canada’s extensive coastal regions encompass a rich range of marine habitats, necessitating accurate mapping techniques utilizing advanced technologies, such as remote sensing (RS). This study focused on a study area in Pistolet Bay in Newfoundland and Labrador (NL), Canada, with an area of approximately 170 km2 and depths varying between 0 and −28 m. Considering the relatively large coverage and shallow depths of water of the study area, it was decided to use airborne bathymetric Light Detection and Ranging (LiDAR) data, which used green laser pulses, to map the marine habitats in this region. Along with this LiDAR data, Remotely Operated Vehicle (ROV) footage, high-resolution multispectral drone imagery, true color Google Earth (GE) imagery, and shoreline survey data were also collected. These datasets were preprocessed and categorized into five classes of Eelgrass, Rockweed, Kelp, Other vegetation, and Non-Vegetation. A marine habitat map of the study area was generated using the features extracted from LiDAR data, such as intensity, depth, slope, and canopy height, using an object-based Random Forest (RF) algorithm. Despite multiple challenges, the resulting habitat map exhibited a commendable classification accuracy of 89%. This underscores the efficacy of the developed Artificial Intelligence (AI) model for future marine habitat mapping endeavors across the country.

Activation of H2O2-HCO3- by Ca2Co2O5 for pollutant degradation.

The bicarbonate-activated hydrogen peroxide (BAP) system is widely studied for organic pollutant degradation in wastewater treatment. Ca2Co2O5, a heterogeneous catalyst containing multivalent cobalt including Co(II) and Co(III), was herein investigated as a BAP activator, and Acid Orange 7 (AO7) was used as a model pollutant. Ca2Co2O5 exhibited good activation performance. The degradation rate and the initial rate constant of the Ca2Co2O5-activated BAP system were 5.4 and 11.2 times as high as the BAP system, respectively. The removal rate of AO7 reached 90.9% in 30min under optimal conditions (AO7 20mg/L, Ca2Co2O5 0.2g/L, H2O2 1mM, NaHCO3 5mM, pH 8.5, 25℃). The Ca2Co2O5 catalyst exhibited good stability and recyclability, retaining 85% of AO7 removal rate in the fifth run. Compared to the BAP system, a lower dosage of H2O2 was required and a higher initial concentration of pollutants allowed for effective degradation in the Ca2Co2O5-BAP system. X-ray photoelectron spectroscopy was used to analyze the catalytic mechanism. The analysis showed that the good catalytic performance of Ca2Co2O5 attributes to its high proportion of oxygen vacancies and Co(III) species, and the presence of Ca. The active species O2•-, •OH, and 1O2 are responsible for the degradation, as indicated by the quenching experiments. The degradation mechanism of AO7 was speculated based on UV-Vis spectral analysis and the identification of degradation intermediates. The azo form, naphthalene and benzoic rings in the AO7 structure are destroyed in the decomposition. This research provides a feasible approach to designing effective and reusable BAP activators for pollutant degradation in wastewater treatment.

Tetragonal/orthorhombic phase Bi2WO6 homojunction for photoelectrochemical degradation of rhodamine B with high efficiency

Photoelectrochemical (PEC) degradation of organic pollutants to CO2 and H2O is a promising strategy to solve the growing environmental problems. Bismuth tungstate (Bi2WO6) has attracted much attention due to its good chemical stability and moderate conduction band valence band position. However, the PEC activity of Bi2WO6 catalysts is greatly limited due to its rapidly complex electron-hole. This article reports a rational low-cost design that successfully prepares tetragonal/orthorhombic Bi2WO6 homojunction on FTO conductive glass substrates through a simple two-step solvothermal method, significantly enhancing the PEC performance. The study investigated the effectiveness of photoelectrochemical degradation of the recalcitrant organic pollutant Rhodamine B (RhB) and conducted an in-depth exploration of the photoelectrocatalytic reaction process and mechanism. The experimental results indicate that the homojunction achieves a degradation rate of up to 100 % for the recalcitrant organic pollutant RhB within 30 minutes, significantly surpassing that of single-phase Bi2WO6, and at the same time the sample maintains good stability after five cycles of operation. Further analysis of the capture experiments indicates that holes (h+) and superoxide radicals (·O2⁻) are the primary active species responsible for RhB degradation. This study not only provides new insights into the design of high-efficiency photoelectrode, but also offers new solutions for environmental pollution control.

High-power single-longitudinal-mode visible Pr:YLF ring lasers

We present the development and characterization of high-power single-longitudinal-mode (SLM) Pr:YLF lasers across the visible spectrum using a ring cavity design integrated with an optical diode (OD) and Fabry-Perot etalons. Our study achieved notable single-frequency outputs at 639 nm (red), 604 nm, and 607 nm (orange), and 522 nm (green). Specifically, we obtained a maximum output of 1.4 W at 639 nm, while the orange lasers produced outputs of 435 mW at 604 nm and 1.03 W at 607 nm. The green laser achieved a maximum output of 313 mW at 522 nm. The narrowest linewidths recorded were 7.8 MHz for red, 9.4 MHz and 7.6 MHz for orange, and 9.7 MHz for green. These results demonstrate the feasibility of using a ring cavity combined with an F-P etalon to achieve high-power, narrow-linewidth SLM operation across a significant portion of the visible spectra, offering potential applications in precision spectroscopy, optical communications, and metrology.

Photocatalytic degradation of antibiotics by N-doped carbon nanoflakes-nickel ferrite composite derived from algal biomass

This work reports the synthesis of nickel ferrite (NiFe) nanoparticles, N-doped mesoporous carbon nanoflakes (NCF) and novel nickel ferrite-carbon nanoflakes (NiFe@NCF) nanocomposite using solvothermal method. NCF was derived from a cyanobacterial consortium consisting of Anabaena, Lyngbya and Weistiellopsis, rich in carbon and nitrogen. The synthesized nanoparticles were used as heterogeneous photocatalyst for degradation of two harmful water pollutants, ciprofloxacin (CIP) and levofloxacin (LEV). 99.91% LEV and 98.86% CIP were degraded within 50 and 70 min of visible light irradiation using NiFe@NCF following pseudo first order kinetics. This improved efficiency of the nanocomposite may be attributed to its higher surface area, reduction of band gap (from 2.42 to 2.19 eV), more active sites as well as charge carrier mobility with decreasing agglomeration tendency of the magnetic nickel nanoparticles upon being embedded on NCF. N-doping improves light harvesting property, retards charge recombination and extends as well as delocalises ᴨ-conjugated system resulting in enhanced photocatalytic activity. The scavenging experiments and EPR analysis reveal that and •OH are the main active species taking part in the degradation process. The material performs well within a wide range of pH and can be effectively used up to 5 repetitive cycles. A feasible photocatalytic degradation mechanism of the antibiotics against NiFe@NCF nanocomposite is also put forwarded along with their possible degradation pathways from LCMS studies.

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity.

Solar-driven methanation of carbon dioxide (CO2) with water (H2O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO2 was often hindered by the sluggish kinetics and the multiple competition of other C1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co3O4/SiC catalyst. The substantial difference in work functions between SiC and Co3O4 served as a significant source of the charge driving force, facilitating the conversion of CO2 to CH4. The high-valent cobalt Co(IV) in Co3O4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO2 methanation. DFT calculation showed that the energy barrier of CO2 hydrogenation was significantly reduced at the Co3O4/SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH4. The optimum CH4 evolution rate of Co3O4/SiC samples was 21.3 μmol g-1 h-1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO2 to CH4 products in photocatalysis applications.

Pulse-doubling perovskite nanowire lasers enabled by phonon-assisted multistep energy funneling

Laser pulse multiplication from an optical gain medium has shown great potential in miniaturizing integrated optoelectronic devices. Perovskite multiple quantum wells (MQWs) structures have recently been recognized as an effective gain media capable of doubling laser pulses that do not rely on external optical equipment. Although the light amplifications enabled with pulse doubling are reported based on the perovskite MQWs thin films, the micro-nanolasers possessed a specific cavity for laser pulse multiplication and their corresponding intrinsic laser dynamics are still inadequate. Herein, a single-mode double-pulsed nanolaser from self-assembled perovskite MQWs nanowires is realized, exhibiting a pulse duration of 28 ps and pulse interval of 22 ps based on single femtosecond laser pulse excitation. It is established that the continuous energy building up within a certain timescale is essential for the multiple population inversion in the gain medium, which arises from the slowing carrier localization process owning to the stronger exciton–phonon coupling in the smaller-n QWs. Therefore, the double-pulsed lasing is achieved from one fast energy funnel process from the adjacent small-n QWs to gain active region and another slow process from the spatially separated ones. This report may shed new light on the intrinsic energy relaxation mechanism and boost the further development of perovskite multiple-pulse lasers.

Enhanced solar light-driven photocatalysis of norfloxacin using Fe-doped TiO2: RSM optimization, DFT simulations, and toxicity study.

This study investigates the photocatalytic degradation of norfloxacin (NFX) utilizing Fe-doped TiO2 nanocomposite under natural sunlight. TiO2-based photocatalysts were synthesized using chemical precipitation varying Fe-dopant concentration and characterized in detail. Theoretical modelling, centred on density functional theory (DFT), elucidated that Fe ions within the TiO2 lattice are effectively confined, thereby narrowing the wide band gap of TiO2. The findings strongly support that Fe3+ ions augmented the photocatalytic activity of TiO2 by facilitating an intermediate interfacial route for electron and hole transfer, particularly up to an optimal dopant concentration of 1.5M%. Subsequently, a three-level Box-Behnken design (BBD) was developed to determine the initial pH, optimal catalyst concentration, and drug dosage. High-performance liquid chromatography-mass spectrometry (HPLC-MS) was employed to identify reaction intermediates, thereby establishing a potential degradation pathway. Notably, sustained recyclability was achieved, with 82% degradation efficiency maintained over five cycles. Additionally, the toxicity of degradation intermediates was evaluated through bacterial and phytotoxicity tests, affirming the environmental safety of treated water. In vitro toxicity of the nanomaterial was also examined, emphasizing its environmental implications. Scavenger experiments revealed that hole and hydroxyl radicals were the primary active species in Fe-TiO2-based photocatalysis. Furthermore, the antibacterial potential of the synthesized catalyst was assessed using Escherichia coli and Staphylococcus aureus to observe their respective antibacterial responses.

CeO2 nanospheres incorporated with Bi2MoO6/g-C3N4 enhanced photocatalysis towards environmental pollutant Rhodamine B removal.

We have adopted a novel CeO2/Bi2MoO6/g-C3N4-based ternary nanocomposite that was synthesized via hydrothermal technique. The physiochemical characterization of as-prepared samples was examined through various analytical techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy TEM, photoluminescent spectra (PL), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), and ultraviolet diffuse reflectance spectroscopy (UV-DRS) technique. In addition, the photocatalytic performance was carried out by degradation of Rhodamine B dye under visible light irradiation using this nanocatalyst. The ternary nanocomposite achieved 94% of the degradation efficiency within 100min which is higher than the pristine and binary composites under the predetermined condition pH = 7, Rhodamine B dye = 5mg/L, and catalyst concentration = 150mg/L. The experimental synergetic effect of CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite has been ascribed to the interfacial charge carrier migration between CeO2, Bi2MoO6, and g-C3N4. The optical absorption range of CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite was enhanced, and the band gap was reduced up to 2.2eV. In addition, scavenger trapping experiment proves that the super oxide anions (O2-.) and photogenerated holes are the major active species. The reusability and stability experiment proved the CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite keeps good durability during the photocatalytic degradation process after the five successive cycles. Furthermore, based on the results, the charge carrier transfer photocatalytic mechanism was also discussed. This CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite may offer the cheapest material and extend the great opportunity for clean and environmental remediation approach under the visible light irradiation.

Constructing Functional Radiation-Resistant Thorium Clusters for Catalytic Redox Reactions.

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th12L3-MA12, Th12L3-MA6-BF6, and Th12L3-Fcc12, which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H+, O2•-, or tBuO/tBuOO•) and activation of substrate molecules, thus achieving superior catalytic performance. This work is not only the first to develop radiation-resistant thorium cluster catalysts to perform efficient redox reactions but also provides design ideas for the construction of high-nuclearity thorium clusters under mild conditions.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

AbstractCeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.