Lasers Research Articles

Wavelength-Dependent Activity of Oxygen Species in Propane Conversion on Rutile TiO2(110).

Photocatalytic oxidative dehydrogenation of propane (C3H8) into propene (C3H6) under mild conditions holds great potential in the chemical industry, but understanding how active species participate in C3H8 conversion remains a significant challenge. Here, the wavelength-dependent activities of bridging oxygen (Ob2-) and the Ti5c-bound oxygen adatom (OTi2-) of model rutile (R) TiO2(110) in C3H8 conversion have been investigated. Under 257 and 343 nm irradiation, hole-trapped OTi- and Ob- can abstract the hydrogen atom of C3H8, forming the CH3CH•CH3 radical and C3H6. However, the rate of C3H8 conversion with hole-trapped Ob- is strongly dependent on the wavelength, primarily producing the C3H7• radical. In the case of hole-trapped OTi-, C3H6 is the main product, which is nearly independent of wavelength. The differences in the wavelength-dependent activity and product selectivity are likely due to dynamic control rather than thermodynamic control. The result provides a deeper understanding of the dynamic processes involved in the conversion of light alkanes in TiO2 photocatalysis.

Insights into the Electrochemical CO2RR Performance and Binding of Small Molecules on Quaternary Thiospinels Ag2FeSn3S8 and Cu2FeSn3S8.

Using a mechanical synthesis method in the form of ball milling and an additional annealing step, a novel and accelerated route for the synthesis of the thiospinels toyohaite (Ag2FeSn3S8) and rhodostannite (Cu2FeSn3S8) was discovered. Both thiospinels display faradaic efficiencies of up to 73% for CO2 reduction to CO using an organic electrolyte in an H-type cell. The materials were furthermore implemented in a zero-gap electrolyzer, with toyohaite producing 22% CO and 52% H2 at 100 mA cm-2 and rhodostannite 28% CO and 37% H2. The catalytically active sites are studied using density functional theory, revealing strong CO binding interactions on both Ag and Cu, whereas Sn is found to contribute to the decomposition of Ag2FeSn3S8 and Cu2FeSn3S8 by coordination with oxygen. Postmortem analysis of the thiospinel-based electrodes by means of SEM-EDX, XRD, XPS, and Mössbauer spectroscopy showed sulfur leaching from the catalysts after applying 100 mA cm-2. These spectroscopic results-in conjunction with DFT calculations of the oxidized surfaces-suggest that the catalytically active species consists of metal oxides. As a conversion of the metal sulfides into the corresponding metallic species was observed via XRD, the decomposition pathways of both catalysts were also computed using DFT; thus, elucidating the energetically most favorable decomposition products and expanding the possible composition of the catalysts postelectrolysis.

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl3-tert-butyl chloride (TBC) adducts, which are formed by the dissociation of Al2Cl7− in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

All-in-One Alkaline Phosphatase-Response Aggregation-Induced Emission Probe for Cancer Discriminative Imaging and Combinational Chemodynamic-Photodynamic Therapy.

Currently, specific cancer-responsive fluorogenic probes with activatable imaging and therapeutic functionalities are in great demand in the accurate diagnostics and efficient therapy of malignancies. Herein, an all-in-one strategy is presented to realize fluorescence (FL) imaging-guided and synergetic chemodynamic-photodynamic cancer therapy by using a multifunctional alkaline phosphatase (ALP)-response aggregation-induced emission (AIE) probe, TPE-APP. By responding to the abnormal expression levels of an ALP biomarker in cancer cells, the phosphate groups on the AIE probe are selectively hydrolyzed, accompanied by in situ formation of strong emissive AIE aggregates for discriminative cancer cell imaging over normal cells and highly active quinone methide species with robust chemodynamic-photodynamic activities. Consequently, the activated AIE probes can efficiently destroy cancer cell membranes and lead to the death of cancer cells within 30 min. A superior efficacy in cancer cell ablation is demonstrated in vitro and in vivo. The cancer-associated biomarker response-derived discriminative FL imaging and synergistic chemodynamic-photodynamic therapy are expected to provide a promising avenue for precise image-guided cancer therapy.

Stimulating Electron Delocalization of Lanthanide Elements through High-Entropy Confinement to Promote Electrocatalytic Water Splitting.

High-entropy alloys (HEAs) have aroused extensive attention in the field of catalysis. However, due to the integration of multiple active sites in HEA, it exhibits excessive adsorption behavior resulting in difficult desorption of active species from the catalyst surfaces, which hinders the catalytic efficiency. Therefore, adjusting the adsorption strength of the active site in HEA to enhance the catalytic activity is of great importance. By introducing rare-earth (RE) elements into the high-entropy alloy, the delocalization of 4f electrons can be achieved through the interaction between the multimetal active site and RE, which benefits to regulate the adsorption strength of the HEA surface. Herein, the RE Ce-modified hexagonal-close-packed PtRuFeCoNiZn-Ce/C HEAs are synthesized and showed an excellent electrocatalytic activity for hydrogen evolution reaction and oxygen evolution reaction with ultralow overpotentials of 4, 7 and 156, 132 mV, respectively, to reach 10 mA cm-2 in 0.5 M H2SO4 and 1.0 M KOH solutions, and the assembled water electrolysis cell only requires a voltage of 1.43 V to reach 10 mA cm-2, which is much better than the performance of PtRuFeCoNiZn/C. Combined with the results of in situ attenuated total reflection infrared spectroscopy and density functional theory (DFT), the fundamental reasons for the improvement of catalyst activity come from two aspects: (i) local lattice distortion of HEA caused by the introduction of RE with large atomic radius induces 4f orbital electron delocalization of RE elements and enhances electron exchange between RE and active sites. (ii) The electronegativity difference between the RE element and the active site forms a surface dipole in HEA, which optimizes the adsorption of the active intermediate by the HEA surface site. This study provides an insightful idea for the rational design of high-performance HEA- and RE-based electrocatalysts.

Ultrabroadband two-beam coherent anti-Stokes Raman scattering and spontaneous Raman spectroscopy of organic fluids: A comparative study.

Spontaneous Raman spectroscopy is a well-established diagnostic tool, allowing for the identification of all Raman active species with a single measurement. Yet, it may suffer from low-signal intensity and fluorescent background. In contrast, coherent anti-Stokes Raman scattering (CARS) offers laser-like signals, but the traditional approach lacks the multiplex capability of spontaneous Raman spectroscopy. We present an ultrabroadband CARS setup which aims at exciting the full spectrum (300-3700 cm-1) of biological molecules. A dual-output optical parametric amplifier provides a ~7 fs pump/Stokes and a ~700 fs probe pulse. CARS spectra of DMSO, ethanol, and methanol show great agreement with spontaneous Raman spectroscopy and superiority in fluorescent environments. The spectral resolution proves sufficient to differentiate between the complex spectra of L-proline and hydroxyproline. Moreover, decay constants in the sub picosecond range are determined for individual Raman transitions, providing an additional approach for sample characterization.

Enhancing Performance of Organic Pollutant Degradation via Building Heterojunctions with ZnO Nanowires and Na Doped Conjugated 2,4,6-Triaminopyrimidin-g-C3N4

Organic pollutants were one of the main sources of environmental pollutants. The degradation of organic pollutants through photocatalytic technology was one of the effective solutions. By preparing zinc oxide(ZnO) nanowires modified with sodium-doped conjugated 2,4,6-triaminopyrimidin-g-C3N4 (NaTCN) heterojunction (ZnO/NaTCN), the photocatalytic performance of NaTCN modified with different ratios of ZnO was systematically studied. The photocatalytic performance was studied through the degradation performance of methyl blue (MB) dye. The results showed that 22.5 wt% ZnO/NaTCN had the best degradation effect on MB dye. The degradation rate of MB reached 98.54% in 70 min. After three cycles, it shows good cycling stability (degradation rate is 96.99%) for dye degradation. It was found that there are two types of active species: ·OH and h+, of which h+ is the main active species produced by photocatalytic degradation of dyes. The excellent degradation performance was attributed to the fact that ZnO facilitated the extraction and transport of photogenerated carriers. The doping of sodium facilitated charge transfer. The NaTCN conjugated system promoted the extraction and transfer of photogenerated carriers. It provided guidance for designing efficient composite catalysts for use in other renewable energy fields.

Promoting energy transfer via manipulation of crystallization kinetics of quasi-2D Dion–Jacobson phase perovskites for high-performance green lasers

Promoting energy transfer via manipulation of crystallization kinetics of quasi-2D Dion–Jacobson phase perovskites for high-performance green lasers

Mechanically Mixed Thermally Expanded Graphite/Cobalt(II) Perrhenate—Co(ReO4)2—As Electrodes in Hybrid Symmetric Supercapacitors

A mechanically homogenized composite of expanded graphite and cobalt(II) perrhenate has been described. Cobalt(II) perrhenate was obtained in a reaction of perrhenic acid with cobalt(II) nitrate. A simple mortar homogenization method was used to enhance the intercalation of cobalt species within the carbon matrix. The specific capacitance of the composite was enhanced by 50% (to 78 F/g) in comparison to bare expanded graphite (52 F/g). The electrochemical characteristics were significantly improved, including better cyclability (7% capacitance loss), a lower resistance of the electrode material, and a lower iR drop, with respect to expanded graphite without cobalt(II) perrhenate active species. Expanded graphite, with its unique specific surface area and pore size diameter, was proved to be a potential and cheap carbon support.

Elucidating Mechanism and Selectivity in Pyridine Functionalization through Silylium Catalysis.

The functionalization of aromatic N-heterocycles through silylium activation demonstrates exceptional selectivity and efficiency. Density functional theory (DFT) calculations unveil the detailed silylium catalysis mechanism and elucidate the origins of selectivity in this reaction. The phosphoramidimidate sulfonamide (PADI) precatalyst orchestrates of the catalytic cycle via three elementary steps. The Brønsted acidity of precatalyst significantly influences both the formation of silylium-based Lewis acid active species and the silylium activation of pyridine. Unlike disulfonimide (DSI)-type precatalysts, both Tf2NH and PADI precatalysts with strong acidities can easily promote the generation of activated silylium pyridine species. A semi-enclosed 'rigid' electronegative cavity in PADI-type anions constructs a well-defined recognition site, facilitating engagement with the positively charged silylium pyridine species. Due to the high electrophilicity and less steric demand at the C4-position of the pyridine substrate, the product with C4-regioselectivity was predominantly generated.

Identification of Key Active Species in the Conversion of C6 and C4 Sugars by Tungsten and Molybdenum Homogeneous Salts

Identification of Key Active Species in the Conversion of C6 and C4 Sugars by Tungsten and Molybdenum Homogeneous Salts

CO2‐Mediated Hydrogen Energy Release‐Storage Enabled by Arc‐Discharge‐Synthesized High‐Dispersion Platinum Catalysts

AbstractDeveloping and fabricating a heterogeneous material for efficient dehydrogenation of formic acid (FA) to H2 coupled with hydrogenation of CO2 back to FA is a promising strategy to forming a carbon‐neutral CO2‐mediated hydrogen energy release‐storage system, which remains challenging. Herein, a facile one‐step ultrahigh‐temperature method of arc‐discharge route for synthesizing efficient single‐crystal α‐MoC supported platinum catalysts with high dispersion of Pt single atoms (SAs), nanoclusters (NCs), and nanoparticles (NPs) is reported. These catalysts exhibit remarkable performance for the adsorption properties and chemical conversion of small molecules including room‐temperature FA dehydrogenation, CO2 hydrogenation to FA (formate), and low‐temperature CO oxidation reactions. The enhanced electron transfer from MoC to active Pt species improves catalyst's surface electron density, thus modulating the chemical adsorption of these small molecules. The engineered 0.1Pt/MoC with Pt SAs shows an outstanding FA dehydrogenation efficiency, with ca. 100% FA conversion and an initial TOF of up to 7739 h−1 at 25 °C. The versatile 0.1Pt/MoC also displays the ability for converting CO2 hydrogenation back to the hydrogen storage carrier FA (formate) with 88.3% yield under mild conditions. Moreover, in‐depth insights into the material microstructure, Pt−MoC electronic interactions, reaction‐dependent particle size effect, and adsorption energy are comprehensively investigated.

A novel Type-II Bi-based oxyhalide: Bi4O5I2/BiOBr microspheres for improved photocatalytic performance

Enhancing the oxidation and reduction capabilities of semiconductor catalysts through Type-II heterojunction engineering is a viable approach. A new photocatalytic material, Bi4O5I2/BiOBr, has been successfully developed by integrating Bi4O5I2 into the structure of BiOBr using a straightforward solvothermal technique. The significantly reducing electrons of Bi4O5I2 and the initially strongly oxidizing holes of BiOBr are effectively preserved in the hybrid material through a Type-II heterojunction. The formation of a heterostructure facilitates the movement and separation of photogenerated carriers. The 0.3 wt% Bi4O5I2/BiOBr exhibited the highest catalytic activity for degrading organic pollutants under visible light, with •O2− and h+ as the primary active species. The mechanism preserves the charge carrier's robust redox capability by utilizing the remarkably stable and reusable Bi4O5I2/BiOBr composite material for environmental protection. A hypothesis was proposed regarding the potential performance of Bi4O5I2/BiOBr under visible light mechanisms as direct Type-II heterojunction photocatalytic materials.

Glucose-montmorillonite hydrochar composite activating peroxymonosulfate for sulfentrazone rapid degradation and phytotoxicity alleviation to rice

Sulfentrazone is an excellent herbicide for the control of broad-leaved weeds and some grasses. However, its herbicidal residues pose potential risks to the environment. The use of carbonaceous materials as catalysts for activating peroxymonosulfate (PMS) for managing pesticide contamination has attracted considerable attention. Herein, the rapid degradation of sulfentrazone in water and the alleviation of sulfentrazone-induced phytotoxicity alleviation to rice were investigated using glucose-montmorillonite hydrochar (GM-HC) activating PMS. The findings revealed that the GM-HC/PMS system can rapidly degrade sulfamethoxazole and achieved 93.90% of removal efficiency in 24 h. Specifically, GM-HC activating PMS generated the active species, including sulfate radicals (SO4•–), singlet oxygens (1O2) and superoxide radicals (O2•−), which speeds up the degradation of sulfentrazone. Five major degradation products of sulfentrazone and two possible degradation pathways were proposed. The C-Cl and C-CH3 of sulfentrazone molecules are the initiation sites attacked by active species for degradation according to density functional theory (DFT) calculation. Additionally, after the sulfentrazone was degraded by GM-HC/PMS system, sulfentrazone-induced phytotoxicity to rice seeds and seedlings was significantly alleviated. This work presents a novel approach for addressing herbicide wastewater pollution.Graphical

Structure and Reactivity of Active Oxygen Species on Silver Surfaces for Ethylene Epoxidation.

The epoxidation of ethylene stands as one of the most important industrial catalytic reactions, and silver-based catalysts show superior activity and selectivity. Oxygen is activated on the surface of silver during the reaction and exerts a substantial impact on product selectivity. Notably, the oxygen species residing in the topmost atomic layers profoundly influence the reactivity of a catalyst. However, their characterization under in situ reaction conditions remains a huge challenge, and specific structures have not been identified yet. In this study, we employ in situ X-ray photoelectron spectroscopy and density functional theory calculations to determine the oxygen species formed at the topmost atomic layers of a silver foil and to assign them a structure. Three different groups of oxygen species activated on silver are identified: (i) surface lattice oxygen and two oxygen species originating from associatively adsorbed dioxygen and (ii) top and (iii) subsurface oxygen. Transient in situ photoelectron spectroscopy experiments are carried out to reveal the dynamic evolution and thus reactivity of the different oxygen species under ethylene epoxidation reaction environments. The top oxygen atom from the adsorbed associated dioxygen is the most active. Meanwhile, a frequency-selective data analysis method, developed to process time-resolved data, provides insights into the evolving trends of peak intensities for different oxygen species. The versatility of this method suggests its potential application in future time-resolved characterization studies.

In situ copper photocatalysts triggering halide atom transfer of unactivated alkyl halides for general C(sp3)-N couplings

Direct reduction of unactivated alkyl halides for C(sp3)-N couplings under mild conditions presents a significant challenge in organic synthesis due to their low reduction potential. Herein, we introduce an in situ formed pyridyl-carbene-ligated copper (I) catalyst that is capable of abstracting halide atom and generating alkyl radicals for general C(sp3)-N couplings under visible light. Control experiments confirmed that the mono-pyridyl-carbene-ligated copper complex is the active species responsible for catalysis. Mechanistic investigations using transient absorption spectroscopy across multiple decades of timescales revealed ultrafast intersystem crossing (260 ps) of the photoexcited copper (I) complexes into their long-lived triplet excited states (>2 μs). The non-Stern-Volmer quenching dynamics of the triplets by unactivated alkyl halides suggests an association between copper (I) complexes and alkyl halides, thereby facilitating the abstraction of halide atoms via inner-sphere single electron transfer (SET), rather than outer-sphere SET, for the formation of alkyl radicals for subsequent cross couplings.

Highly Stable Carboranyl Ligated Gold Nano-catalysts for Regioselective Aromatic Bromination.

Achieving electronic/steric control and realizing selectivity regulation in nanocatalysis remains a formidable challenge, as the dynamic nature of metal-ligand interfaces, including dissolution (metal leaching) and structural reconstruction, poses significant obstacles. Herein, we disclose carboranyls (CBs) as unprecedented carbon-bonded functional ligands (Eads.CB-Au(111) = -2.90 eV) for gold nanoparticles (AuNPs), showcasing their exceptional stabilization capability that is attributed by strong Au-C bonds combined with B-H⋯Au interactions. The synthesized CB@AuNPs exhibit core(Aun)-satellite(CB2Au-) structure, showing high stability towards multiple stimuli (110oC, pH = 1-12, thiol etchants). In addition, different from conventional AuNP catalysts such as triphenylphosphine (PPh3) stabilized AuNPs, dissolution of catalytically active gold species was suppressed in CB@AuNPs under the reaction conditions. Leveraging these distinct features, CB@AuNPs realized outstanding p:o selectivities in aromatic bromination. Unbiased arenes including chlorobenzene (up to > 30:1), bromobenzene (15:1) and phenyl acrylate were examined using CB@AuNPs as catalysts to afford highly-selective p-products. Both carboranyl ligands and carboranyl derived counterions are crucial for such regioselective transformation. This work has provided valuable insights for AuNPs in realizing diverse regioselective transformations.

Synthesis of ZnV2O6 nanosheet photocatalysts for efficient photodegradation of Rhodamine B: Experimental and RSM modeling

A ZnV2O6 photocatalyst with nano-sheet morphology was synthesized using a facile solvothermal approach. To optimize the photo-decomposition of Rhodamine B (RhB), a new surface response methodology (RSM) based on the Central Composite Design (CCD) approach was employed. Several structural/microstructural and spectroscopic characterization techniques were utilized to describe the physical and chemical characteristics of ZnV2O6 (ZVO) nanosheet such as XRD, Raman, SEM-TEM, DRS, PL/TRF. The optimal conditions for RhB photo-decomposition were mathematically discussed as a function of four variables such as pollutant dose, pH values, photocatalyst-weight, and irradiation time, which were modeled by CCD-RSM employing a quadratic statistical model and an optimization approach (ANOVA analysis). RhB degradation efficiency of 97 % was achieved for the optimal conditions of pH = 8, photocatalyst mass = 95 mg, RhB concentration = 9 ppm, and irradiation time = 120. The registered reaction constant was 0.029 min−1. The removal efficiencies of TOC and COD when using the ZVO photo-catalyst for the RhB degradation were 83 % and 88 % respectively. The re-usability of ZnV2O6 samples has been assessed in 4 consecutive series revealing a high stability of the material after extended periods of photo-catalytic reaction. Furthermore, the active radical species involved in the breakdown of RhB were further confirmed through quenching tests in which hydroxyls and holes were found to be the major species contributing to the decomposition of RhB.

Efficient removal of moxifloxacin through PMS activation by CuFeS2/MXene.

Due to the frequent detection and potential toxicity of moxifloxacin (MOX), its removal technology had attracted attention in recent years. In this research, CuFeS2/MXene was prepared and used to activate peroxymonosulfate (PMS) to remove MOX. The degradation efficiencies, kinetics, influences, and reaction mechanism of MOX by CuFeS2/MXene/PMS were investigated. The synergistic effect of CuFeS2 and MXene significantly enhanced PMS activation, producing SO4•-, HO•, and 1O2 as the main active species. By adding 0.12g/L CuFeS2/MXene and 0.12mM PMS, MOX removal efficiency reached 99.1% within 40min, with a rate constant of 0.1073min-1. The composite ratios of CuFeS2/MXene impacted PMS activation more significantly than catalyst dosages and PMS concentrations. Acidic conditions were favorable for the degradation of MOX, while HCO3-, HPO42-, Mn2+, and HA had the inhibitory effects. Twelve major products were detected by HPLC-MS, and DFT was used to illustrate possible degradation pathways of MOX, including the removal of nitrogen-containing heterocycle and transformations of quinolone moieties. Toxicity analysis showed that the developmental toxicity, mutagenicity, and acute toxicity of degradation products tended to decrease. CuFeS2/MXene could exhibit excellent reusability, maintaining an average MOX degradation efficiency of 90.8% in the 7-cycle experiments.

Study on the reducible metal oxide carriers to regulate the catalytic reaction performance of CO2 with ethane

Aiming at the resource utilization of CO2 and the value-added catalytic conversion of ethane, different reducibility oxide carriers were used to study. Through catalytic reaction experiments, catalyst characterization and kinetic analysis, the interaction between reducible carriers and active metals and their regulation on the catalytic reaction performance of ethane with CO2 were revealed. Fe1.5Ni0.5/CeO2 has the highest ethylene selectivity of 87% near 650 °C, and is a good catalyst for the CO2-assisted ethane oxidative dehydrogenation to ethylene reaction. The strong interaction between the reducible CeO2 and ZrO2 carriers and active metals makes the Fe–O–Ce and Fe–O–Zr covalent bonds on the Fe1.5Ni0.5/CeO2 and Fe1.5Ni0.5/ZrO2 catalysts stronger than Fe–O–Ti and Fe–O–Al covalent bonds on Fe1.5Ni0.5/TiO2 and Fe1.5Ni0.5/γ-Al2O3 catalysts. The lattice oxygen on the reducible catalyst is more readily involved in the reaction. The strong interaction between the active metal and the carrier results in the reduction of the FeOx species and the formation of new active sites, resulting in a high reactivity of the catalyst. The mutually promoted redox cycle between the active species Fe3+/2+-Ni2+/0 and the reducible carrier variable metal Ce4+/3+ species improves the catalytic performance for the reaction of ethane awith CO2.