Consumer Grade Polyethylene Recycling via Hydrogenolysis on Ultrafine Supported Ruthenium Nanoparticles.

Catalytic hydrogenolysis has the potential to convert high-density polyethylene (HDPE), which comprises about 30 % of plastic waste, into valuable alkanes. Most investigations have focused on increasing activity for lab grade HDPEs displaying low molecular weight, with limited mechanistic understanding of the product distribution. No efficient catalyst is available for consumer grades due to their lower reactivity. This study targets HDPE used in bottle caps, a waste form generated globally at a rate of approximately one million units per hour. Ultrafine ruthenium particles (1 nm) supported on titania (anatase) achieved up to 80 % conversion into light alkanes (C1 -C45 ) under mild conditions (498 K, 20 bar H2 , 4 h) and were reused for three cycles. Small ruthenium nanoparticles were critical to achieving relevant conversions, as activity sharply decreased with particle size. Selectivity commonalities and peculiarities across HDPE grades were disclosed by a reaction modelling approach applied to products. Isomerization cedes to backbone scission as the reaction progresses. Within this trend, low molecular weight favor isomerization whilst high molecular weight favor cleavage. Commercial caps obeyed this trend with decreased activity, anticipating the influence of additives in realistic processing. This study demonstrates effective hydrogenolysis of consumer grade polyethylene and provides selectivity patterns for product control.

Very Low Temperature CO Oxidation over Atomically Precise Au25 Nanoclusters on MnO2.

Atomically precise Au25 nanoclusters have garnered significant interest in the field of heterogeneous catalysis due to their remarkable activity and selectivity. However, for the extensively studied reaction of low-temperature CO oxidation, their performance has not been competitive compared to other known gold nanocatalysts. To address this, we deposited Au25(SR)18 (R = CH2CH2Ph) nanoclusters onto a manganese oxide support (Au25/MnO2), resulting in a very stable and highly active catalyst. By optimizing the pretreatment temperature, we were able to significantly enhance the performance of the Au25/MnO2 catalyst, which outperformed most other gold catalysts. Impressively, 100% conversion of CO was achieved at temperatures as low as -50 °C, with 50% conversion being reached below -70 °C. Furthermore, the existence of ligands could also influence the negative apparent activation energy observed at intermediate temperatures. Analysis using X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and X-ray diffraction (XRD) techniques indicated that the Au25 nanoclusters remained stable on the catalyst surface even after pretreatment at high temperatures. In-situ modulation excitation spectroscopy (MES) spectra also confirmed that the Au cluster was the active site for CO oxidation, highlighting the potential of atomically precise Au25 nanoclusters as primary active sites at very low temperatures.

Lattice-Stabilized Chromium Atoms on Ceria for N2O Synthesis.

The development of selective catalysts for direct conversion of ammonia into nitrous oxide, N2O, will circumvent the conventional five-step manufacturing process and enable its wider utilization in oxidation catalysis. Deviating from commonly accepted catalyst design principles for this reaction, reliant on manganese oxide, we herein report an efficient system comprised of isolated chromium atoms (1 wt %) stabilized in the ceria lattice by coprecipitation. The latter, in contrast to a simple impregnation approach, ensures firm metal anchoring and results in stable and selective N2O production over 100 h on stream up to 79% N2O selectivity at full NH3 conversion. Raman, electron paramagnetic resonance, and in situ UV-vis spectroscopies reveal that chromium incorporation enhances the density of oxygen vacancies and the rate of their generation and healing. Accordingly, temporal analysis of products, kinetic studies, and atomistic simulations show lattice oxygen of ceria to directly participate in the reaction, establishing the cocatalytic role of the carrier. Coupled with the dynamic restructuring of chromium sites to stabilize intermediates of N2O formation, these factors enable catalytic performance on par with or exceeding benchmark systems. These findings demonstrate how nanoscale engineering can elevate a previously overlooked metal into a highly competitive catalyst for selective ammonia oxidation to N2O, paving the way toward industrial implementation.

Support-facet-dependent morphology of small Pt particles on ceria.

Direct atomic scale information on how the structure of supported nanoparticles is affected by the metal-support interaction is rare. Using scanning transmission electron microscopy, we provide direct evidence of a facet-dependent support interaction for Pt nanoparticles on CeO2, governing the dimensionality of small platinum particles. Our findings indicate that particles consisting of less than ∼130 atoms prefer a 3D shape on CeO2(111) facets, while 2D raft structures are favored on CeO2(100) facets. Measurements of stationary particles on both surface facets are supplemented by time resolved measurements following a single particle with atomic resolution as it migrates from CeO2(111) to CeO2(100), undergoing a dimensionality change from 3D to 2D. The intricate transformation mechanism reveals how the 3D particle disassembles and completely wets a neighboring CeO2(100) facet. Density functional theory calculations confirm the structure-trend and reveal the thermodynamic driving force for the migration of small particles. Knowledge of the presented metal-support interactions is crucial to establish structure-function relationships in a range of applications based on supported nanostructures.

Reaction-Induced Metal-Metal Oxide Interactions in Pd-In2 O3 /ZrO2 Catalysts Drive Selective and Stable CO2 Hydrogenation to Methanol.

Ternary Pd-In2 O3 /ZrO2 catalysts exhibit technological potential for CO2 -based methanol synthesis, but developing scalable systems and comprehending complex dynamic behaviors of the active phase, promoter, and carrier are key for achieving high productivity. Here, we show that the structure of Pd-In2 O3 /ZrO2 systems prepared by wet impregnation evolves under CO2 hydrogenation conditions into a selective and stable architecture, independent of the order of addition of Pd and In phases on the zirconia carrier. Detailed operando characterization and simulations reveal a rapid restructuring driven by the metal-metal oxide interaction energetics. The proximity of InPdx alloy particles decorated by InOx layers in the resulting architecture prevents performance losses associated with Pd sintering. The findings highlight the crucial role of reaction-induced restructuring in complex CO2 hydrogenation catalysts and offer insights into the optimal integration of acid-base and redox functions for practical implementation.

Oriented Porous NASICON 3D Framework via Freeze-Casting for Sodium-Metal Batteries.

Sodium-metal batteries are promising candidates for low-cost, large-format energy storage systems. However, sodium-metal batteries suffer from high interfacial resistance between the electrodes and the solid electrolyte, leading to poor electrochemical performance. We demonstrate a sodium superionic conductor (NASICON) with an oriented porous framework of sodium aluminum titanium phosphate (NATP) fabricated by the freeze-casting technique, which shows excellent properties as a solid electrolyte. Using X-ray computed tomography, we confirm the uniform low-tortuosity channels present along the thickness of the scaffold. We infiltrated the porous NATP scaffolds with sodium vanadium phosphate (NVP) cathode nanoparticles achieving mass loadings of ∼3-4 mg cm-2, which enables short sodium ion diffusion path lengths. For the resulting hybrid cell, we achieved a capacity of ∼90 mAh g-1 at a specific current of 50 mA g-1 (∼300 Wh kg-1) for over 100 cycles with ∼94% capacity retention. Our study offers valuable insights for the design of hybrid solid electrolyte-cathode active material structures to achieve improved electrochemical performance through low-tortuosity ion transport networks.

Low-Valent Manganese Atoms Stabilized on Ceria for Nitrous Oxide Synthesis.

Nitrous oxide, N2 O, exhibits unique reactivity in oxidation catalysis, but the high manufacturing costs limit its prospective uses. Direct oxidation of ammonia, NH3 , to N2 O can ameliorate this issue but its implementation is thwarted by suboptimal catalyst selectivity and stability, and the lack of established structure-performance relationships. Systematic and controlled material nanostructuring offers an innovative approach for advancement in catalyst design. Herein low-valent manganese atoms stabilized on ceria, CeO2 , are discovered as the first stable catalyst for NH3 oxidation to N2 O, exhibiting two-fold higher productivity than the state-of-the-art. Detailed mechanistic, computational and kinetic studies reveal CeO2 as the mediator of oxygen supply, while undercoordinated manganese species activate O2 and facilitate N2 O evolution via NN bond formation between nitroxyl, HNO, intermediates. Synthesis via simple impregnation of a small metal quantity (1 wt%) predominantly generates isolated manganese sites, while full atomic dispersion is achieved upon redispersion of sporadic oxide nanoparticles during reaction, as confirmed by advanced microscopic analysis and electron paramagnetic resonance spectroscopy. Subsequently, manganese speciation is maintained, and no deactivation is observed over 70 h on stream. CeO2 -supported isolated transition metals emerge as a novel class of materials for N2 O production, encouraging future studies to evaluate their potential in selective catalytic oxidations at large.

Improved mitigation of self-phase modulation induced impairments in 28 GBaud phase-sensitive amplified links.

The improved mitigation of self-phase modulation (SPM) induced nonlinear impairments by the use of a multi-span dispersion map optimization in 28 GBaud phase-sensitive amplifier (PSA) links is numerically investigated. We show that a four-span dispersion map optimized PSA link provides 2.1 times reach improvement over a single-span optimized PSA link with a total nonlinear phase shift tolerance increase from 2.1 radians to 8.8 radians. Furthermore, the optimized PSA link increases the maximum transmission reach by 6.9 times compared to a single-span optimized in-line dispersion managed phase-insensitive amplifier (PIA) link and 4.3 times reach extension is achieved compared to a dispersion unmanaged PIA link.

Publisher Correction: Long-haul optical transmission link using low-noise phase-sensitive amplifiers.

The original version of this Article incorrectly listed an affiliation of Samuel L.I. Olsson as 'Thomas Johann Seebeck Department of Electronics, Tallinn University of Technology, Tallinn 19086, Estonia', instead of the correct 'Present address: Nokia Bell Labs, 791 Holmdel Road, Holmdel, NJ 07733, USA'. Similarly, Egon Astra had an incorrect affiliation of 'Present address: Nokia Bell Labs, 791 Holmdel Road, Holmdel, NJ 07733, USA', instead of the correct 'Thomas Johann Seebeck Department of Electronics, Tallinn University of Technology, Tallinn 19086, Estonia'. This has been corrected in both the PDF and HTML versions of the Article.

Phase-sensitive amplifier link with distributed Raman amplification.

We demonstrate long-haul transmission using a hybrid amplifier approach combining distributed Raman amplification and lumped phase-sensitive amplification. Aside from the well-known resulting SNR improvement, distributed Raman amplification is included in an effort to improve the nonlinearity mitigation capability of the phase-sensitive amplifiers. When changing from phase-insensitive operation to phase-sensitive operation in a link employing distributed Raman amplification, the transmission reach at BER = 10-3 is increased from 15 to 44 spans of length 81 km while simultaneously increasing the optimal launch power by 2 dB.

Long-haul optical transmission link using low-noise phase-sensitive amplifiers.

The capacity and reach of long-haul fiber optical communication systems is limited by in-line amplifier noise and fiber nonlinearities. Phase-sensitive amplifiers add 6 dB less noise than conventional phase-insensitive amplifiers, such as erbium-doped fiber amplifiers, and they can provide nonlinearity mitigation after each span. Realizing a long-haul transmission link with in-line phase-sensitive amplifiers providing simultaneous low-noise amplification and nonlinearity mitigation is challenging and to date no such transmission link has been demonstrated. Here, we demonstrate a multi-channel-compatible and modulation-format-independent long-haul transmission link with in-line phase-sensitive amplifiers. Compared to a link amplified by conventional erbium-doped fiber amplifiers, we demonstrate a reach improvement of 5.6 times at optimal launch powers with the phase-sensitively amplified link operating at a total accumulated nonlinear phase shift of 6.2 rad. The phase-sensitively amplified link transmits two data-carrying waves, thus occupying twice the bandwidth and propagating twice the total power compared to the phase-insensitively amplified link.

Dispersion management for nonlinearity mitigation in two-span 28 GBaud QPSK phase-sensitive amplifier links.

We present an investigation of dispersion map optimization for two-span single-channel 28 GBaud QPSK transmission systems with phase-sensitive amplifiers (PSAs). In experiments, when the PSA link is operated in a highly nonlinear regime, a 1.4 dB error vector magnitude (EVM) improvement is achieved compared to a one-span optimized dispersion map link due to improved nonlinearity mitigation. The two-span optimized dispersion map of a PSA link differs from the optimized dispersion map of a dispersion managed phase-insensitive amplifier (PIA) link. Simulations show that the performance of the two-span dispersion map optimized PSA link does not improve by residual dispersion optimization. Further, by using the two-span optimized dispersion maps repeatedly in a long-haul PSA link instead of one-span optimized maps, the maximum transmission reach can be improved 1.5 times.

Mitigation of nonlinear distortion in hybrid Raman/phase-sensitive amplifier links.

Hybrid systems combining distributed Raman amplification and phase-sensitive amplifiers (PSAs) are investigated in numerical simulations. We focus on the mitigation of fiber nonlinearities and the impact of the span power map which is also important in systems employing optical phase conjugation or phase-conjugated twin waves. We simulate multi-span PSA links with and without distributed Raman amplification and show that by including distributed Raman amplification, the transmission distance increases more at optimum launch power than in the linear regime. For a 5-channel WDM QPSK PSA-amplified system, we observe a transmission reach increase by a factor of 8.1 by including ideal distributed Raman amplification.

Mitigation of nonlinearities using conjugate data repetition.

We investigate a time-domain implementation of generalized phase-conjugated twin waves which we call conjugate data repetition. A theory based on time-domain perturbation analysis explaining the mitigation of nonlinear effects is provided, and the concept is evaluated using numerical simulations. Compared to PM-QPSK at the same channel bit rate, the single-channel transmission reach in a conventional system with standard single-mode fiber of conjugate data repetition-QPSK is increased by approximately a factor of 2.

Landscape epidemiology of tularemia outbreaks in Sweden.

Summer outbreaks of tularemia that occurred from 1995 through 2005 in 2 locations in Sweden affected 441 persons. We performed an epidemiologic investigation of these outbreaks using a novel strategy, involving high-resolution genotyping of Francisella tularensis isolates obtained from 136 patients (using 18 genetic markers developed from 6 F. tularensis genome sequences) and interviews with the patients. Strong spatial associations were found between F. tularensis subpopulations and the places of disease transmission; infection by some subpopulations occurred within areas as small as 2 km(2), indicating unidentified environmental point sources of tularemia. In both locations, disease clusters were associated with recreational areas beside water, and genetic subpopulations were present throughout the tularemia season and persisted over years. High-resolution genotyping in combination with patients' statements about geographic places of disease transmission provided valuable indications of likely sources of infection and the causal genotypes during these tularemia outbreaks.

Kinetics of the immune response associated with tularemia: comparison of an enzyme-linked immunosorbent assay, a tube agglutination test, and a novel whole-blood lymphocyte stimulation test.

We have developed and evaluated a novel and simplified whole-blood lymphocyte stimulation assay that focuses on the measurement of gamma interferon after 24 h of stimulation with whole-cell tularemia antigen and a tularemia enzyme-linked immunosorbent assay (ELISA) based on highly purified lipopolysaccharide antigen. Comparison of the kinetics of the two assays and those of the traditional tube agglutination test shows that the cellular immune response can be detected earlier by the lymphocyte stimulation assay. This test already shows a high proportion of positive results during the first week after the onset of the disease, may be applicable in everyday laboratory practice, and has the potential of changing routine diagnostics for tularemia. The new ELISA has a high sensitivity and becomes positive to a high degree during the second week of disease.

Tularaemia in an emergent area in Sweden: an analysis of 234 cases in five years.

A retrospective study of clinical tularaemia in an emergent area in Sweden is presented. 234 patients seen during the y 2000-2004 were studied, using case files and a questionnaire. There was a predominance of ulceroglandular tularaemia (89%), occurring in late summer and early autumn, reflecting the dominance of mosquito-borne transmission. The incubation period varied from a few hours to 11 d, with a median of 3 d. Cutaneous manifestations of tularaemia, apart from primary lesions, were noted in 43% of the cases. Coughing was common, even in patients with ulceroglandular tularaemia, supporting the view that haematogenous spread to the respiratory system occurs. Regular laboratory tests, such as WBC, ESR and C-reactive protein, were in general only moderately elevated. In the earlier y studied, the Doctor's Delay was substantial as was the misdiagnosis and prescription of inadequate antibiotics. In the later y, however, the delay and misdiagnosis were significantly lower, reflecting the increased recognition of the disease by the physicians in the area. A few relapses occurred, all in patients treated with doxycycline. No lethality was seen, reflecting the benign course of tularaemia type B infection.

Clinical use of a diagnostic PCR for Francisella tularensis in patients with suspected ulceroglandular tularaemia.

A retrospective analysis to evaluate the clinical use of a diagnostic PCR for Francisella tularensis in patients with suspected ulceroglandular tularaemia was performed. 154 samples, 129 from patients with definitive tularaemia and 25 from patients where tularaemia could be ruled out, were analysed. The diagnostic PCR had a specificity of 96%, a sensitivity of 78.3%, and a Positive Predictive Value of 99%. Especially samples from encrusted lesions, even up to 4 weeks old, in patients with tularaemia, were PCR positive to a high degree when taken properly. The diagnostic PCR is useful in suspected ulceroglandular tularaemia, giving a fast and accurate diagnosis.