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Primary alkyl halides have broad utility as fine chemicals in organic synthesis. The direct halogenation of alkenes is one of the most efficient approaches for the synthesis of these halides. Internal alkenes, in particular mixtures of isomers from refineries, constitute readily available and inexpensive feedstock and are the most attractive starting materials for this synthesis. However, the hydrohalogenation of alkenes generally affords branched alkyl halides; there are no catalytic methods to prepare linear alkyl halides directly from internal alkenes, let alone from a mixture of alkene isomers. Here we report the remote oxidative halogenation of alkenes under palladium catalysis via which both terminal and internal alkenes yield primary alkyl halides efficiently. Engineering pyridine-oxazoline ligands by introducing a hydroxyl group is essential for achieving excellent chemo- and regioselectivity. The catalytic system is also good for the mixture of alkene isomers generated from dehydrogenation of alkanes, providing a window to investigate the high-value utilization of inexpensive alkanes.

Imitating the natural photosynthesis to synthesize hydrocarbon fuels represents a viable strategy for solar-to-chemical energy conversion, where utilizing low-energy photons, especially near-infrared photons, has been the ultimate yet challenging aim to further improving conversion efficiency. Plasmonic metals have proven their ability in absorbing low-energy photons, however, it remains an obstacle in effectively coupling this energy into reactant molecules. Here we report the broadband plasmon-induced CO2 reduction reaction with water, which achieves a CH4 production rate of 0.55 mmol g−1 h−1 with 100% selectivity to hydrocarbon products under 400 mW cm−2 full-spectrum light illumination and an apparent quantum efficiency of 0.38% at 800 nm illumination. We find that the enhanced local electric field plays an irreplaceable role in efficient multiphoton absorption and selective energy transfer for such an excellent light-driven catalytic performance. This work paves the way to the technique for low-energy photon utilization.

Summary Synthetic understanding is crucial for designing halide perovskites with controlled properties and for paving ways to create a new family of structures. With expanding synthetic approaches, it is especially necessary to elucidate the formation of halide perovskites and how that influences their associated properties to inform a unifying design principle. In this perspective, we summarize key milestones in the synthesis community of inorganic halide perovskite nanostructures and highlight how the reaction kinetics and thermodynamics of halide perovskites distinguish them from traditional inorganic semiconductors. We then present a retrospective view that conceptually unites physical chemistry theories with advanced synthesis and address lingering questions in the field along with possible solutions. This perspective aims to articulate the relation between structural properties, synthetic tunability, and the environmental stability of halide perovskites and to provide an outlook for new generations of halide perovskite nanostructures for efficient and stable devices.

The soft, dynamic lattice of inorganic lead halide perovskite CsPbX3 (X = Cl-, Br-, I-) leads to the emergence of many interesting photophysical and optoelectronic phenomena. However, probing their lattice dynamics with vibrational spectroscopy remains challenging. The influence of the fundamental octahedral building block in the perovskite lattice can be better resolved in zero-dimensional (0D) vacancy-ordered double perovskites of form A2BX6. Here we study Cs2TeX6 (X = Cl-, Br-, I-) single crystals to yield detailed insight into the fundamental octahedral building block and to explore the effect that its isolation in the crystal structure has on structural and electronic properties. The isolated [TeX6]2- octahedral units serve as the vibrational, absorbing, and emitting centers within the crystal. Serving as the vibrational centers, the isolated octahedra inform the likelihood of a random distribution of 10 octahedral symmetries within the mixed-halide spaces, as well as the presence of strong exciton-phonon coupling and anharmonic lattice dynamics. Serving as the absorbing and emitting centers, the isolated octahedra exhibit compositionally tunable absorption (1.50-3.15 eV) and emission (1.31-2.11 eV) energies. Due to greater molecular orbital overlap between neighboring octahedra with increasing halide anion size, there is a transition from a more molecule-like electronic structure in Cs2TeCl6 and Cs2TeBr6-as expected from the effective 0D nature of these single crystals-to a dispersive electronic structure in Cs2TeI6, typical of three-dimensional (3D) bulk single crystals.

Oxidative stress plays a key role in the progress of acute lung injury (ALI), which is an acute, progressive respiratory failure characterized by alveolar capillary injury caused by various external and internal factors other than cardiogenic factors. Pulmonary vascular endothelial cells are the main target cells during ALI, and therefore the mitochondrial targeting antioxidant derivative triphenylphosphine-melatonin (TPP-MLT) was encapsulated in VCAM-1 antibodies-conjugated nanostructured lipid carriers (VCAM@TPP-MLT NLCs) for lung targeting delivery. VCAM@TPP-MLT NLCs could be preferentially internalized by inflammatory endothelial cells in lung tissues, and then the released TPP-MLT from NLCs effectively eliminated the excessive reactive oxide species (ROS) and ameliorated cell apoptosis. Overall, the results suggested that VCAM@TPP-MLT NLCs exhibited remarkable in vitro and in vivo therapeutic effect on ALI, and could be a promising and efficient strategy for the treatment of ALI.

Electrochemical water splitting operated under acidic conditions provides a clean approach to generate hydrogen fuels. Currently, the sluggish kinetics of oxygen evolution reaction (OER) at the anode is a bottleneck limiting the acidic water splitting. Here, we report that the OER activity of Ir, one of the most commonly used OER catalysts, can be boosted by forming phase boundaries with Au. Mixed Au and Ir catalysts were synthesized on carbon paper electrodes, which underwent structural evolution under the OER environment to form an Au-Ir interface-rich structure. Compared with Ir catalyst, which requires an overpotential of ∼393 mV to achieve a current density of 10 mA/cm2 in 0.1 M HClO4 electrolyte, the evolved Au-Ir catalyst shows a lower overpotential at ∼351 mV. X-ray photoelectronic spectrum (XPS) study, in conjunction with electrochemical analysis on the surface-site-normalized activity, reveals that the improved OER performance is due to the presence of Au/Ir interfaces in the catalysts. In addition to Ir, the strategy of accelerating OER via Au/Ir interfaces has been further applied to IrCo, IrNi, and IrCu alloy catalysts. With the broad applicability of the strategy demonstrated, this study opens a new route to design OER catalysts for efficient acidic water splitting.

Phase-separation is commonly observed in multimetallic nanomaterials, yet it is not well understood how immiscible elements distribute in a thermodynamically stable nanoparticle. Herein, we studied the phase-separation of Au and Rh in nanoparticles using electron microscopy and tomography techniques. The nanoparticles were thermally annealed to form thermodynamically stable structures. HAADF-STEM and EDS characterizations reveal that Au and Rh segregate into two domains while their miscibility is increased. Using aberration-corrected HAADF-STEM and atomic electron tomography, we show that the increased solubility of Au in Rh is achieved by forming Au clusters and single atoms inside the Rh domains and on the Rh surface. Furthermore, based on the three-dimensional reconstruction of a AuRh nanoparticle, we can visualize the uneven interface that is embedded in the nanoparticle. The results advance our understanding on the nanoscale thermodynamic behavior of metal mixtures, which is crucial for the optimization of multimetallic nanostructures for many applications.

The structural diversity and tunable optoelectronic properties of halide perovskites originate from the rich chemistry of the metal halide ionic octahedron [MX6]n- (M = Pb2+, Sb3+, Te4+, Sn4+, Pt4+, etc.; X = Cl-, Br-, and I-). The properties of the extended perovskite solids are dictated by the assembly, connectivity, and interaction of these octahedra within the lattice environment. Hence, the ability to manipulate and control the assembly of the octahedral building blocks is paramount for constructing new perovskite materials. Here, we propose a systematic supramolecular strategy for the assembly of [MX6]n- octahedra into a solid extended network. Interaction of alkali metal-bound crown ethers with the [M(IV)X6]2- octahedron resulted in a structurally and optoelectronically tunable "dumbbell" structural unit in solution. Single crystals with diverse packing geometries and symmetries will form as the solid assembly of this new supramolecular building block. This supramolecular assembly route introduces a new general strategy for designing halide perovskite structures with potentially new optoelectronic properties.

Triiodide perovskites $${\rm CsPbI}_{3}$$ , $${\rm CsSnI}_{3}$$ , and $${\rm FAPbI}_{3}$$ (where FA is formamidinium) are highly promising materials for a range of optoelectronic applications in energy conversion. However, they are thermodynamically unstable at room temperature, preferring to form low-temperature (low-T) non-perovskite phases with one-dimensional anisotropic crystal structures. While such thermodynamic behavior represents a major obstacle toward realizing high-performance devices based on their high-temperature (high-T) perovskite phases, the underlying phase transition dynamics are still not well understood. Here we use in situ optical micro-spectroscopy to quantitatively study the transition from the low-T to high-T phases in individual $${\rm CsSnI}_{3}$$ and $${\rm FAPbI}_{3}$$ nanowires. We reveal a large blueshift in the photoluminescence (PL) peak (~38 meV) at the low-T/high-T two-phase interface of partially transitioned $${\rm FAPbI}_{3}$$ wire, which may result from the lattice distortion at the phase boundary. Compared to the experimentally derived activation energy of CsSnI3 (~1.93 eV), the activation energy of $${\rm FAPbI}_{3}$$ is relatively small (~0.84 eV), indicating a lower kinetic energy barrier when transitioning from a face-sharing octahedral configuration to a corner-sharing one. Further, the phase propagation rate in CsSnI3 is observed to be relatively high, which may be attributed to a high concentration of Sn vacancies. Our results could not only facilitate a deeper understanding of phase transition dynamics in halide perovskites with anisotropic crystal structures, but also enable controllable manipulation of optoelectronic properties via local phase engineering. Metal halide perovskites are a new class of semiconductors with great promise for a variety of optoelectronic applications. Owing to their soft ionic lattice, halide perovskites often exhibit rich phase transitions between different crystal structures, frequently from the “active” perovskite phases to undesirable “inactive” non-perovskite phases. Understanding and controlling this transition is vital for developing stable, high-performance devices. However, there is limited understanding on how different symmetry, crystal structure, and defect would impact such a phase transition process. In this report, in situ optical micro-spectroscopy is used to systematically investigate the phase transitions from non-perovskite to perovskite phases in individual CsSnI3 and FAPbI3 wires. Compared to the transition from an edge-sharing octahedral non-perovskite structure to a corner-sharing perovskite structure in CsSnI3, the activation energy for the FAPbI3 phase transition is relatively small, indicating a lower energy barrier when starting from a face-sharing octahedral structure in FAPbI3. The high concentration of Sn vacancies is probably responsible for the much higher phase propagation rate in CsSnI3 when compared to a CsPbBrxI3-x system with the same crystal structure but different halide vacancies. Our experimental results expand the knowledge of phase transition in halide perovskites and offer important guidance toward rationally designing more stable and efficient perovskite devices.

Exposure to air pollution may increase the risk of obesity, but living in greener space may reduce this risk. Epidemiological evidence, however, is inconsistent.Using data from the China Health and Retirement Longitudinal Study (2011-2015), we conducted a nationwide cohort study of 7424 adults. We measured overweight/obesity according to body mass index. We used annual average ground-level air pollutants, including ozone (OWe found that lower risk of overweight/obesity was associated with more greenness exposure and lower levels of air pollution. We identified that an interquartile increment in NDVI was correlated with a lower hazard ratio (HR) of becoming overweight or obese (HR = 0.806, 95% confidence interval [CI]: 0.754-0.862). Although a 10 μg/mAn increased risk of being overweight or obese in middle-aged and older adults in China was associated with long-term exposure to higher levels of PM

Greenness is an emerging modifiable environmental factor of high blood pressure and hypertension. However, current evidence is inconsistent, and high-quality studies are urgently needed, especially in developing country with high disease burden of hypertension.A longitudinal study was designed and 9,649 participants (aged ≥45 years) with 22,854 number of visits among three waves between 2011 and 2015 were included based on the China Health and Retirement Longitudinal Study. Long term greenness exposure was assessed by annual normalized difference vegetation index (NDVI). Linear and generalized linear mixed effect models were used to estimate the associations between greenness and blood exposure level and hypertension risk, respectively.The median NDVI level was 0.51, with a range from 0.09 to 0.74. An interquartile range (0.15) increase in NDVI was related to 1.05 mmHg reduction (95% CI: -1.65, -0.45) of systolic blood pressure, 0.72 mmHg reduction (95% CI: -1.06, -0.37) of diastolic blood pressure, and 12% (95% CI: 1%, 22%) lower odds of hypertension risk. The association of greenness and blood pressure was significantly stronger in the younger (60 years) than in the older (≥60 years), and partially mediated by body mass index.These findings highlight the protective effect of greenness on blood pressure and hypertension in Chines middle-aged and elderly population, especially in the younger (60 years), and suggest policy makers to take greenness level into special consideration in the process of urbanization.

Summary Tandem electrocatalysis decouples individual steps within a chemically complicated pathway via multicomponent catalyst design. Such a concept is attractive for CO2 electro-conversion to multicarbons (C2+), especially at high rates. Here, we show that a Cu-Ag tandem catalyst on a gas diffusion electrode (GDE) can enhance the C2+ production rate from CO2 through CO2 reduction to CO on Ag and subsequent carbon coupling on Cu. With added Ag, the C2+ partial current over a Cu surface increases from 37 to 160 mA/cm2 at −0.70 V versus reversible hydrogen electrode (RHE) in 1 M KOH with no mutual interference between the two metals. Moreover, the intrinsic C2H4 and C2H5OH activity in the tandem platform is significantly higher than Cu alone under either pure CO2 or CO atmosphere. Our results indicate that the CO-enriched local environment generated by Ag can enhance C2+ formation on Cu beyond CO2 or CO feeding, suggesting new mechanisms in a tandem three-phase environment.

A platinum-based nanoframe is a hollow frame with superior catalytic behavior, and a metal-organic framework (MOF) is another porous frame with multifunctionalities. Here, we present the combination of these two components into an individually encapsulated frame-in-frame structure. Via the surface functionalization with hexadecyltrimethylammonium bromide (CTAB) as the bridging layer, the Pt-Ni nanoframe is encased in a special MOF, zeolitic imidazolate framework-8 (ZIF-8), to achieve a single core-shell structure, as evidenced by the three-dimensional tomography. The growth trajectory of such frame-in-frame nanocomposite is also tracked, revealing that ZIF-8 first nucleates in the solution, then attaches to the surface of the nanoframe, and finally grows to capture the entire nanoframe, accomplishing the one-in-one encapsulation. Following the same concept, by utilizing ZIF-67 as the sacrificial layer, the Pt-Ni nanoframe is further solely embedded in ZIF-8 to form the single yolk-shell structure, which has a cavity between the core and the shell. This work provides a new method to build frame-in-frame structures, consisting of different frameworks, and to explore their synergistic properties.

Ferroelectric semiconductors are rare materials with both spontaneous polarizations and visible light absorptions that are promising for designing functional photoferroelectrics, such as optical switches and ferroelectric photovoltaics. The emerging halide perovskites with remarkable semiconducting properties also have the potential of being ferroelectric, yet the evidence of robust ferroelectricity in the typical three-dimensional hybrid halide perovskites has been elusive. Here, we report on the investigation of ferroelectricity in all-inorganic halide perovskites, CsGeX 3 , with bandgaps of 1.6 to 3.3 eV. Their ferroelectricity originates from the lone pair stereochemical activity in Ge (II) that promotes the ion displacement. This gives rise to their spontaneous polarizations of ~10 to 20 μC/cm 2 , evidenced by both ab initio calculations and key experiments including atomic-level ionic displacement vector mapping and ferroelectric hysteresis loop measurement. Furthermore, characteristic ferroelectric domain patterns on the well-defined CsGeBr 3 nanoplates are imaged with both piezo-response force microscopy and nonlinear optical microscopic method.

Temperature is increasingly understood to impact mental health. However, evidence of the long-term effect of temperature exposure on the risk of depressive symptoms is still scarce. Based on the China Health and Retirement Longitudinal Study (CHARLS), this study estimated associations between long-term apparent temperature, extreme temperature, and depressive symptoms in middle-aged and older adults. Results showed that a 1 °C increase or decrease from optimum apparent temperature (12.72 °C) was associated with a 2.7% (95% CI: 1.3%, 4.1%) and 2.3% (95% CI: 1.1%, 3.5%) increased risk of depressive symptoms, respectively. This study also found that each percent increase in annual change in ice days, cool nights, cool days, cold spell durations, and tropical nights was associated with higher risk of depressive symptoms, with HRs (95%CI) of 1.289 (1.114–1.491), 2.064 (1.507–2.825), 1.315 (1.061–1.631), 1.645 (1.306–2.072), and 1.344 (1.127–1.602), respectively. The results also indicated that people living in northern China have attenuated risk of low apparent temperature. Older people were also observed at higher risk relating to more cool nights. Middle-aged people, rural residents, and people with lower household income might have higher related risk of depressive symptoms due to increased tropical nights. Given the dual effect of climate change and global aging, these findings have great significance for policy making and adaptive strategies for long-term temperature and extreme temperature exposure.

According to animal and human epidemiologic studies, exposure to outdoor light at night (LAN) may cause circadian disruption, which may disturb sleep quality and lead to incident type 2 diabetes mellitus (T2DM).We followed 283,374 persons from 2006 through 2020. Outdoor LAN exposure was estimated using satellite data for individual address with 500 mWe identified 7,775 incident T2DM cases over 3,027,505 person-years. Higher outdoor LAN exposures were significantly associated with higher risk of T2DM. The estimated HR for incident T2DM with an interquartile range (IQR: 11.22 nW/cmAlthough further work is required to clarify potential mechanisms, our findings indicate that exposure to residential outdoor LAN may contribute to T2DM risk and low sleep quality.

Long-term temperature variability (TV) has been examined to be associated with cardiovascular disease (CVD). TV-related dyslipidemia helps us understand the mechanism of how climate change affects CVD.Based on the China Health and Retirement Longitudinal Study (CHARLS) from 2011 to 2018, this study estimated the long-term effect of TV on dyslipidemia in middle-aged and elderly adults.This study suggested that long-term TV may increase the risk of dyslipidemia. With the threat of climate change, these findings have great significance for making policies and adaptive strategies to reduce relevant risk of CVD.

Traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs2TeX6 (X = Cl-, Br-, I-) in polar aprotic solvents, leading to the stabilization of isolated [TeX6]2- octahedral anions and free Cs+ cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

Conventional colloidal syntheses typically produce nanostructures with positive curvatures due to thermodynamic preference. Here, we demonstrate the creation of surface concavity in Au nanorods through seed-mediated growth in confined spaces and report their thermochromic responses to temperature changes. The unique surface concavity is created by templating against Fe3O4 nanorods, producing a new concavity-sensitive plasmonic band. Due to the high surface energy, the metastable nanorods can be reconstructed at a moderate temperature, enabling convenient and precise tuning of their plasmonic properties by aging in different solvents. Such structural reconstruction of concave Au nanorods enables the fabrication of thermochromic plasmonic films that can display images with vivid color changes or exhibit encrypted, invisible information upon aging. This templating strategy is universal in creating concave nanostructures, which may open the door to designing new nanostructures with promising applications in sensing, anticounterfeiting, information encryption, and displays.

Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au(25) nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO(2) to CO. The Au(25) nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤−0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au(25) nanoclusters concomitantly. The thermally and electrochemically treated Au(25) nanoclusters show enhanced activity and selectivity for the electrochemical CO(2)-to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.

Background Gestational diabetes (GDM) is a global problem affecting millions of pregnant women, including in mainland China. These women are at high risk of Type II diabetes (T2DM). Cost-effective and clinically effective interventions are needed. We aimed to explore Chinese women’s perspectives, concerns and motivations towards participation in early postpartum interventions and/or research to prevent the development of T2DM after a GDM-affected pregnancy. Methods We conducted a qualitative study in two hospitals in Chengdu, Southwest China. Face-to-face semi-structured interviews were conducted with 20 women with recent experience of GDM: 16 postpartum women and 4 pregnant women. Women were asked about their attitudes towards postpartum screening for type 2 diabetes, lifestyle interventions, mHealth delivered interventions and pharmacologic interventions (specifically metformin). An inductive approach to analysis was used. Interviews were recorded, transcribed, and coded using NVivo 12 Pro. Results Most women held positive attitudes towards participating in T2DM screening, and were willing to participate in postpartum interventions to prevent T2DM through lifestyle change or mHealth interventions. Women were less likely to agree to pharmacological intervention, unless they had family members with diabetes or needed medication themselves during pregnancy. We identified seven domains influencing women’s attitudes towards future interventions: (1) experiences with the health system during pregnancy; (2) living in an enabling environment; (3) the experience of T2DM in family members; (4) knowledge of diabetes and perception of risk; (5) concerns about personal and baby health; (6) feelings and emotions, and (7) lifestyle constraints. Those with more severe GDM, an enabling environment and health knowledge, and with experience of T2DM in family members expressed more favourable views of postpartum interventions and research participation to prevent T2DM after GDM. Those who perceived themselves as having mild GDM and those with time/lifestyle constraints were less likely to participate. Conclusions Women with experiences of GDM in Chengdu are generally willing to participate in early postpartum interventions and/or research to reduce their risk of T2DM, with a preference for non-drug, mHealth based interventions, integrating lifestyle change strategies, blood glucose monitoring, postpartum recovery and mental health. Supplementary Information The online version contains supplementary material available at 10.1186/s12978-021-01180-1., Plain language summary Gestational diabetes mellitus (GDM) is a common pregnancy complication affecting up to 1 in 6 pregnant women worldwide. Whilst the condition usually resolves soon after delivery, women are at high risk of developing type 2 diabetes mellitus (T2DM). In this study, we asked women living in Chengdu, a city in western China, about what they knew about their risk of diabetes and how they felt about participating in interventions after birth to prevent T2DM. After listening to the views of 20 women, we concluded that in this setting most women are happy to attend T2DM screening programs after birth, and would be willing to consider participating in interventions and research after birth to prevent T2DM. The interventions most preferred were those that aimed at lifestyle changes, and many women said would like to receive this information through their smartphone, for example through an app or social media channel. Women were reluctant to take medications to prevent T2DM. The main factors that influenced how women felt towards interventions to prevent T2DM were: (1) their experiences with the health system during pregnancy; (2) whether the home environment was supportive to make changes to diet and lifestyle; (3) any experiences of T2DM in family members; (4) their knowledge of diabetes and perception of risk; (5) concerns about personal and baby health; (6) feelings and emotions in the postnatal period, and (7) lifestyle constraints making it difficult to make dietary changes. Supplementary Information The online version contains supplementary material available at 10.1186/s12978-021-01180-1.

The metal halide ionic octahedron, [MX6] (M = metal cation, X = halide anion), is considered to be the fundamental building block and functional unit of metal halide perovskites. By representing the metal halide ionic octahedron in halide perovskites as a super ion/atom, the halide perovskite can be described as an extended ionic octahedron network (ION) charge balanced by selected cations. This new perspective of halide perovskites based on ION enables the prediction of different packing and connectivity of the metal halide octahedra based on different solid-state lattices. In this work, a new halide perovskite Cs8Au3.5In1.5Cl23 was discovered on the basis of a BaTiO3-lattice ION {[InCl6][AuCl5][Au/InCl4]3}8-, which is assembled from three different ionic octahedra [InCl6], [AuCl6], and [Au/InCl6] and balanced by positively charged Cs cations. The success of this ION design concept in the discovery of Cs8Au3.5In1.5Cl23 opens up a new venue for the rational design of new halide perovskite materials.

Organic-inorganic layered perovskites are two-dimensional quantum wells with layers of lead-halide octahedra stacked between organic ligand barriers. The combination of their dielectric confinement and ionic sublattice results in excitonic excitations with substantial binding energies that are strongly coupled to the surrounding soft, polar lattice. However, the ligand environment in layered perovskites can significantly alter their optical properties due to the complex dynamic disorder of soft perovskite lattice. Here, we observe the dynamic disorder through phonon dephasing lifetimes initiated by ultrafast photoexcitation employing high-resolution resonant impulsive stimulated Raman spectroscopy of a variety of ligand substitutions. We demonstrate that vibrational relaxation in layered perovskite formed from flexible alkyl-amines as organic barriers is fast and relatively independent of the lattice temperature. Relaxation in aromatic amine based layered perovskite is slower, though still fast relative to pure inorganic lead bromide lattices, with a rate that is temperature dependent. Using molecular dynamics simulations, we explain the fast rates of relaxation by quantifying the large anharmonic coupling of the optical modes with the ligand layers and rationalize the temperature independence due to their amorphous packing. This work provides a molecular and time-domain depiction of the relaxation of nascent optical excitations and opens opportunities to understand how they couple to the complex layered perovskite lattice, elucidating design principles for optoelectronic devices., 7 pages, 4 figures, SI

The EC-system of the TCV tokamak is progressively being upgraded with the addition of two MW-class dual-frequency gyrotrons (84 and 126 GHz/2s/1MW). In order to connect the two gyrotrons to the existing low field side and top launchers, new waveguide routing from gyrotron hall to TCV tokamak was designed and dedicated Matching Optics Units (MOU) have been developed. The internal optics of the system have been determined aiming at optimal coupling to the HE11 waveguides. The laws of quasi-optics were used to find quadratic surfaces to shape an incoming Gaussian beam representative of the gyrotron output into a beam matching the proper field distribution at the waveguide entrance and with HE11 content compatible with the system requirements. A solution with one flat (movable) mirror and two shaping mirrors was found and characterized with the physical optics code GRASP. The resulting field distribution is then truncated and projected onto the HE11 component to evaluate the design solution (coupled power at the waveguide entrance >98.4% and HE11 content >96.8% for both frequencies). The model and the results of this analysis will be presented and compared to a model based on the Rayleigh–Sommerfeld scalar diffraction integral. GRASP was also used to evaluate preliminary misalignment effects in terms of coupled power to the waveguide and the MOU design moved to the manufacturing phase. In parallel to the gyrotron integration and to extend the level of flexibility of the TCV EC-system, a modular closed divertor chamber is developed, requiring the X3 top-launcher to be redesigned. Preliminary antenna conceptual design studies including new curvature to cope with the requirements of modularity and flexibility will be presented.

The self-assembly of nanoparticles, a process whereby nanocrystal building blocks organize into even more ordered superstructures, is of great interest to nanoscience. Here we report the layer-by-layer assembly of 2D perovskite nanosheet building blocks. Structural analysis reveals that the assembled superlattice nanocrystals match with the layered Ruddlesden-Popper perovskite phase. This assembly proves reversible, as these superlattice nanocrystals can be reversibly exfoliated back into their building blocks via sonication. This study demonstrates the opportunity to further understand and exploit thermodynamics to increase order in a system of nanoparticles and to study emergent optical properties of a superlattice from 2D, weakly attracted, perovskite building blocks.

Nitrogen fixation in a simulated natural environment (i.e., near ambient pressure, room temperature, pure water, and incident light) would provide a desirable approach to future nitrogen conversion. As the N≡N triple bond has a thermodynamically high cleavage energy, nitrogen reduction under such mild conditions typically undergoes associative alternating or distal pathways rather than following a dissociative mechanism. Here, we report that surface plasmon can supply sufficient energy to activate N2 through a dissociative mechanism in the presence of water and incident light, as evidenced by in situ synchrotron radiation-based infrared spectroscopy and near ambient pressure X-ray photoelectron spectroscopy. Theoretical simulation indicates that the electric field enhanced by surface plasmon, together with plasmonic hot electrons and interfacial hybridization, may play a critical role in N≡N dissociation. Specifically, AuRu core-antenna nanostructures with broadened light adsorption cross section and active sites achieve an ammonia production rate of 101.4 μmol g-1 h-1 without any sacrificial agent at room temperature and 2 atm pressure. This work highlights the significance of surface plasmon to activation of inert molecules, serving as a promising platform for developing novel catalytic systems.

The hollow Fep-reinforced Cu-matrix homogeneous immiscible alloys were successfully produced by the combination of Kirkendall effect and laser powder deposition. The microstructure and corrosion resistance depended not only on chemical composition, but also on cooling rate. When Fe content decreased from 30% to 12% and cooling rate decreased from ∼2 × 104 to ∼1 × 104 K/s, the demixing was eliminated, the mixed Fep (α-Fe/γ-Fe) were uniformly embedded within e-Cu matrix and the "single-void" Fep transformed into the "multi-voids" Fep. The "multi-voids" immiscible alloy exhibited higher corrosion resistance than the "single-void" immiscible alloy and Brass after immersing for 5 days.

Background Ozone (O3) has become a prominent air pollutant problem as other pollutants concentrations have decreased obviously since China published Air Pollution Action Plan Pollution Prevention Action Plan in 2013. Few studies examined the association between O3 and diabetes especially in developing countries. This study was designed to investigate the above topic in China. Methods We conducted a prospective cohort study based on a nationwide survey of 13,548 adults from China Health and Retirement Longitudinal Study. City-level exposure to ozone for each participant was matched through ChinaHighO3 dataset. Time-varying cox proportional hazard regression model was applied to determine the association. Stratification analyses were conducted to explore potential effect modification. Results The annual mean concentration of O3 was 86.6 μg/m3. A 10 μg/m3 increase in 1-year average O3 concentration was associated with 5.7% (95% CI: 1.004–1.114) relative increment in hazards ratio of diabetes incidence in the fully adjusted model. Results stayed stable when controlling for physical activity, PM2.5 and mean temperature. Conclusions Our findings provided initial support for a positive and robust association between long-term exposure to O3 and diabetes incidence in a developing country. More scientific and social attention should be attached to the ozone-induced risks of diabetes occurrence.

Pt-based alloy catalysts are promising candidates for fuel-cell applications, especially for cathodic oxygen reduction reaction (ORR) and anodic methanol oxidation reaction (MOR). The rational design of composition and morphology is crucial to promoting catalytic performances. Here, we report the synthesis of Pt-Co nanoframes via chemical etching of Co from solid rhombic dodecahedra. The obtained Pt-Co nanoframes exhibit excellent ORR mass activity in acidic electrolyte, which is as high as 0.40 A mgPt-1 initially and 0.34 A mgPt-1 after 10 000 potential cycles at 0.95 VRHE. Furthermore, their MOR mass activity in alkaline media is up to 4.28 A mgPt-1 and is 4-fold higher than that of commercial Pt/C catalyst. Experimental studies indicate that the weakened binding of intermediate carbonaceous poison contributes to the enhanced MOR behavior. More impressively, the Pt-Co nanoframes also demonstrate remarkable stability under long-term testing, which could be attributed to the negligible electrochemical Co dissolution.

Karlsruhe Institute of Technology (KIT) is doing research and development in the field of megawatt-class radio frequency (RF) sources (gyrotrons) for the Electron Cyclotron Resonance Heating (ECRH) systems of the International Thermonuclear Experimental Reactor (ITER) and the DEMOnstration Fusion Power Plant that will follow ITER. In the focus is the development and verification of the European coaxial-cavity gyrotron technology which shall lead to gyrotrons operating at an RF output power significantly larger than 1 MW CW and at an operating frequency above 200 GHz. A major step into that direction is the final verification of the European 170 GHz 2 MW coaxial-cavity pre-prototype at longer pulses up to 1 s. It bases on the upgrade of an already existing highly modular short-pulse (ms-range) pre-prototype. That pre-prototype has shown a world record output power of 2.2 MW already. This paper summarizes briefly the already achieved experimental results using the short-pulse pre-prototype and discusses in detail the design and manufacturing process of the upgrade of the pre-prototype toward longer pulses up to 1 s.

Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au25 nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO2 to CO. The Au25 nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤-0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au25 nanoclusters concomitantly. The thermally and electrochemically treated Au25 nanoclusters show enhanced activity and selectivity for the electrochemical CO2-to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.

A numerical synthesis method for the optimization of launchers with hybrid-type wall surface for high-power fusion gyrotrons is proposed in this paper. The profile of such a launcher is built from a novel combination of a periodic harmonic wall perturbation followed by a mirror-line-type deformation, so we named it hybrid-type launcher. The synthesis method has been tested to design a hybrid-type launcher to transform the TE32,9 mode of the ITER EU 1-MW gyrotron operating at 170 GHz. The simulation results show that the fundamental Gaussian mode content (FGMC) of the millimeter-wave beam at the radiating aperture of the hybrid-type launcher is approximately 99.1%. In comparison with the corresponding harmonically deformed launcher, the simulations results reveal that the launcher with hybrid-type surface contour provides higher conversion efficiency combined with low diffraction loss (0.7%). The computation time for the design of hybrid-type launchers is just half of that for mirror-line launchers. In the case of not very short launchers, hybrid-type launchers can provide high FGMCs of RF beams with low diffraction losses that are comparable with those of mirror-line launchers.

Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In + /In 3+ ) inorganic halide perovskite with the composition of Cs 2 In(I)In(III)Cl 6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I 4/ m with a = 17.2604(12) Å, c = 11.0113(16) Å if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications.

The DEMO-relevant gyrotron research at Karlsruhe Institute of Technology is driven by the European concept for a demonstration fusion reactor (EU DEMO). This paper reports on the recent results of the theoretical and experimental studies towards the development of gyrotrons fulfilling the DEMO needs.

The status of the THALES 140 GHz 1 MW CW industrial gyrotron program for the W7-X stellarator is discussed in this paper. The industrial design and performances arc briefly discussed with a focus on the tube reliability and endurance.