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Abstract A bimetallic heterostructure has been shown effective to enhance the multi-carbon (C2+) product selectivity in CO2 electroreduction. Clarifying the interfacial structure under electrolysis and its decisive role in the pathway selection are crucial, yet challenging. Here, we conceive a well-defined Ag-Cu biphasic heterostructure to understand the interfacial structure-steered product selectivity: The Cu-rich interface prefers ethylene, while the dominant product switch to alcohols with an increasing Ag fraction, and finally to CO as Ag occupying the main surface. We unravel a *CO intermediate-regulated interfacial restructuring, and observe abundant of Cu atoms migrating onto the neighboring Ag surface under a locally high *CO concentration. The evolving structure alters the oxyphilic characteristic at the interface, which profoundly determines the hydrogenation energetics of CO2 and ultimately, the dominant C2+ product. This work explicitly links the evolving interfacial structure with distinct C2+ pathway, formulating design guidelines for bimetallic electrocatalysts with selectively enhanced C2+ yields.

Abstract Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end‐of‐life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation.

The atomic structural features and the mechanical properties of amorphous silicoboron carbonitride ceramics with 13 different compositions in the Si–BN–C phase diagram are investigated employing ab-initio calculations. Both chemical bonds and local structures within the amorphous network relate to the elemental composition. The distribution of nine types of chemical bonds is composition-dependent, where the B–C, Si–N, Si–C, and B–N bonds hold a large proportion for all compositions. Si prefers to be tetrahedrally coordinated, while B and N prefer sp2-like trigonal coordination. In the case of C, the tetrahedral coordination is predominant at relatively low C contents, while the trigonal coordination is found to be the main feature with the increasing C content. Such local structural characteristics greatly influence the mechanical properties of SiBCN ceramics. Among the studied amorphous ceramics, SiB2C3N2 and SiB3C2N3 with low Si contents and moderate C and/or BN contents have high elastic moduli, high tensile/shear strengths, and good debonding capability. The increment of Si, C, and BN contents on this basis results in the decrease of mechanical properties. The increasing Si content leads to the increment of Si-contained bonds that reduce the bond strength of SiBCN ceramics, while the latter two cases are attributed to the raise of sp2-like trigonal configuration of C and BN. These discoveries are expected to guide the composition-tailored optimization of SiBCN ceramics.

Abstract Understanding and mastering the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we demonstrate that surface reconstruction of spinel oxides originates from the metal-oxygen covalency polarity in the MT–O–MO backbone. A stronger MO–O covalency relative to MT–O covalency is found beneficial for a more thorough reconstruction towards oxyhydroxides. The structure-reconstruction relationship allows precise prediction of the reconstruction ability of spinel pre-catalysts, based on which the reconstruction degree towards the in situ generated oxyhydroxides can be controlled. The investigations of oxyhydroxides generated from spinel pre-catalysts with the same reconstruction ability provide guidelines to navigate the cation selection in spinel pre-catalysts design. This work reveals the fundamentals for manipulating the surface reconstruction of spinel pre-catalysts for water oxidation.

Abstract Solid polymer electrolytes (SPEs), which are favorable to form intimate interfacial contacts with electrodes, are promising electrolyte of choice for long-cycling lithium metal batteries (LMBs). However, typical SPEs with easily oxidized oxygen-bearing polar groups exhibit narrow electrochemical stability window (ESW), making it impractical to increase specific capacity and energy density of SPE based LMBs with charging cut-off voltage of 4.5 V or higher. Here, we apply a polyfluorinated crosslinker to enhance oxidation resistance of SPEs. The crosslinked network facilitates transmission of the inductive electron-withdrawing effect of polyfluorinated segments. As a result, polyfluorinated crosslinked SPE exhibits a wide ESW, and the Li|SPE|LiNi0.5Co0.2Mn0.3O2 cell with a cutoff voltage of 4.5 V delivers a high discharge specific capacity of ~164.19 mAh g−1 at 0.5 C and capacity retention of ~90% after 200 cycles. This work opens a direction in developing SPEs for long-cycling high-voltage LMBs by using polyfluorinated crosslinking strategy.

The urgent demand for terawatt-scale clean energy necessitates the rational design of noble metal catalysts with minimal noble metal loading while maintaining high catalytic activity. However, the durability of low-loading catalysts is a critical concern for their successful industrial implementation. Here, we present a capping strategy using an amorphous HfO2 (m-HfO2) to address this issue. Take Pt/C catalysts with Pt loading as low as 81.39 ng cm−2 as an example, we demonstrate that the m-HfO2 layer (10 nm) serves as an efficient mass transport channel for underneath Pt active sites, and effectively mitigates bubble-induced blockage of active sites by separating bubble formation sites with Pt active sites. Thus, the resulting catalyst exhibits a remarkable mass activity of 122.87 A mg−1 and an overpotential of 11 mV at 10 mA cm−2. Furthermore, the m-HfO2 plays a crucial role in eliminating the structural transformation and extending the lifetime of Pt-based catalysts, as evidenced by no loss of specific activity after consecutively cycling the catalyst for over 100 h. Such a capping strategy is potentially applied to other types of reactions and catalyst systems.

Transition metal dichalcogenides (TMDs) and perovskites are among the most attractive and widely investigated semiconductors in the recent decade. They are promising materials for various applications, such as photodetection, solar energy harvesting, light emission, and many others. Combining these materials to form heterostructures can enrich the already fascinating properties and bring up new phenomena and opportunities. Work in this field is growing rapidly in both fundamental studies and device applications. Here, we review the recent findings in the perovskite-TMD heterostructures and give our perspectives on the future development of this promising field. The fundamental properties of the perovskites, TMDs, and their heterostructures are discussed first, followed by a summary of the synthesis methods of the perovskites and TMDs and the approaches to obtain high-quality interfaces. Particular attention is paid to the TMD-perovskite heterostructures that have been applied in solar cells and photodetectors with notable performance improvement. Finally through our analysis, we propose an outline on further fundamental studies and the promising applications of perovskite-TMD heterostructures.

Abstract Metal alloys are usually fabricated by melting constituent metals together or sintering metal alloy particles made by high energy ball milling (mechanical alloying). All these methods only allow for bulk alloys to be formed. This manuscript details a new method of fabricating Rhodium–Iridium (Rh–Ir) metal alloy films using atomic layer deposition (ALD) and rapid Joule heating induced alloying that gives functional thin film alloys, enabling conformal thin films with high aspect ratios on 3D nanostructured substrate. In this work, ALD was used to deposit Rh thin film on an Al2O3 substrate, followed by an Ir overlayer on top of the Rh film. The multilayered structure was then alloyed/sintered using rapid Joule heating. We can precisely control the thickness of the resultant alloy films down to the atomic scale. The Rh–Ir alloy thin films were characterized using scanning and transmission electron microscopy (SEM/TEM) and energy dispersive spectroscopy (EDS) to study their microstructural characteristics which showed the morphology difference before and after rapid Joule heating and confirmed the interdiffusion between Rh and Ir during rapid Joule heating. The diffraction peak shift was observed by Grazing-incidence X-ray diffraction (GIXRD) indicating the formation of Rh–Ir thin film alloys after rapid Joule heating. X-ray photoelectron spectroscopy (XPS) was also carried out and implied the formation of Rh–Ir alloy. Molecular dynamics simulation experiments of Rh–Ir alloys using Large-Scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) were performed to elucidate the alloying mechanism during the rapid heating process, corroborating the experimental results.

While the conversion of CO2 to high-value products provides a promising means to remove and utilize atmospheric carbon, few materials can do so without wasteful, sacrificial reagents. Here, authors prepare single-atom Co on Bi3O4Br nanosheets as CO2 reduction catalysts using water and light.

Abstract The rational design of previously unidentified materials that could realize excellent electrochemical‐controlled optical and charge storage properties simultaneously, are especially desirable and useful for fabricating smart multifunctional devices. Here, a facile synthesis of a 1D π–d conjugated coordination polymer (Ni‐BTA) is reported, consisting of metal (Ni)‐containing nodes and organic linkers (1,2,4,5‐benzenetetramine), which could be easily grown on various substrates via a scalable chemical bath deposition method. The resulting Ni‐BTA film exhibits superior performances for both electrochromic and energy storage functions, such as large optical modulation (61.3%), high coloration efficiency (223.6 cm2 C−1), and high gravimetric capacity (168.1 mAh g−1). In particular, the Ni‐BTA film can maintain its electrochemical recharge‐ability and electrochromic properties even after 10 000 electrochemical cycles demonstrating excellent durability. Moreover, a smart energy storage indicator is demonstrated in which the energy storage states can be visually recognized in real time. The excellent electrochromic and charge storage performances of Ni‐BTA films present a great promise for Ni‐BTA nanowires to be used as practical electrode materials in various applications such as electrochromic devices, energy storage cells, and multifunctional smart windows.

Traditional optical organic vapor sensors with solvatochromic shift mechanisms have lower sensitivity due to weak intermolecular interactions. Here, the authors report a general strategy to prepare a higher sensitivity optical organic vapor sensor through polymeric swelling-induced variation of fluorescent intensity.

Observing the Peltier effect, e.g. cooling/heating at material junctions due to current flow, in organic thermoelectric films remains a challenge due the inherent properties of these materials. Here, the authors use IR imaging to experimentally observe the Peltier effect in poly(Ni-ett)-based films.

High performance flexible strain sensors with accurate signal detection and noise screening are key to the development of smart sensing systems. Here, the authors demonstrate metal–organic framework based strain sensors that are ultrasensitive, robust, and non-responsive to environmental noise.

Crystals with multiple structures often perform special functions in nature, inspiring the creation of synthetic analogues. Here, the authors subject polyhedral nanoparticles to two self-assembly micro-environments to realize supercrystals with dual structures, in which the order of the surface layer differs from the bulk structure.

This paper reports flow direction-dependent elastic instability in a symmetry-breaking microchannel. The microchannel consisted of a square chamber and a nozzle structure. A viscoelastic polyacrylamide solution was used for the instability demonstration. The instability was realized as the viscoelastic flow became asymmetric and unsteady in the microchannel when the flow exceeded a critical Weissenberg number. The critical Weissenberg number was found to be different for the forward-directed flow and the backward-directed flow in the microchannel.

Small modular reactor (SMR) has drawn wide attention in the past decades, and Lead cooled fast reactor (LFR) is one of the most promising advanced reactors which are able to meet the safety economic goals of Gen-IV nuclear energy systems. A small modular natural circulation lead cooled fast reactor-100 MWth (SNRLFR-100) is being developed by University of Science and Technology of China (USTC). In the present work, a 3D CFD model, primary heat exchanger model, fuel pin model, and point kinetic model were established based on some reasonable simplifications and assumptions, the steady-state natural circulation characteristics of SNCLFR-100 primary cooling system were discussed and illustrated, and some reasonable suggestions were proposed for the reactor’s thermal-hydraulic and structural design. Moreover, in order to have a first evaluation of the system behavior in accident conditions, an unprotected loss of heat sink (ULOHS) transient simulation at beginning of the reactor cycle (BOC) has been analyzed and discussed based on the steady-state simulation results. The key temperatures of the reactor core are all under the safety limits at transient state; the reactor has excellent thermal-hydraulic performance.

AbstractThe benefits of using social annotations to promote collaborative learning experiences have been investigated in the context of digital reading and listening, while its implications in multimedia learning contexts remain unclear. To investigate the influence of social annotations on multimedia language learning, we invited 16 African participants who were learning Chinese as a second language through a MOOC platform in China. They were given full autonomy to study and to shift instructional videos between three modes: no visual aids, linguistic captions, and social annotations. Guided by self-determination theory, the qualitative data were collected through one-to-one interviews, while quantitative data, such as the duration of watching and the number of questions raised by participants, were obtained from observations. Statistical analysis suggests that MOOC learners demonstrated a higher level of engagement and motivation in the social annotation mode than in the other two modes. These statistical findings can be explained from the following three perspectives: content and emotion-related social annotations by other L1 viewers can assist in (1) checking their comprehension of the video by comparing their understanding with others; (2) adjusting learning goals at both the linguistic and content level and therefore using self-regulated learning strategies to a greater extent, especially in actively seeking assistance and other learning resources, and (3) relating the video content to the teaching curriculum/personal experience/learning goals, therefore creating a sense of belonging to a larger language learner community as language learners, interpreters and contributors to the video social annotations.

As an important node of transportation network, it is the mainstream trend to improve the development quality of port city and build a high-quality port city. Based on the perspective of flow space, from the two dimensions of "dynamic" and "static" , this paper explored the characteristics and types of comprehensive development quality of 47 coastal port cities, and put forward countermeasures and suggestions. The results showed that: (1) The comprehensive development quality of each port city formed a relatively reasonable gradient distribution, but the driving role of the core port city and the ability of cooperation and mutual assistance among the port cities needed to be improved; (2) The comprehensive development quality of China's port cities can be divided into four types: very high, high, average and low. The number of low type port cities was much higher than that of very high type port cities, and the comprehensive development quality of China's port cities wa still not optimistic; (3) From the internal point of view of different port urban agglomerations, Bohai Rim, Yangtze River Delta and Pearl River Delta port urban agglomerations were concentrated, complete and homogeneous; (4) The key factors affecting the comprehensive development quality of port cities were technology flow, capital flow, logistics and container throughput.

Vibrational lifetimes of the asymmetric stretch fundamental of azide anion in normal and heavy water have been measured experimentally, with results in the range of a few picoseconds. This is an interesting problem for theoretical study because of the competition between intramolecular (relaxation to the other excited vibrational states of azide) and purely intermolecular (relaxation to azide’s ground vibrational state) pathways. In addition it is important to understand the origin of the solvent isotope effect. Building on the seminal work of Morita and Kato [J. Chem. Phys. 109, 5511 (1998)], the authors develop a simple model based on a two-dimensional description of the azide stretching vibrations. A novel aspect of their theory is the use of an “on-the-fly” optimized quantum mechanical/molecular mechanical approach to calculate the system-bath coupling. Their theoretical lifetimes are in good agreement with experiment for azide in both normal and heavy water. They find that the predominant relaxation pathway is intramolecular. The solvent isotope effect arises from the different librational frequencies in normal and heavy water. [ABSTRACT FROM AUTHOR]

Ultrafast vibrational spectroscopy experiments, together with molecular-level theoretical interpretation, can provide important information about the structure and dynamics of complex condensed phase systems, including liquids. The theoretical challenge is to calculate the instantaneous vibrational frequencies of a molecule in contact with a molecular environment, accurately and quickly, and to this end a number of different methods have been developed. In this paper we critically analyze these different methods by comparing their results to accurate benchmark calculations on azide/water clusters. We also propose an optimized quantum mechanics/molecular mechanics method, which for this problem is superior to the other methods. [ABSTRACT FROM AUTHOR]

Vibrational spectral diffusion denotes the time-dependent fluctuations of a solute's vibrational frequencies due to local environmental dynamics. A report on theoretical studies of spectral diffusion of the asymmetric stretch of the azide anion in heavy water is presented.

The social contact rate has influenced the transmission of COVID-19, with more social contact resulting in more contagion cases. We chose 18 countries with the most confirmed cases in the first 200 days after the Wuhan lockdown. This was the first study using the dynamic social contact rate to simulate the epidemic under diverse restriction policies over 500 days since the COVID-19 outbreak. The developed General Dynamic Model suggested that the probability of contagion ranged from 12.52% to 39.39% in the epidemic. The geometric mean of the social contact rates differed from 18.21% to 96.00% between countries. The restriction policies in developed economies were 3.5 times more efficient than in developing economies. We compare the effectiveness of different policies for disease prevention and discuss the influence of policy adjustment frequency for each country. Maintaining the tightest restriction or alternate tightening and loosening restrictions was recommended, with each having an average 72.45% and 79.78% reduction in maximum active cases, respectively.

BackgroundActive surveillance has been considered a safe alternative to surgery for low-risk papillary thyroid microcarcinoma. This study aimed to assess the oncological outcomes and psychological status of active surveillance of highly suspicious thyroid nodules ≤10 mm in China.MethodsThis prospective single-center cohort study enrolled 336 patients with highly suspicious thyroid nodules for active surveillance to assess oncological outcomes and psychological status. The psychological status of patients was assessed by two different questionnaires and compared among different patient groups.ResultsDuring a median follow-up period of 28.5 months, eight patients underwent delayed surgery for tumor enlargement and one for lymph node metastases. The cumulative incidence of disease progression at 5 and 10 years was 6.0% and 12.8%, respectively. Patients who underwent delayed surgery had no permanent complications, and no patient had distant metastasis or death. Patients ≤30 years old had a higher baseline anxiety score (4.9 vs. 3.8, p=0.024), a higher proportion of baseline anxiety score, i.e., ≥8 points (24.0% vs. 12.6%, p=0.033), and a worse baseline emotional function (62.7 vs. 70.7, p=0.013) than patients >30. During AS, patients ≤30 years of age had higher overall anxiety levels (p=0.005) and a worse overall emotional function (p=0.001).ConclusionsActive surveillance in Chinese patients with highly suspicious subcentimetre thyroid nodules has good oncological outcomes and can be used as a safe alternative to surgery. Younger patients (≤30) show a worse psychological status; therefore, more attention should be paid to younger patients.

The mechanism of chromyl chloride epoxidation that is thermodynamically driven by the formation of dimeric Cr(V) product is analyzed using the complete active space perturbation theory to second order (CASPT2). The results are tabulated and show that the CASPT2 predicts epoxidation endothermicity consistent with the experimental estimate, and predicts the oxetane species, to be endothermic, and the dioxylate, exothermic.

Enhancement of the semiconductor–molecule interaction, in particular, promoting the interfacial charge transfer process (ICTP), is key to improving the sensitivity of semiconductor-based surface enhanced Raman scattering (SERS). Herein, by developing amorphous ZnO nanocages (a-ZnO NCs), we successfully obtained an ultrahigh enhancement factor of up to 6.62×105. This remarkable SERS sensitivity can be attributed to high-efficiency ICTP within a-ZnO NC molecule system, which is caused by metastable electronic states of a-ZnO NCs. First-principles density functional theory (DFT) simulations further confirmed a stronger ICTP in a-ZnO NCs than in their crystalline counterparts. The efficient ICTP can even generate π bonding in Zn−S bonds peculiar to the mercapto molecule adsorbed a-ZnO NCs, which has been verified through the X-ray absorption near-edge structure (XANES) characterization. To the best of our knowledge, this is the first time such remarkable SERS activity has been observed within amorphous semiconductor nanomaterials, which could open a new frontier for developing highly sensitive and stable SERS technology. [ABSTRACT FROM AUTHOR]

We developed a novel method for the real-time monitoring of the delicate change in refractive index (RI) when DNA or RNA hybridize near a DNA-capped silver nanocube (AgNC) surface. This method offers an alternative platform in the quantitative analysis of the trace lung cancer-associated miRNAs in label-free detection. [ABSTRACT FROM AUTHOR]

Gapped rods provide a unique platform for elucidating structure/function relationships, both for single-molecule electrochemical techniques and for surface-enhanced Raman scattering (SERS). This paper attempts to elucidate the dependence of SERS intensities on gap topography and gap distance for gold gapped rods with segment lengths varying over a wide range (40−2000 nm). Significantly, we have determined that rough gaps lead to a smaller SERS enhancement than smooth gaps for these structures even though the rough gaps have a larger total surface area. Both theory and experiment show periodic variation of SERS intensity with segment length as determined by odd-symmetry plasmon multipoles. Excitation of even-symmetry modes is dipole forbidden (for polarization along the rod axis), but this selection rule can be relaxed by roughness or, for smooth gaps, by near-field coupling between the rod segments. [ABSTRACT FROM AUTHOR]

In rural China, the ratio of newborn boys to newborn girls [sex ratio at birth (SRB)1 has been rising for several decades, to values significantly above its biological norm. This trend has a number of alarming societal consequences, and has attracted the attention of scholars and politicians. The root of the problem lies in a 2,500year-old culture of son preference. This culture is intricately linked with the economic reality of each couple's life, so that there are financial and psychological repercussions to parents who have no sons. To bring greater clarity and understanding to this issue, we present a quantitative framework .that describes the, interaction between economics and cultural transmission. We start with an explicit mechanism by which economic incentives can change cultural beliefs of a given individual, and go on to include a mechanism of cultural inheritance from generation to generation. We then show how economic conditions can affect the dynamics of cultural change in an entire society, and may lead to a decrease in the country's sex ratio at birth. [ABSTRACT FROM AUTHOR]

We report the observation of energy transfer from a gold (Au) nanodisk pair to a silver (Ag) nanowire across a 120 nm gap via surface plasmon resonance (SPR) excitation. The enhanced electromagnetic (EM) fields generated by Au SPR excitation induce oscillation of the conduction electrons in the Ag segment, transferring energy to it even though the Ag segment has only weak resonant interactions with the incident EM radiation. The induced Ag SPR produces strong EM fields at the position of the Ag segment, leading to a Raman signal ∼15 times greater than when the Ag segment is alone (not adjacent to the Au nanodisk pair). The Raman intensity is found to depend nonlinearly on the incident laser intensity for laser power densities of 10 kW/cm 2, which is consistent with the results of EM theory calculations which are not able to account for the factor of 15 enhancement based on a linear mechanism. This suggests that energy transfer from the Au disk pair to the Ag segment involves an enhanced nonlinear polarization mechanism such as can be produced by the electronic Kerr effect or stimulated Raman scattering. [ABSTRACT FROM AUTHOR]

In this paper, we report on the results of an investigation into dual-mode operation of microstrip triangular patch resonators and their applications for designing dual-mode bandpass filters. It has been found theoretically that the dual modes can result from the rotation and superposition of a fundamental mode. The characteristics of the dual modes and their mode splitting are described. The applications of this new type of dual-mode microstrip patch resonator in the design of microwave planar filter are presented. A circuit model for operation of this type of filter is proposed. Two- and four-pole filters of this type are demonstrated for the first time. Both theoretical and experimental results are presented. [ABSTRACT FROM AUTHOR]

Inert dielectric shells coating the surface of metallic nanoparticles (NPs) are important for enhancing the NPs’ stability, biocompatibility, and realizing targeting detection, but they impair NPs’ sensing ability due to the electric fields damping. The dielectric shell not only determines the distance of the analyte from the NP surface, but also affects the field decay. From a practical point of view, it is extremely important to investigate the critical thickness of the shell, beyond which the NPs are no longer able to effectively detect the analytes. The plasmon decay length of the shell-coated NPs determines the critical thickness of the coating layer. Extracting from the exponential fitting results, we quantitatively demonstrate that the critical thickness of the shell exhibits a linear dependence on the NP volume and the dielectric constants of the shell and the surrounding medium, but only with a small variation influenced by the NP shape where the dipole resonance is dominated. We show the critical thickness increases with enlarging the NP sizes, or increasing the dielectric constant differences between the shell and surrounding medium. The findings are essential for applications of shell-coated NPs in plasmonic sensing. [ABSTRACT FROM AUTHOR]