High Thermoelectric Performance in Rhombohedral GeSe-LiBiTe2.

GeSe, an analogue of SnSe, shows promise in exhibiting exceptional thermoelectric performance in the Pnma phase. The constraints on its dopability, however, pose challenges in attaining optimal carrier concentrations and improving ZT values. This study demonstrates a crystal structure evolution strategy for achieving highly doped samples and promising ZTs in GeSe via LiBiTe2 alloying. A rhombohedral phase (R3m) can be stabilized in the GeSe-LiBiTe2 system, further evolving into a cubic (Fm3̅m) phase with a rising temperature. The band structures of GeSe-LiBiTe2 in the rhombohedral and cubic phases feature a similar multiple-valley energy-converged valence band of L and Σ bands. The observed high carrier concentration (∼1020 cm-3) reflects the effective convergence of these bands, enabling a high density-of-states effective mass and an enhanced power factor. Moreover, a very low lattice thermal conductivity of 0.6-0.5 W m-1 K-1 from 300 to 723 K is achieved in 0.9GeSe-0.1LiBiTe2, approaching the amorphous limit value. This remarkably low lattice thermal conductivity is related to phonon scattering from point defects, planar vacancies, and ferroelectric instability-induced low-energy Einstein oscillators. Finally, a maximum ZT value of 1.1 to 1.3 at 723 K is obtained, with a high average ZT value of over 0.8 (400-723 K) in 0.9GeSe-0.1LiBiTe2 samples. This study establishes a viable route for tailoring crystal structures to significantly improve the performance of GeSe-related compounds.

Ultra-high Performance Thermochromic Polymers via a Solid-solid Phase Transition Mechanism and Their Applications.

Thermochromic materials are substances that change colour in response to temperature variations. Today, sustainability concerns are the main drivers of thermochromic research, with smart, energy efficient windows being one of primary applications. While vanadium oxides and leuco dyes are traditionally the main thermochromic materials, hydrogels operating based on change of solvation have risen as some of the most promising materials due to their high optical transparency and good solar modulating abilities. In this work, a distinct mechanism for thermochromism arising from the crystalline solid to amorphous solid polymer transition, with a corresponding transition from an opaque state to a transparent state is disclosed. Both ultra-high optical transparency (Tlum up to 99%) and ultra-high solar modulation (ΔTsolar up to 87%) were observed. The transition temperature was tunable from 11 to 61 ͦ C by tuning the polymer structure. When incorporated into applications such as greenhouse materials and thermoelectric devices, significant performance enhancement was observed, due to the thermochromic material functioning as a thermal valve, speeding up solar heat absorbance while inhibiting the cooling process via its phase transition. This article is protected by copyright. All rights reserved.

Correction: Thermoelectric nanowires for dense 3D printed architectures.

Correction for 'Thermoelectric nanowires for dense 3D printed architectures' by Danwei Zhang et al., Mater. Horiz., 2024, 11, 847-854, https://doi.org/10.1039/D3MH01646C.

Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Synergistic Combination of Sb2Si2Te6 Additives for Enhanced Average ZT and Single-Leg Device Efficiency of Bi0.4Sb1.6Te3-based Composites.

Thermoelectric materials are highly promising for waste heat harvesting. Although thermoelectric materials research has expanded over the years, bismuth telluride-based alloys are still the best for near-room-temperature applications. In this work, a ≈38% enhancement of the average ZT (300-473 K) to 1.21 is achieved by mixing Bi0.4Sb1.6Te3 with an emerging thermoelectric material Sb2Si2Te6, which is significantly higher than that of most BiySb2-yTe3-based composites. This enhancement is facilitated by the unique interface region between the Bi0.4Sb1.6Te3 matrix and Sb2Si2Te6-based precipitates with an orderly atomic arrangement, which promotes the transport of charge carriers with minimal scattering, overcoming a common factor that is limiting ZT enhancement in such composites. At the same time, high-density dislocations in the same region can effectively scatter the phonons, decoupling the electron-phonon transport. This results in a ≈56% enhancement of the thermoelectric quality factor at 373 K, from 0.41 for the pristine sample to 0.64 for the composite sample. A single-leg device is fabricated with a high efficiency of 5.4% at ΔT = 164 K further demonstrating the efficacy of the Sb2Si2Te6 compositing strategy and the importance of the precipitate-matrix interface microstructure in improving the performance of materials for relatively low-temperature applications.

Thermoelectric nanowires for dense 3D printed architectures.

The large-scale employment of 3D printed inorganic thermoelectrics is primarily constrained because of their lower efficiencies as compared to those fabricated from conventional methods such as spark plasma sintering and hot-pressing. This originates from the significant challenge in the densification of printed parts, particularly through the direct-ink-writing fabrication process, which demands a high binder content for printability. To achieve high-density printed thermoelectrics, the ink formulation process often involves the addition of substantial filler content and sintering aids, coupled with prolonged sintering periods. Here, we propose a strategy to resolve the low densification issue of 3D printed thermoelectrics through a binder-less and sintering aid-free thermoelectric nanowire ink system that can achieve dense thermoelectric structures (up to 82.5% theoretical density). The increase in density and corresponding enhancement of thermoelectric material efficiency are attained in a more tunable and controlled manner without compromising the material composition. A high filler-derived density index (FDI) of 2.51 is also achieved, implying the potential to obtain high-density parts with minimal filler content, thus unlocking a cascade of profound impacts. Crucially, this advancement enables the possibilities of anisotropic engineering in thermoelectric materials, thereby shattering the limitations that have hindered the widespread adoption of 3D printed inorganic thermoelectrics.

Suppressing Ag2Te nanoprecipitates for enhancing thermoelectric efficiency of AgSbTe2.

Thermoelectrics are a class of materials that provide interconversion between heat and electricity, with desirable traits such as low thermal conductivity and low electrical resistivity. AgSbTe2 has emerged as one of the leading materials in recent years due to its ultra-low thermal conductivity. However, one major hindrance in undoped AgSbTe2 is its high electrical resistivity and low Seebeck coefficient due to the presence of Ag2Te nanoprecipitates. In this work, we leverage on the combination of an off-stoichiometric composition and a non-equilibrium process to simultaneously enhance the properties of AgSbTe2 and its thermoelectric device performance. Microscopically, the Ag2Te-deficient starting composition combined with a non-equilibrium thermal process suppresses the Ag2Te nanoprecipitates in the material. In addition, it is evident from the density functional theory (DFT) electronic structure that Ag2Te deficiency results in a smaller lattice and higher density-of-states near the Fermi level, which simultaneously lower the electrical resistivity and increase the Seebeck coefficient. As a result, zT as high as 1.7 was achieved at 573 K. Additionally, when combined with a high room temperature zT of 0.75, a power conversion efficiency of 7.3% was achieved at a ΔT of 290 K. Crucially, the strategy in this work can inspire application in other ABX2 material systems to achieve improved thermoelectric performances.

N-Type Thermoelectric AgBiPbS3 with Nanoprecipitates and Low Thermal Conductivity.

Thermoelectric sulfide materials are of particular interest due to the earth-abundant and cost-effective nature of sulfur. Here, we report a new n-type degenerate semiconductor sulfide, AgBiPbS3, which adopts a Fm3̅m structure with a narrow band gap of ∼0.32 eV. Despite the homogeneous distribution of elements at the scale of micrometer, Ag2S nanoprecipitates with dimensions of several nanometers were detected throughout the matrix. AgBiPbS3 exhibits a low room-temperature lattice thermal conductivity of 0.88 W m-1 K-1, owing to the intrinsic low lattice thermal conductivity of Ag2S and the effective scattering of phonons at nanoprecipitate boundaries. Moreover, compared to AgBiS2, AgBiPbS3 demonstrates a significantly improved weighted mobility of >16 cm2 V-1 s-1 at 300 K, leading to an enhanced PF of 1.6 µW cm-1 K-2 at 300 K. The superior electrical transport in AgBiPbS3 can be attributed to the high valley degeneracy of the L point (the conduction band minimum), which is contributed by the Pb s and Pb p orbitals. Further, Ga doping is found to be effective in modulating the Fermi levels of AgBiPbS3, leading to further enhancement of PF with a PFave of 2.7 µW cm-1 K-2 in the temperature range of 300-823 K. Consequently, a relatively high ZTave of 0.22 and a peak ZT of ∼0.4 at 823 K have been achieved in 3% Ga-doped AgBiPbS3, highlighting the potential of AgBiPbS3 as an n-type thermoelectric sulfide.

Moisture-Tailored 2D Dion-Jacobson Perovskites for Reconfigurable Optoelectronics.

Humidity- and moisture-induced degradation has been a longstanding problem in perovskite materials, affecting their long-term stability during applications. Counterintuitively, the moisture is leveraged to tailor the reversible hydrochromic behaviors of a new series of 2D Dion-Jacobson (DJ) perovskites for reconfigurable optoelectronics. In particular, the hydrogen bonds between organic cations and water molecules can be dynamically modulated via moisture removal/exposure. Remarkably, such modulation confines the movement of the organic cations close to the original position, preventing their escape from crystal lattices. Furthermore, this mechanism is elucidated by theoretical analysis using first-principles calculations and confirmed with the experimental characterizations. The reversible fluorescent transition 2D DJ perovskites show excellent cyclical properties, presenting untapped opportunities for reconfigurable optoelectronic applications. As a proof-of-concept demonstration, an anti-counterfeiting display is shown based on patterned reversible 2D DJ perovskites. The results represent a new avenue of reconfigurable optoelectronic application with 2D DJ perovskites for humidity detection, anti-counterfeiting, sensing, and other emerging photoelectric intelligent technologies.

Valorization of Spent coffee Grounds: A sustainable resource for Bio-based phase change materials for thermal energy storage.

Spent coffee grounds (SCGs) are waste residues arising from the process of coffee brewing and are usually sent to landfills, causing environmental concerns. SCGs contain a considerable amount of fatty acids and is therefore a promising green alternative bio-based phase change material (PCMs) compared to conventional organic and inorganic PCMs. In this study, the extraction of coffee oil from SCGs was conducted using three different organic solvents-ethanol, acetone, and hexane. The chemical composition, chemical, and thermophysical properties of these coffee oil extracts were studied to evaluate their feasibility as a bio-based PCM. Gas chromatography-mass spectroscopy (GC-MS) analysis indicated that coffee oil contains about 60-80 % of fatty acids while the phase transition temperature of the coffee oil extracts is approximately 4.5 ± 0.72 °C, with latent heat values of 51.15 ± 1.46 J/g as determined by differential scanning calorimetry (DSC). Fourier Transform Infrared Spectroscopy (FTIR) and DSC results of coffee oil extracts after thermal cycling revealed good thermal and chemical stability. An application study to evaluate coffee oil extract as a potential cold therapy modality showed that it can maintain temperatures below normal body temperature for up to 46 min. In conclusion, this work exemplifies the potential of SCGs as a promising green and sustainable resource for bio-based PCMs for low-temperature thermal energy storage applications such as cold-chain transportation and cold therapy.

Bio-Polypropylene and Polypropylene-based Biocomposites: Solutions for a Sustainable Future.

Polypropylene (PP) is among the most widely used commodity plastics in our everyday life due to its low cost, lightweight, easy processability, and exceptional chemical, thermo-mechanical characteristics. The growing awareness on energy and environmental crisis has driven global efforts for creating a circular economy via developing sustainable and eco-friendly alternatives to traditional plastics produced from fossil fuels for a variety of end-use applications. This review paper presents a brief outline of the emerging bio-based PP derived from renewable natural resources, covering its production routes, market analysis and potential utilizations. This contribution also provides a comprehensive review of the PP-based biocomposites produced with diverse green fillers generated from agro-industrial wastes, with particular emphasis on the structural modification, processing techniques, mechanical properties, and practical applications. Furthermore, given that the majority of PP products are currently destined for landfills, research progress on enhancing the degradation of PP and its biocomposites is also presented in light of the environmental concerns. Finally, a brief conclusion with discussions on challenges and future perspectives are provided.

Controlled Formation of Conduction Channels in Memristive Devices Observed by X-ray Multimodal Imaging.

Neuromorphic computing provides a means for achieving faster and more energy efficient computations than conventional digital computers for artificial intelligence (AI). However, its current accuracy is generally less than the dominant software-based AI. The key to improving accuracy is to reduce the intrinsic randomness of memristive devices, emulating synapses in the brain for neuromorphic computing. Here using a planar device as a model system, the controlled formation of conduction channels is achieved with high oxygen vacancy concentrations through the design of sharp protrusions in the electrode gap, as observed by X-ray multimodal imaging of both oxygen stoichiometry and crystallinity. Classical molecular dynamics simulations confirm that the controlled formation of conduction channels arises from confinement of the electric field, yielding a reproducible spatial distribution of oxygen vacancies across switching cycles. This work demonstrates an effective route to control the otherwise random electroforming process by electrode design, facilitating the development of more accurate memristive devices for neuromorphic computing.

Recent Advances in Host-Guest Supramolecular Hydrogels for Biomedical Applications.

The recognition-directed host-guest interaction is recognized as a valuable tool for creating supramolecular polymers. Functional hydrogels constructed through the dynamic and reversible host-guest complexation are endowed with a great many appealing features, such as superior self-healing, injectability, flexibility, stimuli-responsiveness and biocompatibility, which are crucial for biological and medicinal applications. With numerous topological structures and host-guest combinations established previously, recent breakthroughs in this area mostly focus on further improvement and fine-tuning of various properties for practical utilizations. The current contribution provides a comprehensive overview of the latest developments in host-guest supramolecular hydrogels, with a particular emphasis on the innovative molecular-level design strategies and hydrogel formation methodologies targeting at a wide range of active biomedical domains, including drug delivery, 3D printing, wound healing, tissue engineering, artificial actuators, biosensors, etc. Furthermore, a brief conclusion and discussion on the steps forward to bring these smart hydrogels to clinical practice is also presented.

Modulation of Spin Dynamics in 2D Transition-Metal Dichalcogenide via Strain-Driven Symmetry Breaking.

Transition metal dichalcogenides (TMDs) possess intrinsic spin-orbit interaction (SOI) with high potential to be exploited for various quantum phenomena. SOI allows the manipulation of spin degree of freedom by controlling the carrier's orbital motion via mechanical strain. Here, strain modulated spin dynamics in bilayer MoS2 field-effect transistors (FETs) fabricated on crested substrates are demonstrated. Weak antilocalization (WAL) is observed at moderate carrier concentrations, indicating additional spin relaxation path caused by strain fields arising from substrate crests. The spin lifetime is found to be inversely proportional to the momentum relaxation time, which follows the Dyakonov-Perel spin relaxation mechanism. Moreover, the spin-orbit splitting is obtained as 37.5 ± 1.4 meV, an order of magnitude larger than the theoretical prediction for monolayer MoS2 , suggesting the strain enhanced spin-lattice coupling. The work demonstrates strain engineering as a promising approach to manipulate spin degree of freedom toward new functional quantum devices.

Upcycling Silicon Photovoltaic Waste into Thermoelectrics.

Two decades after the rapid expansion of photovoltaics, the number of solar panels reaching end-of-life is increasing. While precious metals such as silver and copper are usually recycled, silicon, which makes up the bulk of a solar cells, goes to landfills. This is due to the defect- and impurity-sensitive nature in most silicon-based technologies, rendering it uneconomical to purify waste silicon. Thermoelectrics represents a rare class of material in which defects and impurities can be engineered to enhance the performance. This is because of the majority-carrier nature, making it defect- and impurity-tolerant. Here, the upcycling of silicon from photovoltaic (PV) waste into thermoelectrics is enabled. This is done by doping 1% Ge and 4% P, which results in a figure of merit (zT) of 0.45 at 873 K, the highest among silicon-based thermoelectrics. The work represents an important piece of the puzzle in realizing a circular economy for photovoltaics and electronic waste.

Photon-upconverters for blue organic light-emitting diodes: a low-cost, sky-blue example.

In the research ecosystem's quest towards having deployable organic light-emitting diodes with higher-energy emission (e.g., blue light), we advocate focusing on fluorescent emitters, due to their relative stability and colour purity, and developing design strategies to significantly improve their efficiencies. We propose that all triplet-triplet annihilation upconversion (TTA-UC) emitters would make good candidates for triplet fusion-enhanced OLEDs ("FuLEDs"), due to the energetically uphill nature of the photophysical process, and their common requirements. We demonstrate this with the low-cost sky-blue 1,3-diphenylisobenzofuran (DPBF). Having satisfied the criteria for TTA-UC, we show DPBF as a photon upconverter (I th 92 mW cm-2), and henceforth demonstrate it as a bright emitter for FuLEDs. Notably, the devices achieved 6.5% external quantum efficiency (above the ∼5% threshold without triplet contribution), and triplet-exciton-fusion-generated fluorescence contributes up to 44% of the electroluminescence, as shown by transient measurements. Here, triplet fusion translates to a quantum yield (Φ TTA-UC) of 19%, at an electrical excitation of ∼0.01 mW cm-2. The enhancement is meaningful for commercial blue OLED displays. We also found DPBF to have decent hole mobilities of ∼0.08 cm2 V-1 s-1. This additional finding can lead to DPBF being used in other capacities in various printable electronics.

SARS-CoV-2 in wastewater: From detection to evaluation.

SARS-CoV-2 presence in wastewater has been reported in several studies and has received widespread attention among the Wastewater-based epidemiology (WBE) community. Such studies can potentially be used as a proxy for early warning of potential COVID-19 outbreak, or as a mitigation measure for potential virus transmission via contaminated water. In this review, we summarized the latest understanding on the detection, concentration, and evaluation of SARS-CoV-2 in wastewater. Importantly, we discuss factors affecting the quality of wastewater surveillance ranging from temperature, pH, starting concentration, as well as the presence of chemical pollutants. These factors greatly affect the reliability and comparability of studies reported by various communities across the world. Overall, this review provides a broadly encompassing guidance for epidemiological study using wastewater surveillance.

Machine Learning-Driven Biomaterials Evolution.

Biomaterials is an exciting and dynamic field, which uses a collection of diverse materials to achieve desired biological responses. While there is constant evolution and innovation in materials with time, biomaterials research has been hampered by the relatively long development period required. In recent years, driven by the need to accelerate materials development, the applications of machine learning in materials science has progressed in leaps and bounds. The combination of machine learning with high-throughput theoretical predictions and high-throughput experiments (HTE) has shifted the traditional Edisonian (trial and error) paradigm to a data-driven paradigm. In this review, each type of biomaterial and their key properties and use cases are systematically discussed, followed by how machine learning can be applied in the development and design process. The discussions are classified according to various types of materials used including polymers, metals, ceramics, and nanomaterials, and implants using additive manufacturing. Last, the current gaps and potential of machine learning to further aid biomaterials discovery and application are also discussed.

Improved zT in Nb5Ge3-GeTe thermoelectric nanocomposite.

Robust electronic transport properties is a crucial in designing high performance thermoelectrics. A key similarity between superconductor and thermoelectric lies in their generally high electrical conductivity, even at above its superconducting temperature. In this work, we design a nanocomposite between Nb5Ge3 and GeTe-based thermoelectric to improve its thermoelectric figure of merit zT. Phase and microstructural characterization shows distinct Nb5Ge3 precipitates embed in Ge0.9Sb0.1Te matrix. In addition, experimental electronic and thermal transport analysis, together with density functional theory calculation were employed to show the synergistic effect of doping Sb and Nb5Ge3 nanocomposite approach. 10% Sb doping was found to optimize the electronic properties of the GeTe-based matrix. Further addition of 2 wt% Nb5Ge3 nanocomposite to the matrix enhances the phonon scattering, which consequently lowers the lattice thermal conductivity, which results in zT of up to 2.0 at 723 K. Such superconductor nanocomposite approach shown in this work can be employed to enhance the properties of other thermoelectric materials.

Electronic transport descriptors for the rapid screening of thermoelectric materials.

The discovery of novel materials for thermoelectric energy conversion has potential to be accelerated by data-driven screening combined with high-throughput calculations. One way to increase the efficacy of successfully choosing a candidate material is through its evaluation using transport descriptors. Using a data-driven screening, we selected 12 potential candidates in the trigonal ABX2 family, followed by charge transport property simulations from first principles. The results suggest that carrier scattering processes in these materials are dominated by ionised impurities and polar optical phonons, contrary to the oft-assumed acoustic-phonon-dominated scattering. Using these data, we further derive ground-state transport descriptors for the carrier mobility and the thermoelectric powerfactor. In addition to low carrier mass, high dielectric constant was found to be an important factor towards high carrier mobility. A quadratic correlation between dielectric constant and transport performance was established and further validated with literature. Looking ahead, dielectric constant can potentially be exploited as an independent criterion towards improved thermoelectric performance. Combined with calculations of thermal conductivity including Peierls and inter-branch coherent contributions, we conclude that the trigonal ABX2 family has potential as high performance thermoelectrics in the intermediate temperature range for low grade waste heat harvesting.