Self-oscillating polymeric refrigerator with high energy efficiency.

Electrocaloric1,2 and electrostrictive3,4 effects concurrently exist in dielectric materials. Combining these two effects could achieve the lightweight, compact localized thermal management that is promised by electrocaloric refrigeration5. Despite a handful of numerical models and schematic presentations6,7, current electrocaloric refrigerators still rely on external accessories to drive the working bodies8-10 and hence result in a low device-level cooling power density and coefficient of performance (COP). Here we report an electrocaloric thin-film device that uses the electro-thermomechanical synergy provided by polymeric ferroelectrics. Under one-time a.c. electric stimulation, the device is thermally and mechanically cycled by the working body itself, resulting in an external-driver-free, self-cycling, soft refrigerator. The prototype offers a directly measured cooling power density of 6.5 W g-1 and a peak COP exceeding 58 under a zero temperature span. Being merely a 30-µm-thick polymer film, the device achieved a COP close to 24 under a 4 K temperature span in an open ambient environment (32% thermodynamic efficiency). Compared with passive cooling, the thin-film refrigerator could immediately induce an additional 17.5 K temperature drop against an electronic chip. The soft, polymeric refrigerator can sense, actuate and pump heat to provide automatic localized thermal management.

High-Temperature Protonic Conduction in La2 NiO4+ δ -Based Ruddlesden-Popper Type Oxides: Correlation with Concentration of Interstitial Oxide Ions.

Oxygen-excess La2 NiO4+ δ (LNO) conducts oxide ions, electron holes, and hydroxide ions simultaneously on exposing to wet oxygen, exhibiting the potential as a cathode material in protonic ceramic fuel cells. Since the incorporation of protons in oxygen-excess LNO is via the hydration reaction assisted by interstitial oxide ions, in this work, the concentration of interstitial oxide ions is reduced and increased by substituting Ni with Cu and Co, respectively. A higher concentration of interstitial oxide ions leads to a high proton concentration, indicating the predominant role of interstitial oxide ions in the hydration reaction, different from that in the oxygen-deficient oxides, where protons are introduced by dissociative absorption of water molecules by oxygen vacancies. The theoretical calculation indicates that protons in Co-doped LNO prefer to locate between the interstitial oxide ions and unshared apical oxide ions. A trapping effect is found between protons and the oxide ions near Cu, leading to decreased proton mobility. Protonic conductivity at 400-575 °C is then directly measured by a Hebb-Wagner direct current polarization method with La0.99 Ca0.01 NbO4- δ as the blocking electrode, enabling the observation that Co-doped LNO has the highest protonic conductivity among the samples studied in this work.

Low-k nano-dielectrics facilitate electric-field induced phase transition in high-k ferroelectric polymers for sustainable electrocaloric refrigeration.

Ferroelectric polymer-based electrocaloric effect may lead to sustainable heat pumps and refrigeration owing to the large electrocaloric-induced entropy changes, flexible, lightweight and zero-global warming potential. Herein, low-k nanodiamonds are served as extrinsic dielectric fillers to fabricate polymeric nanocomposites for electrocaloric refrigeration. As low-k nanofillers are naturally polar-inactive, hence they have been widely applied for consolidate electrical stability in dielectrics. Interestingly, we observe that the nanodiamonds markedly enhances the electrocaloric effect in relaxor ferroelectrics. Compared with their high-k counterparts that have been extensively studied in the field of electrocaloric nanocomposites, the nanodiamonds introduces the highest volumetric electrocaloric enhancement (~23%/vol%). The resulting polymeric nanocomposite exhibits concurrently improved electrocaloric effect (160%), thermal conductivity (175%) and electrical stability (125%), which allow a fluid-solid coupling-based electrocaloric refrigerator to exhibit an improved coefficient of performance from 0.8 to 5.3 (660%) while maintaining high cooling power (over 240 W) at a temperature span of 10 K.

Au doped metal organic frameworks as di-functional photocatalysts for clearing organics in wastewater.

Along with the development of productive forces, the use of organic compounds including diversified dyes and multiple drugs has become more and more commonly, resulting in the accelerating water contamination. Herein in this paper, Au doped PCN 224 are designed as bi-functional wastewater treatment agents to absorb and decompose organics molecules efficiently under light irradiation. After inserted with Au, the PCN 224 nanoparticles, which is kind of porous, stable and photosensitive metal-organic framework, show enhanced photodegradeability. Because the Au inserted could inhibit the re-combination of electrons and holes by absorbing photo-electrons; decrease the nanoparticles' band gap, and finally produce much more free radicals. In the meanwhile, due to the lower binding energy between S and Au, the Au modified PCN 224 perform better in absorbing organic compounds consisted of S contained heterocyclic ring (such as methylene blue). This work provides new insights into the precious design of materials in clearing organic compounds.

Colossal electrocaloric effect in an interface-augmented ferroelectric polymer.

The electrocaloric effect demands the maximized degree of freedom (DOF) of polar domains and the lowest energy barrier to facilitate the transition of polarization. However, optimization of the DOF and energy barrier-including domain size, crystallinity, multiconformation coexistence, polar correlation, and other factors in bulk ferroelectrics-has reached a limit. We used organic crystal dimethylhexynediol (DMHD) as a three-dimensional sacrificial master to assemble polar conformations at the heterogeneous interface in poly(vinylidene fluoride)-based terpolymer. DMHD was evaporated, and the epitaxy-like process induced an ultrafinely distributed, multiconformation-coexisting polar interface exhibiting a giant conformational entropy. Under a low electric field, the interface-augmented terpolymer had a high entropy change of 100 J/(kg·K). This interface polarization strategy is generally applicable to dielectric capacitors, supercapacitors, and other related applications.

Compact effective surface plasmon polariton transmission line with undiminished bandwidth and enhanced field confinement.

In this work, we propose a compact effective surface plasmon polariton (CESPP) transmission line (TL) based on a structural dispersion-induced surface plasmon polaritons (SPPs) mode, which can enhance confinement while ensuring that the working bandwidth is not reduced. The dispersion relation of the CESPPs proposed in this article indicates that the shallower the groove, the stronger the confinement. Furthermore, the CESPPs may facilitate longitudinal miniaturization, since the configuration of the unit cell is simple. The coupling effect between two CESPP TLs has been well studied, revealing that excellent cross talk suppression can be achieved. The measurement results exhibit strong agreement with full-wave simulations, suggesting that the proposed CESPP TL holds significant potential for valuable applications in modern high-speed circuits.

Statistical Mechanical Model of the Giant Electrocaloric Effect in Ferroelectric Polymers.

The development of highly efficient cooling technologies has been identified as a key strategy to address the mitigation of global warming. Especially, electrocaloric materials have emerged as promising candidates for cooling applications, owing to their potential to provide high cooling capacity with low energy consumption. To advance the development of electrocaloric materials with a significant electrocaloric effect (ECE), a thorough understanding of the underlying mechanisms is required. Previous studies have estimated the maximum ECE temperature change by calculating the entropy change between two assumed states of a dipole model, assuming polarization saturation with a sufficiently large electric field. However, it is more relevant to assess the ECE under continuously changing electric fields as this is more reflective of real-world conditions. To this end, we establish a continuous transition between the complete disorder state and the polarization saturation state using the partition function to derive the entropy change. Our results demonstrate excellent agreement with experimental data, and our analysis of energy items within the partition function attributes the increase in the ECE entropy change with decreasing crystal size to interfacial effects. This statistical mechanical model reveals the in-depth ferroelectric polymers producing the ECE and offers significant potential for predicting the ECE in ferroelectric polymers and thus guides the design of high-performance ECE materials.

Thermochemical Expansion and Protonic and Electronic Hole Conductivity of Grain Interior and Grain Boundaries in 10 Mole% Y-Substituted SrZrO3.

Proton conducting acceptor-doped SrZrO3 has a history as long as that of BaZrO3 , but has attracted less interest. Inspired by its higher transport number of ionic conduction in wet oxygen revealed by our recent work, we here explore further aspects of doped SrZrO3 as electrolyte in proton ceramic electrochemical cells. In-situ high temperature XRD (HT-XRD) analysis of SrZr0.9 Y0.1 O3-δ (SZY10) indicated an anisotropic chemical expansion of hydration, stronger along the b than the a direction, and negative in the c direction. A systematic electromotive force (EMF) and impedance spectroscopy study as a function of p O 2 ${p_{{\rm{O}}_{\rm{2}} } }$ and p H 2 O ${p_{{\rm{H}}_{\rm{2}} {\rm{O}}} }$ allowed determination of partial conductivities of electron holes and ions (mainly protons) in bulk (grain interior) and grain boundaries. Enthalpies and preexponentials were determined and interpreted for bulk and grain boundary partial conductivities based on defect chemistry and a brick layer model. The hole conductivity in bulk is modest and ensures high ionic transport numbers in oxidizing atmospheres, while grain boundaries exhibit lower ionic transport numbers from a relatively higher hole conductivity attributed primarily to tunnelling past the deepest part of the space charge region. Y-doped SrZrO3 (SZY) materials exhibit lower proton conductivities but excel over Y-doped BaZrO3 (BZY) in terms of thermal expansion compatibility with electrode materials and higher ionic transport numbers in oxidizing atmospheres and may hence be candidates for functional layers between BZY-based electrolytes and positrodes in proton ceramic electrochemical cells.

The effect of surface nucleation modulation on the mechanical and biocompatibility of metal-polymer biomaterials.

The deployment of hernia repair patches in laparoscopic procedures is gradually increasing. In this technology, however, understanding the new phases of titanium from the parent phase on polymer substrates is essential to control the microstructural transition and material properties. It remains a challenging area of condensed matter physics to predict the kinetic and thermodynamic properties of metals on polymer substrates from the molecular scale due to the lack of understanding of the properties of the metal-polymer interface. However, this paper revealed the mechanism of nucleation on polymer substrates and proposed for the first record a time-dependent regulatory mechanism for the polymer-titanium interface. The interconnection between polymer surface chain entanglement, nucleation and growth patterns, crystal structure and surface roughness were effectively unified. The secondary regulation of mechanical properties was accomplished simultaneously to satisfy the requirement of biocompatibility. Titaniumized polypropylene patches prepared by time-dependent magnetron sputtering technology demonstrated excellent interfacial mechanical properties and biocompatibility. In addition, modulation by low-temperature plasma metal deposition opened a new pathway for biomaterials. This paper provides a solid theoretical basis for the research of titanium nanofilms on medical polypropylene substrates and the medical industry of implantable biomaterials, which will be of great value in the future.

Ladderphane copolymers for high-temperature capacitive energy storage.

For capacitive energy storage at elevated temperatures1-4, dielectric polymers are required to integrate low electrical conduction with high thermal conductivity. The coexistence of these seemingly contradictory properties remains a persistent challenge for existing polymers. We describe here a class of ladderphane copolymers exhibiting more than one order of magnitude lower electrical conductivity than the existing polymers at high electric fields and elevated temperatures. Consequently, the ladderphane copolymer possesses a discharged energy density of 5.34 J cm-3 with a charge-discharge efficiency of 90% at 200 °C, outperforming the existing dielectric polymers and composites. The ladderphane copolymers self-assemble into highly ordered arrays by π-π stacking interactions5,6, thus giving rise to an intrinsic through-plane thermal conductivity of 1.96 ± 0.06 W m-1 K-1. The high thermal conductivity of the copolymer film permits efficient Joule heat dissipation and, accordingly, excellent cyclic stability at elevated temperatures and high electric fields. The demonstration of the breakdown self-healing ability of the copolymer further suggests the promise of the ladderphane structures for high-energy-density polymer capacitors operating under extreme conditions.

Gas Diffusion Layer for Proton Exchange Membrane Fuel Cells: A Review.

Proton exchange membrane fuel cells (PEMFCs) are an attractive type of fuel cell that have received successful commercialization, benefitted from its unique advantages (including an all solid-state structure, a low operating temperature and low environmental impact). In general, the structure of PEMFCs can be regarded as a sequential stacking of functional layers, among which the gas diffusion layer (GDL) plays an important role in connecting bipolar plates and catalyst layers both physically and electrically, offering a route for gas diffusion and drainage and providing mechanical support to the membrane electrode assemblies. The GDL commonly contains two layers; one is a thick and rigid macroporous substrate (MPS) and the other is a thin microporous layer (MPL), both with special functions. This work provides a brief review on the GDL to explain its structure and functions, summarize recent progress and outline future perspectives.

(La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ (M=Ca, Sr, Ba) Ionic Conductors Promoted by Foreign/Domestic Dual Acceptor-Doping Strategies.

In this work, a class of ionic conductor (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ (M=Ca, Sr, and Ba) with a cubic pyrochlore structure was reported. Two strategies were adopted to increase the concentration of oxygen vacancies favoring the hydration reaction to introduce protons. One was increasing the cation ratio between Yb and Nb over unity, the other was doping divalent alkaline earth elements to replace trivalent La. Proton conduction was evidenced by confirming the proton incorporation and H/D isotope effect in electrical conductivity. Doping Ca, Sr, and Ba further promoted the proton conduction. The results of crystal structure refinement indicated that the extrinsically introduced oxygen vacancies by the two strategies were accommodated in the tetrahedra (48 f) containing two La and two Yb/Nb cations, while the tetrahedra containing four La cations (8a) were fully occupied by oxide ions. A discussion was thereby performed, leading to the suggestion that not all the tetrahedra in the cubic pyrochlore structure of (La1-x Mx )2 (Nb0.45 Yb0.55 )2 O7-δ helped in incorporating and conducting protons, and only the oxygen vacancies surrounded by four Y cations (48 f site) or two La and two Y cations (8b site) were hydratable. It is thereby suggested that to enhance the proton conduction in pyrochlore oxides, an effective strategy might be tuning the ability of hydration or protonation of the tetrahedra to increase the proton concentration and expand the route for proton conduction.

Mathematical modeling of the dynamics of COVID-19 variants of concern: Asymptotic and finite-time perspectives.

The COVID-19 pandemic has seen multiple waves, in part due to the implementation and relaxation of social distancing measures by the public health authorities around the world, and also caused by the emergence of new variants of concern (VOCs) of the SARS-Cov-2 virus. As the COVID-19 pandemic is expected to transition into an endemic state, how to manage outbreaks caused by newly emerging VOCs has become one of the primary public health issues. Using mathematical modeling tools, we investigated the dynamics of VOCs, both in a general theoretical framework and based on observations from public health data of past COVID-19 waves, with the objective of understanding key factors that determine the dominance and coexistence of VOCs. Our results show that the transmissibility advantage of a new VOC is a main factor for it to become dominant. Additionally, our modeling study indicates that the initial number of people infected with the new VOC plays an important role in determining the size of the epidemic. Our results also support the evidence that public health measures targeting the newly emerging VOC taken in the early phase of its spread can limit the size of the epidemic caused by the new VOC (Wu et al., 2139Wu, Scarabel, Majeed, Bragazzi, & Orbinski, ; Wu et al., 2021).

Metal organic framework-based antibacterial agents and their underlying mechanisms.

Bacteria, as the most abundant living organisms, have always been a threat to human life until the development of antibiotics. However, with the wide use of antibiotics over a long time, bacteria have gradually gained tolerance to antibiotics, further aggravating threat to human beings and environmental safety significantly. In recent decades, new bacteria-killing methods based on metal ions, hyperthermia, free radicals, physical pricks, and the coordination of several multi-mechanisms have attracted increasing attention. Consequently, multiple types of new antibacterial agents have been developed. Among them, metal organic frameworks (MOFs) appear to play an increasingly important role. The unique characteristics of MOFs make them suitable multiple-functional platforms. By selecting the appropriate metastable coordination bonds, MOFs can act as reservoirs and release antibacterial metal ions or organic linkers; by constructing a porous structure, MOFs can act as carriers for multiple types of agents and achieve slow and sustained release; and by designing their composition and the pore structure precisely, MOFs can be endowed with properties to produce heat and free radicals under stimulation. Importantly, in combination with other materials, MOFs can act as a platform to kill bacteria effectively through the synergistic effect of multiple types of mechanisms. In this review, we focus on the recent development of MOF-based antibacterial agents, which are classified according to their antibacterial mechanisms.

Quantifiable models for surface protonic conductivity in porous oxides - case of monoclinic ZrO2.

The surface protonic conductivity of porous monoclinic ZrO2 sintered at temperatures in the range 700-1100 °C yielding relative densities of around 60% and grain sizes of approximately 160 nm has been studied using impedance spectroscopy as a function of temperature well below the sintering temperature in wet atmospheres (pH2O = 0.03 bar). The sum of two high-frequency impedance responses is argued to represent surface conductance according to a new model of impedance over curved surfaces. A simple brick layer model is applied to compare the measured macroscopic conductivities with predicted surface conductances. The well-faceted samples sintered at the highest temperatures exhibited activation enthalpies up to 58 kJ mol-1 of surface protonic conduction in wet atmospheres at temperatures above 300 °C. We attribute this to the mobility of dissociated protons over surface oxide ions, and the high preexponential is in good agreement with a model comprising relatively strong dissociative chemisorption. With decreasing sintering temperature, the particles appear more rounded, with less developed facets, and we obtain activation enthalpies of surface protonic conduction in the chemisorbed layer down to around 30 kJ mol-1, with correspondingly smaller preexponentials and an observed dependency. Supported by the thermogravimetry of adsorption, we attribute this to weaker and more molecular chemisorption on the more randomly terminated less faceted surfaces, providing water layers with fewer dissociated charge carrying protons, but also smaller activation enthalpies of mobility. Below 200 °C, all samples exhibit a strongly inverse temperature dependency characteristic of conduction in the 1st physisorbed layer with increasing coverage. The preexponentials correspond well to the models of physisorption, with dissociation to and proton migration between physisorbed water molecules. The enthalpies fit well to physisorption and with enthalpies of dissociation and proton mobility close to those of liquid water. We have by this introduced models for proton conduction in chemisorbed and physisorbed water on ZrO2, applicable to other oxides as well, and shown that preexponentials are quantitatively assessable in the order-of-magnitude level to discriminate models via a simple brick layer model based topographical analysis of the ceramic microstructure.

Submicron particle formation from co-firing of coal and municipal sewage sludge.

With the increasing production of municipal sewage sludge (MSS) in China every year, the co-firing of MSS and pulverized coal is getting more and more widely applied in large coal-fired power plants. The co-firing of MSS and pulverized coal will produce a large amount of particulate matter (PM) emissions, especially submicron particles. In this paper, the formation characteristics of submicron particles in the co-firing process of coal and MSS were studied in a drop tube furnace. The influence of the furnace temperature and the addition ratio of sludge on the particle size distribution and element composition of submicron particles in MSS, pulverized coal combustion and co-firing was mainly studied. The experimental results show that the furnace temperature has an influence on the formation of PM0.4. For sludge combustion, increasing the furnace temperature will promote the formation of PM0.4. The main reason is that increasing the furnace temperature promotes the gasification of Si, S, Fe, and P to form the precursor of PM0.4 or PM0.4. At same furnace temperature, the volume concentration and mass concentration of PM0.4 produced from pulverized coal combustion are less than that of sludge. Different from sludge combustion, co-firing of pulverized coal and sludge has a synergistic effect on eliminating PM0.4 formation. Increasing the addition ratio of sludge can decrease the volume concentration and mass concentration of PM0.4. This is because that aluminosilicates formed during co-firing promotes the scavenge Si, Ca, Fe, thereby reducing the precursors of PM0.4 and the mass yield of PM0.4. Increasing the furnace temperature in co-firing can inhibit the formation of PM0.4. When the furnace temperature is between 1100 °C and 1300 °C, increasing the furnace temperature will reduce the Fe content and increase the content of Si, Ca, Na, K, and P in PM0.4. However, the reduction of Fe and the increase of Si, Ca, Na, K, and P in PM0.4 offset each other, resulting in an insensitive relationship between the mass yield of PM0.4 and the furnace temperature.

Prognostic Bone Metastasis-Associated Immune-Related Genes Regulated by Transcription Factors in Mesothelioma.

Mesothelioma (MESO) is a mesothelial originate neoplasm with high morbidity and mortality. Despite advancement in technology, early diagnosis still lacks effectivity and is full of pitfalls. Approaches of cancer diagnosis and therapy utilizing immune biomarkers and transcription factors (TFs) have attracted more and more attention. But the molecular mechanism of these features in MESO bone metastasis has not been thoroughly studied. Utilizing high-throughput genome sequencing data and lists of specific gene subsets, we performed several data mining algorithm. Single-sample Gene Set Enrichment Analysis (ssGSEA) was applied to identify downstream immune cells. Potential pathways involved in MESO bone metastasis were identified using Gene Oncology (GO) analysis, Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis, Gene Set Variation Analysis (GSVA), Gene Set Enrichment Analysis (GSEA), and Cox regression analysis. Ultimately, a model to help early diagnosis and to predict prognosis was constructed based on differentially expressed immune-related genes between bone metastatic and nonmetastatic MESO groups. In conclusion, immune-related gene SDC2, regulated by TFs TCF7L1 and POLR3D, had an important role on immune cell function and infiltration, providing novel biomarkers and therapeutic targets for metastatic MESO.

High-entropy polymer produces a giant electrocaloric effect at low fields.

More than a decade of research on the electrocaloric (EC) effect has resulted in EC materials and EC multilayer chips that satisfy a minimum EC temperature change of 5 K required for caloric heat pumps1-3. However, these EC temperature changes are generated through the application of high electric fields4-8 (close to their dielectric breakdown strengths), which result in rapid degradation and fatigue of EC performance. Here we report a class of EC polymer that exhibits an EC entropy change of 37.5 J kg-1 K-1 and a temperature change of 7.5 K under 50 MV m-1, a 275% enhancement over the state-of-the-art EC polymers under the same field strength. We show that converting a small number of the chlorofluoroethylene groups in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer into covalent double bonds markedly increases the number of the polar entities and enhances the polar-nonpolar interfacial areas of the polymer. The polar phases in the polymer adopt a loosely correlated, high-entropy state with a low energy barrier for electric-field-induced switching. The polymer maintains performance for more than one million cycles at the low fields necessary for practical EC cooling applications, suggesting that this strategy may yield materials suitable for use in caloric heat pumps.

Multifunctional Membrane for Thermal Management Applications.

Space cooling and heating consume a large proportion of global energy, so passive thermal management materials (i.e., without energy input), especially dual-mode materials including cooling and heating bifunctions, are becoming more and more attractive in many areas. Herein, a function-switchable Janus membrane between cooling and heating consisting of a multilayer structure of polyvinylidene fluoride nanofiber/zinc oxide nanosheet/carbon nanotube/Ag nanowire/polydimethylsiloxane was fabricated for comprehensive thermal management applications. In the cooling mode, the high thermal radiation emissivity (89.2%) and sunlight reflectivity (90.6%) of the Janus membrane resulted in huge temperature drops of 8.2-12.6, 9.0-14.0, and 10.9 °C for a substrate, a closed space, and a semiclosed space, respectively. When switching to the heating mode, temperature rises of 3.8-4.6, 4.0-4.8, and 12.5 °C for the substrate, closed space, and semiclosed space, respectively, were achieved owing to the high thermal radiation reflectivity (89.5%) and sunlight absorptivity (74.1%) of the membrane. Besides, the Janus membrane has outstanding comprehensive properties of the membrane, including infrared camouflaging/disguising, electromagnetic shielding (53.1 dB), solvent tolerance, waterproof properties, and high flexibility, which endow the membrane with promising application prospects.

Erratum: Blood TfR+ exosomes separated by a pH-responsive method deliver chemotherapeutics for tumor therapy: Erratum.

[This corrects the article DOI: 10.7150/thno.37220.].