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Although a variety of methods to predict the effective thermal conductivity of porous foams have been proposed, the response of such materials under dynamic compressive loading has generally not been considered. Understanding the dynamic thermal behavior will widen the potential applications of porous foams and provide insights into methods of modifying material properties to achieve desired performance. Previous experimental work on the thermal conductivity of a flexible graphene composite under compression showed intriguing behavior: the cross-plane thermal conductivity remained approximately constant with increasing compression, despite the increasing mass density. In this work, we use molecular dynamics (MD) simulations and finite element analysis to study the variation in both the cross-plane and in-plane thermal conductivities by compressing isotropic graphene foams. We have found that, interestingly, the cross-plane thermal conductivity decreases with compression while the in-plane thermal conductivity increases; hence, the dynamic thermal transport of the graphene foam becomes anisotropic with a significant anisotropy ratio. Such observations cannot be explained by the conventional effective medium theory, which describes the increase of thermal conductivity to be proportional to mass density. Thus, we propose a model that can describe such anisotropic effective thermal conductivity of highly porous open-cell media during compression. The model is validated against the MD simulations as well as a larger-scale finite element simulation of an open-cell foam geometry.

Monte Carlo simulations for photon transport are commonly used to predict the spectral response, including reflectance, absorptance, and transmittance in nanoparticle laden media, while the computational cost could be high. In this study, we demonstrate a general purpose fully connected neural network approach, trained with Monte Carlo simulations, to accurately predict the spectral response while dramatically accelerating the computational speed. Monte Carlo simulations are first used to generate a training set with a wide range of optical properties covering dielectrics, semiconductors, and metals. Each input is normalized, with the scattering and absorption coefficients normalized on a logarithmic scale to accelerate the training process and reduce error. A deep neural network with ReLU activation is trained on this dataset with the optical properties and medium thickness as the inputs, and diffuse reflectance, absorptance, and transmittance as the outputs. The neural network is validated on a validation set with randomized optical properties, as well as nanoparticle medium examples including barium sulfate, aluminum, and silicon. The error in the spectral response predictions is within 1% which is sufficient for many applications, while the speedup is 1–3 orders of magnitude. This machine learning accelerated approach can allow for high throughput screening, optimization, or real-time monitoring of nanoparticle media's spectral response.

Efficient and direct conversion of methane to value-added products has been a long-term challenge in shale gas applications. Here, we show that atomically thin nanolayers of Pt with a single or double atomic layer thickness, supported on a two-dimensional molybdenum titanium carbide (MXene), catalyse non-oxidative coupling of methane to ethane/ethylene (C2). Kinetic and theoretical studies, combined with in-situ spectroscopic and microscopic characterizations, demonstrate that Pt nanolayers anchored at the hexagonal close-packed sites of the MXene support can activate the first C–H bond of methane to form methyl radicals that favour desorption over further dehydrogenation and thus suppress coke deposition. At 750 °C and 7% methane conversion, the catalyst runs for 72 hours of continuous operation without deactivation and exhibits >98% selectivity towards C2 products, with a turnover frequency of 0.2–0.6 s−1. Our findings provide insights into the design of highly active and stable catalysts for methane activation and create a platform for developing atomically thin supported metal catalysts. The challenge in non-oxidative coupling of methane lies in the activation of the first C–H bond while avoiding further dehydrogenations, which lead to the formation of coke. Here, atomically thin platinum nanolayers on two-dimensional molybdenum titanium carbides are reported as a superior catalyst for this reaction owing to reduced coke formation.

Previous multitemperature model (MTM) resolving phonon temperatures at the polarization level and measurements have uncovered remarkable nonequilibrium among different phonon polarizations in laser irradiated graphene and metals. Here, we develop a semiconductor-specific MTM (SC-MTM) by including electron-hole pair generation, diffusion, and recombination, and show that a phonon polarization-level model does not yield observable polarization-based nonequilibrium in laser-irradiated molybdenum disulfide (MoS$_2$). In contrast, appreciable nonequilibrium is predicted between zone-center optical phonons and the other modes. The momentum-based nonequilibrium ratio is found to increase with decreasing laser spot size and interaction with a substrate. This finding is relevant to the understanding of the energy relaxation process in two-dimensional optoelectronic devices and Raman measurements of thermal transport.

Bismuth telluride (Bi2Te3) and its alloys with antimony telluride (Sb2Te3) have long been considered to be the best room-temperature bulk thermoelectric (TE) materials. In recent decades, proof-of-concept demonstrations on Bi2Te3-Sb2Te3 nanostructures have shown high TE performance due to reduction in lattice thermal conductivities. Particularly, ultra-low thermal conductivities have been observed in Bi2Te3-Sb2Te3 1D superlattices, leading to thermoelectric figures of merit (ZT) as high as 2.4. In contrast, very few computational studies have been performed to provide insight into the phonon transport across these nanostructures. In this work, we use non-equilibrium molecular dynamics simulations with previously developed force fields to simulate thermal transport across Bi2Te3-Sb2Te3 interfaces and superlattices. We first calculate the thermal conductance associated with a Bi2Te3-Sb2Te3 interface across a temperature range of 200-400 K. The values are also compared with thermal conductances calculated by a modified Landauer transport formalism using phonon transmission coefficients obtained from the diffuse mismatch model. Our results show that inelastic scattering processes contribute to an increase in interfacial thermal conductance at higher temperatures. Finally, we calculate the thermal conductivities of Bi2Te3-Sb2Te3 superlattices with varying period lengths from 2 to 18 nm. A minimum thermal conductivity of 0.27 W/mK is observed at a period length of 4 nm, which is attributed to the competition between incoherent and coherent phonon transport regimes. In comparison with previous experimental measurements in the literature, our results show good agreement with respect to the range of thermal conductivity values and the period length corresponding to the minimum superlattice thermal conductivity.

Atmospheric water harvesting (AWH) has received tremendous interest because of population growth, limited freshwater resources, and water pollution. However, key challenges remain in developing efficient, flexible, and lightweight AWH materials with scalability. Here, we demonstrated a radiative cooling fabric for AWH via its hierarchically structured cellulose network and hybrid sorption-dewing mechanisms. With 8.3% solar absorption and ∼0.9 infrared (IR) emissivity, the material can drop up to 7.5 °C below ambient temperature without energy consumption via radiative cooling. Water adsorption onto the hydrophilic functional groups of cellulose is dominated by sorption at low relative humidity (RH) and dewing at high RH. The cellulose network provides desirable mechanical properties with entangled high-aspect-ratio fibers over tens of adsorption-extraction cycles. In the field test, the cellulose sample exhibited water uptake of 1.29 kg/kg at 80% RH during the night. The profusion of radiative cooling fabric features desirable cost effectiveness and allows fast deployment into large-scale AWH applications.

Emerging atmospheric water harvesting (AWH) technologies promise water supply to underdeveloped regions that have no access to liquid water resources. The prevailing AWH systems, including condensation- or sorption-based, mostly rely on a single mechanism and thus have a limited range of working conditions and inferior performance. In this study, we synergistically integrate multiple mechanisms, including thermosorption effect, radiative cooling, and multiscale cellulose-water interactions, and demonstrate a low-cost (~ 4 USD kg− 1) and high performance (up to 6.75 L kg− 1 day− 1 in field tests) AWH system requiring zero active energy input. The proposed system consists of a highly scalable and sustainable cellulose scaffold impregnated with hygroscopic deliquescent lithium chloride (LiCl) salt. Cellulose scaffold and coated LiCl synergistically interact with water at different scales from molecular, to nanometer, and micrometer scales, providing a fast harvesting rate and high yield over a wide operation range. Iterating radiative cooling and solar heating workflow achieves simultaneous enhancement of water capture and release through the so-called temperature-swing strategy. The captured water in return facilitates radiative cooling due to the intrinsically high infrared (IR) emissivity of the LiCl-cellulose composite. With our simple yet effective material design, the AWH working range extends to lower than ~ 10% relative humidity (RH), and the water uptake in the controlled lab test reaches 16 kg kg− 1 at 90% RH (sample at 19°C, i.e. 6°C below 25°C ambient temperature). In addition, we propose a theoretical model capable of elucidating the experimental water uptake curves and demonstrating the synergy among cellulose-LiCl-water-energy interaction. The promising performance emphasizes the potential of involving multiple AWH mechanisms and points to an alternative pathway to stimulate future improvement.

The Raman peak position and linewidth provide insight into phonon anharmonicity and electron-phonon interactions in materials. For monolayer graphene, prior first-principles calculations have yielded decreasing linewidth with increasing temperature, which is opposite to measurement results. Here, we explicitly consider four-phonon anharmonicity, phonon renormalization, and electron-phonon coupling, and find all to be important to successfully explain both the G peak frequency shift and linewidths in our suspended graphene sample over a wide temperature range. Four-phonon scattering contributes a prominent linewidth that increases with temperature, while temperature dependence from electron-phonon interactions is found to be reversed above a doping threshold (ℏω_{G}/2, with ω_{G} being the frequency of the G phonon).

Micro-Raman spectroscopy has become an important tool in probing thermophysical behavior in emerging functional materials such as two-dimensional (2D) layered structures. Localized heating by the focused Raman excitation laser beam is expected to produce both stress and nonequilibrium temperature distributions in the material. Here we investigate the effects of hot optical phonons in the Raman spectra of molybdenum disulphide (MoS2) and distinguish them from those caused by thermally-induced compressive stress, which causes a Raman frequency blue shift in the focused Raman laser spot. With the stress effect accounted for in micro-Raman measurements, the degree of nonequilibrium between the hot optical phonons and the acoustic phonon bath is found to be much smaller than those observed in prior micro-Raman measurements of suspended graphene. The observation agrees with a first-principles based theoretical prediction of overpopulated zone-center optical phonons compared to other optical phonons in the Brillouin zone and acoustic phonons. The findings provide detailed insight into the energy relaxation processes in this emerging 2D transition metal dichalcogenide (TMD) electronic and optoelectronic material and clarify an important question in micro-Raman measurements of thermal transport in this and other 2D materials., Comment: 19 pages. 4 figures

In heat conduction through a homogenous nanomaterial, various phonons may exhibit diverse temperatures even at the same location at a steady state, known as the local phonon nonequilibrium phenomenon. Different phonons are often considered to behave independently, and the phonons with longer mean free paths (MFPs) have smaller temperature gradients. That is, the temperature gradient exhibits the following order: ballistic phonons semiballistic phonons \ensuremath{\approx} lattice (average) temperature gradient diffusive phonons, where ballistic phonons have MFPs much larger than the characteristic length, semiballistic phonons have MFPs like the characteristic length, and diffusive phonons have MFPs much smaller than the characteristic length. However, in this paper, we reveal that the effect of phonon-phonon coupling leads nonequilibrium phonon temperature gradients to the following trend: diffusive phonon temperature gradients will decrease to the lattice temperature, and temperature gradients of some semiballistic phonons even surpass that of diffusive phonons. The diffusive phonon temperature is merged onto the lattice temperature since they have large scattering rates and can be equilibrated quickly to the lattice temperature after traveling for a short distance away from the boundaries into the nanomaterial. The semiballistic phonons have large scattering rates but not large enough to bring them down to the lattice temperature. To obtain a further understanding of the nonequilibrium phonon temperatures, we have also derived a simple analytical model which can accurately predict the temperature profiles of all individual phonons given their MFPs. Using this model, we find that, near the boundary, phonon temperatures decay with position exponentially (instead of linearly), with a rate inversely proportional to their MFPs. Our findings offer insight for the understanding and prediction of phonon nonequilibrium temperatures within nanodevices.

We demonstrate remarkable full-daytime subambient cooling performance with CaCO3 and BaSO4 nanoparticle paints. These fillers have a high electron band gap for low solar absorptance and phonon resonance or polymer absorption in the sky window for high sky window emissivity. With an appropriate particle size and a broad particle size distribution, the BaSO4 nanoparticle film reaches an ultrahigh solar reflectance of 97.6% and a high sky window emissivity of 0.96. During field tests, the BaSO4 film stays more than 4.5 °C below ambient temperature or achieves an average cooling power of 117 W/m2. The BaSO4-acrylic paint is developed with a 60% volume concentration to enhance the reliability in outdoor applications, achieving a solar reflectance of 98.1% and a sky window emissivity of 0.95. Field tests indicate similar cooling performance to the BaSO4 films. Overall, our BaSO4-acrylic paint shows a standard figure of merit of 0.77.

Conventionally, graphene is a poor thermoelectric material with a low figure of merit (ZT) of 10^− 10^. Although nanostructuring was proposed to improve the thermoelectric performance of graphene, little experimental progress has been accomplished. Here, we carefully fabricated as-grown suspended graphene nanoribbons with quartermicron length and ∼40 nm width. The ratio of electrical to thermal conductivity was enhanced by 1−2 orders of magnitude, and the Seebeck coefficient was several times larger than bulk graphene, which yielded record-high ZT values up to ∼0.1. Moreover, we observed a record-high electronic contribution of ∼20% to the total thermal conductivity in the nanoribbon. Concurrent phonon Boltzmann transport simulations reveal that the reduction of lattice thermal conductivity is mainly attributed to quasi-ballistic phonon transport. The record-high ratio of electrical to thermal conductivity was enabled by the disparate electron and phonon mean free paths as well as the clean samples, and the enhanced Seebeck coefficient was attributed to the band gap opening. Our work not only demonstrates that electron and phonon transport can be fundamentally tuned and decoupled in graphene but also indicates that graphene with appropriate nanostructures can be very promising thermoelectric materials.

A key requirement for achieving passive radiative cooling for an ideal emitter, in the sky window (8–13 µm), during daytime is a total solar reflection >85%, and every 1% above this threshold results in ∼10 W/m2 gain in cooling power. One promising, inexpensive, and scalable solution for achieving high total solar reflectance is a dielectric nanoparticle-polymer composite coating. Past works have widely used a single particle size. However, it is challenging to achieve solar reflectance significantly above 85%. Here, recognizing the broadband nature of the solar irradiation, we propose and test a new concept of enhancing solar reflection at a given particle volume concentration by using hierarchical particle sizes, which we hypothesize to scatter each band of the solar spectrum i.e. VIS, NIR, and UV effectively. The hypothesis is tested using a TiO2 nanoparticle-acrylic system. Using the Mie Theory, the scattering and absorption efficiencies and asymmetric parameter of nanoparticles with different sizes and combinations are calculated, then the Monte Carlo Method is used to solve the Radiative Transfer Equation. When validating our computational model to in-house experimental results it is found that a nanoparticle size distribution of d = 104 ± 37 nm creates an overall better fit to the experimental data and increases the total solar reflection when compared to the single size model of d = 104 nm. We then purposely design hierarchical combinations of particle sizes in the broader range of 50 nm to 800 nm, and we have achieved an overall total solar reflection of ≈91%, which is higher than the ≈78% and ≈88% for 100 nm and 400 nm single particle sizes, respectively. The results confirm our hypothesis that hierarchical particle sizes can scatter over a broad spectrum more effectively rather than any single particle size. Moreover, our findings could also cut the manufacturing cost since no precise control of particle size is necessary.

The coupling of lattice dynamics and phonon transport methodologies with density functional theory has become a powerful tool for calculating lattice thermal conductivity (κ) with demonstrated quantitative accuracy and applicability to a wide range of materials. More importantly, these first-principles transport methods lack empirical tuning parameters so that reliable predictions of κ behaviors in new and old materials can be formulated. Since its inception nearly a decade ago, first-principles thermal transport has vastly expanded the range of materials examined, altered our physical intuition of phonon interactions and transport behaviors, provided deeper understanding of experiments, and accelerated the design of materials for targeted thermal functionalities. Such advances are critically important for developing novel thermal management materials and strategies as heat sets challenging operating limitations on engines, microelectronics, and batteries. This article provides a comprehensive survey of first-principles Peierls-Boltzmann thermal transport as developed in the literature over the last decade, with particular focus on more recent advances. This review will demonstrate the wide variety of calculations accessible to first-principles transport methods (including dimensionality, pressure, and defects), highlight unusual properties and predictions that have been made, and discuss some challenges and behaviors that lie beyond.

Radiative cooling is a passive cooling technology that offers great promises to reduce space cooling cost, combat the urban island effect, and alleviate the global warming. To achieve passive daytime radiative cooling, current state-of-the-art solutions often utilize complicated multilayer structures or a reflective metal layer, limiting their applications in many fields. Attempts have been made to achieve passive daytime radiative cooling with single-layer paints, but they often require a thick coating or show partial daytime cooling. In this work, we experimentally demonstrate remarkable full-daytime subambient cooling performance with both BaSO

FourPhonon is a computational package that can calculate four-phonon scattering rates in crystals. It is built within ShengBTE framework, which is a well-recognized lattice thermal conductivity solver based on Boltzmann transport equation . An adaptive energy broadening scheme is implemented for the calculation of four-phonon scattering rates. In analogy with thirdorder.py in ShengBTE , we also provide a separate python script , Fourthorder.py , to calculate fourth-order interatomic force constants. The extension module preserves all the nice features of the well-recognized lattice thermal conductivity solver ShengBTE , including good parallelism and straightforward workflow. In this paper, we discuss the general theory, program design, and example calculations on Si, BAs and LiCo O 2 . Program summary Program Title: FourPhonon CPC Library link to program files: https://doi.org/10.17632/jjcwt5436h.1 Developer's repository link: https://github.com/FourPhonon Licensing provisions: GNU General Public License version 3 Programming language: Fortran 90, MPI Nature of problem: Calculation of lattice thermal conductivity and related quantities, determination of both three-phonon and four-phonon scattering rates Solution method: Four-phonon scattering rates at RTA level, adaptive broadening scheme Additional comments including restrictions and unusual features: For a productive run, one needs to use High Performance Computing facilities and it takes several hours to several days to finish calculations

Extracting long-lasting performance from electronic devices and improving their reliability through effective heat management requires good thermal conductors. Taking both three- and four-phonon scattering as well as electron-phonon and isotope scattering into account, we predict that semimetallic $\ensuremath{\theta}$-phase tantalum nitride ($\ensuremath{\theta}\text{\ensuremath{-}}\mathrm{TaN}$) has an ultrahigh thermal conductivity ($\ensuremath{\kappa}$), of 995 and $\text{820 }\mathrm{W}\text{ }{\mathrm{m}}^{\ensuremath{-}1}\text{ }{\mathrm{K}}^{\ensuremath{-}1}$ at room temperature along the $a$ and $c$ axes, respectively. Phonons are found to be the main heat carriers, and the high $\ensuremath{\kappa}$ hinges on a particular combination of factors: weak electron-phonon scattering, low isotopic mass disorder, and a large frequency gap between acoustic and optical phonon modes that, together with acoustic bunching, impedes three-phonon processes. On the other hand, four-phonon scattering is found to be significant. This study provides new insight into heat conduction in semimetallic solids and extends the search for high-$\ensuremath{\kappa}$ materials into the realms of semimetals and noncubic crystal structures.

Bismuth telluride (Bi

Thermal switches have gained intense interest recently for enabling dynamic thermal management of electronic devices and batteries that need to function at dramatically varied ambient or operating conditions. However, current approaches have limitations such as the lack of continuous tunability, low switching ratio, low speed, and not being scalable. Here, a continuously tunable, wide-range, and fast thermal switching approach is proposed and demonstrated using compressible graphene composite foams. Large (~8x) continuous tuning of the thermal resistance is achieved from the uncompressed to the fully compressed state. Environmental chamber experiments show that our variable thermal resistor can precisely stabilize the operating temperature of a heat generating device while the ambient temperature varies continuously by ~10 °C or the heat generation rate varies by a factor of 2.7. This thermal device is promising for dynamic control of operating temperatures in battery thermal management, space conditioning, vehicle thermal comfort, and thermal energy storage., Current designs of thermal switches are limited by a lack of continuous tunability, low switching ratio, low speed, and not being scalable. Here the authors report a continuously tunable, wide-range, fast, and cost effective thermal switching approach that is demonstrated using compressible graphene composite foams.

Radiative cooling is a passive cooling technology by reflecting sunlight and emitting radiation in the atmospheric sky window. Although highly desired, full daytime sub-ambient radiative cooling in commercial-like single-layer particle-matrix paints is yet to be achieved. In this work, we have demonstrated full daytime sub-ambient radiative cooling in CaCO3-acrylic paint by adopting large bandgap fillers, a high particle concentration and a broad size distribution. Our paint shows the highest solar reflectance of 95.5% among paints and a high sky-window emissivity of 0.94. Field tests show cooling power exceeding 37 W/m2 and lower surface temperature more than 1.7C below ambient at noon. A figure of merit RC is proposed to compare the cooling performance under different weather conditions. The RC of our cooling paint is 0.62, among the best radiative cooling performance while offering unprecedented benefits of the convenient paint form, low cost, and the compatibility with commercial paint fabrication process., 14 pages, 8 figures, 1 video. For associate video file (Movie S1.mp4), see https://www.dropbox.com/s/wow1vr523km7rwc/MovieS1.mp4

It has been well-known that Raman and infrared linewidths are associated with third-order lattice anharmonicity. Here, the authors go further and establish by means of first-principles calculations and Raman measurements that the previously neglected fourth-order anharmonicity may play a significant, or even dominating, role. The predicted strong fourth-order lattice anharmonicity results from the large four-phonon scattering phase space of zone-center optical phonons. It explains well the significantly broadened Raman or infrared peaks, observed for a wide range of materials at various temperatures. This finding may significantly impact spectroscopy techniques and the understanding of radiative transport.

Recently, first-principles calculations based on density functional theory have been widely used to predict the temperature-dependent infrared spectrum of polar materials, but the calculations are usually limited to the harmonic frequency (0 K) and three-phonon scattering damping for the zone-center infrared-active optical phonon modes, and fail to predict the high-temperature infrared optical properties of materials such as sapphire ($\ensuremath{\alpha}\ensuremath{-}{\text{Al}}_{2}{\text{O}}_{3}$), GaAs, $\text{Ti}{\text{O}}_{2}$, etc., due to the neglect of high-order phonon scattering damping and phonon frequency shift. In this work, we implemented first-principles calculations to predict the temperature-dependent infrared dielectric function of polar materials by including four-phonon scattering and phonon frequency shift. The temperature-dependent phonon damping by including three- and four-phonon scattering as well as the phonon frequency shift by including cubic and quartic anharmonicity and the thermal expansion effect are calculated based on anharmonic lattice dynamics method. The infrared dielectric function of $\ensuremath{\alpha}\ensuremath{-}{\text{Al}}_{2}{\text{O}}_{3}$ is parameterized, and then the temperature-dependent infrared optical reflectance is determined. We find that our predictions agree better with the experimental data than the previous density functional theory-based methods. This work will help to effectively predict the thermal radiative properties of polar materials at elevated temperature, which is generally difficult to measure, and will enable predictive design of new materials for radiative applications.