Numerical homogenization of thermal conductivity of particle-filled thermal interface material by fast Fourier transform method.

Thermal interface material (TIM) is pivotal for the heat dissipation between layers of high-density electronic packaging. The most widely used TIMs are particle-filled composite materials, in which highly conductive particulate fillers are added into the polymer matrix to promote heat conduction. The numerical simulation of heat transfer in the composites is essential for the design of TIMs; however, the widely used finite element method (FEM) requires large memory and presents limited computational time for the composites with dense particles. In this work, a numerical homogenization algorithm based on fast Fourier transform was adopted to estimate the thermal conductivity of composites with randomly dispersed particles in 3D space. The unit cell problem is solved by means of a polarization-based iterative scheme, which can accelerate the convergence procedure regardless of the contrast between various components. The algorithm shows good precision and requires dramatically reduced computation time and cost compared with FEM. Moreover, the effect of the particle volume fraction, interface thermal resistance between particles (R-PP), interface thermal resistance between particle and matrix (R-PM), and particle size have been estimated. It turns out that the effective conductivity of the particulate composites increases sharply at a critical filler volume fraction, after which it is sensitive to the variation of filler loading. We can observe that the effective thermal conductivity of the composites with low filler volume fraction is sensitive to R-PM, whereas the it is governed by R-PP for the composites with high filler content. The algorithm presents excellent efficiency and accuracy, showing potential for the future design of highly thermally conductive TIMs.

Ice-Templated MXene/Ag-Epoxy Nanocomposites as High-Performance Thermal Management Materials.

High-performance thermal management materials are essential in miniaturized, highly integrated, and high-power modern electronics for heat dissipation. In this context, the large interface thermal resistance (ITR) that occurs between fillers and the organic matrix in polymer-based nanocomposites greatly limits their thermal conductive performance. Herein, through-plane direction aligned three-dimensional (3D) MXene/silver (Ag) aerogels are designed as heat transferring skeletons for epoxy nanocomposites. Ag nanoparticles (NPs) were in situ decorated on exfoliated MXene nanosheets to ensure good contact, and subsequent welding of ice-templated MXene/Ag nanofillers at low temperature of ∼200 °C reduced contact resistance between individual MXene sheets. Monte Carlo simulations suggest that thermal interficial resistance (R0) of the MXene/Ag-epoxy nanocomposite was 4.5 × 10-7 m2 W-1 K-1, which was less than that of the MXene-epoxy nanocomposite (Rc = 5.2 × 10-7 m2 W-1 K-1). Furthermore, a large-scale atomic/molecular massively parallel simulator was employed to calculate the interfacial resistance. It was found that RMXene = 2.4 × 10-9 m2 K W-1, and RMXene-Ag = 2.0 ×10-9 m2 K W-1, respectively, indicating that the Ag NP enhanced the interfacial heat transport. At a relatively low loading of 15.1 vol %, through-plane thermal conductivity reached a value as high as 2.65 W m-1 K-1, which is 1225 % higher than that of pure epoxy resin. Furthermore, MXene/Ag-epoxy nanocomposite film exhibits an impressive thermal conductive property when applied on a Millet 8 and Dell computer for heat dissipation.

Efficient photocatalytic nitrogen fixation under ambient conditions enabled by the heterojunctions of n-type Bi2MoO6 and oxygen-vacancy-rich p-type BiOBr.

N2 fixation is one of the most important chemical reactions in the ecosystem of our planet. However, the industrial Haber-Bosch ammonia synthesis process is restricted by harsh reaction conditions (350-550 °C, 150-350 atm) and undesirable environmental effects (a large amount of CO2 emission). Photocatalytic N2 fixation is promising for achieving sustainable ammonia synthesis under ambient conditions with lower energy input and less environmental issues. However, the known photocatalysts for N2 reduction under mild conditions still face the great challenge of very low energy conversion efficiency. Herein, we report a facile solution-phase method to prepare the heterojunctions based on n-type Bi2MoO6 nanorods and oxygen-vacancy-rich p-type BiOBr nanosheets (Bi2MoO6/OV-BiOBr). Originating from the formation of p-n junctions and suitable bandgap configuration, the Bi2MoO6/OV-BiOBr heterojunctions exhibit effective light utilization and photogenerated electron-hole separation properties. Moreover, it is confirmed that the oxygen vacancies on BiOBr nanosheets are propitious to the adsorption and activation of N2 molecules. Benefiting from these merits, the Bi2MoO6/OV-BiOBr heterojunctions exhibit improved photocatalytic performance for N2 conversion to ammonia without any noble metal co-catalysts and sacrificial reagents under ambient conditions.

Surface plasmon resonance enhanced direct Z-scheme TiO2/ZnTe/Au nanocorncob heterojunctions for efficient photocatalytic overall water splitting.

Solar-driven photocatalytic overall water splitting is regarded as one of the ideal strategies to generate renewable hydrogen energy without the initiation of environmental issues. However, there are still a few remaining challenges to develop wide-light-absorption and stable photocatalysts for the simultaneous production of H2 and O2 in pure water without sacrificial reagents. Herein, we report the design and preparation of Z-scheme TiO2/ZnTe/Au nanocorncob heterojunctions by homogeneously decorating Au nanoparticles onto the surface of core-shell TiO2/ZnTe coaxial nanorods for highly efficient overall water splitting. With the appropriate band structure of TiO2/ZnTe heterojunctions and the surface plasmon resonance enhancement of Au nanoparticles, the well-designed TiO2/ZnTe/Au nanocorncob heterojunctions can synergistically make effective utilization of broad-range solar light illunimation and enhance the separation efficency of electron-hole pairs, as evidenced by UV-Vis absorption and time-resolved photoluminescence spectroscopy. Photoelectrochemical characterization confirms that the water-splitting reaction on TiO2/ZnTe/Au nanocorncobs is mainly carried out via a two-electron/two-electron transfer process with an intermediate product of H2O2. As a result, the TiO2/ZnTe/Au nanocorncob photocatalyst can generate H2 and O2 with a stoichiometric ratio of 2 : 1 under light irradiation without any sacrificial agents, exhibiting a high H2 production rate of 3344.0 µmol g-1 h-1 and a solar-to-hydrogen (STH) efficiency of 0.98%. Moreover, the TiO2/ZnTe/Au nanocorncob heterojunctions show high stability and well-preserved morphological integrity after long-term photocatalytic tests. This study provides a prototype route to produce clean hydrogen energy from only sunlight, pure water, and rationally-designed heterojunction photocatalysts.

Pine needle-derived microporous nitrogen-doped carbon frameworks exhibit high performances in electrocatalytic hydrogen evolution reaction and supercapacitors.

The design of electrochemically active materials with appropriate structures and compositions is very important for applications in energy conversion and storage devices. Herein, we demonstrate an effective strategy to prepare microporous heteroatom-doped carbon frameworks derived from naturally-abundant pine needles. The preparation procedure is based on the carbonization of pine needles, followed by KOH activation at a temperature range of 700-1000 °C. The resultant nitrogen-doped carbon consists of abundant micropores and an ultrahigh specific surface area (up to 2433 m2 g-1), leading to high performances in electrocatalytic hydrogen evolution reaction (HER) and supercapacitors. Specifically, when the pine needle-derived carbon (activated at 800 °C) serves as a HER electrocatalyst, it exhibits a low onset potential (∼4 mV), a small Tafel slope (∼45.9 mV dec-1) and a remarkable stability over long-term cycling. When evaluated as an electrode material for supercapacitors, the pine needle-derived carbon (activated at 900 °C) demonstrates high specific capacitance (236 F g-1 at 0.1 A g-1), remarkable rate capability (183 F g-1 at even 20 A g-1) and good long-term stability. Notably, the specific capacitance at 2.0 A g-1 increased from ∼205 to ∼227 F g-1 after cycling for 5000 times, owing to the further activation and wetting of the electrodes. This novel and low-cost biomass-derived carbon material is very promising for many applications, especially in electrocatalytic water splitting and supercapacitors.