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Engineering topics

An, Lu

Publications and source records attributed to An, Lu.

Regulating the surface Pt coordination environment in the PtN overlayers on PtCuN hollow nanospheres for efficient oxygen reduction reaction

Engineering the surface Pt coordination environment is a promising strategy for promoting the kinetically sluggish oxygen reduction reaction (ORR) on Pt-based catalysts. Here, in this study, we achieve the compressive strain effect and electronic effect by Cu and N co-doping to synthesize the PtCuN hollow nanospheres with PtN overlayers (PtCuN@PtN HNSs) using a facile solvothermal synthesis. Electrochemical investigations show that the constructed disordered Pt–N coordination structures effectively facilitate the ORR and stabilize Pt atoms in the compressed lattice, whereas an excessive N-doping can lead to the formation of a structurally unstable Pt nitride phase. Theoretical analyses confirm that the oxygen reduction kinetics on the compressed PtN overlayers are regulated by a synergistic effect resulting from N-doping and lattice compression, circumventing the traditional linear scaling relationships (LSR). The optimized PtCuN@PtN HNSs, with the composition of PtCu 0.29 N 1.1 , demonstrate an area-specific activity of 1.98 mA cm –2 and a mass-specific activity of 1.81 A mg Pt –1 .

36 MATERIALS SCIENCE↗

Releasing chemical energy in spatiallyprogrammed ferroelectrics

Chemical energy ferroelectrics are generally solid macromolecules showing spontaneous polarization and chemical bonding energy. These materials still suffer drawbacks, including the limited control of energy release rate, and thermal decomposition energy well below total chemical energy. To overcome these drawbacks, we report the integrated molecular ferroelectric and energetic material from machine learning-directed additive manufacturing coupled with the ice-templating assembly. The resultant aligned porous architecture shows a low density of 0.35 g cm -3 , polarization-controlled energy release, and an anisotropic thermal conductivity ratio of 15. Thermal analysis suggests that the chlorine radicals react with macromolecules enabling a large exothermic enthalpy of reaction (6180 kJ kg -1 ). In addition, the estimated detonation velocity of molecular ferroelectrics can be tuned from 6.69 ± 0.21 to 7.79 ± 0.25 km s -1 by switching the polarization state. These results provide a pathway toward spatially programmed energetic ferroelectrics for controlled energy release rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creation of hollow silica-fiberglass soft ceramics for thermal insulation

Hollow-structured materials show promise in thermal insulation because the shells encapsulating gaseous voids can interrupt heat transport pathways. Here, in this study, we present two low-cost routes to fabricate hollow silica nanoshells, via gas-phase and liquid-phase methods. The gas-phase synthesis method generates hollow shells by a droplet surface precipitation mechanism in a flame aerosol reactor. The liquid-phase synthesis route forms hollow shells by removal of a carbon template, which is produced by hydrothermal reaction of glucose. Both approaches (gas- and liquid-phase) provide hollow silica with amorphous structure, low thermal conductivity (0.023 and 0.026 W m –1 K –1 ), small particle size (442 and 383 nm), thin shell (35 and 36 nm), and low density (0.015 and 0.033 g cm –3 ). We employed high shear mechanical mixing to fabricate hollow silica-fiberglass composite ceramics. The resulting three-dimensional network provides the ceramics with robust mechanical elasticity and fire-retardancy while maintaining low thermal conductivity, dramatically outperforming an analogous material using commercial silica gel in place of the hollow nanoshells. Our findings provide two practical routes to synthesize hollow silica, either of which can be used to manufacture a class of hollow shell-fiber nanocomposite soft ceramics for energy-saving applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

3D-printed electrically conductive silicon carbide

The development of electrically conductive ceramics could achieve robust mechanical strength as well as practically high conductivity, offering applications in structural electrodes, conductors, catalyst supports, etc. However, its operating temperature is limited due to the intrinsic dense structures inevitably hindering the thermal management capability, thus resulting in a temperature-dependent electrical behavior in high-temperature environments. In this work, we report an additive manufacturing protocol through vat photopolymerization 3D printing to fabricate the architectured conductive silicon carbide (SiC) ceramics that simultaneously possess high electrical conductivity as well as low thermal conductivity, and demonstrate electric reliability under high-temperature environments above 600°C. The percolation of graphene into the ceramic scaffold establishes a uniform conductive network, exhibiting its electrical conductivity up to 1000 S m –1 . The bulk density of the 3D-printed ceramic is measured from 0.366 g cm –3 to 0.897 g cm –3 , with thermal conductivity ranging from 62 mW m –1 K –1 to 88 mW m –1 K –1 . Furthermore, the mechanical performance of conductive ceramic can be effectively reinforced by densifying the microstructures via spark plasma sintering treatment. The proposed additive manufacturing strategy widens the potential of ceramics as a structural and functional material, offering a promising pathway toward high-temperature electronics applications.

36 MATERIALS SCIENCE↗

Tailoring thermal insulation architectures from additive manufacturing

Abstract Tailoring thermal transport by structural parameters could result in mechanically fragile and brittle networks. An indispensable goal is to design hierarchical architecture materials that combine thermal and mechanical properties in a continuous and cohesive network. A promising strategy to create such a hierarchical network targets additive manufacturing of hybrid porous voxels at nanoscale. Here we describe the convergence of agile additive manufacturing of porous hybrid voxels to tailor hierarchically and mechanically tunable objects. In one strategy, the uniformly distributed porous silica voxels, which form the basis for the control of thermal transport, are non-covalently interfaced with polymeric networks, yielding hierarchic super-elastic architectures with thermal insulation properties. Another additive strategy for achieving mechanical strength involves the versatile orthogonal surface hybridization of porous silica voxels retains its low thermal conductivity of 19.1 mW m −1 K −1 , flexible compressive recovery strain (85%), and tailored mechanical strength from 71.6 kPa to 1.5 MPa. The printed lightweight high-fidelity objects promise thermal aging mitigation for lithium-ion batteries, providing a thermal management pathway using 3D printed silica objects.

36 MATERIALS SCIENCE↗

High temperature ceramic thermal insulation material

Flexible and lightweight thermal insulation materials with hierarchical microstructures are ubiquitous in thermal management and protection systems. Ceramic aerogels promise high-temperature thermal insulation but lack mechanical robustness, while the fibrous materials with excellent mechanical elasticity display modest thermal insulation. Here we describe flexible hierarchical superhydrophobic ceramic insulation nanocomposites through the densified architectured hierarchical nanostructures, radiative insulation coating, and interfacial cross-linking among composites. The lightweight flexible ceramic nanocomposites exhibit a density of 0.13 g/cm 3 , high-temperature fire resistance with thermal conductivity of 0.024 W/(m·K), and super-hydrophobicity with the water contact angle of 152°. The mechanical robustness and high-temperature thermal insulation of ceramic nanocomposites, together with its soundproof performance, shed light on the low-cost flexible insulation materials manufacturing with scalability for high-temperature thermal insulation applications under high mechanical loading conditions.

36 MATERIALS SCIENCE↗

Nanoengineering Porous Silica for Thermal Management

Thermal insulation of solid materials originates from the nanoscale porous architectures to regulate thermal management in energy-critical applications from energy-efficient buildings to heat-sensitive energy devices. Here, we show nanoengineering of porous silica materials to control the architecture transition from mesoporous to nanocage networks. A low thermal conductivity of such a porous silica network is achieved at 0.018 W/(m K) while exhibiting a porosity of 92.05%, specific surface area of 504 m 2 /g, and pore volume of 2.37 cm 3 /g after ambient pressure drying. Meanwhile, the crosslinking of the porous silica and ceramic fiber frameworks show a tensile Young’s modulus of 2.8 MPa while maintaining high thermal insulation, which provides an effective thermal runway mitigation strategy for rechargeable lithium-ion batteries. Furthermore, the nanoengineering strategy reported here would shed light on achieving superthermal insulation of nanostructures for energy-critical applications.

36 MATERIALS SCIENCE↗