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We report a method for creating synthetic diatom frustules the biomimetic silicification of polyamine-rich scaffolds assembled by direct ink writing (DIW) [G. M. Gratson, M. Xu and J. A. Lewis, , 2004, , 386, ]. A concentrated polyamine-rich ink is robotically deposited in a complex 3D pattern that mimics the shape of naturally occurring diatom frustules, Ehrenberg (triangular-shaped) and (web-shaped). Upon exposing these scaffolds to silicic acid under ambient conditions, silica formation occurs in a shape-preserving fashion. Our method yields 3D inorganic-organic hybrids structures that may find potential application as templates for photonic materials, novel membranes, or catalyst supports.

The electrosynthesis of value-added multicarbon products from CO

Engineering the electrolyte microenvironment represents an attractive route to tuning the selectivity of electrocatalytic reactions beyond catalyst composition and morphology. However, harnessing the full potential of this approach requires understanding the interplay between voltage, electrolyte composition, and adsorbate binding within the electrical double layer, which is absent from the usual theoretical approaches. In this work, we apply a recently developed density functional theory (DFT)-continuum approach based on the effective screening medium method and reference interaction site model (ESM-RISM) to explore electrolyte effects with an enhanced description of the electrochemical interface. Applying this method to the binding of CO adsorbates in potassium-containing electrolytes on copper, a problem of direct relevance to CO

A lack of predictive methodology is frequently a major bottleneck in materials development for additive manufacturing. Hence, exploration of new printable materials often relies on the serendipity ...

Direct ink writing of silicone elastomers enables printing with precise control of porosity and mechanical properties of ordered cellular solids, suitable for shock absorption and stress mitigation applications. With the ability to manipulate structure and feedstock stiffness, the design space becomes challenging to parse to obtain a solution producing a desired mechanical response. Here, we derive an analytical design approach for a specific architecture. Results from finite element simulations and quasi-static mechanical tests of two different parallel strand architectures were analyzed to understand the structure-property relationships under uniaxial compression. Combining effective stiffness-density scaling with least squares optimization of the stress responses yielded general response curves parameterized by resin modulus and strand spacing. An analytical expression of these curves serves as a reduced order model, which, when optimized, provides a rapid design capability for filament-based 3D printed structures. As a demonstration, the optimal design of a face-centered tetragonal architecture is computed that satisfies prescribed minimum and maximum load constraints.

We report 3D printing of a ‘pure’ thermal cure cyanate ester for the fabrication of robust 3D printed structures through the formulation, tailoring and post processing of a custom ‘ink’ for Direct Ink Writing. Printed structures exhibit impressive thermo-oxidative stability, mechanical response.

Solid-state laser gain media based on the garnet structure with two spatially distinct but optically contiguous regions have been fabricated. Transparent gain media comprised of a central core of Y2.97Nd0.03Al5.00O12.00 (Nd:YAG) and an undoped cladding region of Y3Al5O12 (YAG) were fabricated by direct ink write and transparent ceramic processing. Direct ink write (DIW) was employed to form the green body, offering a general route to preparing functionally structured solid-state laser gain media. Fully-dense transparent optical ceramics in a “top hat” geometry with YAG/Nd:YAG have been fabricated by DIW methods with optical scatter at 1064 nm of

The use of additive manufacturing to 3D print aerogels has the potential to impact several important technologies such as energy storage, catalysis, and desalination. While there has been a great deal of focus on graphene aerogels, reports of 3D printed conventional carbon aerogels (CAs) are sparse. Activated CAs are particularly compelling because in addition to having a lower cost than a comparable graphene aerogel, they can achieve much higher surface areas (>3000 m2 g−1). Herein we report a 3D printable ink based on traditional resorcinol–formaldehyde sol–gel chemistry that can produce a final activated carbon aerogel with surface areas approaching 2000 m2 g−1 and good electrical conductivities (∼200 S m−1). Direct ink writing (DIW) is used to then fabricate electrodes, which demonstrate excellent electrochemical properties with a high specific capacitance of 215 F g−1 at 1 A g−1 and 83% capacitive retention at higher current densities (10 A g−1). The DIW electrode significantly outperformed its bulk counterpart and provides an example of how one can use 3D printed aerogel electrodes to overcome mass transport limitations and boost energy storage performance.

CO2 emissions can be transformed into high-added-value commodities through CO2 electrocatalysis; however, efficient low-cost electrocatalysts are needed for global scale-up. Inspired by other emerging technologies, the authors report the development of a gas diffusion electrode containing highly dispersed Ag sites in a low-cost Zn matrix. This catalyst shows unprecedented Ag mass activity for CO production: -614 mA cm-2 at 0.17 mg of Ag. Subsequent electrolyte engineering demonstrates that halide anions can further improve stability and activity of the Zn-Ag catalyst, outperforming pure Ag and Au. Membrane electrode assemblies are constructed and coupled to a microbial process that converts the CO to acetate and ethanol. Combined, these concepts present pathways to design catalysts and systems for CO2 conversion toward sought-after products.

In comparison with conventional methods, electrochemical CO2 reduction (CO2RR) represents a promising and environmentally friendly method to generate value‐added products and mitigate anthropogenic climate change. Herein, the recently reported CO2RR catalysts that show high selectivity and activity toward alcohol production are highlighted. The current understanding of reaction pathways on different catalyst surfaces for alcohol production is highlighted and strategies to enhance CO2RR catalytic performance are discussed. Finally, the views on the challenges and possible future paths for the field are shared.

Electrochemical energy storage (EES) devices, such as lithium-ion batteries and supercapacitors, are emerging as primary power sources for global efforts to shift energy dependence from limited fossil fuels towards sustainable and renewable resources. These EES devices, while renowned for their high energy or power densities, portability, and long cycle life, are still facing significant performance hindrance due to manufacturing limitations. One major obstacle is the ability to engineer macroscopic components with designed and highly resolved nanostructures with optimal performance, via controllable and scalable manufacturing techniques. 3D printing covers several additive manufacturing methods that enable well-controlled creation of functional nanomaterials with three-dimensional architectures, representing a promising approach for fabrication of next-generation EES devices with high performance. In this review, we summarize recent progress in fabricating 3D functional electrodes utilizing 3D printing-based methodologies for EES devices. Specifically, laser-, lithography-, electrodeposition-, and extrusion-based 3D printing techniques are described and exemplified with examples from the literatures. Current challenges and future opportunities for functional materials fabrication via 3D printing techniques are also discussed.

The performance of pseudocapacitive electrodes at fast charging rates are typically limited by the slow kinetics of Faradaic reactions and sluggish ion diffusion in the bulk structure. This is particularly problematic for thick electrodes and electrodes highly loaded with active materials. Here, a surface-functionalized 3D-printed graphene aerogel (SF-3D GA) is presented that achieves not only a benchmark areal capacitance of 2195 mF cm-2 at a high current density of 100 mA cm-2 but also an ultrahigh intrinsic capacitance of 309.1 µF cm-2 even at a high mass loading of 12.8 mg cm-2 . Importantly, the kinetic analysis reveals that the capacitance of SF-3D GA electrode is primarily (93.3%) contributed from fast kinetic processes. This is because the 3D-printed electrode has an open structure that ensures excellent coverage of functional groups on carbon surface and facilitates the ion accessibility of these surface functional groups even at high current densities and large mass loading/electrode thickness. An asymmetric device assembled with SF-3D GA as anode and 3D-printed GA decorated with MnO2 as cathode achieves a remarkable energy density of 0.65 mWh cm-2 at an ultrahigh power density of 164.5 mW cm-2 , outperforming carbon-based supercapacitors operated at the same power density.

In recent years, 3D printing has led to a disruptive manufacturing revolution that allows complex architected materials and structures to be created by directly joining sequential layers into designed 3D components. However, customized feedstocks for specific 3D printing techniques and applications are limited or nonexistent, which greatly impedes the production of desired structural or functional materials. Colloids, with their stable biphasic nature, have tremendous potential to satisfy the requirements of various 3D printing methods owing to their tunable electrical, optical, mechanical, and rheological properties. This enables materials delivery and assembly across the multiple length scales required for multifunctionality. Here, a state-of-the-art review on advanced colloidal processing strategies for 3D printing of organic, ceramic, metallic, and carbonaceous materials is provided. It is believed that the concomitant innovations in colloid design and 3D printing will provide numerous possibilities for the fabrication of new constructs unobtainable using traditional methods, which will significantly broaden their applications.

3D printing of multi-material objects enables the design of complex 3D architectures such as printed electronics and devices. The ability to detect the composition of multi-material printed inks in real time is an enabling feature in a wide range of manufacturing sectors. In this study, dielectric properties of microscale embedded metal particles in a dielectric matrix have been characterized using impedance measurements as a function of particle size, shape, volume percentage and frequency. Measurements were found to agree well with calculations based on an anisotropic Maxwell-Garnett dielectric function model. Despite the metal loading exceeding the theoretical percolation threshold, a percolation transition was not observed in the experimental results. With this data, a calibration curve can be established to correlate metal loading with impedance or capacitance, which can be used with an in situ sensor for ink composition measurements during extrusion-based 3D printing. We demonstrate how an in situ sensor can locally measure the composition of the ink, allowing greater control over the resulting properties and functionality of printed materials.

Critical to the success of three-dimensional (3D) printing of living materials with high performance is the development of new ink materials and 3D geometries that favor long-term cell functionality. Here we report the use of freeze-dried live cells as the solid filler to enable a new living material system for direct ink writing of catalytically active microorganisms with tunable densities and various self-supporting porous 3D geometries. Baker's yeast was used as an exemplary live whole-cell biocatalyst, and the printed structures displayed high resolution, large scale, high catalytic activity and long-term viability. An unprecedented high cell loading was achieved, and cell inks showed unique thixotropic behavior. In the presence of glucose, printed bioscaffolds exhibited increased ethanol production compared to bulk counterparts due largely to improved mass transfer through engineered porous structures. The new living materials developed in this work could serve as a versatile platform for process intensification of an array of bioconversion processes utilizing diverse microbial biocatalysts for production of high-value products or bioremediation applications.

We present a new class of architected materials that exhibit rapid, reversible, and sizable changes in effective stiffness., Typically, mechanical metamaterial properties are programmed and set when the architecture is designed and constructed, and do not change in response to shifting environmental conditions or application requirements. We present a new class of architected materials called field responsive mechanical metamaterials (FRMMs) that exhibit dynamic control and on-the-fly tunability enabled by careful design and selection of both material composition and architecture. To demonstrate the FRMM concept, we print complex structures composed of polymeric tubes infilled with magnetorheological fluid suspensions. Modulating remotely applied magnetic fields results in rapid, reversible, and sizable changes of the effective stiffness of our metamaterial motifs.

Electrochemical energy storage (EES) and conversion devices (e.g. batteries, supercapacitors, and reactors) are emerging as primary methods for global efforts to shift energy dependence from limited fossil fuels towards sustainable and renewable resources. These electric-based devices, while showing great potential for meeting some key metrics set by conventional technologies, still face significant limitations. For example, an EES device tends to exhibit large energy density (e.g. lithium-ion battery) or power density (e.g. supercapacitor), but not both. This inability of a single device to simultaneously achieve both metrics represents a major obstacle to widespread adoption of EES devices. Improvements in materials, such as the integration of 2D materials (e.g. graphene, dichalcogenides, MXene, etc.) into electrochemical devices has yielded some exciting results towards tackling this issue, but significant improvements are still needed. Our approach to simultaneously achieving high energy and power density is to focus on one of the fundamental processes that occur in these systems: mass (or charge) transport. The efficient transport of ions within EES devices is critical to realizing both large power and energy densities. The pore structure of the electrode is a key factor in determining this transport phenomena, but in many cases, engineering the pore structure in a highly deterministic fashion is not pursued or even possible for many electrode materials. In this work, we explore a number of additive manufacturing methods (e.g. direct ink write, projection microstereolithography, etc.) to engineer the pore structure of device electrodes. We also determine effective electrode geometries using both simple theory and topology optimization techniques. The topology optimization couples the solution of the forward electrochemical problem over the full electrode domain with gradient-based optimization. The output of our code is a three-dimensional CAD representation which optimizes over specific performance metrics and which can be used to print functional electrodes. This work provides a systematic path toward automatic design and fabrication of engineered electrodes with precise control over the fluid and species distribution. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Garnet-type solid electrolytes, such as Li6.4La3Zr1.4Ta0.6O12 (LLZTO), are promising materials for solid-state batteries, but processing remains a challenge, in part due to the high sintering temperature required for densification. This temperature can be lowered by decreasing the initial particle size via solvent-assisted ball milling, but the relationship between solvent choice, particle properties, sintering behavior, and ionic conductivity is not well understood. In this work, we systematically explore these parameters, showing that milling in commonly used protic solvents, such as alcohols, effectively decreases the particle size but results in lithium loss (through Li+/H+ exchange) that leads to poor sintering. By contrast, milling in aprotic solvents with surfactant reduces the particle size to ~220 nm without lithium loss, enabling the fabrication of dense samples (5.1 g/cm3) with good ionic conductivity (0.43 mS/cm at 25 °C) at a lower sintering temperature (1000 °C). We compare ionic conductivities and activation energies for samples prepared with different particle sizes and sintering temperatures and use multiphase-field simulations to identify the mass transport and microstructural mechanisms responsible for the observed sintering dependence on particle size. These results further clarify the relationship between processing parameters and performance and represent important progress toward overcoming fabrication challenges for these materials.

Projection micro stereolithography (PµSL) is an additive manufacturing tool that offers multiple advantages, including unparalleled resolution and throughput, but the ability to print high viscosity resin for large-scale parts is limited. One of the key challenges in PµSL is to separate a newly polymerized layer from the vat floor without damaging the part. Since the separation force scales with the printing area, the risk of damaging the part increases significantly with larger-scale systems and must be addressed. In this paper, a novel roll-to-roll, variable tensioning system is proposed to reduce the separation force during printing. A mathematical model is proposed to predict the separation force for different 2D geometries, and a set of experiments is conducted on an experimental prototype to validate the model. The effects of different separation parameters including peel rate and peel angle are discussed in detail. The results show that the proposed tensioning system reduces the separation force significantly.

The electrosynthesis of value-added multicarbon products from CO2 is a promising strategy to shift chemical production away from fossil fuels. Particularly important is the rational design of gas diffusion electrode (GDE) assemblies to react selectively, at scale, and at high rates. However, the understanding of the gas diffusion layer (GDL) in these assemblies is limited for the CO2 reduction reaction (CO2 RR): particularly important, but incompletely understood, is how the GDL modulates product distributions of catalysts operating in high current density regimes > 300 mA cm-2 . Here, 3D-printable fluoropolymer GDLs with tunable microporosity and structure are reported and probe the effects of permeance, microstructural porosity, macrostructure, and surface morphology. Under a given choice of applied electrochemical potential and electrolyte, a 100× increase in the C2 H4 :CO ratio due to GDL surface morphology design over a homogeneously porous equivalent and a 1.8× increase in the C2 H4 partial current density due to a pyramidal macrostructure are observed. These findings offer routes to improve CO2 RR GDEs as a platform for 3D catalyst design.

Oxide-derived copper (Cu) catalysts often show significantly improved performance for carbon dioxide (CO2) reduction reactions compared with metallic Cu. In this article, we summarize the recently reported methods for preparing oxide-derived Cu catalysts and discuss the current understanding of the reaction mechanisms, including the role of mixed oxidation states of copper, subsurface oxygen, local pH, and electrolyte. Finally, we share our thoughts about the current challenges for oxide-derived Cu catalysts and the potential solutions.

Here we demonstrate a facile electrochemical method that can substantially improve the capacitance of graphene-based electrodes while still retaining their excellent rate capability. This method involves two ion-intercalation steps (lithium-ion intercalation and perchlorate-ion intercalation), followed by hydrolysis of perchlorate ion intercalation compounds. Lithium ion intercalation mainly leads to surface exfoliation, whilst the hydrolysis of perchlorate ion intercalation compounds functionalizes the graphene surface with oxygen moieties. Electrochemically treated graphitic paper electrode shows 1000 times enhancement in areal capacitance. Without the need of post-treatment annealing, the treated graphitic paper maintains an outstanding rate capability of 84 % (0.5 mA cm−2 to 5 mA cm−2). The same strategy can also be extended to boost the gravimetric capacitance of lightweight 3D printed graphene aerogels. The treated graphene aerogel achieved an outstanding gravimetric capacitance of 101.7 F g−1 (10 A g−1) with an excellent rate capability of 81.6 % (0.5 A g−1 to 10 A g−1).

Flow through electrodes are the core, active component in a number of electrochemical systems including fuel cells and flow batteries. Controlling fluid flow and mass transport is a core engineering challenge in these systems and has a dramatic impact on cell power, utilization, and efficiency. Most advanced electrode materials are composed of microscale, disordered porous media. The length scales of these materials allow for very large surface area but at the cost of low flow speeds, low surface mass transfer rates, high pressure drops, and added complexity and cost from the need to use external flow distribution systems like flowfields. The multiscale control over electrode architecture enabled by using additively manufactured electrodes could provide a potential resolution to these trade-offs. To elucidate the mass transport of these electrodes, we use resolved, continuum computation to analyze the fluid flow and species transport in direct ink-write printed, carbon aerogel electrodes. We determine the mass transfer correlations (Sh ~ Pea) across two different lattice aerogel geometries and validate these results against the experimentally manufactured and tested flow-through electrodes operated at limiting current. In contrast to conventional electrodes, the mesoscopic length scales in our electrodes lead to finite Reynolds numbers and we find an increase in the mass correlation exponent (a) as inertial effects become important. We analyze the local mass transfer coefficients in the electrode and correlate regions of enhanced mass transfer with secondary flows in the electrode. Our work provides a promising new pathway to increased mass transfer rates in flow-through electrodes. LLNL-ABS- 810719 This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Electrochemical systems such as fuel cells, flow batteries, and electrochemical reactors are prevalent in industry, but few tools for their numerical design and optimization exist. Controlling fluid flow, active species distribution, and mass transport in the electrode has a dramatic impact on power and efficiency. However, this control is often limited to changing a quasi-two-dimensional flowfield and selecting bulk properties of a monolithic porous material electrode like carbon felt or paper. This can lead to non-uniform reaction rates, underutilized regions of the flow cell, and can limit the ultimate performance of the devices. To address these limitations, we propose using electrodes composed of a micro-architected variable porosity medium. As a specific example, we enable variable porosity by leveraging advances in the additive manufacture of microscale iso-truss lattices. We employ physics-based homogenization of the governing microscopic, continuum transport equations to develop a descriptive model and enable the design of this variable porosity electrode. Our tool is used to generate optimized architectures which are predicted to outperform monolithic electrodes when used in a standard flow-through configuration. We conclude by demonstrating how the optimal porosity distribution changes to retain the performance benefits as the electrode is scaled beyond benchtop-experiments LLNL-ABS- 810799 This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

The electrochemical conversion of CO2 to commodity products such as hydrocarbons and oxygenates is an attractive approach for generating non-fossil derived chemical and fuel stocks and for the storage of energy in chemical bonds. To date, a number of studies have shown that the activity and selectivity of copper-based catalysts for the CO2 reduction reaction towards valuable higher order carbon products are highly sensitive to the local reaction environment. Furthermore, the local electrolyte concentration and local pH is intimately tied to the applied voltage and the mass transport of reactants and products within the interfacial region. In recognition of this, several recent efforts focused on engineering the design of electrochemical reactors to reduce mass transport limitations indicate a pronounced effect on the apparent selectivity of the copper catalyst. While these efforts have highlighted a new direction for improving the efficiency of the CO2 reduction reaction, the rational design of these reactors remains challenging due to the need to optimize features of the reactor across multiple time and length scales. In this talk, we will discuss recent efforts within our laboratory to address the influence of the local pH on the CO2 reduction reaction at the atomistic level. We focus the discussion on the binding of CO, a key reaction intermediate in the CO2 reduction pathway, whose preferential hydrogenation or dimerization leads to the production of C1 and C2 products, respectively. We additionally demonstrate how the use of hybrid approaches employing density functional theory (DFT) and continuum models can help bridge time and length scales within the context of atomistic CO2 electroreduction modeling. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

The electrochemical conversion of CO2 to commodity products such as hydrocarbons and oxygenates is an attractive approach for generating non-fossil derived chemical and fuel stocks and for the storage of energy in chemical bonds. To date, a number of studies have shown that the activity and selectivity of copper-based catalysts for the CO2 reduction reaction towards valuable higher order carbon products are highly sensitive to the local reaction environment. Furthermore, the local electrolyte concentration and local pH is intimately tied to the applied voltage and the mass transport of reactants and products within the interfacial region. In recognition of this, several recent efforts focused on engineering the design of electrochemical reactors to reduce mass transport limitations indicate a pronounced effect on the apparent selectivity of the copper catalyst. While these efforts have highlighted a new direction for improving the efficiency of the CO2 reduction reaction, the rational design of these reactors remains challenging due to the need to optimize features of the reactor across multiple time and length scales. In this talk, we will discuss recent efforts within our laboratory to address the influence of the local pH on the CO2 reduction reaction at the atomistic level. We focus the discussion on the binding of CO, a key reaction intermediate in the CO2 reduction pathway, whose preferential hydrogenation or dimerization leads to the production of C1 and C2 products, respectively. We additionally demonstrate how the use of hybrid approaches employing density functional theory (DFT) and continuum models can help bridge time and length scales within the context of atomistic CO2 electroreduction modeling. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Electrochemical conversion of CO2 is a potentially exciting route towards production of sustainable drop-in fuels and chemicals using renewable electricity. A key obstacle in the commercial scale-up and deployment of CO2 utilization and conversion is the lack of active and selective catalysts. Across all monometallic candidates, Cu exhibits distinctive ability to electrochemically reduce CO2 to several products including methane and ethylene, albeit its multifunctional nature makes selectivity control challenging [1]. Alloying offers a means to break scaling relationships and uniquely manipulate the reactivity and selectivity in ways that would be hard to achieve using monometallic compositions alone. Here, we employ a coupled quantum mechanics/molecular mechanics (QM/MM) scheme [2] to screen various copper alloys for their reactivity and selectivity towards key rate-limiting and selectivity-determining steps in CO2 conversion. The activity-selectivity screening is carried out under reducing conditions to thoroughly probe the influence of the electrolytic ions under the applied potential on the alloy stability and reactivity. The results of these studies show how alloying in conjunction with electrolyte tuning can non-intuitively alter the surface electronic and catalytic properties of the catalyst leading to changes in activity-selectivity towards CO2 conversion. This serves to provide a rationale for improved composition and environment driven design and screening, and allows the use of chemical computation using nuanced, dynamical models of the electrochemical double layer[i]. [1] Y. Hori, in Handbook of Fuel Cells: Fundamentals, Technology and Application (VHC Wiley, Chichester, 2003), Vol. 2, 720-733. [2] J. Haruyama, T. Ikeshoji and M. Otani, Electrode potential from density functional theory calculations combined with implicit solvation theory. Physical Review Materials (2018), 2(9), p.095801. [i] This work was performed under the auspices of the U.S. DOE by Lawrence Livermore National Laboratory under contract DE-AC52-07NA27344.

3D graphene foams exhibit immense degradation of mechanical properties. Micro-architecture can alleviate this problem, but no current technique meets the manufacturing requirements. Herein we developed a light-based 3D printing process to create hierarchical graphene structures with arbitrary complexity and order-of-magnitude finer features, showing enhanced mechanical properties at decreasing density.

Digitally controlled catalyst architectures via 3D printing potentially revolutionize the design of chemical plants., Monolithic nanoporous metals, derived from dealloying, have a unique bicontinuous solid/void structure that provides both large surface area and high electrical conductivity, making them ideal candidates for various energy applications. However, many of these applications would greatly benefit from the integration of an engineered hierarchical macroporous network structure that increases and directs mass transport. We report on 3D (three-dimensional)–printed hierarchical nanoporous gold (3DP-hnp-Au) with engineered nonrandom macroarchitectures by combining 3D printing and dealloying. The material exhibits three distinct structural length scales ranging from the digitally controlled macroporous network structure (10 to 1000 μm) to the nanoscale pore/ligament morphology (30 to 500 nm) controlled by dealloying. Supercapacitance, pressure drop, and catalysis measurements reveal that the 3D hierarchical nature of our printed nanoporous metals markedly improves mass transport and reaction rates for both liquids and gases. Our approach can be applied to a variety of alloy systems and has the potential to revolutionize the design of (electro-)chemical plants by changing the scaling relations between volume and catalyst surface area.

Additive manufacturing offers new routes to lightweight optics inaccessible by conventional methods by providing a broader range of reconciled functionality, form factor, and cost. Predictive lattice design combined with the ability to 3D print complex structures allows for the creation of low-density metamaterials with high global and local stiffness and tunable response to static and dynamic loading. This capacity provides a path to fabrication of lightweight optical supports with tuned geometries and mechanical properties. Our approach involves the simulation and optimization of lightweight lattices for anticipated stresses due to polishing and mounting loads via adaptive mesh refinement. The designed lattices are 3D printed using large area projection microstereolithography (LAPuSL), coated with a metallic plating to improve mechanical properties, and bonded to a thin (1.25 mm) fused silica substrate. We demonstrate that this lightweight assembly can be polished to a desired flatness using convergent polishing, and subsequently treated with a reflective coating. *This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 within the LDRD program. LLNL-ABS-738806.

Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and Tg on compressive behavior and compression set in siloxane matrix printed structures. The lower Tg microsphere structures exhibit substantial compression set when heated near and above Tg, with full structural recovery upon reheating without constraint. By contrast, the higher Tg microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuning the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.

Three-dimensional (3D) carbon-based materials are emerging as promising electrode candidates for energy storage devices. In comparison to the 1D and 2D structures, 3D morphology offers new opportunities in rational design and synthesis of novel architectures tailor-made for promoting electrochemical performance. The capability of building hierarchical porous structures with 3D configuration can significantly advance the performance of energy storage devices by simultaneously enhancing the ion-accessible surface area and ion diffusion. This feature article presents an overview of recent progress in design, synthesis and implementation of 3D carbon-based materials as electrodes for electrochemical capacitors. Synthesis methodologies of four types of 3D carbon-based electrodes: 3D exfoliated carbon structures, 3D graphene scaffolds, 3D hierarchical porous carbon foams, as well as 3D architectures with periodic pores derived from direct ink writing, are thoroughly discussed and highlighted with selected experimental works. Finally, key opportunities and challenges in which different 3D carbons can significantly impact the energy storage and conversion communities will be provided.

Three-dimensional printing of viscoelastic inks to create porous, elastomeric architectures with mechanical properties governed by the ordered arrangement of their sub-millimeter struts is reported. Two layouts are patterned, one resembling a “simple cubic” (SC)-like structure and another akin to a “face-centered tetragonal” (FCT) configuration. These structures exhibit markedly distinct load response with directionally dependent behavior, including negative stiffness. More broadly, these findings suggest the ability to independently tailor mechanical response in cellular solids via micro-architected design. Such ordered materials may one day replace random foams in mechanical energy absorption applications.