Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing

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.

[1]  Fang Qian,et al.  Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores. , 2016, Nano letters.

[2]  W. C. Mallard,et al.  Self-Diffusion in Silver-Gold Solid Solutions , 1963 .

[3]  A. Karma,et al.  Evolution of nanoporosity in dealloying , 2001, Nature.

[4]  M. Bäumer,et al.  Nanoporous gold : from an ancient technology to a high-tech material , 2012 .

[5]  Chang Ming Li,et al.  Nanoporous metals: fabrication strategies and advanced electrochemical applications in catalysis, sensing and energy systems. , 2012, Chemical Society reviews.

[6]  Cheng Zhu,et al.  Controlling Material Reactivity Using Architecture , 2016, Advanced materials.

[7]  M. Bäumer,et al.  Nanoporous gold: a new material for catalytic and sensor applications. , 2010, Physical chemistry chemical physics : PCCP.

[8]  James E. Smay,et al.  Catenary shape evolution of spanning structures in direct-write assembly of colloidal gels , 2012 .

[9]  M. Bäumer,et al.  Nanoporous Gold Catalysts for Selective Gas-Phase Oxidative Coupling of Methanol at Low Temperature , 2010, Science.

[10]  R. Kötz,et al.  Principles and applications of electrochemical capacitors , 2000 .

[11]  Tianyu Liu,et al.  3D printed functional nanomaterials for electrochemical energy storage , 2017 .

[12]  Sauro Succi,et al.  Mapping reactive flow patterns in monolithic nanoporous catalysts , 2016, 1607.02874.

[13]  Takeshi Fujita,et al.  Three-dimensional morphology of nanoporous gold , 2008 .

[14]  J. Cesarano,et al.  Direct Ink Writing of Three‐Dimensional Ceramic Structures , 2006 .

[15]  Jonah Erlebacher,et al.  Nanoporous Gold Leaf: “Ancient Technology”/Advanced Material , 2004 .

[16]  L. Zepeda-Ruiz,et al.  Surface-chemistry-driven actuation in nanoporous gold. , 2009, Nature materials.

[17]  John J. Vericella,et al.  Three‐Dimensional Printing of Elastomeric, Cellular Architectures with Negative Stiffness , 2014 .

[18]  T. Baumann,et al.  Ultra‐strong and Low‐Density Nanotubular Bulk Materials with Tunable Feature Sizes , 2014, Advanced materials.

[19]  J. A. Lewis Direct Ink Writing of 3D Functional Materials , 2006 .

[20]  Juergen Biener,et al.  Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation , 2015 .

[21]  M. Bäumer,et al.  Gold catalysts: nanoporous gold foams. , 2006, Angewandte Chemie.

[22]  Rebecca Dylla-Spears,et al.  3D‐Printed Transparent Glass , 2017, Advanced materials.

[23]  John A. Rogers,et al.  Omnidirectional Printing of Flexible, Stretchable, and Spanning Silver Microelectrodes , 2009, Science.

[24]  J. Weissmüller,et al.  Hierarchical nested-network nanostructure by dealloying. , 2013, ACS nano.

[25]  Alexandra M. Golobic,et al.  Highly compressible 3D periodic graphene aerogel microlattices , 2015, Nature Communications.

[26]  Diran Apelian,et al.  Direct metal writing: Controlling the rheology through microstructure , 2017 .

[27]  Ke Wang,et al.  Composites of Nanoporous Gold and Polymer , 2013, Advanced materials.

[28]  Yih Horng Tan,et al.  Surface area and pore size characteristics of nanoporous gold subjected to thermal, mechanical, or surface modification studied using gas adsorption isotherms, cyclic voltammetry, thermogravimetric analysis, and scanning electron microscopy. , 2012, Journal of materials chemistry.

[29]  J. Erlebacher,et al.  Nanoporous metals with controlled multimodal pore size distribution. , 2003, Journal of the American Chemical Society.

[30]  Xiaohong Xu,et al.  Low temperature CO oxidation over unsupported nanoporous gold. , 2007, Journal of the American Chemical Society.

[31]  James E. Smay,et al.  Thixotropic rheology of concentrated alumina colloidal gels for solid freeform fabrication , 2011 .

[32]  S. Bargmann,et al.  3D stochastic bicontinuous microstructures: generation, topology and elasticity , 2018 .

[33]  Amanda S. Wu,et al.  3D-Printing of Meso-structurally Ordered Carbon Fiber/Polymer Composites with Unprecedented Orthotropic Physical Properties , 2017, Scientific Reports.

[34]  Sauro Succi,et al.  Coupled RapidCell and lattice Boltzmann models to simulate hydrodynamics of bacterial transport in response to chemoattractant gradients in confined domains , 2015 .

[35]  E. Stach,et al.  Dynamic restructuring drives catalytic activity on nanoporous gold-silver alloy catalysts. , 2017, Nature materials.

[36]  J. Satcher,et al.  Synthesis and Characterization of Hierarchical Porous Gold Materials , 2006 .

[37]  A. Kobler,et al.  Nanoporous-gold-based composites : toward tensile ductility , 2015 .

[38]  L. Zepeda-Ruiz,et al.  Size effects on the mechanical behavior of nanoporous Au. , 2006, Nano letters.

[39]  M. Biener,et al.  Nanoporous Gold: Understanding the Origin of the Reactivity of a 21st Century Catalyst Made by Pre-Columbian Technology , 2015 .

[40]  J. Markmann,et al.  Nanoporous Gold—Testing Macro-scale Samples to Probe Small-scale Mechanical Behavior , 2016 .

[41]  M. Ritter,et al.  Porous Gold with a Nested‐Network Architecture and Ultrafine Structure , 2015 .