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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Harvard Univ., Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); LLNL Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1515346
Report Number(s):
LLNL-JRNL-772599
Journal ID: ISSN 2375-2548; 964041
Grant/Contract Number:  
AC52-07NA27344; SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 8; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhu, Cheng, Qi, Zhen, Beck, Victor A., Luneau, Mathilde, Lattimer, Judith, Chen, Wen, Worsley, Marcus A., Ye, Jianchao, Duoss, Eric B., Spadaccini, Christopher M., Friend, Cynthia M., and Biener, Juergen. Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing. United States: N. p., 2018. Web. doi:10.1126/sciadv.aas9459.
Zhu, Cheng, Qi, Zhen, Beck, Victor A., Luneau, Mathilde, Lattimer, Judith, Chen, Wen, Worsley, Marcus A., Ye, Jianchao, Duoss, Eric B., Spadaccini, Christopher M., Friend, Cynthia M., & Biener, Juergen. Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing. United States. doi:10.1126/sciadv.aas9459.
Zhu, Cheng, Qi, Zhen, Beck, Victor A., Luneau, Mathilde, Lattimer, Judith, Chen, Wen, Worsley, Marcus A., Ye, Jianchao, Duoss, Eric B., Spadaccini, Christopher M., Friend, Cynthia M., and Biener, Juergen. Fri . "Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing". United States. doi:10.1126/sciadv.aas9459. https://www.osti.gov/servlets/purl/1515346.
@article{osti_1515346,
title = {Toward digitally controlled catalyst architectures: Hierarchical nanoporous gold via 3D printing},
author = {Zhu, Cheng and Qi, Zhen and Beck, Victor A. and Luneau, Mathilde and Lattimer, Judith and Chen, Wen and Worsley, Marcus A. and Ye, Jianchao and Duoss, Eric B. and Spadaccini, Christopher M. and Friend, Cynthia M. and Biener, Juergen},
abstractNote = {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.},
doi = {10.1126/sciadv.aas9459},
journal = {Science Advances},
number = 8,
volume = 4,
place = {United States},
year = {2018},
month = {8}
}

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Cited by: 16 works
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Figures / Tables:

Fig. 1 Fig. 1: 3D printed hierarchical nanoporous gold (3DP-hnp-Au) exhibits control over structure that spans over seven orders of magnitude in length scales, from centimeters to nanometers. A-C, Schematic illustrations of (A) 3D printing inks composed of mixtures of Au and Ag microparticles, polymer binder, and solvent (binder and solvent aremore » represented as a green color), (B) the annealing step alloys the Au and Ag phases and removes the polymer binder to yield microscale porosity, and (C) the dealloying step selectively removes the Ag phase yielding the nanoscale porosity. Optical images of the 1 mm scale for multilayer woodpile-like architectures are shown for (D) printing (E) annealing and alloying, and (F) dealloying steps (D-F scale bars, 1 mm). Scanning electron microscopy (SEM) images are shown depicting the structural evolution after the printing, annealing (and alloying), and dealloying steps for the 100 μm scale (G-I), 10 μm scale (J-L), 1 μm scale (M-O), and 100 nm scale (P-R). The coarsening of the nanostructure after re-annealing is shown in S, T.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.