Manufacturing Molecules for the Carbon Economy

Project Overview

With this Laboratory Directed Research and Development (LDRD) Strategic Initiative (SI), Lawrence Livermore National Laboratory (LLNL) transformed chemical reactor technology by beginning the process of moving away from massive and increasingly expensive chemical plants to mass manufacturable, distributed, and low-cost reactor networks. For the demonstration case, our LDRD SI team harnessed electricity, which is increasingly abundant and cheap due to the emergence of renewable energy sources, to transform a harmful greenhouse gas and combustion waste product, namely carbon dioxide (CO₂), into high-value, low molecular weight hydrocarbon feedstocks such as ethylene and ethanol using electrocatalysis. To accomplish this goal, this LDRD SI rethought, from the ground up, chemical reactor design by using integrated engineering, scientific, and computational approaches. Our new reactor paradigm exhibits control over three-dimensional (3D) materials and structure across many length scales (e.g., from the atomic to the macro-scale), which was achieved by employing a combination of LLNL's unique 3D chemical assembly and additive manufacturing methods.

The team's approach leveraged LLNL's core competencies in additive manufacturing (AM), advanced materials, and computational simulation and design to create modular electrochemical reactor platforms that help answer fundamental scientific questions of micro-environment effects on catalyst activity, selectivity, and lifetime while also understanding and improving mass transport of the system. Our approach consisted of five, highly integrated Tasks that included (1) Theory, (2) Design, (3) Manufacturing, (4) Reactors, and (5) System Analysis. To carry out this effort, we assembled a world-class team and hired over 15 personnel including postdoctoral researchers and academic graduate appointees, a mid-career strategic hire, and a Graduate Education for Minorities (GEM) Fellow. We instantiated requisite laboratory facilities, instrumentation, and equipment that are helping establish LLNL as a leader in CO₂ conversion technologies. Importantly, LLNL demonstrated world-record production of ethanol and near world-record production of ethylene from CO₂ under benign conditions (i.e., room temperature and pressure and at neutral pH).

Mission Impact

This LDRD SI is having broad impact and helping strengthen our nation's resource, economic, climate, and energy security by reducing dependence upon oil and gas for hydrocarbon feedstocks, turning CO₂ waste into "wealth" while lowering greenhouse gas emissions, and serving as a mechanism to use and store excess electrical energy from renewable sources. This LDRD SI advanced LLNL's core competencies in Advanced Materials and Manufacturing and it directly impacted our Climate Mission Focus Area while serving as a cornerstone of the Director's Carbon Initiative. This LDRD SI helped develop rapid, low-cost advanced materials and manufacturing processes and systems that are accelerating material development and reducing infrastructure footprint and development times for chemical reactors. We expect that this effort's innovations and discoveries will be broadly applicable to other chemical reactor systems, which may help LLNL produce other materials classes (e.g., organics, energetic materials, inorganics, metals) and reduce the occurrence of "materials at risk" where we struggle to (re)produce materials from previous generations. This LDRD SI will ultimately benefit every Directorate at LLNL in one way or another—perhaps not immediately, but we fully expect this LDRD will have enduring and wide-ranging impact across LLNL, and beyond.

Publications, Presentations, and Patents

Akhade, Sneha A., Buddhinie S. Jayathilake, Stephen E. Weitzner, Hannah V. Eshelman, Julie Hamilton, Jeremy T. Feaster, David W. Wakerley, et al. "Electrolyte-Guided Design of Electroreductive CO Coupling on Copper Surfaces," ACS Applied Energy Materials 4, no. 8 (August 23, 2021): 8201-10. https://doi.org/10.1021/acsaem.1c01427.

Beck, Victor A., Anna N. Ivanovskaya, Swetha Chandrasekaran, Jean-Baptiste Forien, Sarah E. Baker, Eric B. Duoss, and Marcus A. Worsley. "Inertially Enhanced Mass Transport Using 3D-Printed Porous Flow-through Electrodes with Periodic Lattice Structures," Proceedings of the National Academy of Sciences 118, no. 32 (August 10, 2021). https://doi.org/10.1073/pnas.2025562118.

Beck, Victor A., Jonathan J. Wong, Charles F. Jekel, Daniel A. Tortorelli, Sarah E. Baker, Eric B. Duoss, and Marcus A. Worsley. "Computational Design of Microarchitected Porous Electrodes for Redox Flow Batteries," Journal of Power Sources 512 (November 15, 2021): 230453. https://doi.org/10.1016/j.jpowsour.2021.230453.

Corral, Daniel, Jeremy T. Feaster, Sadaf Sobhani, Joshua R. DeOtte, Dong Un Lee, Andrew A. Wong, Julie Hamilton, et al. "Advanced Manufacturing for Electrosynthesis of Fuels and Chemicals from CO₂," Energy & Environmental Science 14, no. 5 (May 19, 2021): 3064-74. https://doi.org/10.1039/D0EE03679J.

Dudukovic, Nikola A., Erika J. Fong, Hawi B. Gemeda, Joshua R. DeOtte, Maira R. Cerón, Bryan D. Moran, Jonathan T. Davis, Sarah E. Baker, and Eric B. Duoss. "Cellular Fluidics," Nature 595, no. 7865 (July 2021): 58-65. https://doi.org/10.1038/s41586-021-03603-2.

Koshy, David M., Sneha A. Akhade, Adam Shugar, Kabir Abiose, Jingwei Shi, Siwei Liang, James S. Oakdale, et al. "Chemical Modifications of Ag Catalyst Surfaces with Imidazolium Ionomers Modulate H₂ Evolution Rates during Electrochemical CO₂ Reduction," Journal of the American Chemical Society 143, no. 36 (September 15, 2021): 14712-25. https://doi.org/10.1021/jacs.1c06212.

Kou, Tianyi, Shanwen Wang, Rongpei Shi, Tao Zhang, Samuel Chiovoloni, Jennifer Q. Lu, Wen Chen, et al. "Water Splitting: Periodic Porous 3D Electrodes Mitigate Gas Bubble Traffic during Alkaline Water Electrolysis at High Current Densities (Adv. Energy Mater. 46/2020)," Advanced Energy Materials 10, no. 46 (2020): 2070189. https://doi.org/10.1002/aenm.202070189.

Li, Wenqin, Jeremy T. Feaster, Sneha A. Akhade, Jonathan T. Davis, Andrew A. Wong, Victor A. Beck, Joel B. Varley, et al. "Comparative Techno-Economic and Life Cycle Analysis of Water Oxidation and Hydrogen Oxidation at the Anode in a CO₂ Electrolysis to Ethylene System." ACS Sustainable Chemistry & Engineering, October 28, 2021. https://doi.org/10.1021/acssuschemeng.1c01846.

Lin, Tiras Y., Sarah E. Baker, Eric B. Duoss, and Victor A. Beck. "Analysis of the Reactive CO₂ Surface Flux in Electrocatalytic Aqueous Flow Reactors," Industrial & Engineering Chemistry Research 60, no. 31 (August 11, 2021): 11824-33. https://doi.org/10.1021/acs.iecr.1c01851.

Mooraj, Shahryar, Zhen Qi, Cheng Zhu, Jie Ren, Siyuan Peng, Liang Liu, Shengbiao Zhang, et al. "3D Printing of Metal-Based Materials for Renewable Energy Applications," Nano Research 14, no. 7 (July 1, 2021): 2105-32. https://doi.org/10.1007/s12274-020-3230-x.

Mooraj, Shahryar, Samuel S. Welborn, Shuyang Jiang, Siyuan Peng, Jintao Fu, Sarah Baker, Eric B. Duoss, Cheng Zhu, Eric Detsi, and Wen Chen. "Three-Dimensional Hierarchical Nanoporous Copper via Direct Ink Writing and Dealloying," Scripta Materialia 177 (March 1, 2020): 146-50. https://doi.org/10.1016/j.scriptamat.2019.10.013.

Moore, Thomas, Xiaoxing Xia, Sarah E. Baker, Eric B. Duoss, and Victor A. Beck. "Elucidating Mass Transport Regimes in Gas Diffusion Electrodes for CO₂ Electroreduction," ACS Energy Letters 6, no. 10 (October 8, 2021): 3600-3606. https://doi.org/10.1021/acsenergylett.1c01513.

Sullivan, Ian, Huanlei Zhang, Cheng Zhu, Marissa Wood, Art J. Nelson, Sarah E. Baker, Christopher M. Spadaccini, et al. "3D Printed Nickel-Molybdenum-Based Electrocatalysts for Hydrogen Evolution at Low Overpotentials in a Flow-Through Configuration," ACS Applied Materials & Interfaces 13, no. 17 (May 5, 2021): 20260-68. https://doi.org/10.1021/acsami.1c05648.

Wang, S., T. Kou, S. E. Baker, E. B. Duoss, and Y. Li. "Recent Progress in Electrochemical Reduction of CO₂ by Oxide-Derived Copper Catalysts," Materials Today Nano 12 (December 1, 2020): 100096. https://doi.org/10.1016/j.mtnano.2020.100096.

Wang, Shanwen, Tianyi Kou, Sarah E. Baker, Eric B. Duoss, and Yat Li. "Electrochemical Reduction of CO₂ to Alcohols: Current Understanding, Progress, and Challenges," Advanced Energy and Sustainability Research n/a, no. n/a (n.d.): 2100131. https://doi.org/10.1002/aesr.202100131.

Wang, Shanwen, Tianyi Kou, Joel B. Varley, Sneha A. Akhade, Stephen E. Weitzner, Sarah E. Baker, Eric B. Duoss, and Yat Li. "Cu₂O/CuS Nanocomposites Show Excellent Selectivity and Stability for Formate Generation via Electrochemical Reduction of Carbon Dioxide," ACS Materials Letters 3, no. 1 (January 4, 2021): 100-109. https://doi.org/10.1021/acsmaterialslett.0c00520.

Weitzner, Stephen E., Sneha A. Akhade, Joel B. Varley, Brandon C. Wood, Minoru Otani, Sarah E. Baker, and Eric B. Duoss. "Toward Engineering of Solution Microenvironments for the CO₂ Reduction Reaction: Unraveling PH and Voltage Effects from a Combined Density-Functional-Continuum Theory," The Journal of Physical Chemistry Letters 11, no. 10 (May 21, 2020): 4113-18. https://doi.org/10.1021/acs.jpclett.0c00957.

Wicks, Joshua, Melinda L. Jue, Victor A. Beck, James S. Oakdale, Nikola A. Dudukovic, Auston L. Clemens, Siwei Liang, et al. "3D-Printable Fluoropolymer Gas Diffusion Layers for CO₂ Electroreduction." Advanced Materials 33, no. 7 (2021): 2003855. https://doi.org/10.1002/adma.202003855.

Akhade, Sneha A., Stephen Eric Weitzner, Felicia R. Lucci, Jeremy T. Feaster, Anna N. Ivanovskaya, Brandon C. Wood, Joel Basile Varley, Sarah E. Baker, and Eric B. Duoss. "Tuning the Sensitivity of CO₂ Electroreduction on Copper Surfaces Via Electrolyte Engineering." 236th ECS Meeting. Atlanta, GA. Oct 13-17, 2019. http://dx.doi.org/10.1149/MA2019-02/22/1078.

Akhade, Sneha A, Stephen Eric Weitzner, Zhen Qi, Monika M. Biener, Joel Basile Varley, Sarah E Baker, Eric B Duoss, Brandon C. Wood, and Juergen Biener. "Rational Design of Copper Alloy Catalysts for Electrochemical CO₂ Reduction." 237th ECS Meeting with the 18th International Meeting on Chemical Sensors (IMCS 2020). Montreal, Canada. May 10-14, 2020. http://dx.doi.org/10.1149/MA2020-01462625mtgabs.

Akhade, Sneha, Stephen E. Weitzner, Felicia R. Lucci, Jeremy T. Feaster, Joel B. Varley, Brandon C. Wood, Sarah Baker, and Eric B. Duoss. "Electrolyte Based Tuning of CO₂ Electroreduction Selectivity on Copper Surfaces." 2019 AIChE Annual Meeting. Orlando, Fl. November 14, 2019. https://aiche.confex.com/aiche/2019/meetingapp.cgi/Paper/575435.

Beck, Victor A, Anna N Ivanovskaya, Swetha Chandrasekaran, Jean-Baptiste Forien, Sarah E Baker, Eric B Duoss, and Marcus A. Worsley. "Elucidating the Mass Transport Properties of Additively Manufactured Electrodes Using Spatially Resolved Simulation." PRiME 2020 (ECS, ECSJ, & KECS Joint Meeting. Virtual. Oct. 4-9, 2020. http://dx.doi.org/10.1149/MA2020-02332141mtgabs.

Beck, Victor A, Seth E Watts, Jonathan M Wong, Dan A Tortorelli, Sarah E Baker, Eric B Duoss, and Marcus A. Worsley. "Improving Flow-through Electrode Performance Using Computational Design of Architected Porosity." PRiME 2020 (ECS, ECSJ, & KECS Joint Meeting. Virtual. Oct. 4-9, 2020. http://dx.doi.org/10.1149/MA2020-02191541mtgabs.

Duoss, Eric B. "Manufacturing Molecules for the New Carbon Economy." Presented at the 2020 Virtual MRS Fall Meeting & Exhibit. Virtual. Nov. 27-Dec. 4, 2020.

Feaster, Jeremy T., Felicia R. Lucci, Marissa Wood, Joshua R. Deotte, Nikola Dudukovic, Siwei Liang, Clara Druzgalski, et al. "Leveraging Advanced Manufactured Catalysts and Reactors for Electrochemical CO₂ Conversion." 236th ECS Meeting. Atlanta, GA. Oct 13-17, 2019. http://dx.doi.org/10.1149/MA2019-02/22/1081.

Li, Wenqin, Victor Beck, Jeremy T. Feaster, Sarah Baker, and Eric B. Duoss. "Techno-Economic Analysis (TEA) of CO₂ Electrolysis Systems for Ethylene Production." 2019 AIChE Annual Meeting. Orlando, FL. Nov. 10-15, 2019. https://aiche.confex.com/aiche/2019/meetingapp.cgi/Paper/577438.

Weitzner, Stephen Eric, Sneha A. Akhade, Joel Basile Varley, Brandon C. Wood, Sarah E. Baker, and Eric B. Duoss. "CO Site Preference on Copper Surfaces in Electrochemical Environments: Deciphering Voltage and Electrolyte Composition Effects." 235th ECS Meeting. Dallas, TX. May 26-30, 2019. http://dx.doi.org/10.1149/MA2019-01/40/1965.

Weitzner, Stephen Eric, Sneha A Akhade, Joel Basile Varley, Brandon C. Wood, Sarah E Baker, Eric B Duoss, and Minoru Otani. "Assessing PH and Voltage Effects on the Binding of CO to Model Copper Catalyst Surfaces Via a DFT-Continuum Theory." PRiME 2020 (ECS, ECSJ, & KECS Joint Meeting). Virtual. Oct. 4-9, 2020. http://dx.doi.org/10.1149/MA2020-02633214mtgabs.

Wong, Andrew A., Michael Aziz, and Eric B. Duoss. "Fish Gill-Inspired Electrochemical Reactors for High Efficiency Redox Flow Systems." 2020 Virtual MRS Fall Meeting & Exhibit. Virtual. Nov. 27-Dec. 4, 2020.

Deotte, Joshua R., Sarah Baker, Eric Duoss, Jennifer Marie Knipe, Fang Qian, and Samantha Ruelas. Lattice microfluidics. United States US11130131B2. Accessed November 4, 2021. https://patents.google.com/patent/US11130131B2/en.

Dudukovic, Nikola, Roger Aines, Sarah Baker, Joshua R. Deotte, Eric B. Duoss, Jeremy Taylor Feaster, Alexandra Golobic, et al. Multimaterial powder bed patterning for additive manufacturing method. United States US20200147874A1. Accessed November 4, 2021. https://patents.google.com/patent/US20200147874A1/en.

Dudukovic, Nikola, Sarah Baker, Victor Alfred Beck, Swetha Chandrasekaran, Joshua R. Deotte, Eric B. Duoss, Jeremy Taylor Feaster, et al. Systems and methods for reaction and transport engineering via cellular fluidics. United States US20210053056A1. Accessed November 4, 2021. https://patents.google.com/patent/US20210053056A1/en.

Dudukovic, Nikola, Sarah Baker, James Timothy CAHILL, Jonathan Tesner DAVIS, Joshua R. Deotte, Karen Ruth Dubbin, Eric B. Duoss, Erika Jo FONG, Hawi Bacha GEMEDA, and Fang Qian. Systems and methods for reaction and transport engineering via cellular fluidics. United States US20210077999A1. Accessed November 4, 2021. https://patents.google.com/patent/US20210077999A1/en.

Liang, Siwei, Sarah E. Baker, Theodore F. Baumann, Eric B. Duoss, Christopher M. Spadaccini, and Cheng Zhu. Engineering catalytical electrodes for applications in energy areas. United States US20210317586A1. Accessed November 4, 2021. https://patents.google.com/patent/US20210317586A1/en.

Liang, Siwei, Theodore F. Baumann, Eric B. Duoss, Christopher M. Spadaccini, Marcus A. Worsley, and Cheng Zhu. Additive manufacture of hierarchically porous materials with high resolution. United States US20200298466A1. Accessed November 4, 2021. https://patents.google.com/patent/US20200298466A1/en.

Watts, Seth Evan, Nikola Dudukovic, and Eric Duoss. Tailored particles for power-based additive manufacturing. United States US20210008615A1. Accessed November 4, 2021. https://patents.google.com/patent/US20210008615A1/en.