3D Printed Nickel–Molybdenum-Based Electrocatalysts for Hydrogen Evolution at Low Overpotentials in a Flow-Through Configuration

Sullivan, Ian; Zhang, Huanlei; Zhu, Cheng; Wood, Marissa; Nelson, Art J.; Baker, Sarah E.; Spadaccini, Christopher M.; Van Buuren, Tony; Lin, Meng; Duoss, Eric B.; Liang, Siwei; Xiang, Chengxiang

doi:10.1021/acsami.1c05648

Title: 3D Printed Nickel–Molybdenum-Based Electrocatalysts for Hydrogen Evolution at Low Overpotentials in a Flow-Through Configuration

Journal Article · Thu Apr 22 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c05648· OSTI ID:1810667

^[1]; Zhang, Huanlei ^[2];

^[3]; Wood, Marissa ^[3]; Nelson, Art J. ^[3]; Baker, Sarah E. ^[3]; Spadaccini, Christopher M. ^[3]; Van Buuren, Tony ^[3];

^[2]; Duoss, Eric B. ^[3]; Liang, Siwei ^[3];

^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States). Liquid Sunlight Alliance (LiSA)
Southern Univ. of Science and Technology, Shenzhen (China)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Three-dimensional (3D) printed, hierarchically porous nickel molybdenum (NiMo) electrocatalysts were synthesized and evaluated in a flow-through configuration for the hydrogen evolution reaction (HER) in 1.0 M KOH(aq) in a simple electrochemical H-cell. 3D NiMo electrodes possess hierarchically porous structures because of the resol-based aerogel precursor, which generates superporous carbon aerogel as a catalyst support. Relative to a traditional planar electrode configuration, the flow-through configuration allowed efficient removal of the hydrogen bubbles from the catalyst surface, especially at high operating current densities, and significantly decreased the overpotentials required for HER. An analytical model that accounted for the electrokinetics of HER as well as the mass transport with or without the flow-through configuration was developed to quantitatively evaluate voltage losses associated with kinetic overpotentials and ohmic resistance due to bubble formation in the porous electrodes. Furthermore, the chemical composition, electrochemical surface area (ECSA), and roughness factor (RF) were also systematically studied to assess the electrocatalytic performance of the 3D printed, hierarchically porous NiMo electrodes. An ECSA of 25163 cm2 was obtained with the highly porous structures, and an average overpotential of 45 mV at 10 mA cm–2 was achieved over 24 h by using the flow-through configuration. The flow-through configuration evaluated in the simple H-cell achieved high electrochemical accessible surface areas for electrochemical reactions and provided useful information for adaption of the porous electrodes in flow cells.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; SC0021266

OSTI ID:: 1810667

Report Number(s):: LLNL-JRNL-816169; 1025498

Journal Information:: ACS Applied Materials and Interfaces, Vol. 13, Issue 17; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (56)

Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M. Journal of the American Chemical Society, Vol. 137, Issue 13 https://doi.org/10.1021/ja510442p	journal	March 2015
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Platinum single-atom and cluster catalysis of the hydrogen evolution reaction Cheng, Niancai; Stambula, Samantha; Wang, Da Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13638	journal	November 2016
Electrocatalysts for hydrogen evolution reaction Eftekhari, Ali International Journal of Hydrogen Energy, Vol. 42, Issue 16 https://doi.org/10.1016/j.ijhydene.2017.02.125	journal	April 2017
A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction Gong, Ming; Wang, Di-Yan; Chen, Chia-Chun Nano Research, Vol. 9, Issue 1 https://doi.org/10.1007/s12274-015-0965-x	journal	December 2015
Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers Grigoriev, S. A.; Millet, P.; Fateev, V. N. Journal of Power Sources, Vol. 177, Issue 2 https://doi.org/10.1016/j.jpowsour.2007.11.072	journal	March 2008
Promoting Formation of Oxygen Vacancies in Two-Dimensional Cobalt-Doped Ceria Nanosheets for Efficient Hydrogen Evolution Jiang, Shuaihu; Zhang, Ruya; Liu, Hongxian Journal of the American Chemical Society, Vol. 142, Issue 14 https://doi.org/10.1021/jacs.9b13915	journal	March 2020
Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts Liu, Ershuai; Li, Jingkun; Jiao, Li Journal of the American Chemical Society, Vol. 141, Issue 7 https://doi.org/10.1021/jacs.8b13228	journal	January 2019
Electrocatalysts for Hydrogen Evolution in Alkaline Electrolytes: Mechanisms, Challenges, and Prospective Solutions Mahmood, Nasir; Yao, Yunduo; Zhang, Jing-Wen Advanced Science, Vol. 5, Issue 2 https://doi.org/10.1002/advs.201700464	journal	November 2017
The Hydrogen Evolution Reaction in Alkaline Solution: From Theory, Single Crystal Models, to Practical Electrocatalysts Zheng, Yao; Jiao, Yan; Vasileff, Anthony Angewandte Chemie International Edition, Vol. 57, Issue 26 https://doi.org/10.1002/anie.201710556	journal	May 2018
Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer Ramaswamy, Nagappan; Mukerjee, Sanjeev Chemical Reviews, Vol. 119, Issue 23 https://doi.org/10.1021/acs.chemrev.9b00157	journal	November 2019
Pt-like electrocatalytic behavior of Ru–MoO ₂ nanocomposites for the hydrogen evolution reaction Jiang, Peng; Yang, Yang; Shi, Ruohong Journal of Materials Chemistry A, Vol. 5, Issue 11 https://doi.org/10.1039/C6TA09994G	journal	January 2017
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
Bigger is Surprisingly Better: Agglomerates of Larger RuP Nanoparticles Outperform Benchmark Pt Nanocatalysts for the Hydrogen Evolution Reaction Yu, Jie; Guo, Yanan; She, Sixuan Advanced Materials, Vol. 30, Issue 39 https://doi.org/10.1002/adma.201800047	journal	August 2018
Identifying Electrocatalytic Sites of the Nanoporous Copper–Ruthenium Alloy for Hydrogen Evolution Reaction in Alkaline Electrolyte Wu, Qiuli; Luo, Min; Han, Jiuhui ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02374	journal	November 2019
Ni–Mo Nanopowders for Efficient Electrochemical Hydrogen Evolution McKone, James R.; Sadtler, Bryce F.; Werlang, Caroline A. ACS Catalysis, Vol. 3, Issue 2 https://doi.org/10.1021/cs300691m	journal	January 2013
Earth-Abundant Oxygen Electrocatalysts for Alkaline Anion-Exchange-Membrane Water Electrolysis: Effects of Catalyst Conductivity and Comparison with Performance in Three-Electrode Cells Xu, Dongyu; Stevens, Michaela Burke; Cosby, Monty R. ACS Catalysis, Vol. 9, Issue 1 https://doi.org/10.1021/acscatal.8b04001	journal	November 2018
Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities Lu, Xunyu; Zhao, Chuan Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7616	journal	March 2015
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C. Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja407115p	journal	October 2013
Topological Formation of a Mo–Ni-Based Hollow Structure as a Highly Efficient Electrocatalyst for the Hydrogen Evolution Reaction in Alkaline Solutions Zhou, Yuxue; Luo, Min; Zhang, Wei ACS Applied Materials & Interfaces, Vol. 11, Issue 24 https://doi.org/10.1021/acsami.9b03686	journal	May 2019
Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction Zeng, Min; Li, Yanguang Journal of Materials Chemistry A, Vol. 3, Issue 29 https://doi.org/10.1039/C5TA02974K	journal	January 2015
Fe, Co, and Ni ions promote the catalytic activity of amorphous molybdenum sulfide films for hydrogen evolution Merki, Daniel; Vrubel, Heron; Rovelli, Lorenzo Chemical Science, Vol. 3, Issue 8 https://doi.org/10.1039/c2sc20539d	journal	January 2012
Impedance Spectroscopy Modeling of Nickel–Molybdenum Alloys on Porous and Flat Substrates for Applications in Water Splitting Pehlivan, İlknur Bayrak; Arvizu, Miguel A.; Qiu, Zhen The Journal of Physical Chemistry C, Vol. 123, Issue 39 https://doi.org/10.1021/acs.jpcc.9b02714	journal	September 2019
Well‐Dispersed Nickel‐ and Zinc‐Tailored Electronic Structure of a Transition Metal Oxide for Highly Active Alkaline Hydrogen Evolution Reaction Ling, Tao; Zhang, Tong; Ge, Binghui Advanced Materials, Vol. 31, Issue 16 https://doi.org/10.1002/adma.201807771	journal	February 2019
Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics Zhang, Jian; Wang, Tao; Liu, Pan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15437	journal	May 2017
Hydrogen-Evolution Catalysts Based on Non-Noble Metal Nickel-Molybdenum Nitride Nanosheets Chen, Wei-Fu; Sasaki, Kotaro; Ma, Chao Angewandte Chemie International Edition, Vol. 51, Issue 25 https://doi.org/10.1002/anie.201200699	journal	May 2012
Study of Electrodeposited Nickel-Molybdenum, Nickel-Tungsten, Cobalt-Molybdenum, and Cobalt-Tungsten as Hydrogen Electrodes in Alkaline Water Electrolysis Fan, Chonglun Journal of The Electrochemical Society, Vol. 141, Issue 2 https://doi.org/10.1149/1.2054736	journal	January 1994
Hierarchical NiMo-based 3D electrocatalysts for highly-efficient hydrogen evolution in alkaline conditions Fang, Ming; Gao, Wei; Dong, Guofa Nano Energy, Vol. 27 https://doi.org/10.1016/j.nanoen.2016.07.005	journal	September 2016
Amine-Modulated/Engineered Interfaces of NiMo Electrocatalysts for Improved Hydrogen Evolution Reaction in Alkaline Solutions Gao, Wei; Gou, Wangyan; Zhou, Xuemei ACS Applied Materials & Interfaces, Vol. 10, Issue 2 https://doi.org/10.1021/acsami.7b16125	journal	January 2018
Cooperation between holey graphene and NiMo alloy for hydrogen evolution in an acidic electrolyte Ito, Yoshikazu; Ohto, Tatsuhiko; Hojo, Daisuke ACS Catalysis, Vol. 8, Issue 4 https://doi.org/10.1021/acscatal.7b04091	journal	March 2018
Single-Crystalline Mo-Nanowire-Mediated Directional Growth of High-Index-Faceted MoNi Electrocatalyst for Ultralong-Term Alkaline Hydrogen Evolution Liu, Zhenpeng; Zhang, Guoxian; Bu, Jun ACS Applied Materials & Interfaces, Vol. 12, Issue 32 https://doi.org/10.1021/acsami.0c11716	journal	July 2020
Characterization of Ni, NiMo, NiW and NiFe electroactive coatings as electrocatalysts for hydrogen evolution in an acidic medium Navarro-Flores, Elisa; Chong, Zhiwen; Omanovic, Sasha Journal of Molecular Catalysis A: Chemical, Vol. 226, Issue 2 https://doi.org/10.1016/j.molcata.2004.10.029	journal	February 2005
Electrolyte Effects on the Electrocatalytic Performance of Iridium‐Based Nanoparticles for Oxygen Evolution in Rotating Disc Electrodes Arminio‐Ravelo, José Alejandro; Jensen, Anders W.; Jensen, Kim D. ChemPhysChem, Vol. 20, Issue 22 https://doi.org/10.1002/cphc.201900902	journal	November 2019
Measurement of oxygen reduction activities via the rotating disc electrode method: From Pt model surfaces to carbon-supported high surface area catalysts Mayrhofer, K. J. J.; Strmcnik, D.; Blizanac, B. B. Electrochimica Acta, Vol. 53, Issue 7 https://doi.org/10.1016/j.electacta.2007.11.057	journal	February 2008
Effects of electrochemical reaction and surface morphology on electroactive surface area of porous copper manufactured by Lost Carbonate Sintering Zhu, Pengcheng; Zhao, Yuyuan RSC Advances, Vol. 7, Issue 42 https://doi.org/10.1039/C7RA04204C	journal	January 2017
Flow Channel Cell Apparatus for High Rate Electrolysis Studies Landolt, Dieter Review of Scientific Instruments, Vol. 43, Issue 4 https://doi.org/10.1063/1.1685699	journal	April 1972
Alkaline Water Electrolysis at 25 A cm ⁻² with a Microfibrous Flow‐through Electrode Yang, Feichen; Kim, Myung Jun; Brown, Micah Advanced Energy Materials, Vol. 10, Issue 25 https://doi.org/10.1002/aenm.202001174	journal	May 2020
Experimental studies and modeling of advanced alkaline water electrolyser with porous nickel electrodes for hydrogen production Sandeep, K. C.; Kamath, Sachin; Mistry, Krunal International Journal of Hydrogen Energy, Vol. 42, Issue 17 https://doi.org/10.1016/j.ijhydene.2017.03.154	journal	April 2017
The bubble coverage of gas-evolving electrodes in stagnant electrolytes Vogt, H.; Balzer, R. J. Electrochimica Acta, Vol. 50, Issue 10 https://doi.org/10.1016/j.electacta.2004.09.025	journal	March 2005
A comprehensive review on PEM water electrolysis Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen International Journal of Hydrogen Energy, Vol. 38, Issue 12, p. 4901-4934 https://doi.org/10.1016/j.ijhydene.2013.01.151	journal	April 2013
Hydrogen production from a rectangular horizontal filter press Divergent Electrode-Flow-Through (DEFT™) alkaline electrolysis stack Gillespie, M. I.; Kriek, R. J. Journal of Power Sources, Vol. 372 https://doi.org/10.1016/j.jpowsour.2017.10.080	journal	December 2017
Performance evaluation of a membraneless divergent electrode-flow-through (DEFT) alkaline electrolyser based on optimisation of electrolytic flow and electrode gap Gillespie, M. I.; van der Merwe, F.; Kriek, R. J. Journal of Power Sources, Vol. 293 https://doi.org/10.1016/j.jpowsour.2015.05.077	journal	October 2015
High surface area carbon aerogel monoliths with hierarchical porosity Baumann, Theodore F.; Worsley, Marcus A.; Han, T. Yong-Jin Journal of Non-Crystalline Solids, Vol. 354, Issue 29, p. 3513-3515 https://doi.org/10.1016/j.jnoncrysol.2008.03.006	journal	July 2008
Direct ink writing of organic and carbon aerogels Chandrasekaran, Swetha; Yao, Bin; Liu, Tianyu Materials Horizons, Vol. 5, Issue 6 https://doi.org/10.1039/C8MH00603B	journal	January 2018
Triconstituent Co-assembly to Ordered Mesostructured Polymer−Silica and Carbon−Silica Nanocomposites and Large-Pore Mesoporous Carbons with High Surface Areas Liu, Ruili; Shi, Yifeng; Wan, Ying Journal of the American Chemical Society, Vol. 128, Issue 35 https://doi.org/10.1021/ja0633518	journal	September 2006
Inkjet Printing Assisted Synthesis of Multicomponent Mesoporous Metal Oxides for Ultrafast Catalyst Exploration Liu, Xiaonao; Shen, Yi; Yang, Ruoting Nano Letters, Vol. 12, Issue 11 https://doi.org/10.1021/nl302992q	journal	October 2012
Multimaterial 3D-Printed Water Electrolyzer with Earth-Abundant Electrodeposited Catalysts Ambrosi, Adriano; Pumera, Martin ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 12 https://doi.org/10.1021/acssuschemeng.8b04327	journal	November 2018
Benchmarking high surface area electrocatalysts in a gas diffusion electrode: measurement of oxygen reduction activities under realistic conditions Inaba, Masanori; Jensen, Anders Westergaard; Sievers, Gustav Wilhelm Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C8EE00019K	journal	January 2018
Assessment of the roughness factor effect and the intrinsic catalytic activity for hydrogen evolution reaction on Ni-based electrodeposits Herraiz-Cardona, I.; Ortega, E.; Antón, J. García International Journal of Hydrogen Energy, Vol. 36, Issue 16 https://doi.org/10.1016/j.ijhydene.2011.05.047	journal	August 2011
Highly active MoS ₂ /carbon electrocatalysts for the hydrogen evolution reaction – insight into the effect of the internal resistance and roughness factor on the Tafel slope Murthy, Arun Prasad; Theerthagiri, Jayaraman; Madhavan, Jagannathan Physical Chemistry Chemical Physics, Vol. 19, Issue 3 https://doi.org/10.1039/C6CP07416B	journal	January 2017
High-Rate Electrochemical Reduction of Carbon Monoxide to Ethylene Using Cu-Nanoparticle-Based Gas Diffusion Electrodes Han, Lihao; Zhou, Wu; Xiang, Chengxiang ACS Energy Letters, Vol. 3, Issue 4 https://doi.org/10.1021/acsenergylett.8b00164	journal	March 2018
Nanosponge-like Solid Solution of NiMo with a High Hydrogen Evolution Reaction Performance over a Wide Range of Current Densities Shang, Pengfei; Ye, Zhiguo; Ding, Yi ACS Sustainable Chemistry & Engineering https://doi.org/10.1021/acssuschemeng.0c00783	journal	July 2020
NiMo Solid Solution Nanowire Array Electrodes for Highly Efficient Hydrogen Evolution Reaction Nairan, Adeela; Zou, Peichao; Liang, Caiwu Advanced Functional Materials, Vol. 29, Issue 44 https://doi.org/10.1002/adfm.201903747	journal	August 2019
Studies on preparation, microstructure, mechanical properties and corrosion resistance of Ni Mo/micron-sized diamond composite coatings Liu, J. H.; Pei, Z. L.; Shi, W. B. Surface and Coatings Technology, Vol. 385 https://doi.org/10.1016/j.surfcoat.2020.125451	journal	March 2020
Influence of Bubbles on the Energy Conversion Efficiency of Electrochemical Reactors Angulo, Andrea; van der Linde, Peter; Gardeniers, Han Joule, Vol. 4, Issue 3 https://doi.org/10.1016/j.joule.2020.01.005	journal	March 2020
The Quantities Affecting the Bubble Coverage of Gas-Evolving Electrodes Vogt, H. Electrochimica Acta, Vol. 235 https://doi.org/10.1016/j.electacta.2017.03.116	journal	May 2017

Similar Records

Three-Dimensional Printed MoS ₂ /Graphene Aerogel Electrodes for Hydrogen Evolution Reactions

Journal Article · Thu May 05 00:00:00 EDT 2022 · ACS Materials Au · OSTI ID:1810667

Chandrasekaran, Swetha; Feaster, Jeremy; Ynzunza, Jenna; +4 more

Estimation of Mass-Transport Overpotentials During Long-Term PEMFC Operation

Journal Article · Fri Jan 01 00:00:00 EST 2010 · Journal of the Electrochemical Society · OSTI ID:1810667

WoodIII, David L; Borup, Rodney

Mathematical Modeling of Hydroxide-Exchange-Membrane Water Electrolyzer

Journal Article · Mon Nov 23 00:00:00 EST 2020 · ECS Meeting Abstracts · OSTI ID:1810667

Liu, Jiangjin; Gerhardt, Michael R; Li, Dongguo; +6 more

Related Subjects

08 HYDROGEN
hydrogen evolution reaction
electrocatalysis
3D printing
alkaline electrolysis
NiMo
flow-through
electrochemistry
solar fuel

Title: 3D Printed Nickel–Molybdenum-Based Electrocatalysts for Hydrogen Evolution at Low Overpotentials in a Flow-Through Configuration

Citation Formats

References (56)

Similar Records

Related Subjects