Grain boundary engineering for efficient and durable electrocatalysis

Geng, Xin; Vega-Paredes, Miquel; Wang, Zhenyu; Ophus, Colin; Lu, Pengfei; Ma, Yan; Zhang, Siyuan; Scheu, Christina; Liebscher, Christian H.; Gault, Baptiste

doi:10.1038/s41467-024-52919-w

Grain boundary engineering for efficient and durable electrocatalysis

Journal Article · Wed Oct 02 00:00:00 EDT 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-52919-w· OSTI ID:2479501

^[1]; ^[1]; ^[1]; ^[2]; Lu, Pengfei ^[3]; ^[4]; ^[1]; ^[1]; ^[1]; ^[5]

Max Planck Institute for Sustainable Materials, Düsseldorf (Germany)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry
Huazhong University of Science and Technology, Wuhan (China)
Max Planck Institute for Sustainable Materials, Düsseldorf (Germany); Delft Univ. of Technology (Netherlands)
Max Planck Institute for Sustainable Materials, Düsseldorf (Germany); Imperial College, London (United Kingdom)

Grain boundaries in noble metal catalysts have been identified as critical sites for enhancing catalytic activity in electrochemical reactions such as the oxygen reduction reaction. However, conventional methods to modify grain boundary density often alter particle size, shape, and morphology, obscuring the specific role of grain boundaries in catalytic performance. This study addresses these challenges by employing gold nanoparticle assemblies to control grain boundary density through the manipulation of nanoparticle collision frequency during synthesis. We demonstrate a direct correlation between increased grain boundary density and enhanced two-electron oxygen reduction reaction activity, achieving a significant improvement in both specific and mass activity. Additionally, the gold nanoparticle assemblies with high grain boundary density exhibit remarkable electrochemical stability, attributed to boron segregation at the grain boundaries, which prevents structural degradation. This work provides a promising strategy for optimizing the activity, selectivity, and stability of noble metal catalysts through precise grain boundary engineering.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2479501

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Grain‐Boundary‐Rich Noble Metal Nanoparticle Assemblies: Synthesis, Characterization, and Reactivity Geng, Xin; Li, Shuwei; Heo, Jaeyoung Advanced Functional Materials, Vol. 32, Issue 34 https://doi.org/10.1002/adfm.202204169	journal	June 2022
One-Pot Synthesis of Highly Anisotropic Five-Fold-Twinned PtCu Nanoframes Used as a Bifunctional Electrocatalyst for Oxygen Reduction and Methanol Oxidation Zhang, Zhicheng; Luo, Zhimin; Chen, Bo Advanced Materials, Vol. 28, Issue 39 https://doi.org/10.1002/adma.201603075	journal	August 2016
Controlled Doping of Electrocatalysts through Engineering Impurities Kim, Se‐Ho; Yoo, Su‐Hyun; Shin, Sangyong Advanced Materials, Vol. 34, Issue 28 https://doi.org/10.1002/adma.202203030	journal	June 2022
Enhancement of oxygen reduction reaction activity by grain boundaries in platinum nanostructures Zhu, Enbo; Xue, Wang; Wang, Shiyi Nano Research, Vol. 13, Issue 12 https://doi.org/10.1007/s12274-020-3007-2	journal	August 2020
Changes in fractal dimension during aggregation Chakraborti, Rajat K.; Gardner, Kevin H.; Atkinson, Joseph F. Water Research, Vol. 37, Issue 4 https://doi.org/10.1016/S0043-1354(02)00379-2	journal	February 2003
Microstructural evolution of a Ni-based superalloy (617B) at 700°C studied by electron microscopy and atom probe tomography Tytko, Darius; Choi, Pyuck-Pa; Klöwer, Jutta Acta Materialia, Vol. 60, Issue 4 https://doi.org/10.1016/j.actamat.2011.11.020	journal	February 2012
On the effect of boron on grain boundary character in a new polycrystalline superalloy Kontis, P.; Yusof, H. A. Mohd; Pedrazzini, S. Acta Materialia, Vol. 103 https://doi.org/10.1016/j.actamat.2015.10.006	journal	January 2016
Grain-boundary segregation of boron in high-strength steel studied by nano-SIMS and atom probe tomography Da Rosa, G.; Maugis, P.; Portavoce, A. Acta Materialia, Vol. 182 https://doi.org/10.1016/j.actamat.2019.10.029	journal	January 2020
Enabling Direct H2O2 Production in Acidic Media through Rational Design of Transition Metal Single Atom Catalyst Gao, Jiajian; Yang, Hong bin; Huang, Xiang Chem, Vol. 6, Issue 3 https://doi.org/10.1016/j.chempr.2019.12.008	journal	March 2020
From colloidal dispersions to aerogels: How to master nanoparticle gelation Matter, Fabian; Luna, Ana Laura; Niederberger, Markus Nano Today, Vol. 30 https://doi.org/10.1016/j.nantod.2019.100827	journal	February 2020
Structure effects on the energetics of the electrochemical reduction of CO2 by copper surfaces Durand, William J.; Peterson, Andrew A.; Studt, Felix Surface Science, Vol. 605, Issue 15-16 https://doi.org/10.1016/j.susc.2011.04.028	journal	August 2011
Automated Crystal Orientation Mapping in py4DSTEM using Sparse Correlation Matching Ophus, Colin; Zeltmann, Steven E.; Bruefach, Alexandra Microscopy and Microanalysis https://doi.org/10.1017/S1431927622000101	journal	February 2022
Advanced Platinum-Based Oxygen Reduction Electrocatalysts for Fuel Cells Huang, Lei; Zaman, Shahid; Tian, Xinlong Accounts of Chemical Research, Vol. 54, Issue 2 https://doi.org/10.1021/acs.accounts.0c00488	journal	January 2021
Determination of Grain-Boundary Structure and Electrostatic Characteristics in a SrTiO₃ Bicrystal by Four-Dimensional Electron Microscopy Yang, Chao; Wang, Yi; Sigle, Wilfried Nano Letters, Vol. 21, Issue 21, p. 9138-9145 https://doi.org/10.1021/acs.nanolett.1c02960	journal	October 2021
Citrate-Coated, Size-Tunable Octahedral Platinum Nanocrystals: A Novel Route for Advanced Electrocatalysts Moglianetti, Mauro; Solla-Gullón, José; Donati, Paolo ACS Applied Materials & Interfaces, Vol. 10, Issue 48 https://doi.org/10.1021/acsami.8b11774	journal	November 2018
Understanding the Grain Boundary Behavior of Bimetallic Platinum–Cobalt Alloy Nanowires toward Oxygen Electro-Reduction Kabiraz, Mrinal Kanti; Ruqia, Bibi; Kim, Jeonghyeon ACS Catalysis, Vol. 12, Issue 6 https://doi.org/10.1021/acscatal.1c05766	journal	March 2022
Defects do Catalysis: CO Monolayer Oxidation and Oxygen Reduction Reaction on Hollow PtNi/C Nanoparticles Dubau, Laetitia; Nelayah, Jaysen; Moldovan, Simona ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b01106	journal	June 2016
Implementing Structural Disorder as a Promising Direction for Improving the Stability of PtNi/C Nanoparticles Dubau, Laetitia; Nelayah, Jaysen; Asset, Tristan ACS Catalysis, Vol. 7, Issue 4 https://doi.org/10.1021/acscatal.7b00410	journal	March 2017
Toward the Decentralized Electrochemical Production of H ₂ O ₂ : A Focus on the Catalysis Yang, Sungeun; Verdaguer-Casadevall, Arnau; Arnarson, Logi ACS Catalysis, Vol. 8, Issue 5 https://doi.org/10.1021/acscatal.8b00217	journal	March 2018
Dopant Evolution in Electrocatalysts after Hydrogen Oxidation Reaction in an Alkaline Environment Yoo, Su-Hyun; Aota, Leonardo Shoji; Shin, Sangyong ACS Energy Letters, Vol. 8, Issue 8 https://doi.org/10.1021/acsenergylett.3c00842	journal	July 2023
Electrochemical Stability of Elemental Metal Nanoparticles Tang, Lei; Li, Xiaoqian; Cammarata, Robert C. Journal of the American Chemical Society, Vol. 132, Issue 33 https://doi.org/10.1021/ja104421t	journal	August 2010
Facile Synthesis of Gold Wavy Nanowires and Investigation of Their Growth Mechanism Zhu, Cun; Peng, Hsin-Chieh; Zeng, Jie Journal of the American Chemical Society, Vol. 134, Issue 50 https://doi.org/10.1021/ja3091214	journal	December 2012
Electrochemical Stability of Nanometer-Scale Pt Particles in Acidic Environments Tang, Lei; Han, Byungchan; Persson, Kristin Journal of the American Chemical Society, Vol. 132, Issue 2 https://doi.org/10.1021/ja9071496	journal	January 2010
Understanding Alkali Contamination in Colloidal Nanomaterials to Unlock Grain Boundary Impurity Engineering Kim, Se-Ho; Yoo, Su-Hyun; Chakraborty, Poulami Journal of the American Chemical Society, Vol. 144, Issue 2 https://doi.org/10.1021/jacs.1c11680	journal	January 2022
Energy Calculations Predict Nanoparticle Attachment Orientations and Asymmetric Crystal Formation Zhang, Hengzhong; Banfield, Jillian F. The Journal of Physical Chemistry Letters, Vol. 3, Issue 19 https://doi.org/10.1021/jz301161j	journal	September 2012
Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO ₂ Reduction to CO Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A. The Journal of Physical Chemistry Letters, Vol. 4, Issue 3 https://doi.org/10.1021/jz3021155	journal	January 2013
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Atomically ordered solute segregation behaviour in an oxide grain boundary Feng, Bin; Yokoi, Tatsuya; Kumamoto, Akihito Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11079	journal	March 2016
Considerations for the scaling-up of water splitting catalysts Kibsgaard, Jakob; Chorkendorff, Ib Nature Energy, Vol. 4, Issue 6 https://doi.org/10.1038/s41560-019-0407-1	journal	May 2019
Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis Chattot, Raphaël; Le Bacq, Olivier; Beermann, Vera Nature Materials, Vol. 17, Issue 9 https://doi.org/10.1038/s41563-018-0133-2	journal	July 2018
Microstructural origin of locally enhanced CO2 electroreduction activity on gold Mariano, Ruperto G.; Kang, Minkyung; Wahab, Oluwasegun J. Nature Materials, Vol. 20, Issue 7 https://doi.org/10.1038/s41563-021-00958-9	journal	March 2021
Electrochemical synthesis of hydrogen peroxide from water and oxygen Perry, Samuel C.; Pangotra, Dhananjai; Vieira, Luciana Nature Reviews Chemistry, Vol. 3, Issue 7 https://doi.org/10.1038/s41570-019-0110-6	journal	June 2019
Mastering the surface strain of platinum catalysts for efficient electrocatalysis He, Tianou; Wang, Weicong; Shi, Fenglei Nature, Vol. 598, Issue 7879 https://doi.org/10.1038/s41586-021-03870-z	journal	October 2021
A silver catalyst activated by stacking faults for the hydrogen evolution reaction Li, Zhe; Fu, Jian-Yu; Feng, Yi Nature Catalysis, Vol. 2, Issue 12 https://doi.org/10.1038/s41929-019-0365-9	journal	October 2019
Rational strain engineering in delafossite oxides for highly efficient hydrogen evolution catalysis in acidic media Podjaski, Filip; Weber, Daniel; Zhang, Siyuan Nature Catalysis, Vol. 3, Issue 1 https://doi.org/10.1038/s41929-019-0400-x	journal	December 2019
Scanning tunneling microscopy observations on the reconstructed Au(111) surface: Atomic structure, long-range superstructure, rotational domains, and surface defects Barth, J. V.; Brune, H.; Ertl, G. Physical Review B, Vol. 42, Issue 15 https://doi.org/10.1103/PhysRevB.42.9307	journal	November 1990
Effect of Nutrient Diffusion and Flow on Coral Morphology Kaandorp, Jaap A.; Lowe, Christopher P.; Frenkel, Daan Physical Review Letters, Vol. 77, Issue 11 https://doi.org/10.1103/PhysRevLett.77.2328	journal	September 1996
Effect of Strain on the Reactivity of Metal Surfaces Mavrikakis, M.; Hammer, B.; Nørskov, J. K. Physical Review Letters, Vol. 81, Issue 13 https://doi.org/10.1103/PhysRevLett.81.2819	journal	September 1998
Coincidence-site lattices and complete pattern-shift in cubic crystals Grimmer, H.; Bollmann, W.; Warrington, D. H. Acta Crystallographica Section A, Vol. 30, Issue 2 https://doi.org/10.1107/S056773947400043X	journal	March 1974
Grain Boundary Strengthening in Alumina by Rare Earth Impurities Buban, J. P. Science, Vol. 311, Issue 5758 https://doi.org/10.1126/science.1119839	journal	January 2006
Effect of Substrate Strain on Adsorption Gsell, M. Science, Vol. 280, Issue 5364 https://doi.org/10.1126/science.280.5364.717	journal	May 1998
Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors Calle-Vallejo, F.; Tymoczko, J.; Colic, V. Science, Vol. 350, Issue 6257 https://doi.org/10.1126/science.aab3501	journal	October 2015
Combining theory and experiment in electrocatalysis: Insights into materials design Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F. Science, Vol. 355, Issue 6321 https://doi.org/10.1126/science.aad4998	journal	January 2017
Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction Li, Mufan; Zhao, Zipeng; Cheng, Tao Science, Vol. 354, Issue 6318 https://doi.org/10.1126/science.aaf9050	journal	November 2016
Selective increase in CO ₂ electroreduction activity at grain-boundary surface terminations Mariano, Ruperto G.; McKelvey, Kim; White, Henry S. Science, Vol. 358, Issue 6367 https://doi.org/10.1126/science.aao3691	journal	November 2017
Tunable intrinsic strain in two-dimensional transition metal electrocatalysts Wang, Lei; Zeng, Zhenhua; Gao, Wenpei Science, Vol. 363, Issue 6429 https://doi.org/10.1126/science.aat8051	journal	February 2019
Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells Tian, Xinlong; Zhao, Xiao; Su, Ya-Qiong Science, Vol. 366, Issue 6467 https://doi.org/10.1126/science.aaw7493	journal	November 2019
Oriented attachment induces fivefold twins by forming and decomposing high-energy grain boundaries Song, Miao; Zhou, Gang; Lu, Ning Science, Vol. 367, Issue 6473 https://doi.org/10.1126/science.aax6511	journal	November 2019
Direct electrosynthesis of pure aqueous H 2 O 2 solutions up to 20% by weight using a solid electrolyte Xia, Chuan; Xia, Yang; Zhu, Peng Science, Vol. 366, Issue 6462 https://doi.org/10.1126/science.aay1844	journal	October 2019
Steam-created grain boundaries for methane C–H activation in palladium catalysts Huang, Weixin; Johnston-Peck, Aaron C.; Wolter, Trenton Science, Vol. 373, Issue 6562 https://doi.org/10.1126/science.abj5291	journal	September 2021

Similar Records

Nanoscale Alloying in Electrocatalysts

Journal Article · Wed Aug 19 00:00:00 EDT 2015 · Catalysts · OSTI ID:1441168

Grain‐Boundary‐Rich Noble Metal Nanoparticle Assemblies: Synthesis, Characterization, and Reactivity

Journal Article · Wed Jun 15 00:00:00 EDT 2022 · Advanced Functional Materials · OSTI ID:1872651

Core–Shell Nanostructured Cobalt–Platinum Electrocatalysts with Enhanced Durability

Journal Article · Mon Nov 27 23:00:00 EST 2017 · ACS Catalysis · OSTI ID:1485431

Related Subjects

36 MATERIALS SCIENCE
metals and alloys
metamaterials
structural properties

Grain boundary engineering for efficient and durable electrocatalysis

Citation Formats

References (50)

Similar Records

Related Subjects