skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Crystallinity Dependence of Ruthenium Nanocatalyst toward Hydrogen Evolution Reaction

Abstract

The development of highly active and durable inexpensive electrocatalysts for hydrogen evolution reaction (HER) is still a formidable challenge. Herein, an ordered hexagonal-closed-packed (hcp)-Ru nanocrystal coated with a thin layer of N-doped carbon (hcp-Ru@NC) was fabricated through the thermal annealing of polydopamine (PDA)-coated Ru nanoparticle (RuNP@PDA). As an alternative to Pt/C catalyst, the hcp-Ru@NC nanocatalyst exhibited the small overpotential of 27.5 mV at a current density of 10 mA cm–2, as well as long-term stability for HER in acid media. Interestingly, the HER performance of hcp-Ru is highly dependent on its crystallinity. The calculation from density functional theory (DFT) revealed that the difference in HER activity over various exposed surface causes the crystallinity-dependent property of hcp-Ru. The results of this study provided clues to guide the design of Ru-based inexpensive HER electrocatalyst.

Authors:
 [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [3];  [2]; ORCiD logo [2]
  1. Changzhou Univ., Changzhou, Jiangsu (China). School of Petrochemical Engineering, Jiangsu Key Lab. of Advanced Materials and Technology
  2. Georgia Inst. of Technology, Atlanta, GA (United States). School of Materials Science and Engineering
  3. Nanjing Univ. of Information & Technology, Nanjing, Jiangsu (China). School of Environmental Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1543701
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; Ruthenium nanocatalyst; crystallinity-dependence; hydrogen evolution reaction; N-doped graphene; electrocatalyst

Citation Formats

Li, Yutong, Zhang, Lei A., Qin, Yong, Chu, Fuqiang, Kong, Yong, Tao, Yongxin, Li, Yongxin, Bu, Yunfei, Ding, Dong, and Liu, Meilin. Crystallinity Dependence of Ruthenium Nanocatalyst toward Hydrogen Evolution Reaction. United States: N. p., 2018. Web. https://doi.org/10.1021/acscatal.8b01609.
Li, Yutong, Zhang, Lei A., Qin, Yong, Chu, Fuqiang, Kong, Yong, Tao, Yongxin, Li, Yongxin, Bu, Yunfei, Ding, Dong, & Liu, Meilin. Crystallinity Dependence of Ruthenium Nanocatalyst toward Hydrogen Evolution Reaction. United States. https://doi.org/10.1021/acscatal.8b01609
Li, Yutong, Zhang, Lei A., Qin, Yong, Chu, Fuqiang, Kong, Yong, Tao, Yongxin, Li, Yongxin, Bu, Yunfei, Ding, Dong, and Liu, Meilin. Tue . "Crystallinity Dependence of Ruthenium Nanocatalyst toward Hydrogen Evolution Reaction". United States. https://doi.org/10.1021/acscatal.8b01609. https://www.osti.gov/servlets/purl/1543701.
@article{osti_1543701,
title = {Crystallinity Dependence of Ruthenium Nanocatalyst toward Hydrogen Evolution Reaction},
author = {Li, Yutong and Zhang, Lei A. and Qin, Yong and Chu, Fuqiang and Kong, Yong and Tao, Yongxin and Li, Yongxin and Bu, Yunfei and Ding, Dong and Liu, Meilin},
abstractNote = {The development of highly active and durable inexpensive electrocatalysts for hydrogen evolution reaction (HER) is still a formidable challenge. Herein, an ordered hexagonal-closed-packed (hcp)-Ru nanocrystal coated with a thin layer of N-doped carbon (hcp-Ru@NC) was fabricated through the thermal annealing of polydopamine (PDA)-coated Ru nanoparticle (RuNP@PDA). As an alternative to Pt/C catalyst, the hcp-Ru@NC nanocatalyst exhibited the small overpotential of 27.5 mV at a current density of 10 mA cm–2, as well as long-term stability for HER in acid media. Interestingly, the HER performance of hcp-Ru is highly dependent on its crystallinity. The calculation from density functional theory (DFT) revealed that the difference in HER activity over various exposed surface causes the crystallinity-dependent property of hcp-Ru. The results of this study provided clues to guide the design of Ru-based inexpensive HER electrocatalyst.},
doi = {10.1021/acscatal.8b01609},
journal = {ACS Catalysis},
number = 7,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science

Figures / Tables:

Scheme 1 Scheme 1: Illustration of the fabricating process of hcp-Ru@NC on NG.

Save / Share:

Works referenced in this record:

Cleaner energy for sustainable future
journal, July 2009

  • Dovì, Vincenzo Giorgio; Friedler, Ferenc; Huisingh, Donald
  • Journal of Cleaner Production, Vol. 17, Issue 10
  • DOI: 10.1016/j.jclepro.2009.02.001

Towards sustainable production of clean energy carriers from biomass resources
journal, December 2012


Clean energy new deal for a sustainable world: from non-CO2 generating energy sources to greener electrochemical storage devices
journal, January 2011

  • Poizot, Philippe; Dolhem, Franck
  • Energy & Environmental Science, Vol. 4, Issue 6
  • DOI: 10.1039/c0ee00731e

The properties of hydrogen as fuel tomorrow in sustainable energy system for a cleaner planet
journal, July 2005


Hydrogen futures: toward a sustainable energy system
journal, March 2002


Hydrogen Production. Green Algae as a Source of Energy
journal, November 2001

  • Melis, Anastasios; Happe, Thomas
  • Plant Physiology, Vol. 127, Issue 3, p. 740-748
  • DOI: 10.1104/pp.010498

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions
journal, January 2015

  • Jiao, Yan; Zheng, Yao; Jaroniec, Mietek
  • Chemical Society Reviews, Vol. 44, Issue 8
  • DOI: 10.1039/C4CS00470A

Advancing the Electrochemistry of the Hydrogen-Evolution Reaction through Combining Experiment and Theory
journal, November 2014

  • Zheng, Yao; Jiao, Yan; Jaroniec, Mietek
  • Angewandte Chemie International Edition, Vol. 54, Issue 1
  • DOI: 10.1002/anie.201407031

Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
journal, January 2007

  • Skúlason, Egill; Karlberg, Gustav S.; Rossmeisl, Jan
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 25
  • DOI: 10.1039/B700099E

Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers
journal, March 2008


In situ Cobalt–Cobalt Oxide/N-Doped Carbon Hybrids As Superior Bifunctional Electrocatalysts for Hydrogen and Oxygen Evolution
journal, February 2015

  • Jin, Haiyan; Wang, Jing; Su, Diefeng
  • Journal of the American Chemical Society, Vol. 137, Issue 7
  • DOI: 10.1021/ja5127165

C and N Hybrid Coordination Derived Co–C–N Complex as a Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction
journal, November 2015

  • Wang, Zhong-Li; Hao, Xian-Feng; Jiang, Zheng
  • Journal of the American Chemical Society, Vol. 137, Issue 48
  • DOI: 10.1021/jacs.5b09021

Hollow Cobalt-Based Bimetallic Sulfide Polyhedra for Efficient All-pH-Value Electrochemical and Photocatalytic Hydrogen Evolution
journal, January 2016

  • Huang, Zhen-Feng; Song, Jiajia; Li, Ke
  • Journal of the American Chemical Society, Vol. 138, Issue 4
  • DOI: 10.1021/jacs.5b11986

Cobalt-Embedded Nitrogen-Rich Carbon Nanotubes Efficiently Catalyze Hydrogen Evolution Reaction at All pH Values
journal, March 2014

  • Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup
  • Angewandte Chemie International Edition, Vol. 53, Issue 17
  • DOI: 10.1002/anie.201311111

Porous Cobalt Phosphide Polyhedrons with Iron Doping as an Efficient Bifunctional Electrocatalyst
journal, August 2017


Macroporous Inverse Opal-like Mo x C with Incorporated Mo Vacancies for Significantly Enhanced Hydrogen Evolution
journal, July 2017


Improved hydrogen oxidation reaction under alkaline conditions by ruthenium–iridium alloyed nanoparticles
journal, January 2016

  • Ohyama, J.; Kumada, D.; Satsuma, A.
  • Journal of Materials Chemistry A, Vol. 4, Issue 41
  • DOI: 10.1039/C6TA05517F

Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium
journal, June 2017


Mesoporous Ruthenium/Ruthenium Oxide Thin Films: Active Electrocatalysts for the Oxygen Evolution Reaction
journal, July 2017

  • Kibsgaard, Jakob; Hellstern, Thomas R.; Choi, Shin-Jung
  • ChemElectroChem, Vol. 4, Issue 10
  • DOI: 10.1002/celc.201700334

Carbon Monoxide Hydrogenation on the Ru(001) Surface at Low Temperature Using Gas-Phase Atomic Hydrogen: Spectroscopic Evidence for the Carbonyl Insertion Mechanism on a Transition Metal Surface
journal, March 1995

  • Mitchell, William J.; Xie, Jun; Jachimowski, Thomas A.
  • Journal of the American Chemical Society, Vol. 117, Issue 9
  • DOI: 10.1021/ja00114a025

Ruthenium/Graphene-like Layered Carbon Composite as an Efficient Hydrogen Evolution Reaction Electrocatalyst
journal, December 2016

  • Chen, Zhe; Lu, Jinfeng; Ai, Yuejie
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 51
  • DOI: 10.1021/acsami.6b09331

A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions
journal, January 2017

  • Drouet, S.; Creus, J.; Collière, V.
  • Chem. Commun., Vol. 53, Issue 85
  • DOI: 10.1039/C7CC05615J

Size-Dependent Activity of Palladium Nanoparticles: Efficient Conversion of CO 2 into Formate at Low Overpotentials
journal, March 2017


Crystallinity-Modulated Electrocatalytic Activity of a Nickel(II) Borate Thin Layer on Ni 3 B for Efficient Water Oxidation
journal, May 2017

  • Jiang, Wen-Jie; Niu, Shuai; Tang, Tang
  • Angewandte Chemie International Edition, Vol. 56, Issue 23
  • DOI: 10.1002/anie.201703183

An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction
journal, February 2017

  • Mahmood, Javeed; Li, Feng; Jung, Sun-Min
  • Nature Nanotechnology, Vol. 12, Issue 5
  • DOI: 10.1038/nnano.2016.304

High Electrocatalytic Hydrogen Evolution Activity of an Anomalous Ruthenium Catalyst
journal, December 2016

  • Zheng, Yao; Jiao, Yan; Zhu, Yihan
  • Journal of the American Chemical Society, Vol. 138, Issue 49
  • DOI: 10.1021/jacs.6b11291

Highly Durable and Active PtFe Nanocatalyst for Electrochemical Oxygen Reduction Reaction
journal, December 2015

  • Chung, Dong Young; Jun, Samuel Woojoo; Yoon, Gabin
  • Journal of the American Chemical Society, Vol. 137, Issue 49
  • DOI: 10.1021/jacs.5b09653

Porous γ -Fe 2 O 3 spheres coated with N-doped carbon from polydopamine as Li-ion battery anode materials
journal, April 2016


Confined Pyrolysis within Metal–Organic Frameworks To Form Uniform Ru 3 Clusters for Efficient Oxidation of Alcohols
journal, July 2017

  • Ji, Shufang; Chen, Yuanjun; Fu, Qiang
  • Journal of the American Chemical Society, Vol. 139, Issue 29
  • DOI: 10.1021/jacs.7b05018

Crosslinking Graphene Oxide into Robust 3D Porous N-Doped Graphene
journal, August 2015


Amorphous ruthenium nanoparticles for enhanced electrochemical water splitting
journal, September 2015


Growth Confined by the Nitrogen Source: Synthesis of Pure Metal Nitride Nanoparticles in Mesoporous Graphitic Carbon Nitride
journal, January 2007


Nanocrystalline Ni 5 P 4 : a hydrogen evolution electrocatalyst of exceptional efficiency in both alkaline and acidic media
journal, January 2015

  • Laursen, A. B.; Patraju, K. R.; Whitaker, M. J.
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE02940B

Atomic cobalt on nitrogen-doped graphene for hydrogen generation
journal, October 2015

  • Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9668

High Catalytic Activity of Nitrogen and Sulfur Co-Doped Nanoporous Graphene in the Hydrogen Evolution Reaction
journal, December 2014

  • Ito, Yoshikazu; Cong, Weitao; Fujita, Takeshi
  • Angewandte Chemie International Edition, Vol. 54, Issue 7
  • DOI: 10.1002/anie.201410050

A Review of Phosphide-Based Materials for Electrocatalytic Hydrogen Evolution
journal, October 2015


Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction
journal, January 2014

  • Xiao, Peng; Sk, Mahasin Alam; Thia, Larissa
  • Energy Environ. Sci., Vol. 7, Issue 8
  • DOI: 10.1039/C4EE00957F

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Co,N-codoped graphene as efficient electrocatalyst for hydrogen evolution reaction: Insight into the active centre
journal, September 2017


    Works referencing / citing this record:

    Mo modulation effect on the hydrogen binding energy of hexagonal-close-packed Ru for hydrogen evolution
    journal, January 2019

    • Zhang, Zhen; Li, Ping; Wang, Qi
    • Journal of Materials Chemistry A, Vol. 7, Issue 6
    • DOI: 10.1039/c8ta11251g

    Metallic ruthenium-based nanomaterials for electrocatalytic and photocatalytic hydrogen evolution
    journal, January 2019

    • Han, Sumei; Yun, Qinbai; Tu, Siyang
    • Journal of Materials Chemistry A, Vol. 7, Issue 43
    • DOI: 10.1039/c9ta06178a

    Engineering heterometallic bonding in bimetallic electrocatalysts: towards optimized hydrogen oxidation and evolution reactions
    journal, January 2020

    • Huang, Chiu-Ping; Tsai, Meng-Che; Wang, Xiao-Ming
    • Catalysis Science & Technology, Vol. 10, Issue 3
    • DOI: 10.1039/c9cy02181g

    Cable-like Ru/WNO@C nanowires for simultaneous high-efficiency hydrogen evolution and low-energy consumption chlor-alkali electrolysis
    journal, January 2019

    • Zhang, Lu-Nan; Lang, Zhong-Ling; Wang, Yong-Hui
    • Energy & Environmental Science, Vol. 12, Issue 8
    • DOI: 10.1039/c9ee01647c

    An ultrafine ruthenium nanocrystal with extremely high activity for the hydrogen evolution reaction in both acidic and alkaline media
    journal, January 2018

    • Li, Yutong; Chu, Fuqiang; Liu, Yang
    • Chemical Communications, Vol. 54, Issue 93
    • DOI: 10.1039/c8cc08276f

    General Synthesis of Ultrathin Metal Borate Nanomeshes Enabled by 3D Bark‐Like N‐Doped Carbon for Electrocatalysis
    journal, June 2019


    Shaping well-defined noble-metal-based nanostructures for fabricating high-performance electrocatalysts: advances and perspectives
    journal, January 2019

    • Yin, Hai-Jing; Zhou, Jun-Hao; Zhang, Ya-Wen
    • Inorganic Chemistry Frontiers, Vol. 6, Issue 10
    • DOI: 10.1039/c9qi00689c

    Mechanochemically Assisted Synthesis of Ruthenium Clusters Embedded in Mesoporous Carbon for an Efficient Hydrogen Evolution Reaction
    journal, April 2019


    Interface engineering of Ni 5 P 2 nanoparticles and a mesoporous PtRu film heterostructure on Ni foam for enhanced hydrogen evolution
    journal, September 2019


    Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media
    journal, February 2019


    Oriented arrays of Co 3 O 4 nanoneedles for highly efficient electrocatalytic water oxidation
    journal, January 2019

    • Zhang, Jun-Jun; Zhao, Tian-Jian; Wang, Hong-Hui
    • Chemical Communications, Vol. 55, Issue 27
    • DOI: 10.1039/c9cc00791a

    Overall water-splitting reaction efficiently catalyzed by a novel bi-functional Ru/Ni 3 N–Ni electrode
    journal, January 2020

    • Liu, Zong; Zha, Meng; Wang, Quan
    • Chemical Communications, Vol. 56, Issue 15
    • DOI: 10.1039/c9cc09187d

    Recent advances in ruthenium-based electrocatalysts for the hydrogen evolution reaction
    journal, January 2020

    • Bae, Seo-Yoon; Mahmood, Javeed; Jeon, In-Yup
    • Nanoscale Horizons, Vol. 5, Issue 1
    • DOI: 10.1039/c9nh00485h

    Controllable fabrication of uniform ruthenium phosphide nanocrystals for the hydrogen evolution reaction
    journal, January 2019

    • Li, Yutong; Chu, Fuqiang; Bu, Yunfei
    • Chemical Communications, Vol. 55, Issue 54
    • DOI: 10.1039/c9cc03668g

    Electrospun Ru–RuO 2 /MoO 3 carbon nanorods with multi-active components: a Pt-like catalyst for the hydrogen evolution reaction
    journal, January 2020

    • Fan, Libing; Li, Qun; Wang, Dewen
    • Chemical Communications, Vol. 56, Issue 5
    • DOI: 10.1039/c9cc08466e

    Hollow Nanotube Ru/Cu 2+1 O Supported on Copper Foam as a Bifunctional Catalyst for Overall Water Splitting
    journal, November 2019


    Palladium structure engineering induced by electrochemical H intercalation boosts hydrogen evolution catalysis
    journal, January 2019

    • Wang, Guangxia; Liu, Jinyang; Sui, Yongming
    • Journal of Materials Chemistry A, Vol. 7, Issue 24
    • DOI: 10.1039/c9ta03971f

    Nitrogen Atoms as Stabilizers and Promoters for Ru‐Cluster‐Catalyzed Alkaline Water Splitting
    journal, July 2019


    Electronic structure engineering of single atomic Ru by Ru nanoparticles to enable enhanced activity for alkaline water reduction
    journal, January 2019

    • Hu, Qi; Li, Guomin; Huang, Xiaowan
    • Journal of Materials Chemistry A, Vol. 7, Issue 33
    • DOI: 10.1039/c9ta06244k

    Formation of Branched Ruthenium Nanoparticles for Improved Electrocatalysis of Oxygen Evolution Reaction
    journal, March 2019

    • Poerwoprajitno, Agus R.; Gloag, Lucy; Benedetti, Tania M.
    • Small, Vol. 15, Issue 17
    • DOI: 10.1002/smll.201804577

    Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting
    journal, January 2019

    • Hu, Congling; Zhang, Lei; Gong, Jinlong
    • Energy & Environmental Science, Vol. 12, Issue 9
    • DOI: 10.1039/c9ee01202h

    Ruthenium Nanoparticles for Catalytic Water Splitting
    journal, May 2019

    • Creus, Jordi; De Tovar, Jonathan; Romero, Nuria
    • ChemSusChem, Vol. 12, Issue 12
    • DOI: 10.1002/cssc.201900393

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