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

Title: Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction

Abstract

Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble-metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face-centered-cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand-induced amorphization is realized by post-synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application.

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [4];  [5];  [1];  [1]; ORCiD logo [6]
  1. Nanyang Technological Univ. (Singapore)
  2. Nanyang Technological Univ. (Singapore); Chinese Academy of Sciences (CAS), Beijing (China)
  3. Center for Programmable MaterialsSchool of Materials Science and EngineeringNanyang Technological University 50 Nanyang Avenue Singapore 639798 Singapore
  4. Inst. of Chemical and Engineering Sciences (Singapore). A*STAR (Agency for Science, Technology and Research); Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Advanced Photon SourceArgonne National Laboratory 9700 South Cass Avenue Argonne IL 60439 USA
  6. Nanyang Technological Univ. (Singapore); City Univ. of Hong Kong (Hong Kong)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Nanyang Technological University (NTU); City University of Hong Kong
OSTI Identifier:
1603282
Alternate Identifier(s):
OSTI ID: 1598058; OSTI ID: 1630068
Report Number(s):
BNL-213658-2020-JAAM
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
SC0012704; AC02‐06CH11357; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 32; Journal Issue: 11; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; amorphization; electrocatalysis; ligand exchange; Pd nanomaterials

Citation Formats

Cheng, Hongfei, Yang, Nailiang, Liu, Guigao, Ge, Yiyao, Huang, Jingtao, Yun, Qinbai, Du, Yonghua, Sun, Cheng‐Jun, Chen, Bo, Liu, Jiawei, and Zhang, Hua. Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction. United States: N. p., 2020. Web. https://doi.org/10.1002/adma.201902964.
Cheng, Hongfei, Yang, Nailiang, Liu, Guigao, Ge, Yiyao, Huang, Jingtao, Yun, Qinbai, Du, Yonghua, Sun, Cheng‐Jun, Chen, Bo, Liu, Jiawei, & Zhang, Hua. Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction. United States. https://doi.org/10.1002/adma.201902964
Cheng, Hongfei, Yang, Nailiang, Liu, Guigao, Ge, Yiyao, Huang, Jingtao, Yun, Qinbai, Du, Yonghua, Sun, Cheng‐Jun, Chen, Bo, Liu, Jiawei, and Zhang, Hua. Thu . "Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction". United States. https://doi.org/10.1002/adma.201902964. https://www.osti.gov/servlets/purl/1603282.
@article{osti_1603282,
title = {Ligand-Exchange-Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction},
author = {Cheng, Hongfei and Yang, Nailiang and Liu, Guigao and Ge, Yiyao and Huang, Jingtao and Yun, Qinbai and Du, Yonghua and Sun, Cheng‐Jun and Chen, Bo and Liu, Jiawei and Zhang, Hua},
abstractNote = {Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble-metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face-centered-cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand-induced amorphization is realized by post-synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application.},
doi = {10.1002/adma.201902964},
journal = {Advanced Materials},
number = 11,
volume = 32,
place = {United States},
year = {2020},
month = {2}
}

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

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides
journal, December 2014

  • Indra, Arindam; Menezes, Prashanth W.; Sahraie, Nastaran Ranjbar
  • Journal of the American Chemical Society, Vol. 136, Issue 50
  • DOI: 10.1021/ja509348t

Dimeric [Mo 2 S 12 ] 2− Cluster: A Molecular Analogue of MoS 2 Edges for Superior Hydrogen-Evolution Electrocatalysis
journal, October 2015

  • Huang, Zhongjie; Luo, Wenjia; Ma, Lu
  • Angewandte Chemie International Edition, Vol. 54, Issue 50
  • DOI: 10.1002/anie.201507529

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide
journal, March 2016

  • Tran, Phong D.; Tran, Thu V.; Orio, Maylis
  • Nature Materials, Vol. 15, Issue 6
  • DOI: 10.1038/nmat4588

Characterization of Palladium Nanoparticles by Using X-ray Reflectivity, EXAFS, and Electron Microscopy
journal, January 2006

  • Sun, Yuan; Frenkel, Anatoly I.; Isseroff, Rebecca
  • Langmuir, Vol. 22, Issue 2
  • DOI: 10.1021/la052686k

Pd–Au bimetallic catalysts: understanding alloy effects from planar models and (supported) nanoparticles
journal, January 2012

  • Gao, Feng; Goodman, D. Wayne
  • Chemical Society Reviews, Vol. 41, Issue 24
  • DOI: 10.1039/c2cs35160a

Thiol Treatment Creates Selective Palladium Catalysts for Semihydrogenation of Internal Alkynes
journal, May 2018


Amorphous Molybdenum Sulfides as Hydrogen Evolution Catalysts
journal, July 2014

  • Morales-Guio, Carlos G.; Hu, Xile
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar5002022

A View from the Inside:  Complexity in the Atomic Scale Ordering of Supported Metal Nanoparticles
journal, December 2001

  • Frenkel, Anatoly I.; Hills, Charles W.; Nuzzo, Ralph G.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 51
  • DOI: 10.1021/jp012769j

Efficient hydrogen evolution reaction catalyzed by molybdenum carbide and molybdenum nitride nanocatalysts synthesized via the urea glass route
journal, January 2015

  • Ma, Liang; Ting, Louisa Rui Lin; Molinari, Valerio
  • Journal of Materials Chemistry A, Vol. 3, Issue 16
  • DOI: 10.1039/C5TA00139K

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

Lithiation-induced amorphization of Pd3P2S8 for highly efficient hydrogen evolution
journal, May 2018


Amorphous/Crystalline Hetero-Phase Pd Nanosheets: One-Pot Synthesis and Highly Selective Hydrogenation Reaction
journal, August 2018

  • Yang, Nailiang; Cheng, Hongfei; Liu, Xiaozhi
  • Advanced Materials, Vol. 30, Issue 39
  • DOI: 10.1002/adma.201803234

Recent advances in palladium-based electrocatalysts for fuel cell reactions and hydrogen evolution reaction
journal, November 2016


Electrochemical and X-ray Photoelectron Spectroscopy Characterization of Alkanethiols Adsorbed on Palladium Surfaces
journal, March 2009

  • Corthey, Gastón; Rubert, Aldo A.; Benitez, Guillermo A.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 16
  • DOI: 10.1021/jp9001077

Engineering the crystallinity of MoS 2 monolayers for highly efficient solar hydrogen production
journal, January 2017

  • Hai, Xiao; Zhou, Wei; Chang, Kun
  • Journal of Materials Chemistry A, Vol. 5, Issue 18
  • DOI: 10.1039/C7TA00953D

Vertical Growth of 2D Amorphous FePO 4 Nanosheet on Ni Foam: Outer and Inner Structural Design for Superior Water Splitting
journal, October 2017


EXAFS study of size dependence of atomic structure in palladium nanoparticles
journal, April 2014

  • Srabionyan, Vasiliy V.; Bugaev, Aram L.; Pryadchenko, Vasiliy V.
  • Journal of Physics and Chemistry of Solids, Vol. 75, Issue 4
  • DOI: 10.1016/j.jpcs.2013.12.012

Trends in the Exchange Current for Hydrogen Evolution
journal, January 2005

  • Nørskov, J. K.; Bligaard, T.; Logadottir, A.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1856988

Ni–Mo Nanopowders for Efficient Electrochemical Hydrogen Evolution
journal, January 2013

  • McKone, James R.; Sadtler, Bryce F.; Werlang, Caroline A.
  • ACS Catalysis, Vol. 3, Issue 2
  • DOI: 10.1021/cs300691m

Amorphous CuPt Alloy Nanotubes Induced by Na 2 S 2 O 3 as Efficient Catalysts for the Methanol Oxidation Reaction
journal, May 2016


Nanostructured hydrotreating catalysts for electrochemical hydrogen evolution
journal, January 2014

  • Morales-Guio, Carlos G.; Stern, Lucas-Alexandre; Hu, Xile
  • Chemical Society Reviews, Vol. 43, Issue 18
  • DOI: 10.1039/C3CS60468C

A Facile Synthesis of MPd (M = Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation
journal, January 2012

  • Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max N.
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl2045588

Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes <10 nm for application in CO oxidation
journal, October 2010


Photochemical Route for Accessing Amorphous Metal Oxide Materials for Water Oxidation Catalysis
journal, March 2013

  • Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D.
  • Science, Vol. 340, Issue 6128
  • DOI: 10.1126/science.1233638

Palladium-Based Nanomaterials: Synthesis and Electrochemical Applications
journal, September 2015