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Title: Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon

Abstract

In this paper we report the use of phosphorus-doped carbon (P-C) as support to grow ultrasmall (1–3 nm) and ligand-free precious metal nanocrystals (PMNCs) via chemical reduction. We show that the valence states of surface phosphorus species are critical in tuning the affinity between the carbon support and metal precursors, which rationally controls the loading size and uniformity of resultant PMNCs. Five kinds of PMNCs, including Ru, Ag, Au, Rh, and Pd, were grown in situ to demonstrate the key role of surface phosphorus sites on the P-C support. As a proof-of-concept application, Ru nanocatalysts with an average diameter of 1.0±0.2 nm supported on P-C were examined for the electrocatalytic hydrogen evolution reaction (HER). Ultrasmall and ligand-free Ru nanocatalysts exhibited superior HER activity and stability compared to its counterparts with surface agents or larger sizes. An overpotential of 27.6 mV (vs. reversible hydrogen electrode) for Ru nanocatalysts was achieved at a current density of 10 mA cm -2. This novel method opens a new avenue to immobilize ligand-free and well-dispersed PMNCs on carbon; and, more importantly, it provides a new library of supported PMNCs with high catalytic activity.

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [2];  [2]
  1. Nanjing Normal Univ. (People's Republic of China); Univ. of Connecticut, Storrs, CT (United States)
  2. Univ. of Connecticut, Storrs, CT (United States)
Publication Date:
Research Org.:
Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE); National Science Foundation (NSF); University of Connecticut; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Jiangsu Specially Appointed Professor Plan; Green Emulsions Micelles and Surfactants (GEMS) Center
OSTI Identifier:
1597803
Alternate Identifier(s):
OSTI ID: 1418421
Grant/Contract Number:  
FG02-86ER13622; CBET-1705566
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 11; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogen evolution reaction; phosphorus-doped carbon; ruthenium; nanocatalysts; nanomaterials

Citation Formats

Liu, Ben, Jin, Lei, Zhong, Wei, Lopes, Aaron, Suib, Steven L., and He, Jie. Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon. United States: N. p., 2018. Web. doi:10.1002/chem.201705504.
Liu, Ben, Jin, Lei, Zhong, Wei, Lopes, Aaron, Suib, Steven L., & He, Jie. Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon. United States. doi:10.1002/chem.201705504.
Liu, Ben, Jin, Lei, Zhong, Wei, Lopes, Aaron, Suib, Steven L., and He, Jie. Mon . "Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon". United States. doi:10.1002/chem.201705504. https://www.osti.gov/servlets/purl/1597803.
@article{osti_1597803,
title = {Ultrafine and Ligand-Free Precious Metal (Ru, Ag, Au, Rh and Pd) Nanoclusters Supported on Phosphorus-Doped Carbon},
author = {Liu, Ben and Jin, Lei and Zhong, Wei and Lopes, Aaron and Suib, Steven L. and He, Jie},
abstractNote = {In this paper we report the use of phosphorus-doped carbon (P-C) as support to grow ultrasmall (1–3 nm) and ligand-free precious metal nanocrystals (PMNCs) via chemical reduction. We show that the valence states of surface phosphorus species are critical in tuning the affinity between the carbon support and metal precursors, which rationally controls the loading size and uniformity of resultant PMNCs. Five kinds of PMNCs, including Ru, Ag, Au, Rh, and Pd, were grown in situ to demonstrate the key role of surface phosphorus sites on the P-C support. As a proof-of-concept application, Ru nanocatalysts with an average diameter of 1.0±0.2 nm supported on P-C were examined for the electrocatalytic hydrogen evolution reaction (HER). Ultrasmall and ligand-free Ru nanocatalysts exhibited superior HER activity and stability compared to its counterparts with surface agents or larger sizes. An overpotential of 27.6 mV (vs. reversible hydrogen electrode) for Ru nanocatalysts was achieved at a current density of 10 mA cm-2. This novel method opens a new avenue to immobilize ligand-free and well-dispersed PMNCs on carbon; and, more importantly, it provides a new library of supported PMNCs with high catalytic activity.},
doi = {10.1002/chem.201705504},
journal = {Chemistry - A European Journal},
number = 11,
volume = 24,
place = {United States},
year = {2018},
month = {1}
}

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