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:

Liu, Ben  ^[1];

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Jin, Lei ^[2]; Zhong, Wei ^[2]; Lopes, Aaron ^[2]; Suib, Steven L. ^[2]; He, Jie ^[2]

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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:

Mon Jan 08 00:00:00 EST 2018

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). Chemical Sciences, Geosciences, and 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