Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

The role of ligands in atomically precise nanocluster-catalyzed CO2 electrochemical reduction

Journal Article · · Nanoscale
DOI:https://doi.org/10.1039/d0nr07832h· OSTI ID:1765359
 [1];  [2];  [3];  [4];  [2];  [3]
  1. Carnegie Mellon Univ., Pittsburgh, PA (United States); National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
  2. Univ. of Pittsburgh, PA (United States)
  3. Carnegie Mellon Univ., Pittsburgh, PA (United States)
  4. National Energy Technology Lab. (NETL), Pittsburgh, PA (United States)
+ Show Author Affiliations
Ligand effects are of major interest in catalytic reactions owing to their potential critical role in determining the reaction activity and selectivity. Herein, we report ligand effects in the CO2 electrochemical reduction reaction at the atomic level with three unique Au25 nanoclusters comprising the same kernel but different protecting ligands (–XR, where X = S or Se, and R represents the carbon tail). It is observed that a change in the carbon tail shows no obvious impact on the catalytic selectivity and activity, but the anchoring atom (X = S or Se) strongly affects the electrocatalytic selectivity. Specifically, the S site acts as the active site and sustains CO selectivity, while the Se site shows a higher tendency of hydrogen evolution. Density functional theory (DFT) calculations reveal that the energy penalty associated with the *COOH formation is lower on the S site by 0.26 eV compared to that on the Se site. Additionally, the formation energy of the product (*CO) is lower on the sulfur-based Au nanocluster by 0.43 eV. Furthermore, we attribute these energetic differences to the higher electron density on the sulfur sites of the Au nanocluster, resulting in a modified bonding character of the reaction intermediates that reduce the energetic penalty for the *COOH and *CO formation. Overall, this work demonstrates that S/Se atoms at the metal–ligand interface can play an important role in determining the overall electrocatalytic performance of Au nanoclusters.
Research Organization:
National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Fossil Energy (FE)
Grant/Contract Number:
AC02-05CH11231; FE0026825
OSTI ID:
1765359
Alternate ID(s):
OSTI ID: 2325174
Report Number(s):
10.1039/D0NR07832H
Journal Information:
Nanoscale, Journal Name: Nanoscale Journal Issue: 4 Vol. 13; ISSN 2040-3364
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (37)

A Surface Reconstruction Route to High Productivity and Selectivity in CO 2 Electroreduction toward C 2+ Hydrocarbons journal October 2018
Boosting Electrochemical CO 2 Reduction on Metal–Organic Frameworks via Ligand Doping journal February 2019
Au 130− x Ag x Nanoclusters with Non‐Metallicity: A Drum of Silver‐Rich Sites Enclosed in a Marks‐Decahedral Cage of Gold‐Rich Sites journal November 2019
Noble and valuable: atomically precise gold nanoclusters journal October 2015
Elucidating the stability of ligand-protected Au nanoclusters under electrochemical reduction of CO2 journal March 2020
Hydrophobically made Ag nanoclusters with enhanced performance for CO2 aqueous electroreduction journal November 2020
Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles journal October 2018
Toward Active-Site Tailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters with Crystallographic Structures journal September 2020
Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities journal September 2016
Efficient Electrochemical CO 2 Conversion Powered by Renewable Energy journal July 2015
Monopalladium Substitution in Gold Nanoclusters Enhances CO 2 Electroreduction Activity and Selectivity journal September 2020
Influence of Atomic-Level Morphology on Catalysis: The Case of Sphere and Rod-Like Gold Nanoclusters for CO 2 Electroreduction journal April 2018
Opportunities and Challenges in CO 2 Reduction by Gold- and Silver-Based Electrocatalysts: From Bulk Metals to Nanoparticles and Atomically Precise Nanoclusters journal January 2018
Tailoring the Electronic and Catalytic Properties of Au 25 Nanoclusters via Ligand Engineering journal July 2016
Experimental and Computational Investigation of Au 25 Clusters and CO 2 : A Unique Interaction and Enhanced Electrocatalytic Activity journal June 2012
Particle Size Effects in the Catalytic Electroreduction of CO 2 on Cu Nanoparticles journal May 2014
Correlating the Crystal Structure of A Thiol-Protected Au25 Cluster and Optical Properties
  • Zhu, Manzhou; Aikens, Christine M.; Hollander, Frederick J.
  • Journal of the American Chemical Society, Vol. 130, Issue 18, p. 5883-5885 https://doi.org/10.1021/ja801173r
journal May 2008
A Molecular Surface Functionalization Approach to Tuning Nanoparticle Electrocatalysts for Carbon Dioxide Reduction journal June 2016
Sharp Transition from Nonmetallic Au 246 to Metallic Au 279 with Nascent Surface Plasmon Resonance journal April 2018
Synergistic geometric and electronic effects for electrochemical reduction of carbon dioxide using gold–copper bimetallic nanoparticles journal September 2014
Catalysis of the electrochemical reduction of carbon dioxide journal January 2013
Crystal structure of Au 25 (SePh) 18 nanoclusters and insights into their electronic, optical and catalytic properties journal January 2014
Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets journal January 2016
Diphosphine-protected ultrasmall gold nanoclusters: opened icosahedral Au 13 and heart-shaped Au 8 clusters journal January 2018
Elucidating the active sites for CO 2 electroreduction on ligand-protected Au 25 nanoclusters journal January 2018
Hydride-induced ligand dynamic and structural transformation of gold nanoclusters during a catalytic reaction journal January 2018
Morphology-controlled Au nanostructures for efficient and selective electrochemical CO 2 reduction journal January 2018
Size dependent selectivity of Cu nano-octahedra catalysts for the electrochemical reduction of CO 2 to CH 4 journal January 2019
[Au 18 (dppm) 6 Cl 4 ] 4+ : a phosphine-protected gold nanocluster with rich charge states journal January 2019
Monodisperse nanoparticles for catalysis and nanomedicine journal January 2019
Engineering ultrasmall metal nanoclusters for photocatalytic and electrocatalytic applications journal January 2019
Understanding the role of functional groups of thiolate ligands in electrochemical CO 2 reduction over Au(111) from first-principles journal January 2019
Towards elucidating structure of ligand-protected nanoclusters journal January 2020
Gold nanoclusters as electrocatalysts: size, ligands, heteroatom doping, and charge dependences journal January 2020
AgPd nanoparticles for electrocatalytic CO 2 reduction: bimetallic composition-dependent ligand and ensemble effects journal January 2020
Metal–ligand bond strength determines the fate of organic ligands on the catalyst surface during the electrochemical CO 2 reduction reaction journal January 2020
Green synthesis of silver nanoclusters supported on carbon nanodots: enhanced photoluminescence and high catalytic activity for oxygen reduction reaction journal January 2013

Similar Records

Ligand removal energetics control CO2 electroreduction selectivity on atomically precise, ligated alloy nanoclusters
Journal Article · Thu Apr 28 20:00:00 EDT 2022 · Environmental Science: Nano · OSTI ID:1982249
Dissecting Critical Factors for Electrochemical CO2 Reduction on Atomically Precise Au Nanoclusters
Journal Article · Mon Oct 24 20:00:00 EDT 2022 · Angewandte Chemie (International Edition) · OSTI ID:1899592

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY