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
 

Boosting the H2–D2 Exchange Activity of Dilute Nanoporous Ti–Cu Catalysts through Oxidation–Reduction Cycle–Induced Restructuring

Journal Article · · Advanced Engineering Materials
 [1];  [2];  [3];  [4];  [5];  [5];  [4];  [2];  [3];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Harvard Univ., Cambridge, MA (United States)
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Ames Lab., Ames, IA (United States)
+ Show Author Affiliations
The use of nanoporous metals as catalysts has attracted significant interest in recent years. Their high-curvature, nanoscale ligaments provide not only high surface area but also a high density of undercoordinated step edge and kink sites. However, their long-term stability, especially at higher temperatures, is often limited by thermal coarsening and the associated loss of surface area. Herein, it is demonstrated that the nanoscale morphology of nanoporous Cu can be regenerated by applying oxidation/reduction cycles at 250 °C. Specifically, the morphological evolution and H2 dissociation activity of hierarchical nanoporous Cu catalysts doped with Ti during structural rearrangement triggered by oxidative and reductive atmospheres at elevated temperatures are studied. In addition to coarsening of the structure at elevated temperatures, oxidation at 400 °C causes an expansion of the ligaments. Further, subsequent reduction at 400 °C leads to the formation of particles and a drop in the H2 dissociation activity compared the fresh catalyst. However, performing the redox cycle at 250 °C reverses coarsening and boosts the H2 dissociation activity for the hydrogen–deuterium (H2–D2) reaction. Herein, the possibility to reverse coarsening is demonstrated, thereby mitigating the loss of activity frequently observed in nanoporous catalysts.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC52-07NA27344; SC0012573; SC0012704
OSTI ID:
1958562
Alternate ID(s):
OSTI ID: 1909052
Report Number(s):
BNL-224059-2023-JAAM
Journal Information:
Advanced Engineering Materials, Journal Name: Advanced Engineering Materials Journal Issue: 9 Vol. 25; ISSN 1438-1656
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Morphology, Oxidation, and Mechanical Behavior of Nanoporous Cu Foams journal November 2011
Nanoporous Metal Enhanced Catalytic Activities of Amorphous Molybdenum Sulfide for High-Efficiency Hydrogen Production journal February 2014
Tuning Surface Structure of 3D Nanoporous Gold by Surfactant-Free Electrochemical Potential Cycling journal September 2017
Beating Thermal Coarsening in Nanoporous Materials via High‐Entropy Design journal December 2019
Electron Energy Loss Spectroscopy (EELS) book January 2013
Single-Atom Catalysis: How Structure Influences Catalytic Performance journal February 2019
Dissociative adsorption of hydrogen on Cu(100) at low temperatures journal May 1993
Electronic factors determining the reactivity of metal surfaces journal December 1995
Surface segregation and oxidation of Ti in a V–Ti alloy journal December 2002
Coarsening of nanoporous Au: Relationship between structure and mechanical properties journal October 2015
In situ STEM/SEM study of the coarsening of nanoporous gold journal January 2019
Enhancement of catalytic activity by increasing surface area in heterogeneous catalysis journal December 2009
Impact of Surface Area in Evaluation of Catalyst Activity journal June 2018
Synthesis of copper and zinc nanostructures by discharges in liquid nitrogen journal March 2018
High resolution EELS of Cu–V oxides: Application to batteries materials journal July 2006
Dilute Pd/Au Alloy Nanoparticles Embedded in Colloid-Templated Porous SiO 2 : Stable Au-Based Oxidation Catalysts journal July 2019
Single-Atom Alloy Catalysis journal June 2020
Size Distribution Control of Copper Nanoparticles and Oxides: Effect of Wet-Chemical Redox Cycling journal January 2019
Dynamical Change of Valence States and Structure in NiCu 3 Nanoparticles during Redox Cycling journal January 2022
Ligament Evolution in Nanoporous Cu Films Prepared by Dealloying journal October 2018
Binary Transition-Metal Oxide Hollow Nanoparticles for Oxygen Evolution Reaction journal June 2018
Facet-Dependent Selectivity of Cu Catalysts in Electrochemical CO 2 Reduction at Commercially Viable Current Densities journal March 2020
Entropic Control of HD Exchange Rates over Dilute Pd-in-Au Alloy Nanoparticle Catalysts journal June 2021
Structural and Valence State Modification of Cobalt in CoPt Nanocatalysts in Redox Conditions journal November 2021
Reversible Redox Cycling of Well-Defined, Ultrasmall Cu/Cu 2 O Nanoparticles journal February 2017
The Titanium-Hydrogen System2 journal October 1956
Facilitating Hydrogen Dissociation over Dilute Nanoporous Ti–Cu Catalysts journal September 2022
Visualizing the Cu/Cu 2 O Interface Transition in Nanoparticles with Environmental Scanning Transmission Electron Microscopy journal December 2016
Understanding and Controlling Nanoporosity Formation for Improving the Stability of Bimetallic Fuel Cell Catalysts journal February 2013
Atomic Observation of Catalysis-Induced Nanopore Coarsening of Nanoporous Gold journal February 2014
Surface engineering of hierarchical platinum-cobalt nanowires for efficient electrocatalysis journal June 2016
A causal role of the right inferior frontal cortex in implementing strategies for multi-component behaviour journal April 2015
Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts journal December 2016
Morphological evolution of Pt-modified nanoporous gold after thermal coarsening in reductive and oxidative environments journal December 2020
The facet-dependent enhanced catalytic activity of Pd nanocrystals journal January 2014
Oxygen adsorption-induced surface segregation of titanium oxide by activation in carbon nanofibers for maximizing photocatalytic performance journal January 2015
Deactivation of bimetallic nickel–copper alloy catalysts in thermocatalytic decomposition of methane journal January 2018
Excellent degradation performance of 3D hierarchical nanoporous structures of copper towards organic pollutants journal January 2018
Resolving single Cu nanoparticle oxidation and Kirkendall void formation with in situ plasmonic nanospectroscopy and electrodynamic simulations journal January 2019
Stabilization of a nanoporous NiCu dilute alloy catalyst for non-oxidative ethanol dehydrogenation journal January 2020
The oxidation state of copper in bimetallic (Pt–Cu, Pd–Cu) catalysts during water denitration journal January 2012
Nanoporous Materials as New Engineered Catalysts for the Synthesis of Green Fuels journal March 2015

Figures / Tables (10)

Figure 1(p. 5)figure Figure 1
Figure 2(p. 6)figure Figure 2
Figure 3(p. 7)figure Figure 3
Figure 4(p. 8)figure Figure 4
Figure 5(p. 9)figure Figure 5
Figure 6(p. 10)figure Figure 6
Figure 7(p. 11)figure Figure 7
Table 1(p. 12)table Table 1
Figure 8(p. 13)figure Figure 8
Table 2(p. 13)table Table 2

Similar Records

Related Subjects

36 MATERIALS SCIENCE
H2–D2 exchange reaction
X-ray photoelectron spectroscopy
catalysis
in situ
nanoporous material
transmission electron microscopy