skip to main content

DOE PAGESDOE PAGES

Title: Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches

Alloy nanoparticle catalysts are known to afford unique activities that can differ markedly from their parent metals, but there remains a generally limited understanding of the nature of their atomic (and likely dynamic) structures as exist in heterogeneously supported forms under reaction conditions. Notably unclear is the nature of their active sites and the details of the varying oxidation states and atomic arrangements of the catalytic components during chemical reactions. In this work, we describe multimodal methods that provide a quantitative characterization of the complex heterogeneity present in the chemical and electronic speciations of Pt–Ni bimetallic catalysts supported on mesoporous silica during the reverse water gas shift reaction. The analytical protocols involved a correlated use of in situ X-ray Absorption Spectroscopy (XAS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), complimented by ex-situ aberration corrected Scanning Transmission Electron Microscopy (STEM). The data reveal that complex reactions occur between the metals and support in this system under operando conditions. These reactions, and the specific impacts of strong metal–silica bonding interactions, prevent the formation of alloy phases containing Ni–Ni bonds. This feature of structure provides high activity and selectivity for the reduction of CO 2 to carbon monoxide without significant competitive levelsmore » of methanation. In conclusion, we show how these chemistries evolve to the active state of the catalyst: bimetallic nanoparticles possessing an intermetallic structure (the active phase) that are conjoined with Ni-rich, metal-silicate species.« less
Authors:
ORCiD logo [1] ;  [2] ;  [1] ;  [3] ;  [3] ;  [4] ; ORCiD logo [5] ;  [5] ;  [5] ; ORCiD logo [6] ; ORCiD logo [7] ;  [1] ; ORCiD logo [8]
  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry
  2. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry; Columbia Univ., New York, NY (United States). Dept. of Chemical Enginerring
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering
  8. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
Publication Date:
Report Number(s):
BNL-207996-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 5; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bimetallic nanoparticles; catalysis; DRIFTS; nickel; platinum; reverse water gas shift; STEM; XAS
OSTI Identifier:
1466591

Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., and Frenkel, Anatoly I.. Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches. United States: N. p., Web. doi:10.1021/acscatal.8b00706.
Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., & Frenkel, Anatoly I.. Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches. United States. doi:10.1021/acscatal.8b00706.
Liu, Deyu, Li, Yuanyuan, Kottwitz, Matthew, Yan, Binhang, Yao, Siyu, Gamalski, Andrew, Grolimund, Daniel, Safonova, Olga V., Nachtegaal, Maarten, Chen, Jingguang G., Stach, Eric A., Nuzzo, Ralph G., and Frenkel, Anatoly I.. 2018. "Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches". United States. doi:10.1021/acscatal.8b00706. https://www.osti.gov/servlets/purl/1466591.
@article{osti_1466591,
title = {Identifying Dynamic Structural Changes of Active Sites in Pt–Ni Bimetallic Catalysts Using Multimodal Approaches},
author = {Liu, Deyu and Li, Yuanyuan and Kottwitz, Matthew and Yan, Binhang and Yao, Siyu and Gamalski, Andrew and Grolimund, Daniel and Safonova, Olga V. and Nachtegaal, Maarten and Chen, Jingguang G. and Stach, Eric A. and Nuzzo, Ralph G. and Frenkel, Anatoly I.},
abstractNote = {Alloy nanoparticle catalysts are known to afford unique activities that can differ markedly from their parent metals, but there remains a generally limited understanding of the nature of their atomic (and likely dynamic) structures as exist in heterogeneously supported forms under reaction conditions. Notably unclear is the nature of their active sites and the details of the varying oxidation states and atomic arrangements of the catalytic components during chemical reactions. In this work, we describe multimodal methods that provide a quantitative characterization of the complex heterogeneity present in the chemical and electronic speciations of Pt–Ni bimetallic catalysts supported on mesoporous silica during the reverse water gas shift reaction. The analytical protocols involved a correlated use of in situ X-ray Absorption Spectroscopy (XAS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), complimented by ex-situ aberration corrected Scanning Transmission Electron Microscopy (STEM). The data reveal that complex reactions occur between the metals and support in this system under operando conditions. These reactions, and the specific impacts of strong metal–silica bonding interactions, prevent the formation of alloy phases containing Ni–Ni bonds. This feature of structure provides high activity and selectivity for the reduction of CO2 to carbon monoxide without significant competitive levels of methanation. In conclusion, we show how these chemistries evolve to the active state of the catalyst: bimetallic nanoparticles possessing an intermetallic structure (the active phase) that are conjoined with Ni-rich, metal-silicate species.},
doi = {10.1021/acscatal.8b00706},
journal = {ACS Catalysis},
number = 5,
volume = 8,
place = {United States},
year = {2018},
month = {4}
}