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Title: Highly active subnanometer Rh clusters derived from Rh-doped SrTiO3 for CO2 reduction

Journal Article · · Applied Catalysis B: Environmental
 [1];  [2];  [2];  [2];  [3];  [4];  [5];  [5];  [4];  [2];  [6]
  1. Tsinghua Univ., Beijing (China). Dept. of Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  2. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  5. Stony Brook Univ., NY (United States). Chemistry Dept.
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
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Here, sub-nanometer Rh clusters derived from Rh-doped SrTiO3, demonstrated by in-situ X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements, are applied as highly active catalysts for CO2 reduction. Compared to the supported Rh/SrTiO3, the catalyst synthesized by a doping-segregation method exhibits a higher space-time yield (STY) to CO with a selectivity of 95% for CO2 reduction by hydrogen; it also shows a higher activity with a larger turnover frequency (TOF) for CO2 reduction by ethane. According to the in-situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) experiments, the higher CO selectivity for CO2 hydrogenation is attributed to the lower CO binding strength resulted by the strong interactions (e.g., charge transfer) between Rh atoms and the oxide support with surface defects. The superior activity is suggested to be originated from the cooperative effect between the highly dispersed sub-nanometer Rh clusters for efficient dissociation of H2/C2H6 and the reconstructed SrTiO3 with oxygen vacancies for preferential adsorption/activation of CO2. Finally, the doping-segregation method provides a unique opportunity to tune the size of active metal clusters and the physicochemical properties of the oxide support, offering the potential for applications in a variety of chemical reactions.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States); Tsinghua Univ., Beijing (China)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
SC0012704; AC02-76SF00515; FG02-03ER15476; 1254600; 21673125; DESC0012335
OSTI ID:
1476271
Alternate ID(s):
OSTI ID: 1495314
Report Number(s):
BNL-209139-2018-JAAM
Journal Information:
Applied Catalysis B: Environmental, Vol. 237; ISSN 0926-3373
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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Cited By (3)

Towards efficient use of noble metals via exsolution exemplified for CO oxidation journal January 2019
Hydrogenation of Carbon Dioxide to Value-Added Chemicals by Heterogeneous Catalysis and Plasma Catalysis journal March 2019
A review of synthesis and morphology of SrTiO 3 for energy and other applications journal May 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
subnanometer
perovskite
doping-segregation
selectivity