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Title: Single rhodium atoms anchored in micropores for efficient transformation of methane under mild conditions

Journal Article · · Nature Communications
ORCiD logo [1];  [1];  [2]; ORCiD logo [2];  [3];  [3];  [4];  [4];  [3];  [5];  [6]; ORCiD logo [3]
  1. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry
  2. Univ. of California, Riverside, CA (United States). Dept. of Chemistry
  3. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry; Univ. of Notre Dame, IN (United States). Dept. of Chemistry and Biochemistry
  4. Univ. of Electro-Communications, Chofu (Japan). Innovation Research Center for Fuel Cells. Graduate School of Informatics and Engineering
  5. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemical and Petroleum Engineering. Dept. of Chemistry; Fuzhou Univ. (China). State Key Lab. of Photocatalysis on Energy and Environment. College of Chemistry
  6. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Division of Chemistry
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Catalytic transformation of CH4 under a mild condition is significant for efficient utilization of shale gas under the circumstance of switching raw materials of chemical industries to shale gas. Here, we report the transformation of CH4 to acetic acid and methanol through coupling of CH4, CO and O2 on single-site Rh1O5 anchored in microporous aluminosilicates in solution at ≤150 °C. The activity of these singly dispersed precious metal sites for production of organic oxygenates can reach about 0.10 acetic acid molecules on a Rh1O5 site per second at 150 °C with a selectivity of ~70% for production of acetic acid. It is higher than the activity of free Rh cations by >1000 times. Computational studies suggest that the first C–H bond of CH4 is activated by Rh1O5 anchored on the wall of micropores of ZSM-5; the formed CH3 then couples with CO and OH, to produce acetic acid over a low activation barrier.

Research Organization:
Univ. of Kansas, Lawrence, KS (United States); Stony Brook Univ., NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15476; SC0014561
OSTI ID:
1499949
Journal Information:
Nature Communications, Vol. 9; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 161 works
Citation information provided by
Web of Science

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Cited By (14)

Thermolysis of Noble Metal Nanoparticles into Electron‐Rich Phosphorus‐Coordinated Noble Metal Single Atoms at Low Temperature journal August 2019
Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO 3 − Cluster Anions journal November 2019
Thermolysis of Noble Metal Nanoparticles into Electron‐Rich Phosphorus‐Coordinated Noble Metal Single Atoms at Low Temperature journal August 2019
Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO 3 − Cluster Anions journal November 2019
Direct Conversion of Methanol to Ethanol on the Metal‐Carbon Interface journal March 2019
Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes journal April 2019
In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation journal March 2019
Heterogeneous single-atom catalysis journal May 2018
Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution journal December 2018
Atomic (single, double, and triple atoms) catalysis: frontiers, opportunities, and challenges journal January 2019
Selective mild oxidation of methane to methanol or formic acid on Fe–MOR catalysts journal January 2019
Construction of a tandem HZSM-5 with CuZnAl catalyst for alkylation of benzene with syngas journal January 2020
Partial oxidation of methane to methanol by isolated Pt catalyst supported on a CeO 2 nanoparticle journal February 2020
High-efficiency direct methane conversion to oxygenates on a cerium dioxide nanowires supported rhodium single-atom catalyst journal February 2020

Figures / Tables (8)

Fig. 1(p. 3)figure Fig. 1
Fig. 2(p. 4)figure Fig. 2
Table 1(p. 5)table Table 1
Table 2(p. 5)table Table 2
Fig. 3(p. 6)figure Fig. 3
Fig. 4(p. 7)figure Fig. 4
Fig. 5(p. 8)figure Fig. 5
Fig. 6(p. 9)figure Fig. 6

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
carbon capture and storage
catalytic mechanisms
heterogeneous catalysis