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Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production

Journal Article · · Nature Communications
 [1];  [2];  [3];  [4];  [5];  [2];  [2];  [2];  [3];  [3];  [3];  [2];  [3];  [3];  [6];  [5]
  1. Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China); OSTI
  2. Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China)
  3. Soochow University, Suzhou (China)
  4. Shanghai Institute of Technology, Shanghai (China)
  5. Soochow University, Suzhou (China); Key Laboratory of Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province, Suzhou (China); Jiangsu Engineering Laboratory of New Materials for Sewage Treatment and Recycling, Suzhou (China)
  6. California Institute of Technology (CalTech), Pasadena, CA (United States)
+ Show Author Affiliations
Direct implementation of metal-organic frameworks as the catalyst for CO2 electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e- products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au3+ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO2 reduction reaction pathway.
Research Organization:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Organization:
Collaborative Innovation Center of Suzhou Nano Science & Technology; National Key R&D Program of China; National Natural Science Foundation of China; Natural Science Foundation of Jiangsu Higher Education Institutions; Natural Science Foundation of Jiangsu Province; Six Talent Peaks Project in Jiangsu Province; Soochow University; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021266
OSTI ID:
1904263
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
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Physical Insight on Mechanism of Photoinduced Charge Transfer in Multipolar Photoactive Molecules journal July 2018
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrocatalysis
energy
metal-organic frameworks