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Ammonia synthesis by photocatalytic hydrogenation of a N2-derived molybdenum nitride

Journal Article · · Nature Synthesis
 [1];  [2];  [2];  [2];  [2]
  1. Princeton University, NJ (United States); Princeton University
  2. Princeton University, NJ (United States)
+ Show Author Affiliations
Although metal complexes are known to split dinitrogen at ambient temperature and pressure, the synthesis of ammonia from these compounds and using H2 as the terminal reductant has been rarely achieved. Here, we report photocatalytic ammonia synthesis from a N2-derived terminal molybdenum nitride and by using H2 as the terminal reductant. An iridium hydride photocatalyst mediates the reaction upon irradiation with blue light. A molybdenum pentahydride was identified as the principal metal product arising following ammonia release. Conversion of the molybdenum pentahydride back to the terminal molybdenum nitride was accomplished in three-steps and completes a synthetic cycle for NH3 formation from N2 and H2. Mechanistic investigations support a pathway involving photoexcitation of the iridium hydride and subsequent energy transfer rather than electron transfer. Deuterium labelling confirmed H2 as the source of the N–H bonds. This photodriven, proton coupled electron transfer allows the use of H2 as the terminal reductant for catalytic formation of NH3 from N2 using metal catalysts.
Research Organization:
Princeton University, NJ (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Samsung Scholarship
Grant/Contract Number:
SC0006498
OSTI ID:
1987945
Journal Information:
Nature Synthesis, Journal Name: Nature Synthesis Journal Issue: 4 Vol. 1; ISSN 2731-0582
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical bonding
homogeneous catalysis