Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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:
Samsung Scholarship; USDOE Office of Science (SC), Basic Energy Sciences (BES)
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

References (56)

Photolytic N 2 Splitting: A Road to Sustainable NH 3 Production? journal November 2014
A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity journal August 2016
Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation journal August 2019
Relating N-H Bond Strengths to the Overpotential for Catalytic Nitrogen Fixation: Relating N-H Bond Strengths to the Overpotential for Catalytic Nitrogen Fixation journal April 2020
On the Basicity of Organic Bases in Different Media: On the Basicity of Organic Bases in Different Media journal September 2019
Determining and Understanding N-H Bond Strengths in Synthetic Nitrogen Fixation Cycles book January 2017
Photochemical reaction of phosphine hydride complexes of molybdenum and tungsten with molecular nitrogen
  • Pivovarov, A. P.; Gak, Yu. V.; Doronina, T. N.
  • Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 30, Issue 6 https://doi.org/10.1007/BF00950268
journal June 1981
Dinitrogen fixation and activation after 30 years: a puzzle still unsolved journal September 1995
Synthesis and characterization of molybdenum species: dinuclear and mononuclear species of the molecular formulas [Mo2(O2CCH3)2(LL)2][BF4]2 and [Mo(O)(F)(LL)2][BF4] where LL=bis-phosphine. The use of [Mo2(NCCH3)10][BF4]4 as a source for the [Mo2]4+ core journal May 1992
The effect of the wavelength of light upon the extent of dinitrogen exchange in bis(dinitrogen) complexes of molybdenum and tungsten journal January 1980
Base accelerated generation of N2 and NH3 from an osmium nitride journal February 2014
Interplay between Theory and Experiment for Ammonia Synthesis Catalyzed by Transition Metal Complexes journal April 2016
Nitrogen Fixation via Splitting into Nitrido Complexes journal May 2021
Thermodynamic Hydricity of Transition Metal Hydrides journal June 2016
Progress and Prospective of Nitrogen-Based Alternative Fuels journal June 2020
Catalytic N 2 -to-NH 3 (or -N 2 H 4 ) Conversion by Well-Defined Molecular Coordination Complexes journal April 2020
Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen journal May 2020
Determination of the N–H Bond Dissociation Free Energy in a Pyridine(diimine)molybdenum Complex Prepared by Proton-Coupled Electron Transfer journal October 2020
Recent Progress in Transition-Metal-Catalyzed Reduction of Molecular Dinitrogen under Ambient Reaction Conditions journal July 2015
Catalytic N 2 -to-NH 3 Conversion by Fe at Lower Driving Force: A Proposed Role for Metallocene-Mediated PCET journal February 2017
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center journal December 2005
Recent Advances in the Chemistry of Dinitrogen Complexes journal June 1995
Molecular Photoelectrocatalysts for Visible Light-Driven Hydrogen Evolution from Neutral Water journal July 2014
Protonation of Coordinated N2 on Tungsten with H2 Mediated by Sulfido-Bridged Dinuclear Molybdenum Complexes1 journal January 2001
Formation of Ammonia in the Reactions of a Tungsten Dinitrogen with Ruthenium Dihydrogen Complexes under Mild Reaction Conditions 1 journal December 2000
Molybdenum Triamidoamine Systems. Reactions Involving Dihydrogen Relevant to Catalytic Reduction of Dinitrogen journal September 2009
Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)2]+/0 Systems journal October 1998
Preparation and properties of dinitrogen-molybdenum complexes journal January 1972
Catalytic Reduction of N 2 to NH 3 by an Fe–N 2 Complex Featuring a C-Atom Anchor journal January 2014
Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles journal October 2014
Determining Proton-Coupled Standard Potentials and X–H Bond Dissociation Free Energies in Nonaqueous Solvents Using Open-Circuit Potential Measurements journal May 2020
Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia journal April 2020
Ammonia Synthesis by Hydrogenolysis of Titanium–Nitrogen Bonds Using Proton Coupled Electron Transfer journal March 2015
Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation journal September 2016
Characterization of the Earliest Intermediate of Fe-N 2 Protonation: CW and Pulse EPR Detection of an Fe-NNH Species and Its Evolution to Fe-NNH 2 + journal May 2019
Cp* Noninnocence Leads to a Remarkably Weak C–H Bond via Metallocene Protonation journal February 2019
Hydrogenation of N -Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters journal October 2019
Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer journal November 2019
Synthesis, Electrochemistry, and Reactivity of New Iridium(III) and Rhodium(III) Hydrides journal June 2012
A fresh approach to synthesizing ammonia from air and water journal April 2019
Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex journal February 2004
Catalytic conversion of nitrogen to ammonia by an iron model complex journal September 2013
Ammonia formation by metal–ligand cooperative hydrogenolysis of a nitrido ligand journal May 2011
Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron journal May 2013
NH3 formation from N2 and H2 mediated by molecular tri-iron complexes journal June 2020
Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen journal July 2021
Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water journal April 2019
Global Population and the Nitrogen Cycle journal July 1997
Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer journal January 2019
Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins journal January 2020
Model reactions for nitrogen fixation. Photo-induced formation and X-ray crystal structure of [Os2(NH3)8(MeCN)2(N2)]5+ from [Os VI (NH3)4N]3+ journal January 1989
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center journal July 2003
Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex journal May 1995
Bimetallic System for Nitrogen Fixation: Ruthenium-Assisted Protonation of Coordinated N2 on Tungsten with H2 journal January 1998
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex journal November 2016
Beyond fossil fuel–driven nitrogen transformations journal May 2018

Similar Records

Hydrosilylation of a Molecular Molybdenum Nitride Provides Mechanistic Insights into Photodriven Ammonia Synthesis from N2 and H2
Journal Article · Mon Feb 09 19:00:00 EST 2026 · Journal of the American Chemical Society · OSTI ID:3020795
Catalytic Hydrogenation of a Manganese(V) Nitride to Ammonia
Journal Article · Sun Apr 26 20:00:00 EDT 2020 · Journal of the American Chemical Society · OSTI ID:1616530

Related Subjects

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