Periodic Reporting for period 1 - GREEN (S/P-Coordinated Transition Metal Single Sites-doped Carbon Matrices as Electrocatalysts for Nitrogen Reduction)
Reporting period: 2023-09-01 to 2025-08-31
The electrochemical nitrogen reduction reaction (NRR) provides a sustainable alternative to the Haber-Bosch process for ammonia (NH3) production. Transition metal catalysts have poor NRR performance due to the highly competitive hydrogen evolution reaction and the scaling relation between inert dinitrogen (N2) and other reaction intermediates. Single-atom catalysts (SACs) have been
proven to be effective in overcoming these limitations owing to the enhanced active sites and the anomalous quantum size effect.
Inspired by biological rhizobia nitrogen fixation, this proposal, Green Renewable Energy-derived Electrocatalytic Nitrogen reduction reaction that yields NH3 under mild conditions, this project GREEN has focused on the development, characterization and mechanistically understanding of S/P coordinated transition Metal Single sites-doped (Fe, Mo and FeMo) Carbon Matrices (MSCMs) as electrocatalysts for high activity and selectivity NRR.
The specific goals of GREEN and their achievement through its implementation have been as follows:
i) Successfully synthesis of MSCMs electrocatalysts to achieve high performance and selectivity towards NRR;
I have successfully synthesized the MSCMs electrocatalysts to achieve FE (Faradaic Efficiency) of 20% and j (current density) of 10 mA cm-2
ii) Characterize MSCMs to determine their electronic structure, local atomic environment, charge density and affinity with N2 molecules, etc.;
The catalysts were characterized by different techniques: PXRD (X-ray photoelectron spectrometer), FTIR (Fourier transform infrared), HRTEM (high-resolution transmission electron microscopy), SEM (scanning electron microscopy), ICP-OES (Inductively coupled plasma optical emission spectroscopy).
iii) Determine the activity of the MSCMs catalysts and fine-tuning of working conditions and parameters for highly efficient electrocatalytic NRR and the catalytic mechanisms for NRR.
Electrocatalytic test were conducted under different conditions. We optimized the electrolyte (KOH, LiClO4, Kpi), temperature (Room temperature and 40, 60 oC) and pressure (ambient pressure and 4 bars) and also we investigate the ethanol effect during the electrocatalytic process by introducing different volume percentage of ethanol (0%, 5%, 10%, 25% 50% 100%). Furthermore, to study the mechanism, we applied in-situ SEC to track the intermediates and DFT calculations are used for deeper understanding.
proven to be effective in overcoming these limitations owing to the enhanced active sites and the anomalous quantum size effect.
Inspired by biological rhizobia nitrogen fixation, this proposal, Green Renewable Energy-derived Electrocatalytic Nitrogen reduction reaction that yields NH3 under mild conditions, this project GREEN has focused on the development, characterization and mechanistically understanding of S/P coordinated transition Metal Single sites-doped (Fe, Mo and FeMo) Carbon Matrices (MSCMs) as electrocatalysts for high activity and selectivity NRR.
The specific goals of GREEN and their achievement through its implementation have been as follows:
i) Successfully synthesis of MSCMs electrocatalysts to achieve high performance and selectivity towards NRR;
I have successfully synthesized the MSCMs electrocatalysts to achieve FE (Faradaic Efficiency) of 20% and j (current density) of 10 mA cm-2
ii) Characterize MSCMs to determine their electronic structure, local atomic environment, charge density and affinity with N2 molecules, etc.;
The catalysts were characterized by different techniques: PXRD (X-ray photoelectron spectrometer), FTIR (Fourier transform infrared), HRTEM (high-resolution transmission electron microscopy), SEM (scanning electron microscopy), ICP-OES (Inductively coupled plasma optical emission spectroscopy).
iii) Determine the activity of the MSCMs catalysts and fine-tuning of working conditions and parameters for highly efficient electrocatalytic NRR and the catalytic mechanisms for NRR.
Electrocatalytic test were conducted under different conditions. We optimized the electrolyte (KOH, LiClO4, Kpi), temperature (Room temperature and 40, 60 oC) and pressure (ambient pressure and 4 bars) and also we investigate the ethanol effect during the electrocatalytic process by introducing different volume percentage of ethanol (0%, 5%, 10%, 25% 50% 100%). Furthermore, to study the mechanism, we applied in-situ SEC to track the intermediates and DFT calculations are used for deeper understanding.
The performed work has been divided in three main work packages:
Work Package 1 -Synthesis of MSCMs catalysts
Work Package 2 – Characterizaiton of the MSCM catalysts
Work Package 3 – Electrocatalytic N2 reduction test and mechanism investigation
The achieved results have been protected with a patent application and they will be further disseminated through open access publications (in preparation).
Work Package 1 -Synthesis of MSCMs catalysts
Work Package 2 – Characterizaiton of the MSCM catalysts
Work Package 3 – Electrocatalytic N2 reduction test and mechanism investigation
The achieved results have been protected with a patent application and they will be further disseminated through open access publications (in preparation).
The novelty of the GREEN project relies on the design of coordination environment of metal atoms and conducting polymers with specific S/P elements to form high-performance MSCMs electrocatalysts for ammonium production. It is the first time to prepare MSCMs catalysts toward NRR. Besides, the effect of coordination environment and heteroatoms on MSCMs, such as band gap, charge density and affinity with N2 molecules have been explored, which will pave the way for the diverse application of MSCMs.
Considering that the current approach used to NH3 production is still the Haber-Bosch process, which requires extremely high pressure and temperature conditions. Thus, consuming a significant energy input that is derived from fossil fuels, the results of the project have a direct scientific impact, representing a step forward in the clean and sustainable synthesis process to produce NH3.
Considering that the current approach used to NH3 production is still the Haber-Bosch process, which requires extremely high pressure and temperature conditions. Thus, consuming a significant energy input that is derived from fossil fuels, the results of the project have a direct scientific impact, representing a step forward in the clean and sustainable synthesis process to produce NH3.