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Published on: April 10, 2019
Controlling electrocatalytic nitrate reduction efficiency by utilizing dπ-pπ interactions in parallel stacking
Sourav Bhowmick1,2, Ashadul Adalder1, Abhishek Maiti3
1Department of Industrial Chemistry & Applied Chemistry, Swami Vivekananda Research Centre, Ramakrishna Mission Vidyamandira Belur Math Howrah 711202 India uttam.indchem@vidyamandira.ac.in.
Molecular alignment in copper phthalocyanine (CuPc) nanostructures significantly impacts nitrate reduction reaction (NO3RR) performance for green ammonia synthesis and wastewater treatment. Well-aligned beta-CuPc shows superior ammonia production compared to alpha-CuPc.
Area of Science:
- Electrochemistry
- Materials Science
- Green Chemistry
Background:
- Electrochemical nitrate reduction to ammonia (NO3RR) offers a sustainable route for ammonia production and wastewater remediation.
- Developing efficient electrocatalysts is crucial for enhancing NO3RR activity and selectivity.
Purpose of the Study:
- To investigate the influence of molecular alignment on the NO3RR performance of copper phthalocyanine (CuPc) nanostructures.
- To compare the catalytic activity of well-aligned beta-CuPc and less-aligned alpha-CuPc for ammonia synthesis.
Main Methods:
- Synthesis and characterization of alpha-CuPc and beta-CuPc nanostructures.
- Electrochemical evaluation of NO3RR performance, including ammonia yield rate and Faradaic efficiency.
- Scanning tunneling microscopy/spectroscopy (STM/S) for analyzing surface properties.
- Theoretical calculations and gas chromatography for mechanistic insights.
Main Results:
- Well-aligned beta-CuPc demonstrated a significantly higher ammonia yield rate (62,703 μg h⁻¹ mg⁻¹) and Faradaic efficiency (96%) compared to alpha-CuPc (36,889 μg h⁻¹ mg⁻¹, 61%).
- STM/S revealed superior transport properties in beta-CuPc due to optimal Cu-N interactions in its 1D nanostructure.
- Theoretical studies indicated that NO3RR is favored over hydrogen evolution on beta-CuPc due to weaker *NO intermediate binding and lower overpotential.
Conclusions:
- Molecular alignment in CuPc nanostructures is a critical factor determining NO3RR electrocatalytic performance.
- Beta-CuPc's well-aligned structure facilitates efficient ammonia synthesis, highlighting its potential for green ammonia production and wastewater treatment.
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