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All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...

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Nitrous acid and nitric acids are two types of acids containing nitrogen, among which nitrous acid is weaker than nitric acid. Nitrous acid with a pKa value of 3.37 ionizes in water to give a nitrite ion and the hydronium ion.
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A Continuous-flow Photocatalytic Reactor for the Precisely Controlled Deposition of Metallic Nanoparticles

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Controlling electrocatalytic nitrate reduction efficiency by utilizing dπ-pπ interactions in parallel stacking

Sourav Bhowmick^1,2, 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.

Chemical Science

|February 14, 2025

Summary

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.

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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.