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Inorganic Nitrogen Assimilation01:22

Inorganic Nitrogen Assimilation

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Nitrogen is an essential element in biological systems, forming a crucial component of proteins, nucleic acids, and other cellular constituents. Many bacteria and archaea acquire nitrogen in the form of nitrate (NO₃⁻) or ammonia (NH₃), which are then assimilated into biomolecules through specific enzymatic pathways.Assimilatory Nitrate ReductionWhen nitrate enters the cell, it undergoes a two-step reduction process known as assimilatory nitrate reduction. Initially, the enzyme...
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Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...
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1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism01:37

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Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
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Chemolithotrophs are microorganisms that obtain energy by oxidizing inorganic molecules such as hydrogen gas (H₂), ammonia (NH₃), reduced sulfur compounds (H₂S, S²⁻), and ferrous iron (Fe²⁺). Unlike heterotrophic organisms that rely on organic carbon, chemolithotrophs transfer electrons from these inorganic donors to the electron transport chain (ETC), generating a proton motive force (PMF) that drives ATP synthesis through oxidative phosphorylation.
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Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate.
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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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Bioinspired Interfacial Hydration Engineering via Metal-Organic Frameworks for Efficient Nitrate-To-Ammonia

Yuyin Mao1, Minghui Zhang1, Xiangdong Xue1

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Advanced Science (Weinheim, Baden-Wurttemberg, Germany)
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Summary

Researchers engineered copper electrodes with a UiO-66-NH2 coating for efficient electrocatalytic nitrate reduction to ammonia (eNO3RR). This strategy enhances ammonia synthesis by optimizing interfacial hydration and proton transfer kinetics, overcoming key limitations in sustainable ammonia production.

Keywords:
interfacial water structuremetal–organic frameworksmicroenvironment modulationnitrate electroreduction

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Sustainable Chemistry

Background:

  • Electrocatalytic nitrate reduction to ammonia (eNO3RR) is a sustainable synthesis route.
  • Current challenges include slow proton transfer and hydrogen evolution, especially at high current densities in neutral media.

Purpose of the Study:

  • To develop an efficient and selective electrocatalyst for eNO3RR.
  • To investigate the role of interfacial hydration engineering in enhancing catalytic performance.

Main Methods:

  • Fabrication of copper electrodes coated with UiO-66-NH2 metal-organic framework.
  • Electrochemical performance testing at industrially relevant conditions.
  • In situ spectroscopy, molecular dynamics simulations, and density functional theory calculations to elucidate reaction mechanisms.

Main Results:

  • The optimized UiO-66-NH2@Cu electrode achieved 98.6% Faradaic efficiency for ammonia production.
  • High ammonia yield rate (5.02 mmol cm⁻² h⁻¹) and partial current density (>1 A cm⁻²) were sustained.
  • UiO-66-NH2 overlayer promoted interfacial accumulation of hydrated potassium ions, which act as superior proton donors.

Conclusions:

  • Interfacial hydration engineering is crucial for modulating proton-coupled electron transfer in eNO3RR.
  • The UiO-66-NH2 overlayer effectively lowers the activation barrier for ammonia synthesis.
  • This work presents a generalizable strategy for designing efficient electrocatalysts through microenvironment engineering.