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Photocatalytic Conversion of Nitrogen to Ammonia with Water on Surface Oxygen Vacancies of Titanium Dioxide

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TLDR
It is reported that a commercially available TiO2 with a large number of surface oxygen vacancies, when photoirradiated by UV light in pure water with N2, successfully produces NH3.
Abstract
Ammonia (NH3) is an essential chemical in modern society. It is currently manufactured by the Haber–Bosch process using H2 and N2 under extremely high-pressure (>200 bar) and high-temperature (>673 K) conditions. Photocatalytic NH3 production from water and N2 at atmospheric pressure and room temperature is ideal. Several semiconductor photocatalysts have been proposed, but all suffer from low efficiency. Here we report that a commercially available TiO2 with a large number of surface oxygen vacancies, when photoirradiated by UV light in pure water with N2, successfully produces NH3. The active sites for N2 reduction are the Ti3+ species on the oxygen vacancies. These species act as adsorption sites for N2 and trapping sites for the photoformed conduction band electrons. These properties therefore promote efficient reduction of N2 to NH3. The solar-to-chemical energy conversion efficiency is 0.02%, which is the highest efficiency among the early reported photocatalytic systems. This noble-metal-free TiO2 ...

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Citations
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Journal ArticleDOI

Rational design of electrocatalysts and photo(electro)catalysts for nitrogen reduction to ammonia (NH3) under ambient conditions

TL;DR: In this article, the rational design of electrocatalysts and photo(electro) catalysts for N2 reduction to NH3 under ambient conditions is highlighted, with a special emphasis on the relationship between their physicochemical properties and NH3 production performance.
Journal ArticleDOI

A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions

TL;DR: In this paper, the authors summarized the recent progress on the electrochemical nitrogen reduction reaction (NRR) at ambient temperature and pressure from both theoretical and experimental aspects, aiming at extracting instructive perceptions for future NRR research activities.
Journal ArticleDOI

Achieving a Record-High Yield Rate of 120.9 μgNH3 mgcat.-1 h-1 for N2 Electrochemical Reduction over Ru Single-Atom Catalysts.

TL;DR: This work not only develops a superior electrocatalyst for NH3 production, but also provides a guideline for the rational design of highly active and robust single-atom catalysts.
Journal ArticleDOI

Review on the criteria anticipated for the fabrication of highly efficient ZnO-based visible-light-driven photocatalysts

TL;DR: In this article, the main advancements in overcoming the barriers accompanied by pure ZnO and the criteria for fabrication of effective visible-light-responsive (ZnO-based) photocatalysts are reviewed.
References
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Journal ArticleDOI

Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals

TL;DR: It is shown that disorder-engineered TiO2 nanocrystals exhibit substantial solar-driven photocatalytic activities, including the photo-oxidation of organic molecules in water and the production of hydrogen with the use of a sacrificial reagent.
Journal ArticleDOI

Photocatalyst releasing hydrogen from water

TL;DR: An advance in the catalysis of the overall splitting of water under visible light is described: the new catalyst is a solid solution of gallium and zinc nitrogen oxide, modified with nanoparticles of a mixed oxide of rhodium and chromium, which functions as a promising and efficient photocatalyst in promoting the evolution of hydrogen gas.
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Efficient Visible Light Nitrogen Fixation with BiOBr Nanosheets of Oxygen Vacancies on the Exposed {001} Facets

TL;DR: It is demonstrated that efficient fixation of N2 to NH3 can proceed under room temperature and atmospheric pressure in water using visible light illuminated BiOBr nanosheets of oxygen vacancies in the absence of any organic scavengers and precious-metal cocatalysts.
Journal ArticleDOI

Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center

TL;DR: In this paper, the authors explored the catalytic reduction of dinitrogen by molybdenum complexes that contain the [HIPTN3N]3- ligand.
Journal ArticleDOI

Challenges in reduction of dinitrogen by proton and electron transfer

TL;DR: This tutorial review gives an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen.
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