Paper

Effect of Preparation Condition on Ammonia Synthesis over Ru/CeO

Development of the hydrogen carrier system is of great interest to utilization of renewable energy. To store renewable energy, especially for the electricity from photovoltaic and wind turbine, fluctuation of the generated electricity is not appropriate for the stable supply of the electric power. Also, the hydrogen production by the water electrolysis with the fluctuating electricity results in the fluctuation of hydrogen production. When we store the hydrogen derived from renewable energy in the carrier compounds, it is necessary to consider the reduction or smoothing of fluctuation in the hydrogen flow rate as a feed of chemical process. Although the…

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Ammonia Yields during Plasma-Assisted Catalysis Boosted By Hydrogen Sink Effect

Plasma-catalytic ammonia synthesis is known since early 1900s but the possible reaction pathways are currently under investigation. In this article, we present the use of various transition metals and gallium-rich alloys for plasma-catalytic ammonia synthesis. The best three metallic catalysts were identified to be Ni, Sn and Au with the highest ammonia yield of 34%. Furthermore, as compared to its constituent metals some alloys presented about 25-50% better yields. The metals employed were classified in two different categories according to their behavior during ammonia plasma-catalysis. Category I metals are nitrophobic and the measured concentration of Hα in the gas phase…

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Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Renewable production of ammonia, a building block for most fertilizers, via the electrochemical nitrogen reduction reaction (ENRR) is desirable; however, a selective electrocatalyst is lacking. Here we show that vanadium nitride (VN) nanoparticles are active, selective, and stable ENRR catalysts. ENRR with 15N2 as the feed produces both 14NH3 and 15NH3, which indicates that the reaction follows a Mars–van Krevelen mechanism. Ex situ and operando characterizations indicate that VN0.7O0.45 is the active phase for ENRR and the conversion of VN0.7O0.45 to the VN phase leads to catalyst deactivation. Quantitative isotopic labeling results identify the amounts of two different types of…

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Ammonia Synthesis Via Radiofrequency Plasma Catalysis

Introduction: In 1909, a compound named Ammonia was discovered. Through the 20th century, the immense potential of this chemical was exploited by using in almost every product, from process industry for fertilizer and chemical production to every use in cosmetics, household cleaners and medicines. Recently, fuel cells operating on liquid ammonia as working fluid have been developed on research scale. Despite of using 1-2% of total energy production for the synthesis of this compound, no significant changes have been made to the process since the first Haber-Bosch process plant has been setup. Plasma catalysis is the use of plasma and…

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Advanced Catalysts Development for Small, Distributed, Clean Haber-Bosch Reactors

The traditional Haber-Bosch (HB) synthesis of anhydrous ammonia will adapt to clean power by sourcing the hydrogen from renewable electrolysis. However, the very large scale of current HB plant designs are not well-matched to smaller and more distributed clean power resources. Plant/reactor designs need to be made at a smaller scale in order to best utilize clean hydrogen. Small, megawatt scale HB reactors have an additional advantage of being better able ramp up and down with variable renewable power. This talk will detail ARPA-e funded work into the design and optimization of these smaller, clean NH3 reactors, which utilize much…

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Importance of Reaction Mechanism Involved in Design of the Catalyst and the Reactor for Future Ammonia Synthesis

The ammonia synthesis reaction is considered to involve several elementary steps [1]: N2 + 2* → 2N(a) (1) H2 + 2* → 2H(a) (2) N(a) + H(a) → NH(a) + * (3) NH(a) + H(a) → NH2 (a) + * (4) NH2 (a) + H(a) → NH3(a) + * (5) NH3(a) → NH3 + * (6) Here, the symbol * indicates empty sites. For most metal catalysts, the dissociative adsorption of dinitrogen (step 1) is the rate-determining step, and all the other steps and its reverse step (from 2 to 6) are fast enough to be almost in equilibrium for…

Article

Future Ammonia Technologies: Electrochemical (part 3)

This series of articles on the future of ammonia synthesis began with a report on the NH3 Energy+ conference presentation by Grigorii Soloveichik, Program Director at the US Department of Energy's ARPA-E, who categorized the technologies as being either improvements on Haber-Bosch or electrochemical (with exceptions). ARPA-E invests in "transformational, high-risk, early-stage research," and recently began funding ammonia synthesis technologies, not to make renewable fertilizer but to produce "energy-dense zero-carbon liquid fuel." This article will introduce the six electrochemical technologies currently in development with funding from ARPA-E.

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Exploring Peptide-Bound Catalysts for Electrochemical Ammonia Generation

Today, most ammonia (NH3) manufacturing occurs via the Haber-Bosch process. This process consumes hydrogen from fossil fuels, and as a result NH3 contributes the highest amount of greenhouse gas emissions out of the top 18 large-volume chemicals made globally. Because the process is high temperature (400°–500°C) and pressure (150–300 atm) with a low (15%) single-pass conversion efficiency, the plants have to be very large to be economical. This means that ammonia is shipped from centralized locations, further increasing greenhouse gas emissions because of the fuel consumed in transportation. Additionally, their large size makes it difficult to integrate with renewable sources…

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LiH Mediated Ammonia Synthesis Under Mild Condition

Having a hydrogen content of 17.6 wt% NH3 is an attractive hydrogen carrier. The key issue for NH3 synthesis and decomposition is the development of non-noble metal based, highly active and stable catalysts that can be operated under mild condition. With the understanding on the interaction of LiH and Li2NH with 3d metals or their nitrides, novel catalyst systems, i. e., LiH-3d transition metals for NH3 synthesis and Li2NH-3d transition metal for NH3 decomposition, that have activities surpassing the highly active Ru-based catalysts were developed. The unique chemistry among TM, Li, N and H creates a two-reactive center mediated pathway…

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Nitride-Based Step Catalysis for Ammonia Synthesis at Atmospheric Pressure

Formation of metal nitrides to activate dinitrogen is one avenue to ammonia and other nitrogen compounds. Attractive aspects are operation at atmospheric pressure and moderate temperatures, formation of stable chemical intermediates rather than reliance on somewhat sensitive heterogeneous catalysis, and inexpensive materials. If a single metal is used, however, one encounters tradeoffs somewhat akin to the well-known tradeoffs for Haber-Bosch catalysts. Results will be presented for metal nitride-based ammonia synthesis, and new metal alloys that can address some of the tradeoffs between affinity for nitrogen, and formation of ammonia when hydrogen is added. Options using water instead of hydrogen will…