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…

Paper

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…

Paper

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…

Paper

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…

Paper

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…

Paper

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.

Paper

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…

Paper

Nitrogenase Inspired Peptide-Functionalized Catalyst for Efficient, Emission-Free Ammonia Production

Ammonia-based fertilizers have enabled increases in food production to sustain the world’s population. Currently the major source of ammonia is the Haber-Bosch process, which requires high temperature and pressure and has low conversion efficiency, such that very large plants are required for economical production. Ammonia is therefore one of the most energy and carbon intensive chemical processes worldwide, largely due to the steam methane reforming step to produce the required hydrogen. Because of the very large plant scale and resulting centralization of production, ammonia may also be transported long distances to point of use, adding additional energy and emissions. Distributed,…

Paper

Early Transition Metal Carbide and Nitride Supported Catalysts for Ammonia Synthesis

More than 180 million tons of NH3 are produced annual via the Haber-Bosch process which converts N2 and H2 at high temperatures (400 – 500°C) and pressures (150 – 300 bars). Ammonia synthesis also accounts for 1-2% of global energy consumption.1 The development of higher activity catalysts that can operate under less severe conditions would enhance the economics associated with and sustainability of NH3 synthesis. Research described in this paper investigates the performance of transition metal carbide and nitride supported metals for NH3 synthesis. Previously, Mo2C and Mo2N have been reported to be more active than Ru-based catalysts, but slightly…