Dehydrogenation Of Ammonia Research Articles

Synergistic Effect of RuCo and Hierarchical ZSM‐5 for Enhanced Hydrogen Generation

AbstractA unique bifunctional catalyst comprised of acid site containing, hierarchical ZSM‐5 (contains acid sites) supported RuCo bimetal, was synthesized using a facile incipient wetness impregnation method. The synergistic interaction between zeolite acid sites and bimetals of this bifunctional material significantly improves its performance as a catalyst of hydrogen producing, dehydrogenation of ammonia borane.

Ammonia decomposition over La-doped Al2O3 supported Co catalyst

As the hydrogen source of carbon-free fuel cells, the key to realize the green and low-energy decomposition hydrogen production process is to select materials with excellent catalytic performance for ammonia dehydrogenation. In this study, the rare earth element lanthanum (La) was doped onto the surface of Al2O3 by the impregnation method. The aforementioned material was subsequently used as a new material for the synthesis of single metal Co catalysts that catalyzed ammonia decomposition. Various characterization techniques (XRD, HRTEM, N2 physical adsorption-desorption, ICP, XPS, SEM, H2-TPR) were employed to investigate the relationship between the structure and performance of Co/La–Al2O3 catalysts. The findings indicated that the 10Co/La(5)-Al2O3 catalyst was the most active. Under the conditions of 550 °C and 9000 mL h−1·gcat−1, the conversion of ammonia reached 90 %, and the yield of hydrogen reached 8.9 mmol·gcat−1·min−1. A perovskite-type metal oxide layer of LaAlO3 was generated on the surface of Al2O3 support after doping the appropriate amount of lanthanum (5 %), which directly affects the catalytic performance of the catalyst. The small amount of LaAlO3 optimized the strong interaction between the metal Co and the supports, thereby enhancing catalytic performance. While stabilizing the active component Co, XPS and H2-TPR also implied that the presence of La could enhance the electron transfer between the support and Co, as well as facilitate the desorption of nitrogen and hydrogen products, therefore, the low temperature activity of Co/La–Al2O3 catalyst can be improved. The ammonia decomposition efficiency of the catalyst doped with 5 % wt La was much higher than that of the catalyst without La incorporation. The simple modified support developed by us, which loads a monoatomic Co catalyst, provides a new approach for the development of high-activity transition metal catalysts.

Adsorption and dehydrogenation of ammonia on Ru55, Cu55 and Ru@Cu54 nanoclusters: role of single atom alloy catalyst.

Hydrogen production by the catalytic decomposition of ammonia (NH3) is an important process for several important applications, which include energy production and environment-related issues. The role of single Ru-atom substitution in a Cu55 nanocluster (NC) has been illustrated using the NH3 decomposition reaction as a model system. The structural stability of Ru@Cu54 NC has been evaluated using Ru55 and Cu55 NCs for comparison. Ru@Cu54 prefers an icosahedron structure (Ih), like Ru55 and Cu55 NCs, with almost comparable average binding energies of -5.55 eV per atom. The adsorption of NHx (x = 0-3) on different adsorption sites of the icosahedron Ru@Cu54 NC has also been studied and the corresponding adsorption energies have been estimated. The site-preference investigation suggested that NH3 prefers to adsorb vertically to the Ru@Cu54. The stable geometries of the N and H atoms on the high symmetry adsorption sites of Ru@Cu54 NC have been studied. Although the N atom favours top and hollow sites, the H atom prefers to stay in the Ru-Cu bridge site along with the hollow sites. The adsorption energy of N on the Ru@Cu54 NC fcc site is found to be -5.42 eV, which is very close to the optimal value (-5.81 eV) of the ammonia decomposition volcano curve. The reaction energies for stepwise H atom elimination from an adsorbed NH3 molecule have been estimated. Finally, NH3 adsorption and decomposition on Ru@Cu54 have been illustrated in terms of electronic structure analysis. The energetics calculations for the dehydrogenation of NH3 suggest that Ru@Cu54 NC can be a suitable catalyst.

The effect of acidic–basic structural modification of nickel-based catalyst for ammonia decomposition for hydrogen generation

The utilization of non-precious nickel-based catalyst in increasing ammonia dissociation for COx-free hydrogen production was investigated. Typically, Co, La and basic metal oxides (Na, K, Ba) promoters were synthesized with nickel over acidic gamma alumina support. The main objective of the study was to modify the acid-base surface of catalyst structure thereby increasing ammonia dissociation activity. The catalytic activity for ammonia decomposition was strongly influenced by the addition of Na and K oxide promoters over 15 %Ni/Al2O3 resulting in moderate-stronger basic sites suitable for ammonia conversion. The addition of Na and K oxides showed a clear trend in tuning the trimetallic catalyst and significantly reducing the amount of strongly adsorbed hydrogen on the catalyst surface. This results in higher ammonia conversion which increased as a function of temperature to 32.4 %, 67.5 % and 95.3 % at 430 ᵒC, 485 ᵒC, and 533 ᵒC, respectively. Ammonia conversion using promoters was stable with no degradation of performance and the conversion increased with the decrease in WHSV. The catalytic reactivity over trimetallic catalysts was systematically influenced by their basic-acidic property that promoted ammonia dehydrogenation on the surface of nickel oxide-based catalyst.

Proposal of a new mechanism of ammonia on the coking inhibition of n-decane under supercritical conditions

The coking problem of hydrocarbon fuel pyrolysis is the key factor affecting the application of active cooling technology for high-speed aircraft. The purpose of this work is to investigate the coking inhibition performance and coking mechanism of using ammonia as an additive during the thermal cracking. In this study, the pyrolysis and coking characteristics of supercritical n-decane were experimentally studied using an electrically heated tube. ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometer), GC–MS (Gas Chromatograph Mass Spectrometer), SEM (Scanning Electron Microscope), EDS (Energy Dispersive Spectroscopy), TPO (Temperature Programmed Oxidation), and Raman spectroscopy are applied to characterize the anti-coking performance of the additives. The results show that the additive hardly affects the cracking of the fuel under high-temperature conditions, but the coke mass deposited on the inner surface of the tube is significantly reduced, and the coking inhibition rate can reach 80% at 750 °C. The addition of additives reduced the graphitization degree and oxidative activity of the coke. The maximum oxidation temperature of the coke obtained at 750 °C was reduced by 145 °C, and the ID/IG value of the Raman spectroscopy peak-fitting was 3.29. The new mechanism of the effect of additives on the formation of coking precursors and the deposition of coke on the surface of the tube wall is proposed. Ammonia can react with Ni of the inner metal tube and radicals generated by fuel cracking to form a carbonized film, achieving the effect of inhibiting metal catalytic coking. Meanwhile, the amino radicals generated by ammonia dehydrogenation can regulate the coking reaction path by forming a stable p-π conjugate structure with unsaturated radicals. Therefore, the research will contribute to a deeper comprehension of the coking inhibition mechanism and the development of more effective coking inhibitors, providing new technical support for active cooling technologies.

Dispersed surface Ru ensembles on MgO(111) for catalytic ammonia decomposition

Ammonia is regarded as an energy vector for hydrogen storage, transport and utilization, which links to usage of renewable energies. However, efficient catalysts for ammonia decomposition and their underlying mechanism yet remain obscure. Here we report that atomically-dispersed Ru atoms on MgO support on its polar (111) facets {denoted as MgO(111)} show the highest rate of ammonia decomposition, as far as we are aware, than all catalysts reported in literature due to the strong metal-support interaction and efficient surface coupling reaction. We have carefully investigated the loading effect of Ru from atomic form to cluster/nanoparticle on MgO(111). Progressive increase of surface Ru concentration, correlated with increase in specific activity per metal site, clearly indicates synergistic metal sites in close proximity, akin to those bimetallic N2 complexes in solution are required for the stepwise dehydrogenation of ammonia to N2/H2, as also supported by DFT modelling. Whereas, beyond surface doping, the specific activity drops substantially upon the formation of Ru cluster/nanoparticle, which challenges the classical view of allegorically higher activity of coordinated Ru atoms in cluster form (B5 sites) than isolated sites.

Ammonia-assisted reforming and dehydrogenation toward efficient light alkane conversion

Ammonia can be employed as an important co-reactant for efficient light alkane conversion. The reaction is achieved through either ammonia reforming (for COx-free H2 and HCN) or ammonia dehydrogenation (for acetonitrile and H2).

Heteroepitaxial Growth of B5 -Site-Rich Ru Nanoparticles Guided by Hexagonal Boron Nitride for Low-Temperature Ammonia Dehydrogenation.

Ruthenium is one of the most active catalysts for ammonia dehydrogenation and is essential for the use of ammonia as a hydrogen storage material. The B5 -type site on the surface of ruthenium is expected to exhibit the highest catalytic activity for ammonia dehydrogenation, but the number of these sites is typically low. Here, a B5 -site-rich ruthenium catalyst is synthesized by exploiting the crystal symmetry of a hexagonal boron nitride support. In the prepared ruthenium catalyst, ruthenium nanoparticles are formed epitaxially on hexagonal boron nitride sheets with hexagonal planar morphologies, in which the B5 sites predominate along the nanoparticle edges. By activating the catalyst under the reaction condition, the population of B5 sites further increases as the facets of the ruthenium nanoparticles develop. The electron density of the Ru nanoparticles also increases during catalyst activation. The synthesized catalyst shows superior catalytic activity for ammonia dehydrogenation compared to previously reported catalysts. This work demonstrates that morphology control of a catalyst via support-driven heteroepitaxy can be exploited for synthesizing highly active heterogeneous catalysts with tailored atomic structures.

Theoretical insight into the reaction mechanism of ammonia dehydrogenation on iron-based clusters

Ammonia (NH3) molecule decomposition is a promising approach for H2 production with COx-free. Density functional theory (DFT) calculations are employed to investigate the NH3 molecule stepwise dehydrogenation on Fe6M (M = Fe, Mo, Ni, and Co) clusters. The stability of these clusters has been investigated, and the result shows that the stability of Fe-based clusters is enhanced with doping of other metals. The catalytic activity of metal clusters for ammonia decomposition is systematically investigated by analyzing the adsorption property and reaction barriers. NH3 prefers to bind to the atop metal atom through the N end, which is agreement with the electrostatic potential analysis. Moreover, the adsorption energies of NH3 are related to the d-band center of Fe-based clusters. The reaction energy barriers show that the last dehydrogenation step (NH* + * ⇌ N* + H*) is the rate-determining step for most investigated clusters. The overall dehydrogenation process is exothermic reaction, and by comparing the rate-determining step, the Fe6Mo(l) and the Fe6Ni(l) clusters can efficiently promote the NH3 dissociation reaction.

Numerical study on laminar burning velocity of ammonia flame with methanol addition

The combustion characteristics of ammonia/methanol mixtures were investigated numerically in this study. Methanol has a dramatic promotive effect on the laminar burning velocity (LBV) of ammonia. Three mechanisms from literature and another four self-developed mechanisms constructed in this study were evaluated using the measured laminar burning velocities of ammonia/methanol mixtures from Wang et al. (Combust.Flame. 2021). Generally, none of the selected mechanisms can precisely predict the measured laminar burning velocities at all conditions. Aiming to develop a simplified and reliable mechanism for ammonia/methanol mixtures, the constructed mechanism utilized NUI Galway mechanism (Combust.Flame. 2016) as methanol sub-mechanism and the Otomo mechanism (Int. J. Hydrogen. Energy. 2018) as ammonia sub-mechanism was optimized and reduced. The reduced mechanism entitled ‘DNO-NH3’, can accurately reproduce the measured laminar burning velocities of ammonia/methanol mixtures under all conditions. A reaction path analysis of the ammonia/methanol mixtures based on the DNO-NH3 mechanism shows that methanol is not directly involved in ammonia oxidation, instead, the produced methyl radicals from methanol oxidization contribute to the dehydrogenation of ammonia. Besides, NOx emission analysis demonstrates that 60% methanol addition results in the highest NOx emissions. The most important reactions dominating the NOx consumption and production are identified in this study.

Ammonia decomposition over iron-based catalyst: Exploring the hidden active phase

The possible phase transformation of catalysts under reaction conditions brings lots of difficulties in establishing the active phase. Herein, we report a hidden active phase over iron catalyst uniquely for the dehydrogenation of ammonia (NH3). The highest dehydrogenation rate corresponds to an evanescent Fe/Fe4N mixing phase while the nitrogen (N) kept on accumulating and gradually deactivated the catalyst. Density functional theory (DFT) calculations demonstrated that deposition of an N on Fe(100) surface modifies the electronic structure of its surrounding iron atoms, causing a significant reduction of the initial dehydrogenation barrier of NH3. To recover the hidden active phase, ambient-pressure double dielectric barrier discharge (DDBD) plasma was applied to the reaction system in situ to remove the excessive surface N, which yields a pronounced improvement of the catalytic performance. The work demonstrates that hidden active phase in thermal catalysis can be unfolded when the rate-determining step is subdued by applied plasma.

An experimental and modeling study of ammonia oxidation in a jet stirred reactor

Ammonia is a promising carbon-free fuel and has attracted massive attention nowadays. However, there are still large uncertainties in the mechanism of ammonia oxidation that motivate further fundamental investigations. In this work, oxidation experiments of ammonia were carried out in a jet-stirred reactor (JSR) equipped with synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry and gas chromatography. Ammonia/O2/Ar mixtures were tested under wide-range operating conditions covering an oxidation temperature of 700–1200 K and an equivalence ratio of ϕ = 0.1–1.0. Important intermediates and products (e.g., NO, NO2, N2O, N2, H2, and H2O) were detected and quantified. A chemical kinetic model for ammonia oxidation was proposed by integrating the rate constants of critical reactions from different models. The results show that ammonia oxidation reactivity is quite strong at ultra-lean conditions, manifesting lower oxidization temperatures and greater oxidization rates. However, this behavior becomes weakened rapidly with the elevation of equivalence ratio, such that ammonia oxidation characteristics are highly similar between ϕ = 0.5 and 1.0. Meanwhile, important intermediates like NO2 and N2O are only detected under ultra-lean conditions. Reaction pathway analysis for equivalence ratios shows that high oxygen concentration is beneficial to the formation of HO2, which leads to a huge amount of OH and promotes the dehydrogenation of ammonia. With the elevation of equivalence ratio, the dehydrogenation of ammonia becomes difficult and reactions NO+HO2=NO2+OH and NH2+NO2=N2O+H2O are suppressed, which answers for the vanishing of NO2 and N2O at ϕ = 0.5 and 1.0. Reaction pathway analysis for oxidation temperatures also emphasizes the significance of HO2 and its conversion pathway to OH, but they are also strongly influenced by equivalence ratios. The current work provides useful insights into ammonia oxidation and a reliable experimental database for modeling.

Dehydrogenation of ammonia on free-standing and epitaxial hexagonal boron nitride.

We report a thermodynamically feasible mechanism for producing H2 from NH3 using hBN as a catalyst. 2D catalysts have exceptional surface areas with unique thermal and electronic properties suited for catalysis. Metal-free, 2D catalysts, are highly desirable materials that can be more sustainable than the ubiquitously employed precious and transition metal-based catalysts. Here, using density functional theory (DFT) calculations, we demonstrate that metal-free hexagonal boron nitride (hBN) is a valid alternative to precious metal catalysts for producing H2via reaction of ammonia with a boron and nitrogen divacancy (VBN). Our results show that the decomposition of ammonia proceeds on monolayer hBN with an activation energy barrier of 0.52 eV. Furthermore, the reaction of ammonia with epitaxially grown hBN on a Ru(0001) substrate was investigated, and we observed similar NH3 decomposition energy barriers (0.61 eV), but a much more facile H2 associative desorption barrier (0.69 eV vs 5.89 eV). H2 generation from the free-standing monolayer would instead occur through a diffusion process with an energy barrier of 3.36 eV. A detailed analysis of the electron density and charge distribution along the reaction pathways was carried out to rationalise the substrate effects on the catalytic reaction.

Specific reactivity of 4d and 5d transition metals supported over CeO2 for ammonia oxidation

Pt/CeO2 catalysts were most active in selective catalytic oxidation of ammonia, where Pt triggered the activation of surface lattice oxygen, and the dehydrogenation of ammonia assisted by surface lattice oxygen was the rate-determining step.

Theoretical Insight into the Reaction Mechanism of Ammonia Dehydrogenation on Iron-Based Clusters

Theoretical Insight into the Reaction Mechanism of Ammonia Dehydrogenation on Iron-Based Clusters

Ammonia oxidation on iridium electrode in alkaline media: An in situ ATR-SEIRAS study

• ATR-SEIRAS is extended to study the AOR on Ir electrode in basic media. • NH x ,ad species is attributed to the pivot intermediate. • N 2 H x+y ,ad species is identified as the key active intermediate to generate N 2. • NO 2 − and NO 3 − byproducts arise from NO ad oxidation. Mechanistic understanding of electrochemical ammonia oxidation reaction (AOR) is important for designing efficient AOR catalysts. In this work, in situ attenuated total reflection surface-enhanced infrared spectroscopy (ATR-SEIRAS) is employed to study the AOR at varied potentials on an Ir electrode in alkaline media. The AOR on Ir contains two sequential oxidation peaks in the anodic voltammograms. The in situ ATR-SEIRAS results indicate that the small Peak I at a lower potential is mainly due to dehydrogenation of interfacial ammonia and dimerization of as-generated NH x, ad species to N 2 H x+y, ad species. And the broad and intense Peak II at a higher potential mainly involves the N 2 production from N 2 H x+y, ad species, NO ad species generation from NH x ,ad species and further successive oxidation into the NO 2 − and NO 3 − by-products at higher potentials. It is thus inferred that NH x species are the pivotal intermediates for AOR on Ir electrode, and the N 2 H x+y ,ad and NO ad species the key intermediates for the production of N 2 , NO 2 − and NO 3 − , respectively.

Bimetallic Co–M (M = Cu, Ag, and Au) Carbonyl Complexes Supported by N-Heterocyclic Carbene Ligands: Synthesis, Structures, Computational Investigation, and Catalysis for Ammonia Borane Dehydrogenation

The reaction of Na[Co(CO)4] with M(IPr)Cl (M = Cu, Ag, and Au; IPr = C3N2H2(C6H3iPr2)2) affords the neutral heterometallic complexes [Co(CO)4{M(IPr)}] (M = Cu, 1; Ag, 2; and Au, 3). Formation of 2 is accompanied by traces of [Ag(IPr)2][Ag{Co(CO)4}2] (4). The reaction of Na[Co(CO)4] with M(IMes)Cl (IMes = C3N2H2(C6H2Me3)2) results in mixtures of [Co(CO)4{M(IMes)}] (M = Cu, 5; Ag, 6; and Au, 7) and [M(IMes)2][M{Co(CO)4}2] (M = Cu, 8; Ag, 9; and Au, 10). In the cases of Cu and Ag, ionic complexes 8 and 9 are the major products, whereas neutral species 7 is the major product for Au. All species 1–10 have been spectroscopically characterized by IR and 1H and 13C{1H} NMR spectroscopy. Moreover, the molecular structures of 2, 3, and 8 have been determined by single-crystal X-ray diffraction (SC-XRD). Bimetallic Co–M–NHC complexes 1–3 and 7–9 have been tested as catalysts for the dehydrogenation of ammonia–borane (AB) in THF as solvent, and their performances compared to [Fe(CO)4{M(NHC)}2], M(NHC)Cl, and Na[Co(CO)4]. DFT computations have been performed to provide information on the structure, IR spectroscopy, and the thermodynamics of Co–M carbonyl clusters.

NH3 vs. CH4 autoignition: A comparison of chemical dynamics

In order to obtain physical insights on ammonia combustion, which is characterised by exceptionally long ignition delays and increased NOx emissions, the autoignition dynamics of an ammonia/air mixture is analysed using the diagnostics tools derived from the Computational Singular Perturbation (CSP) methodology. The results are compared to the autoignition dynamics of a methane/air mixture of same initial conditions. Methane was chosen for comparison because, even though the two molecules have a formal similarity, the ignition delay of methane is more than 10 times shorter than the one of ammonia. By using the CSP diagnostics tools, we identified the dominant chemical pathways that relate to the explosive components that drive the system towards ignition for both cases. Furthermore, the reactions that hinder the ammonia ignition were identified. This led to the determination of an interesting difference in the electronic configuration of the molecules of the two fuels, which is the root of their drastically different oxidation dynamics. In particular, it was shown that the autoignition process starts with the formation of methyl (CH) and amine (NH) radicals, through dehydrogenation of methane and ammonia, respectively. In the methane case, the methyl-peroxy radical (CH–O–O–) then forms, which initiates a chemical runaway that lasts for approximately 2/3 of the ignition delay and leads to the gradual oxidation of carbon to CO. In the ammonia case, though, the structure of NH is such that it is not possible to form NH–O–O–. As a result, the chemical runaway is suspended.

Dehydrogenation of ammonia for electricity production: Effect of recirculation fraction

Hydrogen (H2) has been widely studied as a promising energy carrier. However, H2 has a challenging technology in the storage and transportation. Since, it is a critical technology for H2 energy system implementation, the H2 storage and transportation is remain to be solved. This work proposes an integrated system of energy utilization of ammonia (NH3), which has been known as one of the promising methods of H2 storage. The system includes the decomposition of ammonia (NH3) through thermo-catalytic process and also power generation process using H2 as fuel. The heat generated from oxy-fuel combustion of H2 is utilized to supply the thermal energy required for the endothermic process of NH3 decomposition, and the remaining heat is converted to electricity by a combined cycle. A portion of exhaust gas is recirculated to the combustion chamber, and the heat circulation of the system is designed and optimized based on enhanced process integration (EPI), resulting in a highly efficient system. The result shows an optimum configuration of the integrated system with a recirculation fraction of 0.5-0.55, which is resulting in high system efficiency of 51.4%. The proposed work demonstrated an integrated system of H2-based energy utilization of NH3 with CO2-free while maintaining a highly efficient system.

Top-Down Syntheses of Nickel-Based Structured Catalysts for Hydrogen Production from Ammonia.

We report the fabrication and catalytic performance evaluation of highly active and stable nickel (Ni)-based structured catalysts for ammonia dehydrogenation with nearly complete conversion using nonprecious metal catalysts. Low-temperature chemical alloying (LTCA) followed by selective aluminum (Al) dealloying was utilized to synthesize foam-type structured catalysts ready for implementation in commercial-scale catalytic reactors. The crystalline phases of Ni-Al alloy (NiAl3, Ni2Al3, or both) in the near-surface layer were controlled by tuning the alloying time. The best-performing catalyst was obtained from a Ni foam substrate with a NiAl3/Ni2Al3 overlayer synthesized by LTCA at 400 °C for 20 h. The developed Ni catalyst exhibited an activity enhancement of 10-fold over the nontreated Ni foam and showed outstanding activities of 15 800 molH2molNi-1h-1 (TOF: 4.39 s-1) and 19 978 molH2molNi-1h-1 (TOF: 5.55 s-1) at 550 and 600 °C, respectively. This performance is unprecedented compared with previously reported Ni-based ammonia cracking catalysts with higher-end performance (TOFs of 0.08-1.45 s-1 at 550 °C). Moreover, this catalyst showed excellent stability for 100 h at 600 °C while discharging an extremely low NH3 concentration of 1034 ppm. The NH3 concentration in the exhaust gas was further reduced to 690 and 271 ppm at 700 and 800 °C, respectively, while no deactivation was observed at these elevated temperatures. Through material characterizations, we clarified that controlling the degree of Al alloying in the outermost layer of Ni is a crucial factor in determining the activity and stability because residual Al possibly modifies the electronic structure of Ni for enhanced activity as well as transforming to acidic alumina for increased intrinsic activity and stability.