Dataset Information

Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at high temperature.

ABSTRACT: Ammonia is an important feedstock for producing fertiliser and is also a potential energy carrier. However, the process currently used for ammonia synthesis, the Haber-Bosch process, consumes a huge amount of energy; therefore the development of new catalysts for synthesising ammonia at a high rate under mild conditions (low temperature and low pressure) is necessary. Here, we show that Ru/La0.5Ce0.5O1.75 pre-reduced at an unusually high temperature (650 °C) catalysed ammonia synthesis at extremely high rates under mild conditions; specifically, at a reaction temperature of 350 °C, the rates were 13.4, 31.3, and 44.4 mmol g-1 h-1 at 0.1, 1.0, and 3.0 MPa, respectively. Kinetic analysis revealed that this catalyst is free of hydrogen poisoning under the conditions tested. Electron energy loss spectroscopy combined with O2 absorption capacity measurements revealed that the reduced catalyst consisted of fine Ru particles (mean diameter < 2.0 nm) that were partially covered with partially reduced La0.5Ce0.5O1.75 and were dispersed on a thermostable support. Furthermore, Fourier transform infrared spectra measured after N2 addition to the catalyst revealed that N2 adsorption on Ru atoms that interacted directly with the reduced La0.5Ce0.5O1.75 weakened the N 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 N bond and thus promoted its cleavage, which is the rate-determining step for ammonia synthesis. Our results indicate that high-temperature pre-reduction of this catalyst, which consists of Ru supported on a thermostable composite oxide with a cubic fluorite structure and containing reducible cerium, resulted in the formation of many sites that were highly active for N2 reduction by hydrogen.

SUBMITTER: Ogura Y

PROVIDER: S-EPMC5897884 | biostudies-other | 2018 Feb

REPOSITORIES: biostudies-other

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Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at high temperature.

Ogura Yuta Y Sato Katsutoshi K Miyahara Shin-Ichiro SI Kawano Yukiko Y Toriyama Takaaki T Yamamoto Tomokazu T Matsumura Syo S Hosokawa Saburo S Nagaoka Katsutoshi K

Chemical science 20180115 8

Ammonia is an important feedstock for producing fertiliser and is also a potential energy carrier. However, the process currently used for ammonia synthesis, the Haber-Bosch process, consumes a huge amount of energy; therefore the development of new catalysts for synthesising ammonia at a high rate under mild conditions (low temperature and low pressure) is necessary. Here, we show that Ru/La0.5Ce0.5O1.75 pre-reduced at an unusually high temperature (650 °C) cata ...[more]

PMID: 29719696

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Project description:The desire for a carbon-free society and the continuously increasing demand for clean energy make it valuable to exploit green ammonia (NH3) synthesis that proceeds via the electrolysis driven Haber-Bosch (eHB) process. The key for successful operation is to develop advanced catalysts that can operate under mild conditions with efficacy. The main bottleneck of NH3 synthesis under mild conditions is the known scaling relation in which the feasibility of N2 dissociative adsorption of a catalyst is inversely related to that of the desorption of surface N-containing intermediate species, which leads to the dilemma that NH3 synthesis could not be catalyzed effectively under mild conditions. The present work offers a new strategy via introducing atomically dispersed Ru onto a single Co atom coordinated with pyrrolic N, which forms RuCo dual single-atom active sites. In this system the d-band centers of Ru and Co were both regulated to decouple the scaling relation. Detailed experimental and theoretical investigations demonstrate that the d-bands of Ru and Co both become narrow, and there is a significant overlapping of t2g and eg orbitals as well as the formation of a nearly uniform Co 3d ligand field, making the electronic structure of the Co atom resemble that of a "free-atom". The "free-Co-atom" acts as a bridge to facilitate electron transfer from pyrrolic N to surface Ru single atoms, which enables the Ru atom to donate electrons to the antibonding π* orbitals of N2, thus resulting in promoted N2 adsorption and activation. Meanwhile, H2 adsorbs dissociatively on the Co center to form a hydride, which can transfer to the Ru site to cause the hydrogenation of the activated N2 to generate N2H x (x = 1-4) intermediates. The narrow d-band centers of this RuCo catalyst facilitate desorption of surface *NH3 intermediates even at 50 °C. The cooperativity of the RuCo system decouples the sites for the activation of N2 from those for the desorption of *NH3 and *N2H x intermediates, giving rise to a favorable pathway for efficient NH3 synthesis under mild conditions.

Project description:A better fundamental understanding of the plasma-catalyst interaction and the reaction mechanism is vital for optimizing the design of catalysts for ammonia synthesis by plasma-catalysis. In this work, we report on a hybrid plasma-enhanced catalytic process for the synthesis of ammonia directly from N2 and H2 over transition metal catalysts (M/Al2O3, M = Fe, Ni, Cu) at near room temperature (?35 °C) and atmospheric pressure. Reactions were conducted in a specially designed coaxial dielectric barrier discharge (DBD) plasma reactor using water as a ground electrode, which could cool and maintain the reaction at near-room temperature. The transparency of the water electrode enabled operando optical diagnostics (intensified charge-coupled device (ICCD) imaging and optical emission spectroscopy) of the full plasma discharge area to be conducted without altering the operation of the reactor, as is often needed when using coaxial reactors with opaque ground electrodes. Compared to plasma synthesis of NH3 without a catalyst, plasma-catalysis significantly enhanced the NH3 synthesis rate and energy efficiency. The effect of different transition metal catalysts on the physical properties of the discharge is negligible, which suggests that the catalytic effects provided by the chemistry of the catalyst surface are dominant over the physical effects of the catalysts in the plasma-catalytic synthesis of ammonia. The highest NH3 synthesis rate of 471 ?mol g-1 h-1 was achieved using Ni/Al2O3 as a catalyst with plasma, which is 100% higher than that obtained using plasma only. The presence of a transition metal (e.g., Ni) on the surface of Al2O3 provided a more uniform plasma discharge than Al2O3 or plasma only, and enhanced the mean electron energy. The mechanism of plasma-catalytic ammonia synthesis has been investigated through operando plasma diagnostics combined with comprehensive characterization of the catalysts using N2 physisorption measurements, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), NH3-temperature-programmed desorption (TPD), and N2-TPD. Four forms of adsorbed NH x (x = 0, 1, 2, and 3) species were detected on the surfaces of the spent catalysts using XPS. It was found that metal sites and weak acid sites could enhance the production of NH3 via formation of NH2 intermediates on the surface.

Dataset Information

Efficient ammonia synthesis over a Ru/La0.5Ce0.5O1.75 catalyst pre-reduced at high temperature.

Publications

Efficient ammonia synthesis over a Ru/La<sub>0.5</sub>Ce<sub>0.5</sub>O<sub>1.75</sub> catalyst pre-reduced at high temperature.

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