Topological insulator as an efficient catalyst for oxidative carbonylation of amines.

Topological materials have received much attention because of their robust topological surface states, which can be potentially applied in electronics and catalysis. Here, we show that the topological insulator bismuth selenide functions as an efficient catalyst for the oxidative carbonylation of amines with carbon monoxide and dioxygen to synthesize urea derivatives. For example, the carbonylation of butylamine can be completed over bismuth selenide nanoparticle catalyst in 4 hours at 20°C with a yield of 99%, whereas most noble metal-based catalysts do not function at such a low temperature. Density functional theory calculations further reveal that the topological surface states facilitate the activation of dioxygen through a triplet-to-singlet spin-conversion reaction, in which active oxygen species are formed with a barrier of 0.4 electron volts for the subsequent reactions with amine and carbon monoxide.

Large Oblate Hemispheroidal Ruthenium Particles Supported on Calcium Amide as Efficient Catalysts for Ammonia Decomposition.

Ammonia decomposition is an important technology for extracting hydrogen from ammonia toward the realization of a hydrogen economy. Herein, it is reported that large oblate hemispheroidal Ru particles on Ca(NH2 )2 function as efficient catalysts for ammonia decomposition. The turnover frequency of Ru/Ca(NH2 )2 increased by two orders of magnitude when the Ru particle size was increased from 1.5 to 8.4 nm. More than 90 % ammonia decomposition was achieved over Ru/Ca(NH2 )2 with large oblate hemispheroidal Ru particles at 360 °C, which is comparable to that of alkali-promoted Ru catalysts with small Ru particle sizes. XAFS analyses revealed that Ru particles are immobilized on Ca(NH2 )2 by Ru-N bonds formed at the metal/support interface, which lead to oblate hemispheroidal Ru particles. Such a strong metal-support interaction in Ru/Ca(NH2 )2 is also substantiated by DFT calculations. The high activity of Ru/Ca(NH2 )2 with large Ru particles primarily originates from the shape and appropriate size of the Ru particles with a high density of active sites rather than the electron-donating ability of Ca(NH2 )2 .

Self-organized Ruthenium-Barium Core-Shell Nanoparticles on a Mesoporous Calcium Amide Matrix for Efficient Low-Temperature Ammonia Synthesis.

A low-temperature ammonia synthesis process is required for on-site synthesis. Barium-doped calcium amide (Ba-Ca(NH2 )2 ) enhances the efficacy of ammonia synthesis mediated by Ru and Co by 2 orders of magnitude more than that of a conventional Ru catalyst at temperatures below 300 °C. Furthermore, the presented catalysts are superior to the wüstite-based Fe catalyst, which is known as a highly active industrial catalyst at low temperatures and pressures. Nanosized Ru-Ba core-shell structures are self-organized on the Ba-Ca(NH2 )2 support during H2 pretreatment, and the support material is simultaneously converted into a mesoporous structure with a high surface area (>100 m2 g-1 ). These self-organized nanostructures account for the high catalytic performance in low-temperature ammonia synthesis.

Ammonia synthesis over Co-Mo alloy nanoparticle catalyst prepared via sodium naphthalenide-driven reduction.

We report the synthesis of Co-Mo alloy nanoparticles with a uniform distribution of the alloy elements on CeO2via sodium naphthalenide-driven reduction. The resulting sample functions as a highly efficient and stable catalyst for ammonia synthesis. Based on the metal weight, the catalytic activity is ca. 20 times higher than that of Co3Mo3N.

Hydride-Based Electride Material, LnH2 (Ln = La, Ce, or Y).

In view of the strong electron-donating nature of H(-) and extensive vacancy formation in metals by hydrogen insertion, a series of LnH2+x (Ln = La, Ce, or Y) compounds with fluorite-type structures were verified to be the first hydride-based electride, where itinerant electrons populating the cage are surrounded by H(-) anions. The electron transfer into the cage probably originates from Ln-cage covalent interaction. To the best of our knowledge, anion-rich electrides are extremely rare, and a key requirement for their formation is that the cage site is not occupied by lone pair electrons of the adjacent ions. In the case of LnH2, the cage site is surrounded by eight H(-) anions with isotopic electronic character caused by the lack of mixing of H p-orbital character. Notably, Ru-loaded LnH2+x electride powders synthesized by hydrogen embrittlement (Ln = La or Ce) were found to work as efficient catalysts for ammonia synthesis at ambient pressure, without showing serious signs of hydrogen poisoning. There are several possible origins of the observed high catalytic activity in the hydride promotors: the small work function of LnH2+x derived from the covalent interaction between Ln cation and the H(-) σ donor, and the formation of Ln nitride during catalytic reaction.

Water Durable Electride Y5Si3: Electronic Structure and Catalytic Activity for Ammonia Synthesis.

We report an air and water stable electride Y5Si3 and its catalytic activity for direct ammonia synthesis. It crystallizes in the Mn5Si3-type structure and confines 0.79/f.u. anionic electrons in the quasi-one-dimensional holes. These anionic electrons strongly hybridize with yttrium 4d electrons, giving rise to improved chemical stability. The ammonia synthesis rate using Ru(7.8 wt %)-loaded Y5Si3 was as high as 1.9 mmol/g/h under 0.1 MPa and at 400 °C with activation energy of ∼50 kJ/mol. Its strong electron-donating ability to Ru metal of Y5Si3 is considered to enhance nitrogen dissociation and reduce the activation energy of ammonia synthesis reaction. Catalytic activity was not suppressed even after Y5Si3, once dipped into water, was used as the catalyst promoter. These findings provide novel insights into the design of simple catalysts for ammonia synthesis.

Gritty Surface Sample Holder Invented To Obtain Correct X-ray Absorption Fine Structure Spectra for Concentrated Materials by Fluorescence Yield.

A gritty surface sample holder has been invented to obtain correct XAFS spectra for concentrated samples by fluorescence yield (FY). Materials are usually mixed with boron nitride (BN) to prepare proper concentrations to measure XAFS spectra. Some materials, however, could not be mixed with BN and would be measured in too concentrated conditions to obtain correct XAFS spectra. Consequently, XAFS spectra will be incorrect typically with decreased intensities of the peaks. We have invented the gritty surface sample holders to obtain correct XAFS spectra even for concentrated materials for FY measurements. Pure Cu and CuO powders were measured mounted on the sample holders, and the same spectra were obtained as transmission spectra of properly prepared samples. This sample holder is useful to measure XAFS for any concentrated materials.

Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts.

The efficient reduction of atmospheric nitrogen to ammonia under low pressure and temperature conditions has been a challenge in meeting the rapidly increasing demand for fertilizers and hydrogen storage. Here, we report that Ca2N:e-, a two-dimensional electride, combined with ruthenium nanoparticles (Ru/Ca2N:e-) exhibits efficient and stable catalytic activity down to 200 °C. This catalytic performance is due to [Ca2N]+·e1-x-H x- formed by a reversible reaction of an anionic electron with hydrogen (Ca2N:e- + xH ↔ [Ca2N]+·e1-x-H x-) during ammonia synthesis. The simplest hydride, CaH2, with Ru also exhibits catalytic performance comparable to Ru/Ca2N:e-. The resultant electrons in these hydrides have a low work function of 2.3 eV, which facilitates the cleavage of N2 molecules. The smooth reversible exchangeability between anionic electrons and H- ions in hydrides at low temperatures suppresses hydrogen poisoning of the Ru surfaces. The present work demonstrates the high potential of metal hydrides as efficient promoters for low-temperature ammonia synthesis.

Correction: Essential role of hydride ion in ruthenium-based ammonia synthesis catalysts.

[This corrects the article DOI: 10.1039/C6SC00767H.].

Mechanism Switching of Ammonia Synthesis Over Ru-Loaded Electride Catalyst at Metal-Insulator Transition.

The substitution of electrons for O(2-) anions in the crystallographic cages of [Ca24Al28O64](4+)(O(2-))2 was investigated to clarify the correlation between the electronic properties and catalytic activity for ammonia synthesis in Ru-loaded [Ca24Al28O64](4+)(O(2-))2-x(e(-))2x (0 ≤ x ≤ 2). This catalyst has low catalytic performance with an electron concentration (Ne) lower than 1 × 10(21) cm(-3) and a high apparent activation energy (Ea) for ammonia synthesis comparable to that for conventional Ru-based catalysts with a basic promoter such as alkali or alkaline earth compounds. Replacement of more than half of the cage O(2-) anions with electrons (Ne ≈ 1 × 10(21) cm(-3)) significantly changes the reaction mechanism to yield a catalytic activity that is an order higher and with half the Ea. The metal-insulator transition of [Ca24Al28O64](4+)(O(2-))2-x(e(-))2x also occurs at Ne ≈ 1 × 10(21) cm(-3) and is triggered by structural relaxation of the crystallographic cage induced by the replacement of O(2-) anions with electrons. These observations indicate that the metal-insulator transition point is a boundary in the catalysis between Ru-loaded [Ca24Al28O64](4+)(O(2-))2 and [Ca24Al28O64](4+)(e(-))4. It is thus demonstrated that whole electronic properties of the support material dominate catalysis for ammonia synthesis.

Electride support boosts nitrogen dissociation over ruthenium catalyst and shifts the bottleneck in ammonia synthesis.

Novel approaches to efficient ammonia synthesis at an ambient pressure are actively sought out so as to reduce the cost of ammonia production and to allow for compact production facilities. It is accepted that the key is the development of a high-performance catalyst that significantly enhances dissociation of the nitrogen-nitrogen triple bond, which is generally considered a rate-determining step. Here we examine kinetics of nitrogen and hydrogen isotope exchange and hydrogen adsorption/desorption reactions for a recently discovered efficient catalyst for ammonia synthesis--ruthenium-loaded 12CaO·7Al2O3 electride (Ru/C12A7:e(-))--and find that the rate controlling step of ammonia synthesis over Ru/C12A7:e(-) is not dissociation of the nitrogen-nitrogen triple bond but the subsequent formation of N-Hn species. A mechanism of ammonia synthesis involving reversible storage and release of hydrogen atoms on the Ru/C12A7:e(-) surface is proposed on the basis of observed hydrogen absorption/desorption kinetics.

NH(2-) dianion entrapped in a nanoporous 12CaO·7Al2O3 crystal by ammonothermal treatment: reaction pathways, dynamics, and chemical stability.

Inorganic imides are useful for hydrogen storage and base-catalyzed reactions but are extremely unstable under ambient conditions, which hinders their practical use as functional materials. Here, we demonstrate that NH2(-) and H(-), as well as NH(2-), can be incorporated into the nanocages of the mayenite crystals, [Ca24Al28O64](4+)(e(-))4 and [Ca24Al28O64](4+)(O(2-))2, by ammonothermal treatment. We evaluated the reaction conditions and found that the anion exchange reaction proceeded at higher than 500 °C. Raman spectroscopy showed that the N-H band position of encaged NH(2-) was close to that of CaNH and MgNH crystals. We also studied the reaction pathways that yield NH2(-) and NH(2-) anions and their dynamic motions by (1)H NMR spectroscopy. Successive reactions of encaged e(-) and O(2-) ions with NH3 yielded NH2(-), NH(2-), and H(-) or OH(-), in which the O(2-) ion reacted more efficiently with NH3. The maximum NH(2-) concentration and content were ∼2.7 × 10(20) cm(-3) and ∼0.25 (wt %)NH, respectively. The short spin-lattice relaxation time found in (1)H NMR suggests that the incorporated NH2(-) and NH(2-) rotate or librate in the cage near room temperature. Stability tests showed that the encaged NH(2-) ions are chemically stable under ambient conditions and in organic solvents. These results are attributed to the encapsulation of active anions within subnanometer-sized cages composed of Ca-O-Al oxide frameworks. The encaged NH(2-) desorbed as NH3 at higher than 500 °C under vacuum (Ea = 172 kJ mol(-1)). It is thus expected that C12A7:NH(2-) will function as a reactive nitrogen source for nitrogen transfer reactions by in situ cage degradation.

Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store.

Industrially, the artificial fixation of atmospheric nitrogen to ammonia is carried out using the Haber-Bosch process, but this process requires high temperatures and pressures, and consumes more than 1% of the world's power production. Therefore the search is on for a more environmentally benign process that occurs under milder conditions. Here, we report that a Ru-loaded electride [Ca(24)Al(28)O(64)](4+)(e(-))(4) (Ru/C12A7:e(-)), which has high electron-donating power and chemical stability, works as an efficient catalyst for ammonia synthesis. Highly efficient ammonia synthesis is achieved with a catalytic activity that is an order of magnitude greater than those of other previously reported Ru-loaded catalysts and with almost half the reaction activation energy. Kinetic analysis with infrared spectroscopy reveals that C12A7:e(-) markedly enhances N(2) dissociation on Ru by the back donation of electrons and that the poisoning of ruthenium surfaces by hydrogen adatoms can be suppressed effectively because of the ability of C12A7:e(-) to store hydrogen reversibly.