scholarly journals Low-temperature ammonia synthesis on electron-rich [RuH6] catalytic centers

2021 ◽  
Author(s):  
Jaysree Pan ◽  
Qianru Wang ◽  
Jianping Guo ◽  
Heine Anton Hansen ◽  
Ping Chen ◽  
...  
Keyword(s):  
Low Temperatures ◽  
Density Functional ◽  
Ruthenium Complex ◽  
Ambient Pressure ◽  
Atomic Scale ◽  
Ambient Conditions ◽  
Catalytic Center ◽  
Synthesis Conditions ◽  
Complex Hydrides ◽  
Reaction Orders

Ammonia is a central vector in sustainable global growth, but the usage of fossil feedstocks and centralized Haber-Bosch synthesis conditions causes >1.4% of the global anthropogenic CO2 emissions. While nitrogenase enzymes convert atmospheric N2 to ammonia at ambient conditions, even the most active manmade inorganic catalysts fail due to low activity and parasitic hydrogen evolution at low temperatures. Here, we show the [RuH6] catalytic center in ternary ruthenium complex hydrides (Li4RuH6 and Ba2RuH6) activate N2 preferentially and avoid hydrogen over-saturation at low temperatures and near ambient pressure by delicately balancing H2 chemisorption and N2 activation. The active [RuH6] catalytic center is capable of achieving an unprecedented yield at low temperatures via a shift in the rate-determining reaction intermediates and transition states, where the reaction orders in hydrogen and ammonia change dramatically. Temperature-dependent atomic-scale understanding of this unique mechanism is obtained with synchronized experimental and density functional theory investigations.

Influence of intramolecular interactions on carbon dioxide gas adsorption capacity in Mesoporous Imine polymers

2018 ◽  
Author(s):  
Jaya Prakash Madda ◽  
Pilli Govindaiah ◽  
Sushant Kumar Jena ◽  
Sabbhavat Krishna ◽  
Rupak Kishor
Keyword(s):  
Carbon Dioxide ◽  
Adsorption Capacity ◽  
Density Functional ◽  
Gas Adsorption ◽  
Ambient Pressure ◽  
Condensation Reaction ◽  
Intramolecular Interactions ◽  
Carbon Dioxide Adsorption ◽  
Nitrogen Gas ◽  
Adsorption Characteristic

<p>Covalent organic Imine polymers with intrinsic meso-porosity were synthesized by condensation reaction between 4,4-diamino diphenyl methane and (para/meta/ortho)-phthaladehyde. Even though these polymers were synthesized from precursors of bis-bis covalent link mode, the bulk materials were micrometer size particles with intrinsic mesoporous enables nitrogen as well as carbon dioxide adsorption in the void spaces. These polymers were showed stability up to 260<sup>o</sup> centigrade. Nitrogen gas adsorption capacity up to 250 cc/g in the ambient pressure was observed with type III adsorption characteristic nature. Carbon dioxide adsorption experiments reveal the possible terminal amine functional group to carbamate with CO<sub>2</sub> gas molecule to the polymers. One of the imine polymers, COP-3 showed more carbon dioxide sorption capacity and isosteric heat of adsorption (Q<sub>st</sub>) than COP-1 and COP-2 at 273 K even though COP-3 had lower porosity for nitrogen gas than COP-1 and COP-2. We explained the trends in gas adsorption capacities and Qst values as a consequence of the intra molecular interactions confirmed by Density Functional Theory computational experiments on small molecular fragments.</p>

Structure, Stability and Water Adsorption on Ultra-Thin TiO2 Supported on TiN

2019 ◽  
Author(s):  
Jose Julio Gutierrez Moreno ◽  
Marco Fronzi ◽  
Pierre Lovera ◽  
alan O'Riordan ◽  
Mike J Ford ◽  
...  
Keyword(s):  
Density Functional ◽  
Water Adsorption ◽  
Chemical Potential ◽  
Energy Gap ◽  
Molecular Water ◽  
Structure Stability ◽  
Ambient Conditions ◽  
Rutile Structure ◽  
The Stability ◽  
The One

<p></p><p>Interfacial metal-oxide systems with ultrathin oxide layers are of high interest for their use in catalysis. In this study, we present a density functional theory (DFT) investigation of the structure of ultrathin rutile layers (one and two TiO<sub>2</sub> layers) supported on TiN and the stability of water on these interfacial structures. The rutile layers are stabilized on the TiN surface through the formation of interfacial Ti–O bonds. Charge transfer from the TiN substrate leads to the formation of reduced Ti<sup>3+</sup> cations in TiO<sub>2.</sub> The structure of the one-layer oxide slab is strongly distorted at the interface, while the thicker TiO<sub>2</sub> layer preserves the rutile structure. The energy cost for the formation of a single O vacancy in the one-layer oxide slab is only 0.5 eV with respect to the ideal interface. For the two-layer oxide slab, the introduction of several vacancies in an already non-stoichiometric system becomes progressively more favourable, which indicates the stability of the highly non-stoichiometric interfaces. Isolated water molecules dissociate when adsorbed at the TiO<sub>2</sub> layers. At higher coverages the preference is for molecular water adsorption. Our ab initio thermodynamics calculations show the fully water covered stoichiometric models as the most stable structure at typical ambient conditions. Interfacial models with multiple vacancies are most stable at low (reducing) oxygen chemical potential values. A water monolayer adsorbs dissociatively on the highly distorted 2-layer TiO<sub>1.75</sub>-TiN interface, where the Ti<sup>3+</sup> states lying above the top of the valence band contribute to a significant reduction of the energy gap compared to the stoichiometric TiO<sub>2</sub>-TiN model. Our results provide a guide for the design of novel interfacial systems containing ultrathin TiO<sub>2</sub> with potential application as photocatalytic water splitting devices.</p><p></p>

Ordered Intermetallic Nanoparticles with High Catalytic Activity Prepared by an Electrochemically Induced Phase Transformation

2019 ◽  
Author(s):  
Du Sun ◽  
yunfei wang ◽  
Kenneth Livi ◽  
chuhong wang ◽  
ruichun luo ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Diffusion Mechanism ◽  
Reduction Reaction ◽  
Atomic Scale ◽  
High Catalytic Activity ◽  
Ambient Conditions ◽  
Magnetic Devices ◽  
Disordered Alloys ◽  
Ordered Intermetallic ◽  
Intermetallic Nanoparticles

<div> <p>The synthesis of alloys with long range atomic scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in materials development. We report a process for converting colloidally synthesized ordered intermetallic PdBi<sub>2</sub> to ordered intermetallic Pd<sub>3</sub>Bi nanoparticles under ambient conditions by an electrochemically induced phase transition. The low melting point of PdBi<sub>2</sub> corresponds to low vacancy formation energies which enables the facile removal of the Bi from the surface, while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd<sub>3</sub>Bi exhibits 11x and 3.5x higher mass activty and high methanol tolerance for the oxygen reduction reaction compared to Pt/C and Pd/C, respectively,which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble metal rich ordered intermetallic phases with high catalytic activity, and sets forth guidelines for the design of ordered intermetallic compounds under ambient conditions.</p> </div>

scholarly journals Porous Characteristics of Three-Dimensional Disordered Graphene Networks

Crystals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 127
Author(s):  
YongChao Wang ◽  
YinBo Zhu ◽  
HengAn Wu
Keyword(s):  
Pore Size ◽  
Low Temperatures ◽  
Gas Adsorption ◽  
Three Dimensional ◽  
Md Simulations ◽  
Structural Features ◽  
Atomic Scale ◽  
Critical Factors ◽  
Chlorination Process ◽  
Porous Morphology

The porous characteristics of disordered carbons are critical factors to their performance on hydrogen storage and electrochemical capacitors. Even though the porous information can be estimated indirectly by gas adsorption experiments, it is still hard to directly characterize the porous morphology considering the complex 3D connectivity. To this end, we construct full-atom disordered graphene networks (DGNs) by mimicking the chlorination process of carbide-derived carbons using annealing-MD simulations, which could model the structure of disordered carbons at the atomic scale. The porous characteristics, including pore volume, pore size distribution (PSD), and specific surface area (SSA), were then computed from the coordinates of carbon atoms. From the evolution of structural features, pores grow dramatically during the formation of polyaromatic fragments and sequent disordered framework. Then structure is further graphitized while the PSD shows little change. For the obtained DGNs, the porosity, pore size, and SSA increase with decreasing density. Furthermore, SSA tends to saturate in the low-density range. The DGNs annealed at low temperatures exhibit larger SSA than high-temperature DGNs because of the abundant free edges.

scholarly journals Atomic Migration Studies with X-Ray Photon Correlation Spectroscopy

2014 ◽  
Vol 2 ◽  
pp. 73-94 ◽  
Author(s):  
Markus Stana ◽  
Manuel Ross ◽  
Bogdan Sepiol
Keyword(s):  
Low Temperatures ◽  
Short Range ◽  
Short Range Order ◽  
Photon Correlation Spectroscopy ◽  
Condensed Matter ◽  
Correlation Spectroscopy ◽  
Atomic Scale ◽  
Photon Correlation ◽  
X Ray ◽  
Amorphous Systems

The new technique of atomic-scale X-ray Photon Correlation Spectroscopy (aXPCS) makesuse of a coherent X-ray beam to study the dynamics of various processes in condensed matter systems.Particularly atomistic migration mechanisms are still far from being understood in most of intermetallicalloys and in amorphous systems. Special emphasis must be given to the opportunity to measureatomistic diffusion at relatively low temperatures where such measurements were far out of reach withpreviously established methods. The importance of short-range order is demonstrated on the basis ofMonte Carlo simulations.

Hydrothermal synthesis of heteroepitaxial Pb(ZrxTi1−x)O3 thin films at 90–150 °C

1997 ◽  
Vol 12 (5) ◽  
pp. 1176-1178 ◽  
Author(s):  
A. T. Chien ◽  
J. S. Speck ◽  
F. F. Lange
Keyword(s):  
Thin Films ◽  
Low Temperatures ◽  
High Dielectric Constant ◽  
Ambient Pressure ◽  
Random Access ◽  
Random Access Memory ◽  
Molar Ratio ◽  
Access Memory ◽  
Eds Analysis ◽  
High Dielectric

Pb(ZrxTi1−x)O3 and PbZrO3 heteroepitaxial thin films were produced in an aqueous solution (10 M KOH) at ambient pressure and low temperatures (90–150 °C) on (001) SrTiO3 and LaAlO3 single crystal substrates. Growth of the Pb(ZrxTi1−x)O3 and PbZrO3 thin films initiates by the formation of {100} faceted islands. Energy dispersive spectroscopy (EDS) analysis of the Pb(ZrxTi1−x)O3 thin film shows that the Zr: Ti ratio is 45: 56, nearly identical to the molar ratio of the precursors. This route might provide a viable low temperature alternative for the formation of high dielectric constant thin films for applications such as dynamic random access memory (DRAM).

Atomic scale surface engineering of micro- to nano-sized pharmaceutical particles for drug delivery applications

Nanoscale ◽  
2017 ◽  
Vol 9 (32) ◽  
pp. 11410-11417 ◽  
Author(s):  
D. Zhang ◽  
M. J. Quayle ◽  
G. Petersson ◽  
J. R. van Ommen ◽  
S. Folestad
Keyword(s):  
Drug Delivery ◽  
Atomic Layer Deposition ◽  
Surface Engineering ◽  
Atomic Layer ◽  
Atomic Scale ◽  
Ambient Conditions ◽  
Surface Layers ◽  
Layer Deposition ◽  
Atomic Surface ◽  
Scale Surface

Few atomic surface layers via atomic layer deposition under near ambient conditions significantly altered dissolution and dispersion of pharmaceutical particles.

scholarly journals Mixed Metal-Antimony Oxide Nanocomposites: Low pH Water Oxidation Electrocatalysts with Outstanding Durability at Ambient and Elevated Temperatures

2021 ◽  
Author(s):  
Luke Sibimol ◽  
Manjunath Chatti ◽  
Asha Yadav ◽  
Brittany Kerr ◽  
Jiban Kangsabanik ◽  
...  
Keyword(s):  
Water Oxidation ◽  
High Performance ◽  
Density Functional ◽  
High Stability ◽  
Proton Exchange Membrane ◽  
Elevated Temperatures ◽  
Antimony Oxide ◽  
Proton Exchange ◽  
Efficient Production ◽  
Ambient Conditions

Proton-exchange membrane water electrolysers provide many advantages for the energy-efficient production of H<sub>2</sub>, but the current technology relies on high loadings of expensive iridium at the anodes, which are often unstable in operation. To address this, the present work scrutinises the properties of antimony-metal (Co, Mn, Ni, Fe, Ru) oxides synthesised as flat thin films by a solution-based method for the oxygen evolution reaction in 0.5 M H<sub>2</sub>SO<sub>4</sub>. Among the non-noble-metal catalysts, only cobalt-antimony and manganese-antimony oxides demonstrate high stability and reasonable activity under ambient conditions, but slowly lose activity at elevated temperatures. The ruthenium-antimony system is highly active, requiring an overpotential of 0.39 ± 0.03 and 0.34 ± 0.01 V to achieve 10 mA cm<sup>-2</sup> at 24 ± 2 and 80 °C, respectively, and remaining remarkably stable during one-week tests at 80 °C. The <i>S</i>-number for this catalyst is higher than that for the high-performance benchmark Ir-based systems. Density functional theory analysis and physical characterisation reveal that this high stability is supported by the enhanced hybridisation of the oxygen p- and metal d-orbitals induced by antimony, and can arise from two distinct structural scenarios: either formation of an antimonate phase, or nanoscale intermixing of metal and antimony oxide crystallites.

scholarly journals Experimental and Computational Investigation of binary drop collisions under elevated pressure

2017 ◽  
Author(s):  
Jan Breitenbach ◽  
Louis Maximilian Reitter ◽  
Muyuan Liu ◽  
Kuan-Ling Huang ◽  
Dieter Bothe ◽  
...  
Keyword(s):  
Relative Velocity ◽  
Computational Study ◽  
Ambient Pressure ◽  
Experimental System ◽  
Elevated Pressure ◽  
Computational Investigation ◽  
Ambient Conditions ◽  
Influencing Parameters ◽  
Gas Layer ◽  
The Impact

Spray systems often operate under extreme ambient conditions like high pressure, which can have a significant influence on important spray phenomena. One of these phenomena is binary drop collisions. Such collisions, depending on the relative velocity and the impact parameter (eccentricity of the collision), can lead to drop bouncing, coalescence or breakup. This experimental and computational study is focused on the description of the phenomenon of drop bouncing, which is caused by a thin gas layer preventing the drops coalescence. To identify the main influencing parameters of this phenomenon, experiments on binary drop collisions are performed in a pressure chamber. This experimental system allows us to investigate the effect of an ambient pressure (namely the density and viscosity of the surrounding gas) on the bouncing/coalescence threshold.DOI: http://dx.doi.org/10.4995/ILASS2017.2017.4758

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