Low Coordination Number Research Articles

Selective Formation of Cu Active Sites with Different Coordination States on Pseudospinel CuAl2O4 and Their NO Reduction Catalysis.

In the spinel framework, copper (Cu) in two distinct coordination states exhibits catalytic activity for NO reduction through different mechanisms. However, detailed exploration of their respective catalytic properties, such as the redox behavior of Cu and substrate molecule adsorption, has been challenging due to difficulties in their separate formation. In this study, we present the controlled formation of pseudospinel CuAl2O4, containing exclusively tetrahedrally or octahedrally coordinated Cu, achieved by manipulating aging temperature and O2 concentration. Through these materials, we observed that in the CO-NO reaction, the step primarily determining the rate differs: NO reduction dominates with octahedrally coordinated Cu, whereas carbon monoxide (CO) oxidation is prominent with tetrahedrally coordinated Cu. The lower coordination number of Cu significantly benefits NO reduction but negatively impacts the CO-NO reaction, albeit positively influencing NO reduction in three-way catalytic reactions.

Electronic Structure of Three-Coordinate FeII and CoII β-Diketiminate Complexes.

The β-diketiminate supporting group, [ArNCRCHCRNAr]-, stabilizes low coordination number complexes. Four such complexes, where R = tert-butyl, Ar = 2,6-diisopropylphenyl, are studied: (nacnactBu)ML, where M = FeII, CoII and L = Cl, CH3. These are denoted FeCl, FeCH3, CoCl, and CoCH3 and have been previously reported and structurally characterized. The two FeII complexes (S = 2) have also been previously characterized by Mössbauer spectroscopy, but only indirect assessment of the ligand-field splitting and zero-field splitting (zfs) parameters was available. Here, EPR spectroscopy is used, both conventional field-domain for the CoII complexes (with S = 3/2) and frequency-domain, far-infrared magnetic resonance spectroscopy (FIRMS) for all four complexes. The CoII complexes were also studied by magnetometry. These studies allow accurate determination of the zfs parameters. The two FeII complexes are similar with nearly axial zfs and large magnitude zfs given by D = -37 ± 1 cm-1 for both. The two CoII complexes likewise exhibit large and nearly axial zfs, but surprisingly, CoCl has positive D = +55 cm-1 while CoCH3 has negative D = -49 cm-1. Theoretical methods were used to probe the electronic structures of the four complexes, which explain the experimental spectra and the zfs parameters.

Boosted Light Alkane Deep Oxidation via Metal Bond Length Modulation-Induced C-C Bond Preferential Activation.

Light alkanes (LAs), typical VOCs existing in both stationary and mobile sources, pose significant environmental concerns. Although noble metal catalysts demonstrate strong C-H bond activation, their effectiveness in degrading LAs is hindered by inherent challenges, including poor chemical stability and water resistance. Here, from a new perspective, we propose a feasible strategy that adjusting the metal bond lengths within Pd clusters through partial substitution of smaller radius 3d transition metals (3dTMs) to prioritize the activation of low-energy C-C bonds within LAs. Benefiting from this, PdCo/CeO2 exhibits exceptional catalytic performance in propane degradation due to their high capacity for C-C cleavage stemming from the shorter Pd-Co length (2.51 Å) and lower coordination number (1.73), boosting the activation of α-H and β-H of propane simultaneously and accelerating the mobility of postactivated oxygen species to prevent Pd center deep oxidation. The presence of 3dTMs on Pd clusters improves the redox and charge transfer ability of catalysts, resulting in an amplified generation of oxygen vacancies and facilitating the adsorption and activation of reactants. Mechanistic studies and DFT calculations suggest that the substitution of 3dTMs significantly accelerate C-C bond cleavage within C3 intermediates to generate the subsequent C2 and C1 intermediates, suppressing the generation of harmful byproducts.

Assessment of shear band evolution using discrete element modelling

PurposeThe objective of this paper is to quantitatively assess shear band evolution by using two-dimensional discrete element method (DEM).Design/methodology/approachThe DEM model was first calibrated by retrospectively modelling existing triaxial tests. A series of DEM analyses was then conducted with the focus on the particle rotation during loading. An approach based on particle rotation was developed to precisely identify the shear band region from the surrounding. In this approach, a threshold rotation angle ω0 was defined to distinguish the potential particles inside and outside the shear band and an index g(ω0) was introduced to assess the discrepancy between the rotation response inside and outside shear band. The most distinct shear band region can be determined by the ω0 corresponding to the peak g(ω0). By using the proposed approach, the shear band development of two computational cases with different typical localised failure patterns were successfully examined by quantitatively measuring the inclination angle and thickness of shear band, as well as the microscopic quantities.FindingsThe results show that the shear band formation is stress-dependent, transiting from conjugated double shear bands to single shear band with confining stress increasing. The shear band evolution of two typical localised failure modes exhibits opposite trends with increasing strain level, both in inclination angle and thickness. Shear band featured a larger volumetric dilatancy and a lower coordination number than the surrounding. The shear band also significantly disturbs the induced anisotropy of soil.Originality/valueThis paper proposed an approach to quantitatively assess shear band evolution based on the result of two-dimensional DEM modelling.

Coordination chemistry effects of the space-demanding solvent molecule N,N'-dimethylpropyleneurea.

Crystallographic investigations of eight homoleptic N,N'-dimethylpropyleneurea (dmpu) coordinated metal ions in the solid state, [Mg(dmpu)5]I2 (1), [Ca(dmpu)6]I2 (2), [Ca(dmpu)6](ClO4)2 (3), [Ca(dmpu)6](CF3SO3)2 (4), [Sr(dmpu)6](CF3SO3)2 (5), [Ba(dmpu)6](CF3SO3)2 (6), [Sc(dmpu)6]I3 (7), and [Pr(dmpu)6]I(I3)2 (8), and the complex [CoBr2(dmpu)2] (9) as well as the structures of the dmpu coordinated calcium, strontium, barium, scandium(III) and cobalt(II) ions and the cobalt(II) bromide complex in dmpu solution as determined by EXAFS are reported. The methyl groups in the dmpu molecule are close to the oxygen donor atom, causing steric restrictions, and making dmpu space-demanding at coordination to metal ions. The large volume required by the dmpu ligand at coordination contributes to crowdedness around the metal ion with often lower coordination numbers than for oxygen donor ligands without such steric restrictions. The crowdedness is seen in M⋯H distances equal to or close to the sum of the van der Waals radii. To counteract the space-demand at coordination, the dmpu molecule has an unusual ability to increase the M-O-C bond angle to facilitate as large coordination numbers as possible. M-O-C bond angles in the range of 125-170° are reported depending on the crowdedness caused by the coordination figure and the M-O bond distance. All reported structures of dmpu coordinated metal ions in both the solid state and dmpu solution are summarized to study the relationship between the M-O-C bond angle and the crowdedness around the metal ion. However, highly symmetric complexes seem to be favoured in the solid state due to favourable lattice energies. As a result, the dmpu coordinated lanthanoid(III) ions are octahedral in the solid state, while they, except lutetium, are seven-coordinate in the dmpu solution.

Fully tricoordinated assembly unveils a pioneering nonlinear optical crystal (SbTeO3)(NO3).

Balancing the critical property requirements is key to surmounting the obstacles in the application of nonlinear optical (NLO) crystals. Tricoordinated units, characterized by nearly the lowest coordination number, are common in inorganic NLO-active oxides; however, crystals solely composed of such units are rare. Herein, by assembling three distinct tricoordinated units (SbO3, TeO3, and NO3) into a single crystal, a pioneering fully tricoordinated NLO material, (SbTeO3)(NO3), was synthesized via a facile volatilization method. As the first reported tellurite-antimonite NLO crystal, (SbTeO3)(NO3) exhibits well-balanced properties: a strong phase-matched second-harmonic generation (SHG) effect (2.2 × KDP), short UV cutoff edge (253 nm) and moderate birefringence (0.081@546 nm). Unlike most deliquescent nitrates, (SbTeO3)(NO3) demonstrates exceptional water resistance (>30 days), attributed to its unique hydrophobic layers and stereochemically active lone pair (SCALP) electrons in the Sb3+ and Te4+ cations. Theoretical calculations reveal that the optical bandgap and SHG effect of (SbTeO3)(NO3) are collectively governed by the three tricoordinated motifs, with individual SHG contributions of 20.92%, 23.88%, and 55.12% from [SbO3], [TeO3] and [NO3], respectively. This breakthrough underscores the efficacy of the fully tricoordinated assembly strategy in engineering NLO materials with optimally balanced properties.

Strongly facet-dependent activity of iron-doped β-nickel oxyhydroxide for the oxygen evolution reaction.

Iron (Fe)-doped β-nickel oxyhydroxide (β-NiOOH) is a highly active, noble-metal-free electrocatalyst for the oxygen evolution reaction (OER), with the latter being the bottleneck in electrochemical water splitting for sustainable hydrogen production. The mechanisms underlying how the Fe dopant modulates this host material's water electro-oxidation activity are still not entirely clear. Here, we combine hybrid density functional theory (DFT) and Hubbard-corrected DFT to investigate the OER activity of the most thermodynamically favorable (and therefore, expected to be the majority) crystallographic facets of β-NiOOH, namely (0001) and (101̄0). By considering active sites involving both oxidation and reduction of the transition-metal active center during the redox cycle on these two different facets, we show that six-fold-lattice-coordinated Fe in β-NiOOH is redox inactive towards both oxidation and reduction while five-fold-lattice-coordinated Fe in β-NiOOH does exhibit redox activity. However, the determined redox activity of Fe (or lack of it) is not indicative of good (or bad) performance as a dopant on these two facets. Three of the four active sites investigated (oxo and hydroxo sites on (0001) and a hydrated site on (101̄0)) exhibit only a marginal (<0.1 V) decrease or increase in the thermodynamic overpotential upon doping with Fe. Only one of the redox-active sites investigated, the hydroxo site on (101̄0), exhibits a large attenuation in the thermodynamic overpotential upon doping (to ∼0.52 V from 0.86 V), although the doped overpotential is larger than that observed experimentally for Fe-doped NiOOH. Thus, although pure β-NiOOH facets containing four-, five-, or six-fold lattice-coordinated Ni sites have roughly equal OER activities, yielding similar OER onset potentials (shown in A. Govind Rajan, J. M. P. Martirez and E. A. Carter, J. Am. Chem. Soc., 2020, 142, 3600-3612), only those facets containing four-fold lattice-coordinated Fe (e.g., as shown in J. M. P. Martirez and E. A. Carter, J. Am. Chem. Soc., 2019, 141, 693-705) would be active under analogous conditions for the Fe-doped material. It follows that, while undoped β-NiOOH demonstrates a roughly facet-independent oxygen evolution activity, the activity of Fe-doped β-NiOOH strongly depends on the crystallographic facet. Our study further motivates the investigation of strategies for the selective growth of facets with low iron coordination number to enhance the water splitting activity of Fe-doped β-NiOOH.

Highly efficient semi-hydrogenation in strained ultrathin PdCu shell and the atomic deciphering for the unlocking of activity-selectivity.

Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core-shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd-Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core-shell nanocatalysts.

The role of vanadium substitution in the oxygen sublattice disorder of Ba7Nb4MoO20-based hexagonal perovskite oxide-ion conductors.

Ba7Nb4MoO20-based hexagonal perovskite derivatives are promising oxygen-ion conductors for solid electrolytes in solid-oxide fuel cells and electrolysers. A thorough understanding of chemical substitution and its impact on structural features conducive to high ionic conductivity is fundamental for decreasing the operation temperature of such devices. Here, a new 7H polytype-based composition, namely Ba7Nb3.9-x V x Mo1.1O20.05, is investigated to assess the effect of vanadium substitution. Structural changes upon V incorporation are studied using X-ray and neutron diffraction, as well as 51V and 93Nb solid-state nuclear magnetic resonance spectroscopy. For the undoped composition at room temperature, two distinct oxygen sites (O1 and O5) are found along the palmierite-like layer, corresponding to a mix of four- and six-fold coordination for adjacent M2 cations. At high temperature (527 °C), reorganization of oxygen results in the major occupation of O1 and four-fold (tetrahedral) coordination of the M2 cations. The same rearrangement is observed upon V-substitution, but already at room temperature. From 51V NMR, we identified a tetrahedral coordination for V5+ cations, indicating their preferential occupation of the M2 site. This preferential occupation by V5+ cations is correlated with increasing tetrahedral coordination of Nb5+ cations as observed from 93Nb NMR. Altogether, these observations indicate that V-substitution impacts the oxygen sublattice so as to mimic the high-temperature structure. Additionally, BVSE calculations demonstrate a decreasing energy barrier for O2- migration associated with the presence of vanadium in the structure. This conclusion corroborates the hypothesis that vanadium's propensity for a lower coordination number is beneficial for promoting high O2- mobility in this promising class of oxide-ion conductors.

Adsorption mechanisms of decomposition species of CHON-containing explosives on aluminum surfaces.

Aluminum (Al) possesses high combustion enthalpy and is thus extensively used as the fuel additive in explosives to form aluminized explosives with excellent energy performance. In the energy release process of aluminized explosives, the adsorption of Al surfaces plays an important role in catalyzing the explosive decomposition and triggering the oxidation of themselves. However, it still remains elusive owing to the multiplicity of adsorbed substances. Herein, the adsorption mechanism of decomposition species of CHON-containing explosives on Al surfaces is studied synoptically by combining reactive molecular dynamics simulations with density functional theory calculations. The results indicate that the Al surface structure and the activity of adsorbed molecules both have an impact on adsorption. The cluster surface generally outperforms the slab one in adsorptivity due to the lower coordination number of Al atoms. Meanwhile, the more active adsorbed molecules lead to chemisorption or even dissociative adsorption, beneficial to the subsequent Al oxidation. Besides, electrons will transfer from the Al surface to the adsorbed molecules as chemisorption occurs; while the density of states of the Al surface and molecules are altered, especially for carbon oxides with significant electronic delocalization. This work is expected to deepen insights into the energy release of aluminized explosives and help provide a proposal for enhancing energy release efficiency.

Stability of intermetallic compounds: Geometrical and topological aspects

We have applied a universal geometrical-topological approach to analyze 23507 robust crystal structures of intermetallic compounds, which are deposited in the Inorganic Crystal Structure Database. All the structures were represented as three-periodic nets and arranged into 2551 topological types each of which possesses a unique system of interatomic bonds. For all 104309 topologically different atoms in these structures their environments (local atomic configurations, LACs) were explored within the first and second coordination shells. In total, 5251 topologically distinct types of coordination polyhedra and 21450 types of two-shell LACs were distinguished and deposited into our interactive database system TopCryst. We have found that the local density of the nearest environment of an atom naturally depends on its coordination number (CN) with a maximum at CN = 9. It was shown that LACs at CN ≥ 9 follow the close packing model of hard balls with Slater's atomic radii. At lower CNs, covalent interactions make a significant contribution that results in a decrease of the local density. Resting upon the dependence between the local density and CN we have proposed criteria for the estimation of the geometric instability (disbalance) of both a separate LAC and the whole intermetallic structure. We have revealed that strong geometric disbalance can be caused by errors in the structural data, incorrect description of the crystal structure, non-metallic nature of the chemical bonding or metastability of the crystalline phase. Thus the instability criteria can serve as important indicators of the structure inconsistency that is especially useful for checking crystallographic information on intermetallics or validating the structural models predicted by theoretical methods.

Theoretical insights into the thermal behaviors and coalescence of truncated octahedral Au nanoparticles

Truncated octahedral Au nanoparticles (NPs) dispersed on Ti-containing supports has been demonstrated as a promising catalyst for the propylene epoxidation with H2 and O2, while the catalytic stability for the industrial application is still challenging. Herein, thermodynamics analysis and molecular dynamics calculations are employed to address the thermal behaviors and coalescence of truncated octahedral Au NPs. The melting temperature of Au NPs is found to decrease with the decreasing particle size, and the melting initiates from the outermost edge and (100) atoms with lower coordination numbers followed by the (111) atoms and proceeds inwards. The coalescence of two Au NPs deforms smaller sized Au NP while remains the larger sized one at low temperatures, but the two nanoparticles melt into a fully mixed spherical one at high temperatures. Moreover, the (111) facet is more facile for the coalescence than other exposed facets on Au NPs.

How *CO spill-over affects C–C coupling on amorphous Cu for converting CO2 to multi-carbon products

Cu-based catalysts, especially oxide-derived Cu, exhibit high multi-carbon product selectivity, thus showing excellent industrialization prospects. Although the mechanism for the superiority is debatable, both experimental and calculation results indicate that the more disordered crystal structure is better for C–C coupling. Herein, we build an amorphous Cu model by making oxygen doping and disordered morphology to approach the actual condition. The oxygen atoms in the subsurface would diffuse to the surface, creating a vacancy that would break the C–C bond. Besides, only limited sites on the amorphous surface with low coordination number and stepped morphology are conducive to the occurrence of CO–CO coupling. Furthermore, we find that the spill-over effect on the amorphous Cu surface could promote the coupling of two *CO intermediates by reducing the reaction energy barrier rather than 50 % of the C–C coupling process on stationary positions. This beneficial strategy encourages the synthesis of C2+ products.

Defect Rich Structure Activated 3D Palladium Catalyst for Methanol Oxidation Reaction.

Controlling the structure and properties of catalysts through atomic arrangement is the source of producing a new generation of advanced catalysts. A highly active and stable catalyst in catalytic reactions strongly depends on an ideal arrangement structure of metal atoms. We demonstrated that the introduction of the defect-rich structures, low coordination number (CN), and tensile strain in three-dimensional (3D) urchin-like palladium nanoparticles through chlorine bonded with sp-C in graphdiyne (Pd-UNs/Cl-GDY) can regulate the arrangement of metal atoms in the palladium nanoparticles to form a special structure. In situ Fourier infrared spectroscopy (FTIR) and theoretical calculation results show that Pd-UNs/Cl-GDY catalyst is beneficial to the oxidation and removal of CO intermediates. The Pd-UNs/Cl-GDY for methanol oxidation reaction (MOR) that display high current density (363.6 mA cm-2) and mass activity (3.6 A mgPd-1), 12.0 and 10.9 times higher than Pd nanoparticles, respectively. The Pd-UNs/Cl-GDY catalyst also exhibited robust stability with still retained 95% activity after 2000 cycles. A defects libraries of the face-centered cubic and hexagonal close-packed crystal catalysts (FH-NPs) were synthesized by introducing chlorine in graphdiyne. Such defect-rich structures, low CN, and tensile strain tailoring methods have opened up a new way for the catalytic reaction of MOR.

Defect Rich Structure Activated 3D Palladium Catalyst for Methanol Oxidation Reaction

AbstractControlling the structure and properties of catalysts through atomic arrangement is the source of producing a new generation of advanced catalysts. A highly active and stable catalyst in catalytic reactions strongly depends on an ideal arrangement structure of metal atoms. We demonstrated that the introduction of the defect‐rich structures, low coordination number (CN), and tensile strain in three‐dimensional (3D) urchin‐like palladium nanoparticles through chlorine bonded with sp‐C in graphdiyne (Pd‐UNs/Cl‐GDY) can regulate the arrangement of metal atoms in the palladium nanoparticles to form a special structure. In situ Fourier infrared spectroscopy (FTIR) and theoretical calculation results show that Pd‐UNs/Cl‐GDY catalyst is beneficial to the oxidation and removal of CO intermediates. The Pd‐UNs/Cl‐GDY for methanol oxidation reaction (MOR) that display high current density (363.6 mA cm−2) and mass activity (3.6 A mgPd−1), 12.0 and 10.9 times higher than Pd nanoparticles, respectively. The Pd‐UNs/Cl‐GDY catalyst also exhibited robust stability with still retained 95 % activity after 2000 cycles. A defects libraries of the face‐centered cubic and hexagonal close‐packed crystal catalysts (FH‐NPs) were synthesized by introducing chlorine in graphdiyne. Such defect‐rich structures, low CN, and tensile strain tailoring methods have opened up a new way for the catalytic reaction of MOR.

Influence of A-Site Deficiency and B-Site Composition on the Electrical and Crystallographic Properties of (La0.25Sr0.25Ca0.45)yTi0.95Ni0.05-xMnxO3-δ Solid Oxide Fuel Cell Anode

(La,Sr)TiO3-δ has attracted specific attention over the past years due to its superior dimensional stability, high conductivity, and significant tolerance against sulfur poisoning and carbon depositions. To increase the catalytic activity and chemical stability, many different doping levels and stoichiometries for LaxSr1-xTiO3-δ (LST) have been investigated [1, 2]. Doping of B-site with Mn has been shown to promote electroreduction under SOFC conditions [3]. Furthermore, Mn is known to accept lower coordination numbers in perovskites, especially for Mn3+ (3d4), and so may enhance oxide-ion migration [4]. In addition, MnO is clearly stable under fuel conditions unlike Co or Ni oxides [4].In this research influence of A-site deficiency and B-site chemical composition on electrical performance of La0.25Sr0.25Ca0.45Ti0.95Ni0.05-xMnxO3-δ (x=0-0.05) (LSCTNM-x) hydrogen electrode has been studied. The crystal structure and microstructure have been studied using X-ray diffraction and SEM to confirm the phase purity and visualize the microstructure of studied electrode layers. To understand the influence of MIEC material composition on electrical conductivities of LSCTNM, the DC four-probe conductivity measurements of porous electrode layers has been performed. Conductivities have been measured at two different atmospheres: 1% H2 + 1.7% H2O + 97.3% Ar and 98.3% H2 + 1.7% H2O. It has been shown that all materials with LSCTNM compositions behave like semiconductor and the conductivity is significantly dependent on composition. The maximal total electrical conductivity of porous electrode layers was characteristic for the LSCTNM materials with 10% A-site deficiency, in 98.3% H2 + 1.7% H2O atmosphere. Keywords: solid oxide fuel cell; conductivity; perovskite; fuel electrode; MIEC.[1] X. Li, H. Zhao, X. Zhou, N. Xu, Z. Xie, N. Chen, Electrical conductivity and structural stability of La-doped SrTiO3 with A-site deficiency as anode materials for solid oxide fuel cells, international journal of hydrogen energy 35 (2010) 7913-7918.[2] A. Gondolini, E. Mercadelli, G. Constantin, L. Dessemond, V. Yurkiv, R. Costa, A. Sanson, On the manufacturing of low temperature activated Sr0.9La0.1TiO3-δ-Ce1-xGdxO2-δ anodes for solid oxide fuel cell, Journal of the European Ceramic Society, 38 (2018) 153–161.[3] P. Holtappels, J. Bradley, J.T.S. Irvine, A. Kaiser, M. Mogensen, Electrochemical characterization of ceramic SOFC anodes, J. Electrochem. Soc. A 148 (2001) 923–929.[4] S. Tao, J.T.S. Irvine, A redox-stable efficient anode for solid-oxide fuel cells, nature materials, 2 (2003) 320-323.

Three-coordinate monoanions of rhodium(1–) and iridium(1–): Isolable examples of coordinatively-unsaturated metalate anions

Metalate complexes – those that possess metal centers in formally negative oxidation states – are typically coordinatively and electronically saturated organometallic species. The reduced nature of the metal centers within these complexes is well understood to be responsible for their high reactivity as metal-based nucleophiles. While the chemistry of such complexes is extensive, there are very few examples where coordinative or electronic unsaturation accompanies highly-reduced d-orbital manifolds as a means to augment reactivity. Reported here is the isolation of the 16e–, d10 rhodium and iridium metalate anions, [M(CNArDipp2)3]–, where coordinative unsaturation is achieved through the use of encumbering m-terphenyl isocyanide ligands. Reactivity studies with electrophiles demonstrate that the Rh and Ir centers in these metalates retain significant nucleophilic character, which enables the formation of unusual metal/main-group-element species on account of low coordination numbers.

Systematic effect of particle roundness/angularity on macro- and microscopic behavior of granular materials

Roundness/angularity is a vital shape descriptor that significantly impacts the mechanical response of granular materials and is closely associated with many geotechnical problems, such as liquefaction, slope stability, and bearing capacity. In this study, a series of biaxial shearing tests are conducted on dual-size aluminum circular and hexagonal rod material. A novel image analysis technique is used to estimate particle kinematics. A discrete element model (DEM) of the biaxial shearing test is then developed and validated by comparing it with the complete experimental data set. To systematically investigate the effect of roundness/angularity on granular behavior, the DEM model is then used to simulate eight non-elongated convex polygonal-shaped particles. Macroscopically, it is observed that angular assemblies exhibit higher shear strengths and volumetric deformations, i.e., dilations. Moreover, a unique relationship is observed between the critical state stress ratio and particle roundness. Microscopically, the roundness shows a considerable effect on rotational behavior such that the absolute mean cumulative rotation at the same strain level increases with roundness. A decrease in roundness results in relatively stronger interlocking, restricting an individual particle’s free rotation. Furthermore, the particles inside the shear band exhibit significantly higher rotations and are always associated with low coordination numbers. Generally, the geometrical shape of a particle is found to have a dominant effect on rotational behavior than coordination number.Graphical

Identifying Underexplored and Untapped Regions in the Chemical Space of Transition Metal Complexes.

We survey more than 240 000 crystallized mononuclear transition metal complexes (TMCs) to identify trends in preferred geometric structure and metal coordination. While we observe that an increased level of d filling correlates with a lower coordination number preference, we note exceptions, and we observe undersampling of 4d/5d transition metals and 3p-coordinating ligands. For the one-third of mononuclear TMCs that are octahedral, analysis of the 67 symmetry classes of their ligand environments reveals that complexes often contain monodentate ligands that may be removable, forming an open site amenable to catalysis. Due to their use in catalysis, we analyze trends in coordination by tetradentate ligands in terms of the capacity to support multiple metals and the variability of coordination geometry. We identify promising tetradentate ligands that co-occur in crystallized complexes with labile monodentate ligands that would lead to reactive sites. Literature mining suggests that these ligands are untapped as catalysts, motivating proposal of a promising octa-functionalized porphyrin.

Achieving super dispersed metallic nickel nanoparticles over MCM-41 for highly active and stable hydrogenation of olefins and aromatics

Hydrogenation of olefins and aromatics is of significance for fuel processing and hydrogen storage, and developing nickel (Ni) catalyst highly active at low reaction temperature is the key to low the process cost. Herein we developed an ammonium citrate assisted impregnation method to fabricate loaded Ni catalyst (NiM-2) for hydrogenation. The Ni2+ species are anchored on the support MCM-41 strongly and evenly in form of Ni-citrate complex via the H-bonding between Si-OH group of MCM-41 and –COO- of citrate. During reduction, the carbon layerstemporarily formed by carbonization of citrate species inhibit the transfer and sintering of Ni species, and finally induces ultra-small metallic Ni nanoparticles after carbon layers slow decomposition by Ni species. Low coordination numbers and strong electron interaction between small metallic Ni nanoparticles and MCM-41 support upshift the d-band center of metallic Ni atoms. In hydrogenation, the small particle size and easier reduction for oxidized Ni species provide abundant active sites for reaction, and the upshifted d-band center induces strongly adsorption and activation of C = C bonds, which is confirmed for the first time in our work. As a result, the catalyst exhibits superior activity compared with reported and commercial Ni-based catalysts for hydrogenation of olefins and aromatics. Specifically, the catalyst with higher Ni loading (18%) exhibits good activity under room temperature and 0.1 MPa for hydrogenation of dicyclopentadiene and are comparable to Pd catalysts, making it as one of the best non-precious metal catalysts for hydrogenation reaction. And also, NiM-2 shows extremely high stability.