Surface Facets Research Articles

Theoretical insights of electrocatalytic hydrogen evolution on MoP nanocrystal

A methodical computational investigation was performed to gain insights into the factors and mechanisms that determine the catalytic activity of molybdenum phosphide (MoP). We analysed the structure and energetics as well as hydrogen adsorption behaviour on the (100) crystallographic plane of MoP. The Gibbs free energy and density of states studies were performed to elucidate the crystal chemistry and bonding mechanism of MoP(100) with the adsorbate. The computed values of ΔGH∗ at different hydrogen coverages are then used to predict the hydrogen evolution reaction (HER) activity on the (100) surface. The obtained values of hydrogen Gibbs free energy of adsorption ΔGH showed HER activity ranging between −0.35 and 0.10 eV. Our study has placed the (100) surface of MoP nanoparticles as highly suited analogues to platinum in the HER. The high intrinsic activity of MoP(100) is a result of a distinct electronic structure induced by the presence of phosphorus a phenomenon known as a ‘ligand effect’. The presence of phosphorus benefits the catalyst by improving intrinsic catalytic activity and enhancing proton adsorption kinetics. The results obtained from this study proved that phosphorizing and surface faceting play a crucial role in enhancing the catalytic performance of transition metals. Key trends that underpin the potential of MoP(100) as a catalyst for improved HER were identified, with a view to implement these findings for the practical design of improved catalysts for hydrogen production based on molybdenum phosphide.

Dual Active Centers Linked by a Reversible Electron Station as a Multifunctional Nanozyme to Induce Synergetically Enhanced Cascade Catalysis for Tumor-Specific Therapy.

Nanozymes have shown great promise in reactive oxygen species (ROS)-mediated tumor therapy with mitigated side effects but are normally limited by the complex tumor microenvironment (TME). Herein, to overcome the adverse effects of TME, such as tumor hypoxia and high endogenous glutathione (GSH), an aptamer-functionalized Pd@MoO3-x nano-hydrangea (A-Pd@MoO3-x NH) is constructed for high-efficiency cancer therapy. Utilizing the irregular shape characteristics of nano Pd, the A-Pd@MoO3-x NH nanozyme simultaneously exposes catalase-like Pd(111) and oxidase-like Pd(100) surface facets as dual active centers. This can catalyze cascade enzymatic reactions to overcome the negative effects of tumor hypoxia caused by the accumulation of cytotoxic superoxide (O2•-) radicals in TME without any external stimuli. In addition, the nanozyme can effectively degrade the overexpressed glutathione (GSH) through the redox reaction to avoid nontherapeutic consumption of O2•- radicals. More significantly, as a reversible electron station, MoO3-x can extract electrons from H2O2 decomposing on Pd(111) or GSH degradation and transfer them back to Pd(100) through oxygen bridges or few Mo-Pd bonds. This can synergistically enhance enzyme-like activities of dual active centers and the GSH-degrading ability to enrich O2•- radicals. In this way, the A-Pd@MoO3-x NH nanozyme can selectively and remarkably kill tumor cells while keeping the normal cell line unharmed.

Coupling covariance matrix adaptation with continuum modeling for determination of kinetic parameters associated with electrochemical CO2 reduction

Coupling covariance matrix adaptation with continuum modeling for determination of kinetic parameters associated with electrochemical CO2 reduction

Surface Facet Dependent Cycling Stability of Layered Cathodes

AbstractHigh chemical and mechanical stability of cathode surface are the prerequisites enabling high‐performance rechargeable battery. Surface facet is among the surface properties that dictate surface stability and cycling performance, while its underlying mechanism remains elusive. Herein, it is reported that surface stability is closely related to the surface facet for a variety of layered cathodes. The investigation shows that surface structure of P2 layered cathode undergoes sequential transformation upon cycling, which results in severe surface degradation. This study finds that the surface facets perpendicular to the (002) planes experience severe cracking and corrosion, while other surface facets are much more stable. The surface stability difference mainly comes from a geometric effect on strain release, which determines the mechanical stability of surface. Chemically, transition metal condensation forms a passivation layer to effectively prevent the inward propagation of surface degradation. Therefore, the surface facets oblique to the layered‐planes are intrinsically more resistant to mechanical cracking and chemical corrosion, which is further verified as a common effect in several O3‐type layered cathodes. This work not only deepens the understanding of the mechanism how surface facet affects surface stability, but also validates surface facet regulation can be a promising strategy for optimizing battery materials.

A machine learning-based prediction of crystal orientations for multicrystalline materials

We established a rapid, low-cost, and accurate technique to measure crystallographic orientations in multicrystalline materials by optical images and machine learning. A long short-term memory neural network was trained with pairs of light reflection patterns and the correct orientations of each grain, successfully predicting orientation with an error median of 8.61°. The model was improved by diverse data taken from various incident light angles and by data augmentation. When trained on different incident angles, the model was capable of estimating different orientations. This is related to the geometrical configuration of the incident light angles and surface facets of the crystal. The failure in certain orientations is thought to be complemented by supplementary data taken from different incident angles. Combining data from multiple incident angles, we acquired an error median of 4.35°. Data augmentation was successfully performed, reducing error by an additional 35%. This technique can provide the crystallographic orientations of a 15 × 15 cm2 sized wafer in less than 8 min, while baseline techniques such as electron backscatter diffraction and Laue scanner may take more than 10 h. The rapid and accurate measurement can accelerate data collection for full-sized ingots, helping us gain a comprehensive understanding of crystal growth. We believe that our technique will contribute to controlling crystalline structure for the fabrication of high-performance materials.

Improving oxygen evolution efficiency in BiVO4 photoanodes through surface facet control with TiCl3 as a structure guide agent

Efficient conversion of solar energy into chemical fuels through photoelectrochemical (PEC) water oxidation replies on highly efficient photoanodes. The surface crystal facet of photoanode plays a critical role in determining the injection efficiency of photocarriers from photoanode to electrolyte. Thus, controlling the formation of surface crystal facets is believed to be an effective strategy for improving the energy conversion efficiency of photoelectrodes. However, it is still challenging to technically control the formation of surface crystal facets. Herein, we proposed to use TiCl3 as structure guide agent in hydrothermally synthesizing BiVO4 photoanodes. By adjusting the amount of structure-directing agent and the temperature of the precursor, we obtained a series of BiVO4 photoanodes with different amount ratios of {010} and {110} facets. It was found that a photocurrent density of 1.07 mA/cm2 could be obtained when the {010} facet was grown perpendicular to the substrate at 75% area ratio, which is much higher than the 0.20 mA/cm2 of the randomly oriented sample of the crystal. The incorporation of structure-directing agents reduces the surface energy of the corresponding crystalline surfaces, leading to an increase in charge separation capacity attributed to the different charge transfer distances in various crystal orientations. This work provides new proposals into the rational design of photoanode crystal surface structures for efficient PEC water oxidation, may have significant implications for the development of highly efficient photoanodes in the future.

Faceting/Roughening of WC/Binder Interfaces in Cemented Carbides: A Review.

Hardmetals (or cemented carbides) were invented a hundred years ago and became one of the most important materials in engineering. The unique conjunction of fracture toughness, abrasion resistance and hardness makes WC-Co cemented carbides irreplaceable for numerous applications. As a rule, the WC crystallites in the sintered WC-Co hardmetals are perfectly faceted and possess a truncated trigonal prism shape. However, the so-called faceting-roughening phase transition can force the flat (faceted) surfaces or interfaces to become curved. In this review, we analyze how different factors can influence the (faceted) shape of WC crystallites in the cemented carbides. Among these factors are the modification of fabrication parameters of usual WC-Co cemented carbides; alloying of conventional cobalt binder using various metals; alloying of cobalt binder using nitrides, borides, carbides, silicides, oxides; and substitution of cobalt with other binders, including high entropy alloys (HEAs). The faceting-roughening phase transition of WC/binder interfaces and its influence on the properties of cemented carbides is also discussed. In particular, the increase in the hardness and fracture toughness of cemented carbides correlates with transition of WC crystallites from a faceted to a rounded shape.

Inductively Coupled Nonthermal Plasma Synthesis of Size-Controlled γ-Al2O3 Nanocrystals.

Gamma alumina (γ-Al2O3) is widely used as a catalyst and catalytic support due to its high specific surface area and porosity. However, synthesis of γ-Al2O3 nanocrystals is often a complicated process requiring high temperatures or additional post-synthetic steps. Here, we report a single-step synthesis of size-controlled and monodisperse, facetted γ-Al2O3 nanocrystals in an inductively coupled nonthermal plasma reactor using trimethylaluminum and oxygen as precursors. Under optimized conditions, we observed phase-pure, cuboctahedral γ-Al2O3 nanocrystals with defined surface facets. Nuclear magnetic resonance studies revealed that nanocrystal surfaces are populated with AlO6, AlO5 and AlO4 units with clusters of hydroxyl groups. Nanocrystal size tuning was achieved by varying the total reactor pressure yielding particles as small as 3.5 nm, below the predicted thermodynamic stability limit for γ-Al2O3.

On the high-temperature oxidation behavior of a niobium-bearing high nickel-chromium alloy: microstructural evolution and implications on oxidation mechanisms

The oxidation behavior of a niobium-bearing high nickel-chromium alloy, widely used in the petrochemical industry, is systematically studied at 800 °C using a combination of transmission electron microscopy and atom-probe tomography experimental techniques and thermodynamic calculations. Oxidation leads to complex surface microstructures consisting of a protective chromia layer, an amorphous SiO2 (silica) layer, Fe- and Ni-rich metallic mushroom-like austenitic protrusions/precipitates, and sub-oxide voids with highly faceted surfaces. The thermodynamic equilibrium oxides of this alloy are studied as a function of oxygen activity using Thermo-Calc and compared to the observed microstructures. The growth kinetics of oxide layers are studied in detail.

Analysis of the oxide formation on Pd catalysts during NO oxidation by Atom Probe Tomography

To investigate the surface change of a palladium catalyst during NO conversion reactions, a combined study using a Flat Bed Reactor (FBR), Temperature-Programmed Reduction (TPR) and Atom Probe Tomography (APT) was performed. The Palladium (Pd) catalysts reveal a decreased conversion rate after the first heating cycle of the FBR measurement, which is attributed to the formation of an oxide layer on top of the metallic catalyst surface. The total oxygen content adsorbed on the surface of the catalyst was determined by TPR for catalyst particles that were produced by the spark discharge method. To analyse oxidation microscopically, Pd tips of comparable curvature radius were treated analogously to the FBR processing, analysed in APT and the effective oxide thicknesses were determined. During the 1st heating cycle, the degree of oxidation increases and once the temperature reaches to 350 °C, an irreversible layer of PdO oxide has been formed, 1.5 nm in thickness, with no preference for particular facets of the crystalline Pd surface.

Bridging Colloidal and Electrochemical Nanoparticle Growth with In Situ Electrochemical Measurements.

ConspectusProspective applications involving the electrification of industrial chemical processes and electrical energy to chemical fuels interconversion as part of the energy transition to renewable energy sources have led to an increasing need for highly tailored nanostructures immobilized on electrode surfaces. Control of surface facet structure across material compositions is of particular importance for ensuring performance in such applications. Colloidal methods for producing shaped nanoparticles in solution are abundant, particularly for noble metals. However, significant technical challenges remain with respect to rationally designing syntheses for the novel compositions and morphologies required to sustainably enable the above technological advances as well as in developing methods for uniformly and reproducibly dispersing colloidally synthesized nanostructures on electrode surfaces. The direct synthesis of nanoparticles on electrodes using chemical reduction approaches remains challenging, though recent advances have been made for certain materials and structures. Electrochemical nanoparticle synthesis─where an applied current or potential instead of a chemical reducing agent drives the redox chemistry of nanoparticle growth─is poised to play an important role in advancing the fabrication of nanostructured electrodes. Specifically, this Account focuses on the colloidal-inspired design of electrochemical syntheses and the interplay between colloidal and electrochemical approaches in terms of understanding the fundamental chemical reaction mechanisms of nanoparticle growth. An initial discussion of the development of electrochemical particle syntheses that incorporate colloidal synthetic tools highlights the promising emergent capabilities that result from blending these two approaches. Furthermore, it demonstrates how existing colloidal syntheses can be directly translated to electrochemical growth on a conductive surface using real-time electrochemical measurements of the chemistry of the growth solution. Measuring the open circuit potential of a colloidal synthesis over time and then replicating that measured potential during electrochemical deposition leads to the formation of the same nanoparticle shape. These in situ open circuit and chronopotentiometric measurements also give fundamental insight about the changing chemical environment during particle growth. We highlight how these time-resolved electrochemical measurements, as well as correlated spectroelectrochemical monitoring of particle formation kinetics, enable the extraction of information regarding mechanisms of particle formation that is difficult to obtain using other approaches. This information can be translated back into colloidal synthesis design via a directed, intentional approach to synthetic development. We additionally explore the added flexibility of synthetic design for methods involving electrochemically driven reduction as compared to the use of chemical reducing agents. The Account concludes with a brief perspective on potential future directions in both fundamental studies and synthetic development enabled by this emerging integrated electrochemical approach.

Synthesis of Petitjeanite Bi3O(OH)(PO4)2 Photocatalytic Microparticles: Effect of Synthetic Conditions on the Crystal Structure and Activity toward Degradation of Aqueous Perfluorooctanoic Acid (PFOA)

The discovery of synthetic Bi3O(OH)(PO4)2 [BOHP] and its application toward photocatalytic oxidation of the water contaminant perfluorooctanoic acid (PFOA) have prompted further interest in development. Despite its high activity toward PFOA degradation, the scarce appearance in the literature and lack of research have left a knowledge gap in the understanding of BOHP synthesis, formation, and photocatalytic activity. Herein, we explore the crystallization of BOHP microparticles via hydrothermal syntheses, focusing on the influence of ions and organics present in the reaction solution when using different hydroxide amendments (NaOH, NH4OH, NMe4OH, and NEt4OH). To better understand the unique structure-activity aspects of BOHP, the related bismuth oxy phosphate (BOP) structural family was also explored, including A-BOP (A = Na+ and K+) and M-BOP derivatives (M = Ca2+, Sr2+, and Pb2+). Results from materials characterization, including X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy, indicated that the crystal structure, morphology, and atomic composition were significantly influenced by solution pH, inorganic metal cations (Na+, K+, Ca2+, Sr2+, and Pb2+), and organic amines. Experiments involving ultraviolet photocatalytic destruction of PFOA by a BOHP suspension revealed that catalytic activity was influenced by the choice of reagents and their variable effect on surface facet growth and crystal defects in the resulting microparticles. Together, this work provides a strategy for crystal facet and surface defect engineering with the potential to expand to other metal oxides within the hydrothermal system.

Surface Rearrangement and Sublimation Kinetics of Supported Gold Nanoparticle Catalysts

Heterogeneous catalysts consisting of supported metallic nanoparticles typically derive exceptional catalytic activity from their large proportion of undercoordinated surface sites which promote adsorption of reactant molecules. Simultaneously, these high energy surface configurations are unstable, leading to nanoparticle growth or degradation and eventually a loss of catalytic activity. Surface morphology of catalytic nanoparticles is paramount to catalytic activity, selectivity, and degradation rates, however it is well-known that harsh reaction conditions can cause the surface structure to change. Still, limited research has focused on understanding the link between nanoparticle surface facets and degradation rates or mechanisms. Here, we study a model Au supported catalyst system over a range of temperatures using a combination of in situ transmission electron microscopy, kinetic Monte Carlo simulations, and density functional theory calculations to establish an atomistic picture of how variations in surface structures and atomic coordination environments lead to shifting evolution mechanisms as a function of temperature. By combining experimental results, which yield direct observation of dynamic shape changes and particle sublimation rates, with computational techniques, which enable understanding the fundamental thermodynamics and kinetics of nanoparticle evolution, we illustrate a two-step evolution mechanism in which mobile adatoms form through desorption from low-coordination facets and subsequently sublimate off the particle surface. By understanding the role of temperature in the competition between surface diffusion and sublimation, we are able to show how individual atomic movements lead to particle scale morphological changes and rationalize why sublimation rates vary between particles in a system of nearly identical nanoparticles.

Analysis of Crystalline Defects Caused by Growth on Partially Planarized Spalled (100) GaAs Substrates

We analyze the effect of growth on non-(100) surfaces resulting from incomplete planarization of spalled GaAs wafers on the defect structure of GaAs solar cell layers grown by hydride vapor phase epitaxy (HVPE). Controlled spalling of (100)-oriented GaAs has the potential to reduce substrate costs for III-V epitaxy; however, it creates regularly faceted surfaces that may complicate the growth of high-quality III-V optoelectronic devices. We leverage the anisotropic growth rate of HVPE to planarize these faceted GaAs substrates, reducing the surface roughness and degree of faceting. We observe degraded solar cell performance and material quality in sample areas where facets are not completely removed. We used dark lock-in thermography and photoluminescence to identify recombination in areas that were not fully planarized. We used cathodoluminescence to identify the presence of extended defects in these regions, which are correlated with bandgap fluctuations in the material. We hypothesize that these defects were created by strain from compositional fluctuations in ternary alloys grown on the faceted surfaces. This work elucidates the potential issues of solar cells grown on faceted surfaces and builds understanding toward realizing high performance III-V photovoltaics with the cost-reduction potential of controlled spalling.

Fold, Twist, and Draw – Techniques of Copper Alloy Wire Production from Hellenistic Jebel Khalid

Abstract Copper alloy wire fragments were examined using XRF, optical light microscopy and SEM-EDS. The specimens come from archaeological excavations at Jebel Khalid in Syria, dating from the 3rd century BCE (the Hellenistic period) to the Roman period. Our results show that several techniques were employed to make the wires: forging, folding, strip twisting, and possibly ‘strip drawing’. We investigated the morphologies, treatments, and fabrications attributed to making wire from copper alloys compared to more ductile materials such as gold and silver. Evidence of extensive annealing and non-uniform, sub-round profiles, and uneven and faceted surfaces represent the challenges of working with the material. There is no obvious evidence of solid wire drawing. The metalworkers used different copper alloys to make wire, some with high levels of lead (Pb). Subtle joins were observed in some samples, whereas others had evident folds and directional structures. The findings contribute new evidence to enhance our understanding of base-metal wire development in antiquity.

Insights into the Synthesis Mechanisms of Ag-Cu3P-GaP Multicomponent Nanoparticles.

Metal-semiconductor nanoparticle heterostructures are exciting materials for photocatalytic applications. Phase and facet engineering are critical for designing highly efficient catalysts. Therefore, understanding processes occurring during the nanostructure synthesis is crucial to gain control over properties such as the surface and interface facets' orientations, morphology, and crystal structure. However, the characterization of nanostructures after the synthesis makes clarifying their formation mechanisms nontrivial and sometimes even impossible. In this study, we used an environmental transmission electron microscope with an integrated metal-organic chemical vapor deposition system to enlighten fundamental dynamic processes during the Ag-Cu3P-GaP nanoparticle synthesis using Ag-Cu3P seed particles. Our results reveal that the GaP phase nucleated at the Cu3P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu+ and Ga3+ cations. After the initial GaP growth steps, the Ag and Cu3P phases formed specific interfaces with the GaP growth front. GaP growth proceeded by a similar mechanism observed for the nucleation involving the diffusion of Cu atoms through/along the Ag phase toward other regions, followed by the redeposition of Cu3P at a specific Cu3P crystal facet, not in contact with the GaP phase. The Ag phase was essential for this process by acting as a medium enabling the efficient transport of Cu atoms away from and, simultaneously, Ga atoms toward the GaP-Cu3P interface. This study shows that enlightening fundamental processes is critical for progress in synthesizing phase- and facet-engineered multicomponent nanoparticles with tailored properties for specific applications, including catalysis.

Degradation of Perfluorooctanoic Acid on Aluminum Oxide Surfaces: New Mechanisms from Ab Initio Molecular Dynamics Simulations.

Perfluorooctanoic acid (PFOA) is a part of a large group of anthropogenic, persistent, and bioaccumulative contaminants known as per- and polyfluoroalkyl substances (PFAS) that can be harmful to human health. In this work, we present the first ab initio molecular dynamics (AIMD) study of temperature-dependent degradation dynamics of PFOA on (100) and (110) surfaces of γ-Al2O3. Our results show that PFOA degradation does not occur on the pristine (100) surface, even when carried out at high temperatures. However, introducing an oxygen vacancy on the (100) surface facilitates an ultrafast (<100 fs) defluorination of C-F bonds in PFOA. We also examined degradation dynamics on the (110) surface and found that PFOA interacts strongly with Al(III) centers on the surface of γ-Al2O3, resulting in a stepwise breaking of C-F, C-C, and C-COO bonds. Most importantly, at the end of the degradation process, strong Al-F bonds are formed on the mineralized γ-Al2O3 surface, which prevents further dissociation of fluorine into the surrounding environment. Taken together, our AIMD simulations provide critical reaction mechanisms at a quantum level of detail and highlight the importance of temperature effects, defects, and surface facets for PFOA degradation on reactive surfaces, which have not been systematically explored or analyzed.

Epitaxial inorganic metal-halide perovskite films with controlled surface terminations

Metal-halide perovskite (MHP) thin films for next-generation solar cells are typically fabricated by wet-chemical synthesis in which surface properties such as the orientation of surface facets and their termination cannot be controlled. MHP device efficiencies depend critically on those surface properties. We demonstrate the epitaxial growth of several nanometer thick purely (001)-orientated films of ${\mathrm{CsPbBr}}_{3}$ and ${\mathrm{CsSnBr}}_{3}$ MHPs on Au(001) by molecular beam epitaxy. The epitaxial films are in a cubic phase aligned with the substrate. Their surfaces are singly terminated and can be modified for the first time. While the CsBr and ${\mathrm{PbBr}}_{2}$ surface terminations differ in terms of their atomic structure and defect content, the films are intrinsic semiconductors irrespective of the termination. The work function of the ${\mathrm{PbBr}}_{2}$-terminated surface is increased by $0.7\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, which has drastic implications for the level alignment at MHP interfaces.

Enhanced Photocatalytic Degradation of Indoor Low Concentration Gaseous Formaldehyde by Asymmetric Silveriodate Composited with 2D or 3D Bismuth Oxybromide.

Formaldehyde is one of the most hazardous and typical indoor VOCs air pollutants. Asymmetric AgIO3 was respectively composited with 3D hierarchically structured BiOBr and 2D BiOBr nanosheets to photodegrade gas-phase formaldehyde. Ag/AgIO3 /BiOBr(CMC) demonstrated better photocatalytic performance than Ag/AgIO3 /BiOBr owning to the role of biomass solvent sodium carboxymethyl cellulose in increasing the specific surface area, reducing the band gap and changing the dominant facets. Moreover, Ag nanoparticles coming from the reduction in AgIO3 were confirmed by XRD, SEM and XPS. The surface plasma resonance effect of Ag NPs improved the efficiency of the light quantum. Besides, different exposed facets of {010} in BiOBr(CMC) and {001} in BiOBr resulted in distinct oxygen vacancy structures. could be generated via a two-electron transfer pathway on the {010} dominant facets surface in AABR-CMC, leading to the change in photolysis pathway and facilitating more · OH produced by AABR-CMC. Compared with pure AgIO3 and BiOBr or BiOBr(CMC), the photocatalytic efficiency of the composites was improved significantly. Optimal photodegradation efficiency for HCHO was achieved for AABR-75 and AABR-CMC50.

Field studies in small streams of the Atlantic Forest of southern subtropical Brazil reveal two new interstitial microcambevine catfishes of the genus Listrura (Siluriformes: Trichomycteridae)

ABSTRACT A great diversity of small fish species inhabiting shallow aquatic biotopes of the South American Atlantic Forest have been reported in recent years, but records of interstitial catfishes of the genus Listrura for the southern subtropical Brazilian region are still rare. During field inventories in this region, two new species were collected, which are herein described. The new species are distinguished from congeners by a combination of morphological characters, including caudal peduncle morphology, number of vertebrae, relative position of fins, and bone morphology. The findings here described indicate that the scarcity of records of Listrura for the subtropical Atlantic Forest is probably due to the absence of collecting efforts in specialised biotopes, since species of Listrura are leaf litter dwellers. Both new species are probably more closely related to L. depinnai than to other congeners as all three uniquely possess an expanded skin fold supporting the procurrent caudal-fin rays, making the caudal peduncle deeper than the body region anterior to the dorsal and anal fins. However, only one of the new species shares with L. depinnai the presence of a process on the dorsal surface of the autopalatine articular facet for the mesethmoid, a condition not occurring in any other congener. The two new species are easily distinguished from L. depinnai by the absence of a dorsal fin in the latter species. http://www.zoobank.org/urn:lsid:zoobank.org:pub:F68F2A3E-B5F7-418E-BFA6-EA6752BAB543 http://www.zoobank.org/urn:lsid:zoobank.org:pub:F703D95A-0F7E-4261-8B97-5EAAAD9BD698