Growth of Size-Tunable Ag2O Polyhedra and Revelation of Their Bulk and Surface Lattices.

By primarily adjusting the reagent amounts, particularly the volume of AgNO3 solution introduced, Ag2O cubes with decreasing sizes from 440 to 79 nm, octahedra from 714 to 106 nm, and rhombic dodecahedra from 644 to 168 nm are synthesized. 733 nm cuboctahedra are also prepared for structural analysis. With in-house X-ray diffraction (XRD) peak calibration, shape-related peak shifts are recognizable. Synchrotron XRD measurements at 100 K reveal the presence of bulk and surface layer lattices. Bulk cell constants also deviate slightly. They show a negative thermal expansion behavior with shrinking cell constants at higher temperatures. The Ag2O crystals exhibit size- and facet-dependent optical properties. Bandgaps red-shift continuously with increasing particle sizes. Optical facet effect is also observable. Moreover, synchrotron XRD peaks of a mixture of Cu2O rhombicuboctahedra and edge- and corner-truncated cubes exposing all three crystal faces can be deconvoluted into three components with the bulk and the [111] microstrain phase as the major component. Interestingly, while the unheated Cu2O sample shows clear diffraction peak asymmetry, annealing the sample to 450 K yields nearly symmetric peaks even when returning the sample to room temperature, meaning even moderately high temperatures can permanently change the crystal lattice.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region.

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu2 O Crystals.

Semiconductor crystals have generally shown facet-dependent electrical, photocatalytic, and optical properties. These phenomena have been proposed to result from the presence of a surface layer with bond-level deviations. To provide experimental evidence of this structural feature, synchrotron X-ray sources are used to obtain X-ray diffraction (XRD) patterns of polyhedral cuprous oxide crystals. Cu2 O rhombic dodecahedra display two distinct cell constants from peak splitting. Peak disappearance during slow Cu2 O reduction to Cu with ammonia borane differentiates bulk and surface layer lattices. Cubes and octahedra also show two peak components, while diffraction peaks of cuboctahedra are comprised of three components. Temperature-varying lattice changes in the bulk and surface regions also show shape dependence. From transmission electron microscopy (TEM) images, slight plane spacing deviations in surface and inner crystal regions are measured. Image processing provides visualization of the surface layer with depths of about 1.5-4 nm giving dashed lattice points instead of dots from atomic position deviations. Close TEM examination reveals considerable variation in lattice spot size and shape for different particle morphologies, explaining why facet-dependent properties are emerged. Raman spectrum reflects the large bulk and surface lattice difference in rhombic dodecahedra. Surface lattice difference can change the particle bandgap.

Photocatalytic Aryl Sulfide Oxidation Using 4-Nitrophenylacetylene-Modified Cu2O Crystals.

4-Nitrophenylacetylene-functionalized Cu2O rhombic dodecahedra and cubes have been used to photocatalyze aryl sulfide oxidation generating aryl sulfoxides. With an oxygen supply and light from a blue light-emitting diode (LED), the reaction can be completed in 12 h with a water and methanol mixed solution. Generally high product yields and excellent product selectivity of sulfoxides over sulfones were achieved. In particular, a thioanisole to methyl phenyl sulfoxide yield of 98% was obtained. A mechanistic study has revealed that photogenerated electrons, holes, and superoxide radicals are involved in the oxidation reaction. The benefit of simple photocatalyst preparation and molecular functionalization to boost catalytic performance shows that surface-controlled ionic solids can be very effective photocatalysts for some organic transformations.

Shape-Tunable BaTiO3 Crystals Presenting Facet-Dependent Optical and Piezoelectric Properties.

BaTiO3 octahedra, edge-, and corner-truncated cubes, and cubes with four tunable sizes from 132 to 438 nm are synthesized by a solvothermal growth approach. Acetic acid treatment can cleanly remove BaCO3 impurity. Rietveld refinement of X-ray diffraction patterns and Raman spectra help to confirm the particles have a tetragonal crystal structure. The crystals also exhibit size- and facet-dependent bandgap shifts. BaTiO3 octahedra show larger piezoelectric, ferroelectric, and pyroelectric effects than truncated cubes and cubes. The measured dielectric constant differences should be associated with their various facet-dependent behaviors. Piezoelectric nanogenerators fabricated from BaTiO3 octahedra consistently show the best performance than those containing truncated cubes and cubes. In particular, a nanogenerator with 30 wt.%-incorporated octahedra displays an open-circuit voltage of 23 V and short-circuit current of 324 nA. The device performance is also highly stable. The maximum output power reaches 3.9 µW at 60 MΩ. The fabricated nanogenerator can provide sufficient electricity to power light-emitting diodes. This work further demonstrates that various physical properties of semiconductor crystals show surface dependence.

Endovascular Management of Acute Iliofemoral Deep Vein Thrombosis.

Lower extremity deep vein thrombosis (DVT) is frequently encountered in clinical practice. Postthrombotic syndrome (PTS) is a common sequela of DVT and encompasses a wide variety of symptoms, including severe pain, edema, and ulceration, all of which may contribute to a negative impact on quality of life. Studies have demonstrated that acute thrombosis of the iliofemoral venous segment is correlated with high rates of PTS, increased severity of symptoms, and high rates of thrombus recurrence, despite patients receiving treatment with standard-of-care anticoagulation therapy. Endovascular interventions, including catheter-directed thrombolysis, pharmacomechanical thrombectomy, and mechanical thrombectomy, have generated significant interest as a method for reduction of short-term symptom severity and potential reduction of downstream PTS severity. While there is high-quality evidence evaluating the role of catheter-directed and pharmacomechanical thrombectomy for acute iliofemoral DVT, newer mechanical-only devices that utilize thrombectomy without fibrinolytic medication are less studied. Currently, there are limited data evaluating the efficacy and safety of these treatment modalities, although investigations are ongoing.

Expression of concern: Surface-dependent band structure variations and bond deviations of GaN.

Expression of concern for 'Surface-dependent band structure variations and bond deviations of GaN' by Chih-Shan Tan et al., Phys. Chem. Chem. Phys., 2022, 24, 9135-9140, https://doi.org/10.1039/D2CP00100D.

Surface-dependent band structure variations and bond deviations of GaN.

Density functional theory (DFT) calculations on a tunable number of GaN (0001) planes give an invariant band structure, density of states (DOS) diagram, and band gap of the GaN unit cell. Dissimilar band structures and DOS diagrams are obtained for 1, 3, 5, 7, and 9 layers of GaN (101̄0) planes, but the same band structure as that of the (0001) plane returns for 2, 4, 6, and 8 (101̄0) planes. Furthermore, 1 to 4 layers of GaN (101̄1) planes exhibit dissimilar band structures, but the GaN unit cell band structure is obtained for 5 (101̄1) planes. While there are no changes to the Ga-N bond length and bond geometry for the (0001) planes, the (101̄0) planes present bond length variation and bond distortion with odd numbers of layers. Bond length and bond direction deviations are also obtained for 1 to 4 (101̄1) planes. These results suggest that slight structural deviations may be present near the GaN surface to produce facet-dependent properties, and such atomic position deviations in the surface layer can be observed in various semiconductors.

Synthesis of Zinc Blende-Phased CdSe Nanocrystals with Size-Tunable Optical Properties and Adjustable Valence Band Positions.

CdSe nanocrystals with average sizes of 15, 24, and 32 nm have been synthesized from an aqueous solution of Na2SeSO3, HCl, and cadmium nitrate at 15, 45, and 70 °C, respectively, for about 1 h. Mixing aqueous CdCl2, HNO3, and Na2SeSO3 at 22 °C for 4 h yields 44 nm CdSe nanocrystals. X-ray and electron diffraction analyses indicate the possession of a zinc blende crystal structure for all the samples. Despite the large particle dimensions, their absorption band red-shifts significantly from 520 to 570 nm with increasing particle sizes, and band gap values decrease from 2.03 eV for 15 nm particles to 1.68 eV for 44 nm crystals. Although these nanocrystals are not emissive, introduction of the cetyltrimethylammonium chloride surfactant during crystal growth can restore their photoluminescence attributed to the improved crystal quality, and the similarly sized CdSe nanocrystals have an emission band red-shifting from 544 nm for 15 nm particles to 583 nm for 47 nm crystals. A band diagram was constructed for these CdSe nanocrystals using information from Mott-Schottky plots. While they have close conduction band positions, the notable size-related band gap variation means that their valence band energies differ considerably with implications of electrochemical and photocatalytic properties. The 44 nm CdSe particles also show the smallest electrochemical charge-transfer resistance.

Current Rectification and Photo-Responsive Current Achieved through Interfacial Facet Control of Cu2O-Si Wafer Heterojunctions.

Conductive atomic force microscopy (C-AFM) was employed to perform conductivity measurements on a facet-specific Cu2O cube, octahedron, and rhombic dodecahedron and intrinsic Si {100}, {111}, and {110} wafers. Similar I-V curves to those recorded previously using a nanomanipulator were obtained with the exception of high conductivity for the Si {110} wafer. Next, I-V curves of different Cu2O-Si heterostructures were evaluated. Among the nine possible arrangements, Cu2O octahedron/Si {100} wafer and Cu2O octahedron/Si {110} wafer combinations show good current rectification behaviors. Under white light illumination, Cu2O cube/Si {110} wafer and Cu2O rhombic dodecahedron/Si {111} wafer combinations exhibit the largest degrees of photocurrent, so such interfacial plane-controlled semiconductor heterojunctions with light sensitivity can be applied to make photodetectors. Adjusted band diagrams are presented highlighting different interfacial band bending situations to facilitate or inhibit current flow for different Cu2O-Si junctions. More importantly, the observation of clear current-rectifying effects produced at the semiconductor heterojunctions with properly selected contacting faces or planes implies that novel field-effect transistors (FETs) can be fabricated using this design strategy, which should integrate well with current chip manufacturing processes.

Growth of CeO2 nanocubes showing size-dependent optical and oxygen evolution reaction behaviors.

CeO2 nanocubes with average sizes of 9, 13, and 18 nm have been synthesized by preparing a slightly basic aqueous mixture of Ce(NO3)3, Na2SO4, and NH4OH and heating the solution to 100 to 150 °C in 4 or 9 h. The nanocubes possess high crystalline quality. Their band gaps decrease gradually beyond the quantum confinement regime from 3.57 eV to 3.45 eV with increasing particle sizes. The 9 nm CeO2 nanocubes have the most positive valence band energy and correspondingly they exhibit the best electrochemical oxygen evolution reaction activity. Since band gaps of semiconductor nanocrystals can be tuned substantially through particle size control to yield different band energies, this fact can be utilized to enhance the electrochemical and photocatalytic properties.

Recent Advances in Bimetallic Cu-Based Nanocrystals for Electrocatalytic CO2 Conversion.

An elevated level of anthropogenic CO2 has been the major cause of global warming, and significant efforts are being made around the world towards the development of CO2 capture, storage and reuse technologies. Among various CO2 conversion technologies, electrochemical CO2 reduction (CO2 RR) by nanocrystals is one of the most promising strategies as it is facile, quick, and can be integrated with other renewable energy techniques. Judiciously designed catalytic nanomaterials promise to be the next generation of electrochemical electrodes that offer cutting-edge performance, low energy consumption and aid in reducing overall carbon footprint. In this minireview, we highlight the recent developments related to the bimetallic Cu-based nanocatalysts and discuss their structure-property relationships. We focus on the design principles and parameters required for the enhancement of CO2 conversion efficiency, selectivity, and stability.

Distinct Carrier Transport Properties Across Horizontally vs Vertically Oriented Heterostructures of 2D/3D Perovskites.

Two-dimensional-on-three-dimensional (2D/3D) halide perovskite heterostructures have been extensively utilized in optoelectronic devices. However, the labile nature of halide perovskites makes it difficult to form such heterostructures with well-defined compositions, orientations, and interfaces, which inhibits understanding of the carrier transfer properties across these heterostructures. Here, we report solution growth of both horizontally and vertically aligned 2D perovskite (PEA)2PbBr4 (PEA = phenylethylammonium) microplates onto 3D CsPbBr3 single crystal thin films, with well-defined heterojunctions. Time-resolved photoluminescence (TRPL) transients of the heterostructures exhibit the monomolecular and bimolecular dynamics expected from exciton annihilation, dissociation, and recombination, as well as evidence for carrier transfer in these heterostructures. Two kinetic models based on Type-I and Type-II band alignments at the interface of horizontal 2D/3D heterostructures are applied to reveal a shift in balance between carrier transfer and recombination: Type-I band alignment better describes the behaviors of heterostructures with thin 2D perovskite microplates but Type-II band alignment better describes those with thick 2D microplates (>150 nm). TRPL of vertically aligned 2D microplates is dominated by directly excited PL and is independent of the height above the 3D film. Electrical measurements reveal current rectification behaviors in both heterostructures with vertical heterostructures showing better electrical transport. As the first systematic study on comparing models of 2D/3D perovskite heterostructures with controlled orientations and compositions, this work provides insights on the charge transfer mechanisms in these perovskite heterostructures and guidelines for designing better optoelectronic devices.

Formation of size-tunable CuI tetrahedra showing small band gap variation and high catalytic performance towards click reactions.

Tetrahedral CuI crystals with broadly tunable sizes from 56 to 645 nm have been synthesized by adjusting the reaction temperature, addition of different amounts of Na2SO4, or the reagent selection. The crystal growth process can be easily scaled up for catalysis applications. Bulk and surface compositions have been determined to be CuI using various characterization methods. Although larger tetrahedra show gradually decreasing band gap values, the changes are quite small. Optical facet effect should also be present for CuI by comparing the band gaps of size-tunable CuI tetrahedra to that of commercially available CuI powder. Emission band also becomes red-shifted for larger tetrahedral samples. The 56 nm CuI tetrahedra exhibit a far better catalytic performance than that of commercially available CuI powder toward click reactions of aromatic alkynes and benzyl azide for the formation of triazoles, attributed to their large surface area and exposed {111} faces. The small CuI tetrahedral nanocrystals should be explored for use in other CuI-catalyzed reactions.

Inactive Cu2O Cubes Become Highly Photocatalytically Active with Ag2S Deposition.

Previously, Cu2O cubes have been shown to remain photocatalytically inert toward methyl orange degradation even after surface decoration with ZnO, ZnS, CdS, and Ag3PO4 nanostructures. Surprisingly, when Ag2S nanoparticles are lightly deposited on Cu2O cubes as seen through scanning electron microscopy (SEM) images, the heterostructures become highly photocatalytically active. X-ray diffraction (XRD) patterns show mainly Cu2O diffraction peaks due to lightly deposited Ag2S, but Ag2S peaks can emerge with increased Ag2S deposition. X-ray photoelectron spectroscopy (XPS) analysis also supports Ag2S formation on Cu2O crystals. The Ag2S-deposited Cu2O octahedra and rhombic dodecahedra show the expected activity enhancement. Electron paramagnetic resonance (EPR) measurements, as well as electron, hole, and radical scavenger tests, all confirmed the emergence of photocatalytic activity from the Ag2S-Cu2O cubes. Photoluminescence lifetimes are shortened after Ag2S deposition. Electrochemical impedance measurements revealed a large decrease in charge transfer resistance for Cu2O cubes after the Ag2S deposition. Unexpectedly, the separately synthesized Ag2S particles are also photocatalytically inactive. No specific lattice planes of Ag2S are formed directly over the {100} face of Cu2O. Diffuse reflectance and ultraviolet photoelectron spectral data were used to construct band diagrams of different Cu2O crystals and Ag2S nanoparticles. A Z-scheme charge transfer mechanism may be involved at the heterojunction interface to promote charge carrier separation. However, to explain the sudden appearance of photocatalytic activity from the Ag2S-deposited Cu2O cubes, a large change in the {100} surface band bending after Ag2S deposition should be used. This work illustrates that an unusual photocatalytic outcome is possible to semiconductor heterojunctions, where two photocatalytically inert components can become highly active when joined together.

Facet-Specific Photocatalytic Activity Enhancement of Cu2O Polyhedra Functionalized with 4-Ethynylanaline Resulting from Band Structure Tuning.

Cu2O rhombic dodecahedra, octahedra, and cubes were densely modified with conjugated 4-ethynylaniline (4-EA) for facet-dependent photocatalytic activity examination. Infrared spectroscopy affirms bonding of the acetylenic group of 4-EA onto the surface copper atoms. The photocatalytically inactive Cu2O cubes showed surprisingly high activity toward methyl orange photodegradation after 4-EA modification, while the already active Cu2O rhombic dodecahedra and octahedra exhibited a photocatalytic activity enhancement. Electron, hole, and radical scavenger experiments prove that the photocatalytic charge transport processes have occurred in the functionalized Cu2O cubes. Electrochemical impedance spectroscopy also indicates reduced charge transfer resistance of the functionalized Cu2O crystals. A band diagram constructed from UV-vis spectral and Mott-Schottky measurements reveals significant band energy shifts in all Cu2O samples after decorating with 4-EA. From density functional theory (DFT) calculations, a new band has emerged slightly above the valence band maximum within the band gap of Cu2O, which has been found to originate from 4-EA through band-decomposed charge density analysis. The increased charge density localized on the 4-EA molecule and the smallest electron transition energy to reach the 4-EA-generated band are factors making {100}-bound Cu2O cubes photocatalytically active. Proper molecular decoration represents a powerful approach to improving the photocatalytic efficiency of semiconductors.

Facet-Dependent Surface Trap States and Carrier Lifetimes of Silicon.

The facet-dependent electrical conductivity properties of silicon wafers result from significant band structure differences and variations in bond length, bond geometry, and frontier orbital electron distribution between the metal-like and semiconducting planes of silicon. To further understand the emergence of conductivity facet effects, electrochemical impedance measurements were conducted on intrinsic Si {100}, {110}, and {111} wafers. The attempt-to-escape frequency, obtained from temperature-dependent capacitance versus applied frequency curves, and other parameters derived from typical semiconductor property measurements were used to construct a diagram of the trap energy level (Et) and the amount of trap states Nt(Et). The trap states are located 0.61-0.72 eV above the silicon conduction band. Compared to {100} and {110} wafers, Si {111} wafer shows far less densities of trap states over the range of -0.2 to 2 V. Since these trap states inhibit direct electron excitation to the conduction band, the {111} wafer having much fewer trap states presents the best electrical conductivity property. Impedance data also provide facet-specific carrier lifetimes. The {111} surface gives consistently the lowest carrier lifetime, which reflects its high electrical conductivity. Lastly, ultraviolet photoelectron spectra and diffuse reflectance spectra were taken to obtain Schottky barriers between Ag and contacting Si wafers. The most conductive {111} surface presenting the largest Schottky barrier means the degrees of surface band bending used to explain facet-dependent electrical behaviors cannot be reliably attained this way.

Formation of Silver Rhombic Dodecahedra, Octahedra, and Cubes through Pseudomorphic Conversion of Ag2O Crystals with Nitroarene Reduction Activity.

Using ethanol as a co-solvent, relatively small-sized Ag2O octahedra (∼645 nm in opposite corner distance) and rhombic dodecahedra (∼540 and 655 nm in opposite face distance) were synthesized in aqueous solutions. Ag2O cubes synthesized in an aqueous solution have an edge length of ∼425 nm. Band gaps of these crystals have been obtained, revealing the presence of facet-dependent light absorption properties. The Ag2O rhombic dodecahedra, octahedra, and cubes were treated with ammonia borane in ethanol at 50 °C for just 10 min to pseudomorphically convert to Ag polyhedra of the corresponding morphologies. Transmission electron microscopy characterization confirms that the Ag cubes, octahedra, and rhombic dodecahedra are bound by the {100}, {111}, and {110} faces, respectively. The Ag rhombic dodecahedra, available for the first time, showed more superior catalytic activity toward 4-nitroaniline reduction at 50 °C than Ag octahedra and cubes, and gave 100% product yield after 1 h of reaction. This work demonstrates the value of forming Ag rhombic dodecahedra, exposing {110} surfaces that may be useful in other organic transformations.

Density Functional Theory Calculations Revealing Metal-like Band Structures and Work Function Variation for Ultrathin Gallium Arsenide (111) Surface Layers.

Density functional theory (DFT) calculations have been performed on tunable numbers of gallium arsenide (100), (110), and (111) planes for their electron density of states (DOS) plots and the corresponding band diagrams. The GaAs (100) and (110) planes show the same semiconducting band structure with tunable plane layers and a band gap of 1.35 eV around the Fermi level. In contrast, metal-like band structures are obtained with a continuous band structure around the Fermi level for 1, 2, 4, 5, 7, and 8 layers of GaAs (111) planes. For 3, 6, and 9 GaAs (111) planes, the same semiconducting band structure as seen in the (100) and (110) planes returns. The results suggest the GaAs {111} face should be more electrically conductive than its {100} and {110} faces, due to the merged conduction band and valence band. GaAs (100) and (110) planes give a fixed work function, but the (111) planes have variable work function values that are smaller than that obtained for the (100) and (110) planes. Furthermore, bond length, bond geometry, and frontier orbital electron number and energy distribution show notable differences between the metal-like and semiconducting plane cases, so the emergence of plane-dependent electronic properties have quantum mechanical origin at the orbital level. GaAs should possess similar facet-dependent electronic properties to those of Si and Ge.

Facet-Dependent Optical Properties of Semiconductor Nanocrystals.

Recent observations of facet-dependent electrical conductivity and photocatalytic activity of various semiconductor crystals are presented. Then, the discovery of facet-dependent surface plasmon resonance absorption of metal-Cu2 O core-shell nanocrystals with tunable sizes and shapes is discussed. The Cu2 O shells also exhibit a facet-specific optical absorption feature. The facet-dependent electrical conductivity, photocatalytic activity, and optical properties are related phenomena, resulting from the presence of an ultrathin surface layer with different band structures and thus varying degrees of band bending for the {100}, {110}, and {111} faces of Cu2 O to absorb light of somewhat different wavelengths. Recently, it is shown that the light absorption and photoluminescence properties of pure Cu2 O cubes, octahedra, and rhombic dodecahedra also display size and facet effects because of their tunable band gaps. A modified band diagram of Cu2 O can be constructed to incorporate these optical effects. Literature also provides examples of facet-dependent optical behaviors of semiconductor nanostructures, indicating that optical properties of nanoscale semiconductor materials are intrinsically facet-dependent. Some applications of semiconductor optical size and facet effects are considered.