Highly Facet‐Dependent Photocatalytic Properties of Cu2O Crystals Established through the Formation of Au‐Decorated Cu2O Heterostructures

This work confirms the presence of a large facet‐dependent photocatalytic activity of Cu₂O crystals through sparse deposition of gold particles on Cu₂O cubes, octahedra, and rhombic dodecahedra. Au‐decorated Cu₂O rhombic dodecahedra and octahedra showed greatly enhanced photodegradation rates of methyl orange resulting from a better separation of the photogenerated electrons and holes, with the rhombic dodecahedra giving the best efficiency. Au–Cu₂O core–shell rhombic dodecahedra also displayed a better photocatalytic activity than pristine rhombic dodecahedra. However, Au‐deposited Cu₂O cubes, pristine cubes, and Au‐deposited small nanocubes bound by entirely {100} facets are all photocatalytically inactive. X‐ray photoelectron spectra (XPS) showed identical copper peak positions for these Au‐decorated crystals. Remarkably, electron paramagnetic resonance (EPR) measurements indicated a higher production of hydroxyl radicals for the photoirradiated Cu₂O rhombic dodecahedra than for the octahedra, but no radicals were produced from photoirradiated Cu₂O cubes. The Cu₂O {100} face may present a high energy barrier through its large band edge bending and/or electrostatic repulsion, preventing charge carriers from reaching to this surface. The conventional photocatalysis model fails in this case. The facet‐dependent photocatalytic differences should be observable in other semiconductor systems whenever a photoinduced charge‐transfer process occurs across an interface.     

Crystal‐Plane‐Controlled Selectivity of Cu2O Catalysts in Propylene Oxidation with Molecular Oxygen

The selective oxidation of propylene with O₂ to propylene oxide and acrolein is of great interest and importance. We report the crystal‐plane‐controlled selectivity of uniform capping‐ligand‐free Cu₂O octahedra, cubes, and rhombic dodecahedra in catalyzing propylene oxidation with O₂: Cu₂O octahedra exposing {111} crystal planes are most selective for acrolein; Cu₂O cubes exposing {100} crystal planes are most selective for CO₂; Cu₂O rhombic dodecahedra exposing {110} crystal planes are most selective for propylene oxide. One‐coordinated Cu on Cu₂O(111), three‐coordinated O on Cu₂O(110), and two‐coordinated O on Cu₂O(100) were identified as the catalytically active sites for the production of acrolein, propylene oxide, and CO₂, respectively. These results reveal that crystal‐plane engineering of oxide catalysts could be a useful strategy for developing selective catalysts and for gaining fundamental understanding of complex heterogeneous catalytic reactions at the molecular level.     

Control of Regioselectivity over Gold Nanocrystals of Different Surfaces for the Synthesis of 1,4‐Disubstituted Triazole through the Click Reaction

Gold nanocubes, octahedra, and rhombic dodecahedra were examined for facet‐dependent catalytic activity in the formation of triazoles. Rhombic dodecahedra gave 100 % regioselective 1,4‐triazoles. The product yield was increased by decreasing the particle size. However, a mixture of 1,4‐ and 1,5‐triazoles was obtained in lower yields when cubes and octahedra of similar sizes were used. The lowest Au‐atom density on the {110} surface and largest unsaturated coordination number of surface Au atoms may explain their best catalytic efficiency and product regioselectivity. Various spectroscopic techniques were employed to verify the formation of the Au–acetylide intermediate and establish the reaction mechanism, in which phenylacetylene binds to the Au {110} surface through the terminal‐binding mode to result in the exclusive formation of 1,4‐triazoles. The smallest rhombic dodecahedra can give diverse 1,4‐disubstituted triazoles in good yields by coupling a wide variety of alkynes and organic halides.     

Synthesis of Cu2O nanocrystals from cubic to rhombic dodecahedral structures and their comparative photocatalytic activity

In this study, a new series of Cu(2)O nanocrystals with systematic shape evolution from cubic to face-raised cubic, edge- and corner-truncated octahedral, all-corner-truncated rhombic dodecahedral, {100}-truncated rhombic dodecahedral, and rhombic dodecahedral structures have been synthesized. The average sizes for the cubes, edge- and corner-truncated octahedra, {100}-truncated rhombic dodecahedra, and rhombic dodecahedra are approximately 200, 140, 270, and 290 nm, respectively. An aqueous mixture of CuCl(2), sodium dodecyl sulfate, NaOH, and NH(2)OH·HCl was prepared to produce these nanocrystals at room temperature. Simple adjustment of the amounts of NH(2)OH·HCl introduced enables this particle shape evolution. These novel particle morphologies have been carefully analyzed by transmission electron microscopy (TEM). The solution color changes quickly from blue to green, yellow, and then orange within 1 min of reaction in the formation of nanocubes, while such color change takes 10-20 min in the growth of rhombic dodecahedra. TEM examination confirmed the rapid production of nanocubes and a substantially slower growth rate for the rhombic dodecahedra. The rhombic dodecahedra exposing only the {110} facets exhibit an exceptionally good photocatalytic activity toward the fast and complete photodegradation of methyl orange due to a high number density of surface copper atoms, demonstrating the importance of their successful preparation. They may serve as effective and cheap catalysts for other photocatalytic reactions and organic coupling reactions.     

Facet‐Dependent Electrical Conductivity Properties of Silver Oxide Crystals

Ag₂O cubes, truncated octahedra, rhombic dodecahedra, and rhombicuboctahedra were synthesized in aqueous solution. Two tungsten probes were brought into contact with a single particle for electrical conductivity measurements. Strongly facet‐dependent electrical conductivity behaviors have been observed. The {111} faces are most conductive. The {100} faces are moderately conductive. The {110} faces are nearly non‐conductive. When electrodes contacted two different facets of a rhombicuboctahedron, asymmetrical I–V curves were obtained. The {111} and {110} combination gives the best I–V curve expected for a p‐n junction with current flowing in one direction through the crystal but not in the opposite direction. Density of states (DOS) plots for varying number of different lattice planes of Ag₂O match with the experimental results, suggesting that the {111} faces are most electrically conductive. The thicknesses of the thin surface layer responsible for the facet‐dependent properties of Ag₂O crystals have been determined.     

Polyhedral Cu2O Crystals for Diverse Aryl Alkyne Hydroboration Reactions

Cu₂O cubes, octahedra, and rhombic dodecahedra have been used to examine facet-dependent catalytic activity in aryl alkyne hydroboration reactions. Although the reaction can proceed by using ethanol or other alcohols as solvent, the use of 1,4-dioxane gave the best product yield. All particle shapes gave exclusively the E-product, but the rhombic dodecahedra exposing {110} surfaces were consistently far more reactive than the other particle morphologies. A product yield of 99 % was achieved by using Cu₂O rhombic dodecahedra to catalyze the hydroboration of phenylacetylene at 60 °C for 5 h. The rhombic dodecahedra have been shown to catalyze a variety of substituted aryl alkynes, which demonstrates their potential as a versatile catalyst.     

The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions

The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O₂ with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.     

Cu2O nanocrystals with various morphology: Synthesis,characterization and catalytic properties

Cu₂O nanocubes, octahedra, spheres and truncated rhombic dodecahedral were prepared and their structural, morphological, and electronic properties were investigated by X-ray diffraction analysis, X-ray absorption near edge structure, scanning electron microscope and transmission electron microscope and X-ray absorption near edge structure. Cu₂O nanocrystals were successfully employed to catalyze the 1,3-dipolar cycloaddition reaction for the synthesis of 1,4-disubstituted triazoles. Cu₂O nanocubes and octahedral showed the superior catalytic performance in the cycloaddition reaction. These results reveal that crystal-plane engineering of oxide catalysts is a useful strategy for developing efficient catalysts for organic reaction.     

Selective Semihydrogenation of Alkynes on Shape‐Controlled Palladium Nanocrystals

A systematic study on the selective semihydrogenation of alkynes to alkenes on shape‐controlled palladium (Pd) nanocrystals was performed. Pd nanocrystals with a cubic shape and thus exposed {100} facets were synthesized in an aqueous solution through the reduction of Na₂PdCl₄ with L ‐ascorbic acid in the presence of bromide ions. The Pd nanocubes were tested as catalysts for the semihydrogenation of various alkynes such as 5‐decyne, 2‐butyne‐1,4‐diol, and phenylacetylene. For all substrates, the Pd nanocubes exhibited higher alkene selectivity (>90 %) than a commercial Pd/C catalyst (75–90 %), which was attributed to a large adsorption energy of the carbon–carbon triple bond on the {100} facets of the Pd nanocubes. Our approach based on the shape control of Pd nanocrystals offers a simple and effective route to the development of a highly selective catalyst for alkyne semihydrogenation.     

Facet-dependent antibacterial activity of Au nanocrystals

Engineered nanomaterials have attracted significantly attention as one of the most promising antimicrobial agents for against multidrug resistant infections. The toxicological responses of nanomaterials are closely related to their physicochemical properties, and establishment of a structure-activity relationship for nanomaterials at the nano-bio interface is of great significance for deep understanding antibacterial toxicity mechanisms of nanomaterials and designing safer antibacterial nanomaterials. In this study, the antibacterial behaviors of well-defined crystallographic facets of a series of Au nanocrystals, including {100}-facet cubes, {110}-facet rhombic dodecahedra, {111}-facet octahedra, {221}-facet trisoctahedra and {720}-facet concave cubes, was investigated, using the model bacteria Staphylococcus aureus. We find that Au nanocrystals display substantial facet-dependent antibacterial activities. The low-index facets of cubes, octahedra, and rhombic dodecahedra show considerable antibacterial activity, whereas the high-index facets of trisoctahedra and concave cubes remained inert under biological conditions. This result is in stark contrast to the previous paradigm that the high-index facets were considered to have higher bioactivity as compared with low-index facets. The antibacterial mechanism studies have shown that the facet-dependent antibacterial behaviors of Au nanocrystals are mainly caused by differential bacterial membrane damage as well as inhibition of cellular enzymatic activity and energy metabolism. The faceted Au nanocrystals are unique in that they do not induce generation of reactive oxygen species, as validated for most antibiotics and antimicrobial nanostructures. Our findings may provide a deeper understanding of facet-dependent toxicological responses and suggest the complexities of the nanomaterial-cell interactions, shedding some light on the development of high performance Au nanomaterials-based antibacterial therapeutics.     

Crystal‐Facet Engineering of Ferric Giniite by Using Ionic‐Liquid Precursors and Their Enhanced Photocatalytic Performances under Visible‐Light Irradiation

In the work presented here, well‐dispersed ferric giniite microcrystals with controlled sizes and shapes are solvothermally synthesized from ionic‐liquid precursors by using 1‐n‐butyl‐3‐methylimidazolium dihydrogenphosphate ([Bmim][H₂PO₄]) as phosphate source. The success of this synthesis relies on the concentration and composition of the ionic‐liquid precursors. By adjusting the molar ratios of Fe(NO₃)₃ ? 9H₂O to [Bmim][H₂PO₄] as well as the composition of ionic‐liquid precursors, we obtained uniform microstructures such as bipyramids exposing {111} facets, plates exposing {001} facets, hollow spheres, tetragonal hexadecahedron exposing {441} and {111} facets, and truncated bipyamids with carved {001} facets. The crystalline structure of the ferric giniite microcrystals is disclosed by various characterization techniques. It was revealed that [Bmim][H₂PO₄] played an important role in stabilizing the {111} facets of ferric giniite crystals, leading to the different morphologies in the presence of ionic‐liquid precursors with different compositions. Furthermore, since these ferric giniite crystals were characterized by different facets, they could serve as model Fenton‐like catalysts to uncover the correlation between the surface and the catalytic performance for the photodegradation of organic dyes under visible‐light irradiation. Our measurements indicate that the photocatalytic activity of as‐prepared Fenton‐like catalysts is highly dependent on the exposed facets, and the surface area has essentially no obvious effect on the photocatalytic degradation of organic dyes in the present study. It is highly expected that these findings are useful in understanding the photocatalytic activity of Fenton‐like catalysts with different morphologies, and suggest a promising new strategy for crystal‐facet engineering of photocatalysts for wastewater treatment based on heterogeneous Fenton‐like process.     

Facet-dependent antibacterial activity of Au nanocrystals

Engineered nanomaterials have attracted significantly attention as one of the most promising antimicrobial agents for against multidrug resistant infections. The toxicological responses of nanomaterials are closely related to their physicochemical properties, and establishment of a structure-activity relationship for nanomaterials at the nano-bio interface is of great significance for deep understanding antibacterial toxicity mechanisms of nanomaterials and designing safer antibacterial nanomaterials. In this study, the antibacterial behaviors of well-defined crystallographic facets of a series of Au nanocrystals, including {100}-facet cubes, {110}-facet rhombic dodecahedra, {111}-facet octahedra, {221}-facet trisoctahedra and {720}-facet concave cubes, was investigated, using the model bacteria Staphylococcus aureus. We find that Au nanocrystals display substantial facet-dependent antibacterial activities. The low-index facets of cubes, octahedra, and rhombic dodecahedra show considerable antibacterial activity, whereas the high-index facets of trisoctahedra and concave cubes remained inert under biological conditions. This result is in stark contrast to the previous paradigm that the high-index facets were considered to have higher bioactivity as compared with low-index facets. The antibacterial mechanism studies have shown that the facet-dependent antibacterial behaviors of Au nanocrystals are mainly caused by differential bacterial membrane damage as well as inhibition of cellular enzymatic activity and energy metabolism. The faceted Au nanocrystals are unique in that they do not induce generation of reactive oxygen species, as validated for most antibiotics and antimicrobial nanostructures. Our findings may provide a deeper understanding of facet-dependent toxicological responses and suggest the complexities of the nanomaterial-cell interactions, shedding some light on the development of high performance Au nanomaterials-based antibacterial therapeutics.     

Semiconductor nanocrystals possessing broadly size‐ and facet‐dependent optical properties

Cu₂O cubes, octahedra, and rhombic dodecahedra have been shown to exhibit continuous light absorption and emission band shifts with increasing particle sizes from 10 nm to sub‐microcrystals. They also possess clear facet‐dependent optical properties. Ag₃PO₄, Ag₂O, SrTiO₃, and CeO₂ crystals show similar optical size and facet effects. Thus, spectral shifts over a broad size range far beyond the quantum‐size regime should be generally observable in many semiconductor materials. Facet‐dependent optical properties of a semiconductor can be understood to arise from the presence of an ultrathin surface layer with subtle bond and orbital level variations for different crystal faces. Although these optical features seem unexpected, they should be the general behaviors of semiconductor crystals. As more examples of these optical effects are available, we will find that these intrinsic properties of semiconductors have been ignored in the past. Furthermore, if valence and conduction band positions are broadly tunable by particle size, the knowledge should have tremendous impacts on the applications of semiconductors, where band energies are important to efficient interfacial charge transfer.     

Unprecedented Eighteen‐Faceted BiOCl with a Ternary Facet Junction Boosting Cascade Charge Flow and Photo‐redox

Exposure of anisotropic crystal facets allows the directional transfer of photoexcited electrons (e^?) and holes (h⁺), for spatial charge separation. High‐index facets with a high density of low‐coordinated atoms always serve as reactive catalytic sites. However, preparation of multi‐facets or high‐index facets is highly challenging for layered bismuth‐based photocatalysts. Herein, we report the preparation of unprecedented eighteen‐faceted BiOCl with {001} top facets and {102} and {112} oblique facets via a hydrothermal process. Compared to the conventional BiOCl square plates with {001} top facets and {110} lateral facets, the eighteen‐faceted BiOCl has highly enhanced photocatalytic activity for H₂ evolution and hydroxyl radicals (^.OH) production. Theoretical calculations and photodeposition results disclose that the of eighteen‐faceted BiOCl has a well‐matched {001}/{102}/{112} ternary facet junction, which provides a cascade path for more efficient charge flow than the binary facet junction in BiOCl square plates.     

Facet-dependent and au nanocrystal-enhanced electrical and photocatalytic properties of Au-Cu2O core-shell heterostructures

We report highly facet-dependent electrical properties of Cu(2)O nanocubes and octahedra and significant enhancement of gold nanocrystal cores to the electrical conductivity of Au-Cu(2)O core-shell octahedra. Cu(2)O nanocubes and octahedra and Au-Cu(2)O core-shell cubes and octahedra were synthesized by following our reported facile procedures at room temperature. Two oxide-free tungsten probes attached to a nanomanipulator installed inside a scanning electron microscope made contacts to a single Cu(2)O nanocrystal for the I-V measurements. Pristine Cu(2)O octahedra bounded by {111} facets are 1100 times more conductive than pristine Cu(2)O cubes enclosed by {100} faces, which are barely conductive. Core-shell cubes are only slightly more conductive than pristine cubes. A 10,000-fold increase in conductivity over a cube has been recorded for an octahedron. Remarkably, core-shell octahedra are far more conductive than pristine octahedra. The same facet-dependent electrical behavior can still be observed on a single nanocrystal exposing both {111} and {100} facets. This new fundamental property may be observable in other semiconductor nanocrystals. We also have shown that both core-shell cubes and octahedra outperform pristine cubes and octahedra in the photodegradation of methyl orange. Efficient photoinduced charge separation is attributed to this enhanced photocatalytic activity. Interestingly, facet-selective etching occurred over the {100} corners of some octahedra and core-shell octahedra during photocatalysis. The successful preparation of Au-Cu(2)O core-shell heterostructures with precise shape control has offered opportunities to discover new and exciting physical and chemical properties of nanocrystals.     

Green synthesis of 1,2,3‐triazoles via Cu2O NPs on hydrogen trititanate nanotubes promoted 1,3‐dipolar cycloadditions

Cu₂O nanoparticles supported on hydrogen trititanate nanotubes (Cu₂O/HTNT) catalysts have been efficiently catalyzed the multicomponent synthesis of 1,2,3‐triazoles in water at room temperature from different azide precursors, for example organic halides, sulfonates and anilines. The catalysts were synthesized by hydrothermal & wet‐impregnation methods and was characterized by HR‐TEM, EDS, XRD, XPS, N₂‐adsorption desorption and ICP‐MS analysis. The catalyst could be recycled by centrifugation and reused up to seven cycles. The 1‐benzyl‐4‐(4‐chlorophenyl)‐1H‐1,2,3‐triazole ( 25 ) structure was proven by single crystal X‐ray diffraction studies.     

Morphology‐Engineered Highly Active and Stable Ru/TiO2 Catalysts for Selective CO Methanation

Ru/TiO₂ catalysts exhibit an exceptionally high activity in the selective methanation of CO in CO₂‐ and H₂‐rich reformates, but suffer from continuous deactivation during reaction. This limitation can be overcome through the fabrication of highly active and non‐deactivating Ru/TiO₂ catalysts by engineering the morphology of the TiO₂ support. Using anatase TiO₂ nanocrystals with mainly {001}, {100}, or {101} facets exposed, we show that after an initial activation period Ru/TiO₂‐{100} and Ru/TiO₂‐{101} are very stable, while Ru/TiO₂‐{001} deactivates continuously. Employing different operando/in situ spectroscopies and ex situ characterizations, we show that differences in the catalytic stability are related to differences in the metal–support interactions (MSIs). The stronger MSIs on the defect‐rich TiO₂‐{100} and TiO₂‐{101} supports stabilize flat Ru nanoparticles, while on TiO₂‐{001} hemispherical particles develop. The former MSIs also lead to electronic modifications of Ru surface atoms, reflected by the stronger bonding of adsorbed CO on those catalysts than on Ru/TiO₂‐{001}.     

A one‐pot method for synthesis of reduced graphene oxide‐supported Cu–Cu2O and catalytic application in tandem reaction of halides and sodium azide with terminal alkynes

Reduced graphene oxide (RGO)‐supported Cu–Cu₂O nanocomposite material (Cu‐Cu₂O@RGO) was prepared through a one‐pot reflux synthesis method. The morphology, crystal structure and composition of the prepared Cu‐Cu₂O@RGO were characterized using transmission electron microscopy, X‐ray diffraction, and X‐ray photoelectron, infrared and Raman spectroscopies. Cu‐Cu₂O@RGO as a heterogeneous catalyst was applied to tandem reactions of halides and sodium azide with terminal alkynes to synthesize effectively 1,4‐disubstituted 1,2,3‐triazoles. Moreover, the catalyst showed excellent recyclability performance with very little leaching of the metal. Compared with homogeneous catalysts, Cu‐Cu₂O@RGO as a green and efficient catalyst was recoverable, easy to separate and highly stable in the tandem method for the synthesis of 1,2,3‐triazole compounds.     

Synthesis of {100} Facet Dominant Anatase TiO2 Nanobelts and the Origin of Facet‐Dependent Photoreactivity

Sword‐like anatase TiO₂ nanobelts exposed with 78 % clean {100} facets were synthesized and the facet‐dependent photoreactivity of anatase TiO₂ was investigated. By quantitative comparison with the reference {001} facets, the {100} facets possessed about ten‐times higher active sites density than that on {001} facets, resulting in higher photoreaction efficiency. After the active sites density normalization, the {100} and {001} facets exhibited distinct wavelength‐dependent photocatalytic performance, attributed to the anisotropic electronic structures in TiO₂ crystals.     

Platinum Multicubes Prepared by Ni2+‐Mediated Shape Evolution Exhibit High Electrocatalytic Activity for Oxygen Reduction

Pt(100) facets are generally considered less active for the oxygen reduction reaction (ORR). Reported herein is a unique Pt‐branched structure, a multicube, whose surface is mostly enclosed by {100} facets but contains high‐index facets at the small junction area between the adjacent cubic components. The synthesis is accomplished by a Ni²⁺‐mediated facet evolution from high‐index {311} to {100} facets on the frameworks of multipods. Despite the high {100} facet coverage, the Pt multicubes exhibit impressive ORR activity in terms of half‐wave potential and current density nearly to the level of the most active Pt‐based catalysts, while the durability of catalysts is well retained. The facet evolution creates a set of samples with tunable ratios of high‐index to low‐index facets. The results reveal that the excellent ORR performance of Pt multicubes is a combined result of active sites by high‐index facets and low resistance by flat surface. It is anticipated that this work will offer a new approach to facet‐controlled synthesis and ORR catalysts design.