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Bismuth oxyhalides (BiOX, X = F, Cl, Br, I) are emerging energy materials because of their remarkable catalytic activity. The BiOX compounds usually have a tetragonal type crystal structure with unique layered morphology consisting of [X-Bi-O-Bi-X] sheets. Although the BiOX nanosheets exposed with {001} facets perform superior photoactivity, there is lack of understanding about their capability in the electrochemical CO2 reduction reaction (CO2RR). Herein, we adopt wet-chemical syntheses to make 2D BiOCl and Pd-doped BiOCl nanosheets for CO2RR. In the results, formic acid is the only one kind of product converted from CO2 along with H2 gas from water reduction over both BiOCl and Pd-doped BiOCl nanosheets. By thorough analyses with ex situ and in situ spectroscopy, the results reflect that (1) metallic Bi0 atoms generated by the applied negative potentials serve as the catalytic sites for the hydrogen evolution reaction (HER) and CO2RR and (2) the existence of doped Pd ions in the BiOCl structure reduces the barrier of charge transfer over the nanosheets, which enhances HER and CO2RR activities. We believe that the observations are important references for making catalysts toward CO2RR performance.

The global ammonia yield is critical to the fertilizer industry as the global food demand is highly dependent on it, whereas, NH3 is also a key chemical for pharmaceutical, textile, plastic, explosive, and dye-making industries. At present, the demand for NH3 is fulfilled by the Haber-Bosch method, which consumes 1-3% of global energy and causes 0.5-1% CO2 emission every year. To reduce emissions and improve energy efficiency, the electrochemical nitrogen gas reduction reaction (N2RR) has received much attention and support after the funding announcement by the U.S. Department of Energy. In this work, we have created hollow CuAu nanoboxes with Cu-rich inner walls to improve the NH3 Faradaic efficiency in N2RR. These beveled nanoboxes are produced in different degrees of corner and edge etching, which produces both polyhedral and concave structures. In N2RR, the binary CuAu nanoboxes enhanced NH3 production compared to individual Au and Cu nanocubes. The results of DFT calculations suggest the Cu-rich inner walls in the hollow beveled CuAu nanoboxes play a major role in their performance by reducing the free energy ΔG*NNH for the potential-determining step to form *NNH (* + N2(g) + H+ + e- → *NNH). Meanwhile, the results in 10-cycle and solar-illuminated N2RR indicate the beveled CuAu nanoboxes are not only robust electrocatalysts but show promise in photocatalysis as well.

Modulation of bimetallic nanocatalysts with atomic precision would allow for significant increases in catalyst activity through the optimization of heteroatomic interplay. In practice, this level o...

Efficient control of the perovskite crystallization and passivation of the defects at the surface and grain boundaries of perovskite films have turned into the most important strategies to restrain charge recombination toward high-performance and long-term stability of perovskite solar cells (PSCs). In this paper, we employed a small amount of natural vitamin B (carnitine) with dual functional groups in the MAPbI3 precursor solution to simultaneously passivate the positive- and negative-charged ionic defects, which would be beneficial for charge transport in the PSCs. In addition, such methodology can efficiently ameliorate crystallinity with texture, better film morphology, high surface coverage, and longer charge carrier lifetime, as well as induce preferable energy level alignment. Benefiting from these advantages, the power conversion efficiency of PSCs significantly increases from 16.43 to 20.12% along with not only a higher open-circuit voltage of 1.12 V but also an outstanding fill factor of 82.78%.

We investigated lattice strain on alloyed surfaces using ∼10 nm core–shell nanoparticles with controlled size, shape, and composition. We developed a wet-chemistry method for synthesizing small octahedral PdPt alloy nanoparticles and Au@PdPt core–shell nanoparticles with Pd–Pt alloy shells and Au cores. Upon introduction of the Au core, the size and shape of the overall nanostructure and the composition of the alloyed PdPt were maintained, enabling the use of the electrooxidation of formic acid as a probe to compare the surface structures with different lattice strain. We have found that the structure of the alloyed surface is indeed impacted by the lattice strain generated by the Au core. To further reveal the impact of lattice strain, we fine-tuned the shell thickness. Then, we used synchrotron-based X-ray diffraction to investigate the degree of lattice strain and compared the observations with the results of the formic acid electrooxidation, suggesting that there is an optimal intermediate shell thickness for high catalytic activity.

Control of morphology in the synthesis of Rh nanocrystals can be used to precisely tailor the electronic surface structure; this in turn directly influences their performance in catalysis applications. Many works bring attention to the development of Rh nanostructures with low-index surfaces, but limited effort has been placed on the study of high-index and surface-defect-enriched nanocrystals as they are not favored by thermodynamics due to the involvement of high-energy surfaces and increased surface-to-volume ratios. In this work, we demonstrate an aqueous synthesis of concave Rh nanotetrahedra (CTDs) serving as efficient catalysts for energy conversion reactions. CTDs are surface-defect-rich structures that form through a slow growth rate and follow the four-step model of metallic nanoparticle growth. By tuning the surfactant concentration, the morphology of Rh CTDs evolved into highly excavated nanotetrahedra (HETDs) and twinned nanoparticles (TWs). Unlike the CTD surfaces with abundant adatoms and v...

Sub-1 nm PtSn nanosheets of 0.6–0.9 nm in thickness were synthesized via a solution colloidal method and were applied as electrooxidation catalysts for methanol oxidation reaction (MOR) and ethanol oxidation (EOR) in alkaline and acid environments. Owing to the specific structural and compositional characteristics, the as-prepared PtSn nanosheets exhibits superior activity and durability relative to commercial Pt black and Pt/carbon catalysts. PtSn nanosheets not only exhibit an outstanding mass activity in MOR (871.6 mA mg Pt−1), which is 2.3 times (371 mA mg Pt−1) and 10.1 times (86.1 mA mg Pt−1) higher than that of commercial Pt/carbon and Pt black respectively, but also display an mass activity in EOR (673.6 mA mg Pt−1) with 5.3 times higher commercial Pt black (127.7 mA mg Pt−1) and 2.3 times higher than commercial Pt/C catalyst (295 mA mgPt−1). The reported value is the highest activity in both MOR and EOR examinations compared to the reported PtSn-based electrocatalysts,. The improved performance may be due to the highly-reactive exposed (1 1 1) facet sites resulted from its sub-1 nm 2D sheet like morphology.

Geometric modification of Au nanostructures is typically achieved in multistep reactions, where synthesis parameters need to be well-controlled. In this work, we report a facile method using IrCl3 to refine morphologically diverse Au nanostructures and trigger their morphological transformations. The synthesis is accomplished at room temperature by an iterative process of galvanic dissolution and recursive growth. Seeds retrieved after the dissolution of different Au nanostructure archetypes served in the structural recovery and morphological transformation via rapid and slow regrowth, respectively. The rapid regrowth was accomplished by adding ascorbic acid (AA), while the slow regrowth occurred spontaneously. In the structural recovery, the nanostructures regrew back to their original morphologies. Improvements in the shape quality and size distributions were observed for the rapid regrowth case. In the spontaneous slow regrowth transformation, the resulting nanostructures were encased by {111} facets, ...

Submicron-sized mesoporous nickel ferrite (NiFe2O4) spheres were prepared by an aerosol spray pyrolysis method using Pluronic F127 as a structure-directing agent, and their photocatalytic performance for hydrogen (H2) evolution was examined in an aqueous MeOH solution by visible light irradiation (λ > 420 nm). The structure of the spherical mesoporous nickel ferrites was studied by transmission electron microscopy, powder X-ray diffraction, and N2 adsorption–desorption isotherm measurements. Mesoporous NiFe2O4 spheres of high specific surface area (278 m2 g–1) with a highly crystalline framework were prepared by adjusting the amount of structure-directing agent and the calcining condition. High photocatalytic activity of mesoporous NiFe2O4 for H2 evolution from water with methanol was achieved due to the combination of high surface area and high crystallinity of the nickel ferrites.

Bimetallic nanoparticle catalysts provide enhanced activity, as combining metals allows tuning of electronic and geometric structure, but the enhancement may vary during the reaction because the nanoparticles can undergo metal migration under catalytic reaction conditions. Using cyclic voltammetry to track the surface composition over time, we carried out a detailed study of metal migration in a well-defined model Au-Pd core-shell nanocatalyst. When subjected to electrochemical conditions, Au migration from the core to the shell was observed. The effect of Pd shell thickness and electrolyte identity on the extent of migration was studied. Migration of metals during catalytic ethanol oxidation was found to alter the particle's surface composition and electronic structure, enhancing the core-shell particles' activity. We show that metal migration in core-shell nanoparticles is a phenomenon common to numerous electrochemical systems and must be considered when studying electrochemical catalysis.

Developing syntheses of more sophisticated nanostructures comprising late transition metals broadens the tools to rationally design suitable heterogeneous catalysts for chemical transformations. Herein, we report a synthesis of Pd-Rh nanoboxes by controlling the migration of metals in a core-shell nanoparticle. The Pd-Rh nanobox structure is a grid-like arrangement of two distinct metal phases, and the surfaces of these boxes are {100} dominant Pd and Rh. The catalytic behaviors of the particles were examined in electrochemistry to investigate strain effects arising from this structure. It was found that the trends in activity of model fuel cell reactions cannot be explained solely by the surface composition. The lattice strain emerging from the nanoscale separation of metal phases at the surface also plays an important role.

Cubic and octahedral Cu2O nanocrystals and Au–Cu2O core–shell heterostructures are used as sacrificial templates for the growth of Cu2S nanocages and Au–Cu2S core–cage structures. A rapid sulfidation process involving a surface reaction of Cu2O nanocrystals with Na2S, followed by etching of the Cu2O cores with HCl solution for ≈5 sec, results in the fabrication of Cu2S cages with a wall thickness of 10–20 nm. Transmission electron microscopy characterization reveals the formation of crystalline walls and the presence of ultrasmall pores with sizes of 1 nm or less. Formation of Cu2O–Cu2S core–shell structures and their conversion into Cu2S cages is verified by UV–vis absorption spectroscopy. X-ray photoelectron spectra further confirm the composition of the cages as Cu2S. The entire hollowing process via the Kirkendall effect is recorded using in-situ transmission X-ray microscopy. After shell formation, continuous ionic diffusion removes the interior Cu2O. Intermediate structures with remaining central Cu2O portions and bridging arms to the surrounding cages are observed. The nanocages are also shown to allow molecular transport: anthracene and pyrene penetration into the cages leads to enhanced fluorescence quenching immediately upon adsorption onto the surfaces of the encapsulated gold nanocrystals.

We report the growth of core−shell Ga−GaN nanostructures by simple refluxing of a mixture of GaCl3 and lithium bis(trimethylsilyl)amide (LiHMDS) in trioctylamine at 380 °C for 24 h under nitrogen flow. The resulting spherical Ga−GaN nanostructures had diameters of ∼550 nm. By immersing the nanostructures in aqua regia, the gallium cores could be removed, and hollow GaN spheres with thicknesses of 15−25 nm were produced. The shells consisted of connected GaN nanocrystals of both cubic and hexagonal phases. Infrared spectroscopy confirmed the presence of silica or silicate in the GaN shells. The silicon source likely comes from the pyrolysis of LiHMDS. The growth process was studied by examining the intermediate products formed. Gallium metal cores appeared below 380 °C, followed by the slow formation of GaN nanocrystals on the core surfaces. The slow growth of the GaN shells is related to the gradual supply of the nitrogen source from the thermal decomposition of LiHMDS. Thinner shells with a thickness of ...

We report the synthesis of pentagonal- and hexagonal-shaped gold nanoparticles with controlled diameters ranging from 5 to 50 nm. These nanoparticles were prepared by a seeding growth approach. Sodium dodecyl sulfate (SDS) molecules served as the capping agent to restrict the particle size. In addition, the formation of highly faceted gold nanoparticles may be facilitated by the possibly ineffective capping interactions between the lamellar micellar structures formed by the SDS molecules and the gold nanoparticles. The crystal structure of the highly faceted particles was found to consist of mostly [111] surfaces as particle size increases, as revealed by both TEM and XRD results.

The effect of lattice strain on the catalytic properties of Pd nanoparticles is systematically studied. Synthetic strategies for the preparation of a series of shape-controlled Pd nanocrystals with lattice strain generated from different sources has been developed. All of these nanocrystals were created with the same capping agent under similar reaction conditions. First, a series of Pd nanoparticles was synthesized that were enclosed in {111} surfaces: Single-crystalline Pd octahedra, single-crystalline AuPd core–shell octahedra, and twinned Pd icosahedra. Next, various {100}-terminated particles were synthesized: Single-crystalline Pd cubes and single-crystalline AuPd core–shell cubes. Different extents of lattice strain were evident by comparing the X-ray diffraction patterns of these particles. During electrocatalysis, decreased potentials for CO stripping and increased current densities for formic-acid oxidation were observed for the strained nanoparticles. In the gas-phase hydrogenation of ethylene, the activities of the strained nanoparticles were lower than those of the single-crystalline Pd nanoparticles, perhaps owing to a larger amount of cetyl trimethylammonium bromide on the surface.

We report a seed-mediated synthesis method for the preparation of gold nanocrystals with systematic shape evolution from truncated cubic to cubic, trisoctahedral, and rhombic dodecahedral structures in aqueous solution for the first time. Nanocrystals with transitional morphologies were also synthesized. The combination of using cetyltrimethylammonium chloride (CTAC) surfactant and a very small amount of NaBr to control the bromide concentration in the growth solution was found to be critical to the formation of nanocubes. Variation in the volume of ascorbic acid added to the growth solution enabled the fine control of nanocrystal morphology. Nanocubes and rhombic dodecahedra with controlled sizes of 30-75 nm were prepared by adjusting the volume of the seed solution added to the growth solution. They can self-assemble into ordered packing structures on substrates because of their uniform sizes. XRD, TEM, and UV-vis absorption characterization of the different products synthesized have been performed. By increasing the bromide concentration 5-fold that used to make the nanocubes, unusual right bipyramids of gold bounded by six {100} faces were produced. The high product purity and excellent size control of this facile synthetic approach should make these novel gold nanostructures be readily available for a wide range of studies.

We report a simple approach for the fabrication of cuprous oxide (Cu 2 O) nanocages and nanoframes. An aqueous solution of CuCl 2 , sodium dodecyl sulfate (SDS) surfactant, NH 2 OH·HCl reductant, HCl, and NaOH was prepared with reagents introduced in the order listed. Rapid seed particle aggregation and surface reconstruction of the intermediate structures resulted in the growth of type I nanoframes with just the {110} skeleton faces and empty {100} faces 45 minutes after mixing the reagents. Continued crystal growth for additional 75 min produced the nanocages with filled {100} faces. The nanocages have diameters of 350–400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol and then sonication of the solution led to the formation of type II nanoframes with elliptical pores on the {110} faces. The morphologies of these nanoframes have been carefully examined by electron microscopy. Without adding ethanol, random etching of the nanocages can occur at a slow rate. These composite materials should display interesting properties and functions.

We report a simple approach for the fabrication of cuprous oxide (Cu 2O) nanocages and nanoframes possessing an unusual truncated rhombic dodecahedral structure. An aqueous solution containing CuCl 2, sodium dodecyl sulfate (SDS) surfactant, NH 2OH.HCl reductant, HCl, and NaOH was prepared, with the reagents introduced in the order listed. Rapid seed-particle aggregation and surface reconstruction of the intermediate structure resulted in the growth of type-I nanoframes, which have only {110} skeleton faces and empty {100} faces, 45 min after mixing the reagents. Continued crystal growth for additional 75 min produced nanocages with filled {100} faces. The nanocages have diameters of 350-400 nm, and their walls are thicker than those of the nanoframes. Selective acidic etching over the {110} faces of the nanocages by HCl via the addition of ethanol followed by sonication of the solution led to the formation of type-II nanoframes, which have elliptical pores on the {110} faces. The morphologies of these nanoframes were carefully examined by electron microscopy. Without addition of ethanol, random etching of the nanocages can occur at a slow rate. Octahedral gold nanocrystals and high-aspect-ratio gold nanorods were successfully encapsulated in the interiors of these Cu 2O nanocages by adding the gold nanostructures into the reaction solution. The formation process for such core-cage composite structures was studied. These composite materials should display interesting properties and functions.

The synthesis of gold nanoplates was carried out in an aqueous solution by thermal reduction of HAuCl(4) with trisodium citrate in the presence of cetyltrimethylammonium bromide (CTAB) surfactant in just 5-40 min. The sizes of the gold nanoplates can be varied from as small as tens of nanometers in width, to several hundreds of nanometers, and even a few microns in width by changing the reagent concentrations, solution temperature, and the reaction time. A [CTAB]/[HAuCl(4)] ratio of 6 in the reaction solution was found to be favorable for the formation of gold nanoplates. The nanoplates possess well-defined shapes with sharp edges. The small nanoplates exhibit mainly a triangular shape, while larger nanoplates show a mixture of triangular, hexagonal, truncated triangular, and other symmetrical structures. The nanoplates are composed of essentially (111) lattice planes, as revealed by both XRD and TEM results. Nanoplates with widths from several hundreds of nanometers to a few microns absorb light strongly in the near-infrared region. The growth mechanism of these nanoplates was investigated. The ability to synthesize gold nanoplates with these different size ranges in large scale in aqueous solution using simple CTAB capping surfactant should allow more diverse applications of gold nanoplates.

Synthesis of branched gold nanocrystals by a seeding growth approach is described. In this process, HAuCl4 aqueous solution was supplied stepwise to grow the gold seeds (approximately 2.5 nm) into larger nanoparticles with a highly faceted particle structure (approximately 15-20 nm in diameter). Sodium dodecyl sulfate (SDS) served as a capping agent to facilitate the formation of highly faceted nanoparticles, and ascorbic acid was used as a weak reducing agent. The highly faceted nanoparticles then transformed into branched nanocrystals (approximately 40 nm in length) by further addition of the SDS-HAuCl4 solution and ascorbic acid for particle growth. The branched nanocrystals show bipod, tripod, tetrapod, and pentapod structures and are composed of mainly (111) lattice planes. These multipods appear to grow along the twin boundaries of the initially formed highly faceted gold nanoparticles, as the twin boundaries on the pods originate from the centers of the branched nanocrystals. The concentration of ascorbate ions in the solution was found to have a profound influence on branch formation. These branched nanocrystals are stable to storage at low temperature (that is, 4 degrees C), but they may slowly evolve into a multitwinned faceted crystal structure (that is, pentagonal-shaped decahedral structure) when stored at 30 degrees C.