Showing papers by "Younan Xia published in 2021"
TL;DR: This review article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addition to their remarkable performance in a large number of catalytic and electrocatalytic reactions.
Abstract: The successful synthesis of noble-metal nanocrystals with controlled shapes offers many opportunities to not only maneuver their physicochemical properties but also optimize their figures of merit in a wide variety of applications. In particular, heterogeneous catalysis and surface science have benefited enormously from the availability of this new class of nanomaterials as the atomic structure presented on the surface of a nanocrystal is ultimately determined by its geometric shape. The immediate advantages may include significant enhancement in catalytic activity and/or selectivity and substantial reduction in materials cost while providing a well-defined model system for mechanistic study. With a focus on the monometallic system, this review article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addition to their remarkable performance in a large number of catalytic and electrocatalytic reactions. We hope that this review article offers the impetus and roadmap for the development of next-generation catalysts vital to a broad range of industrial applications.
282 citations
TL;DR: It is demonstrated that controlling the surface oxidation of Cu nanowires (CuNWs) can greatly improve their C2+ selectivity and stability, and the formation of a relatively thick, smooth oxide sheath can improve the catalytic stability by mitigating the fragmentation issue.
Abstract: Copper nanostructures are promising catalysts for the electrochemical reduction of CO2 because of their unique ability to produce a large proportion of multi-carbon products. Despite great progress, the selectivity and stability of such catalysts still need to be substantially improved. Here, we demonstrate that controlling the surface oxidation of Cu nanowires (CuNWs) can greatly improve their C2+ selectivity and stability. Specifically, we achieve a faradaic efficiency as high as 57.7 and 52.0 % for ethylene when the CuNWs are oxidized by the O2 from air and aqueous H2 O2 , respectively, and both of them show hydrogen selectivity below 12 %. The high yields of C2+ products can be mainly attributed to the increase in surface roughness and the generation of defects and cavities during the electrochemical reduction of the oxide layer. Our results also indicate that the formation of a relatively thick, smooth oxide sheath can improve the catalytic stability by mitigating the fragmentation issue.
93 citations
TL;DR: A synthesis of Pt-Co@Pt octahedral nanocrystals that feature an intermetallic, face-centered tetragonal Pt- Co core and an ultrathin Pt shell, together with the dominance of {111} facets on the surface is reported, promising an outstanding catalyst with optimal performance for ORR and related reactions.
Abstract: Despite extensive efforts devoted to the synthesis of Pt-Co bimetallic nanocrystals for fuel cell and related applications, it remains a challenge to simultaneously control atomic arrangements in the bulk and on the surface. Here we report a synthesis of Pt-Co@Pt octahedral nanocrystals that feature an intermetallic, face-centered tetragonal Pt-Co core and an ultrathin Pt shell, together with the dominance of {111} facets on the surface. When evaluated as a catalyst toward the oxygen reduction reaction (ORR), the nanocrystals delivered a mass activity of 2.82 A mg-1 and a specific activity of 9.16 mA cm-2, which were enhanced by 13.4 and 29.5 times, respectively, relative to the values of a commercial Pt/C catalyst. More significantly, the mass activity of the nanocrystals only dropped 21% after undergoing 30 000 cycles of accelerated durability test, promising an outstanding catalyst with optimal performance for ORR and related reactions.
84 citations
TL;DR: Bimetallic nanocrystals often outperform their monometallic counterparts in catalysis as a result of the electronic coupling and geometric effect arising from two different metals as mentioned in this paper, and they have been shown to perform well in many applications.
Abstract: Bimetallic nanocrystals often outperform their monometallic counterparts in catalysis as a result of the electronic coupling and geometric effect arising from two different metals. Here we report a...
58 citations
TL;DR: Bimetallic Janus nanocrystals have received considerable interest in recent years owing to their unique properties and niche applications as discussed by the authors, and the strategies and experimental controls for achieving the Janus structure, as well as the mechanistic understandings, are specifically discussed.
Abstract: Bimetallic Janus nanocrystals have received considerable interest in recent years owing to their unique properties and niche applications. The side-by-side distribution of two distinct metals provides a flexible platform for tailoring the optical and catalytic properties of nanocrystals. First, a brief introduction to the structural features of bimetallic Janus nanocrystals, followed by an extensive discussion of the synthetic approaches, is given. The strategies and experimental controls for achieving the Janus structure, as well as the mechanistic understandings, are specifically discussed. Then, a number of intriguing properties and applications enabled by the Janus nanocrystals are highlighted. Finally, this article is concluded with future directions and outlooks with respect to both syntheses and applications of this new class of functional nanomaterials.
33 citations
TL;DR: In this article, a simple route based upon seed-mediated growth to the synthesis of Pd@Aux Pd1-x (0.8≤x≤1) core-shell nanocubes was reported.
Abstract: We report a simple route based upon seed-mediated growth to the synthesis of Pd@Aux Pd1-x (0.8≤x≤1) core-shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au0.95 Pd0.05 work as an efficient electrocatalyst toward H2 O2 production, with high selectivity of 93-100 % in the low-overpotential region of 0.4-0.7 V. When the Au0.95 Pd0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2 O2 during oxygen reduction at a high rate of 1.62 mol g(Pd+Au) -1 h-1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.
28 citations
TL;DR: In this paper, the authors reported a simple route to the synthesis of such nanocrystals by selectively growing them from the vertices of Pd icosahedral seeds, and the success of this synthesis critically depends on the introduction of Br- ions to slow the reduction kinetics of the Pt(II) precursor while limiting the surface diffusion of Pt adatoms by conducting the synthesis at 30 °C.
Abstract: Platinum nanocrystals featuring a multiply twinned structure and uniform sizes below 5 nm are superb catalytic materials, but it is difficult to synthesize such particles owing to the high twin-boundary energy (166 mJ/m2) of Pt. Here, we report a simple route to the synthesis of such nanocrystals by selectively growing them from the vertices of Pd icosahedral seeds. The success of this synthesis critically depends on the introduction of Br- ions to slow the reduction kinetics of the Pt(II) precursor while limiting the surface diffusion of Pt adatoms by conducting the synthesis at 30 °C. Owing to the small size and multiply twinned structure of Pt dots, the as-obtained Pd-Pt nanocrystals show remarkably enhanced activity and durability toward oxygen reduction, with a mass activity of 1.23 A mg-1Pt and a specific activity of 0.99 mA cm-2Pt, which are 8.2 and 4.5 times as high as those of the commercial Pt/C.
27 citations
26 citations
TL;DR: In this paper, the authors report a solution-based method for the fabrication of well-controlled Janus particles by simply breaking the symmetry of spherical particles with swelling, which can be used for colloidal assembly, stabilization of emulsions, and development of active colloids, among others.
Abstract: Janus particles are widely sought for applications related to colloidal assembly, stabilization of emulsions, and development of active colloids, among others. Here we report a versatile route to the fabrication of well-controlled Janus particles by simply breaking the symmetry of spherical particles with swelling. When a polystyrene (PS) sphere covered by a rigid shell made of silica or polydopamine is exposed to a good solvent for PS, a gradually increased pressure will be created inside the shell. If the pressure becomes high enough to poke a hole in the shell, the spherical symmetry will break while pushing out the swollen PS through the opening to generate a Janus particle comprised of two distinct components. One of the components is made of PS and its size is controlled by the extent of swelling. The other component is comprised of the rigid shell and remaining PS, with its overall diameter determined by the original PS sphere and the rigid shell. This solution-based route holds promises for the scalable production of complex Janus particles with a variety of compositions and in large quantities.
25 citations
TL;DR: In this article, a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages was reported, which can naturally catalyze at least two different reactions.
Abstract: Janus nanocages with distinctive platinum-group metals on the outer and inner surfaces can naturally catalyze at least two different reactions. Here we report a general method based on successive deposition and then selective etching for the facile synthesis of such nanocages. We have fabricated 11 different types of Janus nanocages characterized by a uniform size and well-defined {100} facets, together with porous, ultrathin, asymmetric walls up to 1.6 nm thick. When tested as dual-electrocatalysts toward oxygen reduction and evolution reactions, the Janus nanocages based on Pt and Ir exhibited superior activities depending on the thickness and relative position of the metal layer. Density functional theory studies suggest that the alloy composition and surface structure of the nanocages both play important roles in enhancing the electrocatalytic activities by modulating the stability of key reaction intermediates.
24 citations
TL;DR: In this article, the authors reviewed the recent efforts in the rational design and fabrication of functionally graded scaffolds based upon electrospun nanofiber mats and inverse opal structures, as well as the evaluation of their applications in augmenting tendon-to-bone repair.
Abstract: Tendon-to-bone repair often fails because the functionally graded attachment is not regenerated during the healing process. Biomimetic scaffolds that recapitulate the unique features of the native tendon-to-bone attachment hold great promise for enhancing the healing process. Among various types of scaffolds that are developed and evaluated for tendon-to-bone repair, those with gradations (in either a stratified or a continuous fashion) in composition, structure, mechanical properties, and cell phenotype have gained the most attention. In this progress report, the recent efforts in the rational design and fabrication of functionally graded scaffolds based upon electrospun nanofiber mats and inverse opal structures, as well as the evaluation of their applications in augmenting tendon-to-bone repair, are reviewed. This report concludes with perspectives on the necessary future steps for clinical translation of the scaffolds.
TL;DR: In this article, a facile route to the fabrication of uniform nanobottles made of polydopamine by leveraging swelling-induced pressure is reported, which makes them ideal carriers for the encapsulation and controlled release of various types of cargos.
Abstract: Nanobottles refer to colloidal particles featuring a hollow body connected to a single opening on the surface. This unique feature makes them ideal carriers for the encapsulation and controlled release of various types of cargos. Here a facile route to the fabrication of uniform nanobottles made of polydopamine by leveraging swelling-induced pressure is reported. When polystyrene spheres are coated with polydopamine and then incubated with a toluene/water emulsion, the polystyrene will be swollen to automatically poke a single hole in the shell because of the pressure inside the shell. After quenching the swelling with ethanol and then removing all the polystyrene with tetrahydrofuran, polydopamine nanobottles are obtained. The dimensions of the hollow body are determined by the polystyrene template, while the size of the opening can be tuned by varying the shell thickness. Through the opening, different types of cargos, including small molecules and biomacromolecules, can be easily loaded with a thermoresponsive material into the cavity. The cargos can be released in a controllable manner through direct heating or polydopamine-enabled photothermal heating. In a proof-of-concept experiment, the polydopamine nanobottles are used for temperature-controlled release of thrombin to trigger the formation of fibrin gels in situ.
TL;DR: This paper concludes with some perspectives on future directions for this class of nanomaterials in terms of fabrication, functionalization, and application.
Abstract: Nanobottles refer to colloidal particles with a hollow interior and a single opening in the wall. These unique features make them ideal carriers for the loading, encapsulation, release, and delivery of various types of theranostic agents in an array of biomedical applications. The hollow interior gives them a high loading capacity while the opening enables quick loading and controlled release of the payload(s). More significantly, on-demand release can be readily achieved by adding a stimuli-responsive material as the inner matrix or cork stopper. This progress report begins with an introduction to the general structures and properties of nanobottles, followed by a brief discussion on the methods developed for their fabrication. The use of nanobottles for loading different types of payloads is then showcased, including small-molecule drugs, biomacromolecules, imaging contrast agents, and functional nanoparticles. The strategies explored for controlling the release by varying the size of the opening and/or integrating with a stimuli-responsive material are also highlighted. This paper concludes with some perspectives on future directions for this class of nanomaterials in terms of fabrication, functionalization, and application.
TL;DR: In this paper, the authors reported the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds, which can be obtained from the same cubic seeds under suitable reduction kinetics for the precursor.
Abstract: We report the synthesis of Rh nanocrystals with different shapes by controlling the kinetics involved in the growth of preformed Rh cubic seeds. Specifically, Rh nanocrystals with cubic, cuboctahedral, and octahedral shapes can all be obtained from the same cubic seeds under suitable reduction kinetics for the precursor. The success of such a synthesis also relies on the use of a halide-free precursor to avoid oxidative etching, as well as the involvement of a sufficiently high temperature to remove Br- ions from the seeds while ensuring adequate surface diffusion. The availability of Rh nanocrystals with cubic and octahedral shapes allows for an evaluation of the facet dependences of their thermal and catalytic properties. The data from in situ electron microscopy studies indicate that the cubic and octahedral Rh nanocrystals can keep their original shapes up to 700 and 500 °C, respectively. When tested as catalysts for hydrazine decomposition, the octahedral nanocrystals exhibit almost 4-fold enhancement in terms of H2 selectivity relative to the cubic counterpart. As for ethanol oxidation, the order is reversed, with the cubic nanocrystals being about three times more active than the octahedral sample.
TL;DR: Synthetic Nanoparticle Antibodies (SNAbs) as discussed by the authors were designed to target myeloid-derived immune-suppressor cells (MDSCs) from mouse-tumor and rat-trauma models.
Abstract: Monoclonal antibodies (mAb) have had a transformative impact on treating cancers and immune disorders. However, their use is limited by high development time and monetary cost, manufacturing complexities, suboptimal pharmacokinetics, and availability of disease-specific targets. To address some of these challenges, we developed an entirely synthetic, multivalent, Janus nanotherapeutic platform, called Synthetic Nanoparticle Antibodies (SNAbs). SNAbs, with phage-display-identified cell-targeting ligands on one "face" and Fc-mimicking ligands on the opposite "face", were synthesized using a custom, multistep, solid-phase chemistry method. SNAbs efficiently targeted and depleted myeloid-derived immune-suppressor cells (MDSCs) from mouse-tumor and rat-trauma models, ex vivo. Systemic injection of MDSC-targeting SNAbs efficiently depleted circulating MDSCs in a mouse triple-negative breast cancer model, enabling enhanced T cell and Natural Killer cell infiltration into tumors. Our results demonstrate that SNAbs are a versatile and effective functional alternative to mAbs, with advantages of a plug-and-play, cell-free manufacturing process, and high-throughput screening (HTS)-enabled library of potential targeting ligands.
TL;DR: The principles, methodologies, and mechanistic insights presented in this Account will help the readers achieve a good understanding of the physical transformations that are expected to take place in noble-metal nanocrystals when they are subjected to thermal activation.
Abstract: ConspectusThe last two decades have witnessed the successful development of noble-metal nanocrystals with well-controlled properties for a variety of applications in catalysis, plasmonics, electron...
TL;DR: In this article, a method was proposed for the facile synthesis of Ru@Pd core-shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell taking either an hcp or face-centered cubic (fcc) phase.
Abstract: A relatively unexplored aspect of noble-metal nanomaterials is polymorphism, or their ability to crystallize in different crystal phases. Here, a method is reported for the facile synthesis of Ru@Pd core-shell nanocrystals featuring polymorphism, with the core made of hexagonally close-packed (hcp)-Ru while the Pd shell takes either an hcp or face-centered cubic (fcc) phase. The polymorphism shows a dependence on the shell thickness, with shells thinner than ≈1.4 nm taking the hcp phase whereas the thicker ones revert to fcc. The injection rate provides an experimental knob for controlling the phase, with one-shot and drop-wise injection of the Pd precursor corresponding to fcc-Pd and hcp-Pd shells, respectively. When these nanocrystals are tested as catalysts toward formic acid oxidation, the Ru@Pdhcp nanocrystals outperform Ru@Pdfcc in terms of both specific activity and peak potential. Density functional theory calculations are also performed to elucidate the origin of this performance enhancement.
TL;DR: This review of colloidal metal nanocrystals in metastable phases in unconventional phases with a focus on noble metals highlights the success of synthesis in terms of mechanistic insights and experimental controls, as well as the enhanced catalytic properties.
Abstract: In addition to the conventional knobs such as composition, size, shape, and defect structure, the crystal structure (or phase) of metal nanocrystals offers a new avenue for engineering their properties. Various strategies have recently been developed for the fabrication of colloidal metal nanocrystals in metastable phases different from their bulk counterparts. With a focus on noble metals, we begin with a brief introduction to their atomic packing, followed by a discussion about five major synthetic approaches to their colloidal nanocrystals in unconventional phases. We then highlight the success of synthesis in terms of mechanistic insights and experimental controls, as well as the enhanced catalytic properties. We end this Minireview with perspectives on the remaining issues and future opportunities.
TL;DR: In situ liquid-cell transmission electron microscopy with first-principles calculations is integrated to shed light on the atomistic details involved in the nucleation and growth of Pt on Pd cubic seeds and offers a general guideline for the rational synthesis of nanocrystals with diverse compositions, structures, shapes, and related properties.
Abstract: Despite the large number of reports on colloidal nanocrystals, very little is known about the mechanistic details in terms of nucleation and growth at the atomistic level. Taking bimetallic core-shell nanocrystals as an example, here we integrate in situ liquid-cell transmission electron microscopy with first-principles calculations to shed light on the atomistic details involved in the nucleation and growth of Pt on Pd cubic seeds. We elucidate the roles played by key synthesis parameters, including capping agent and precursor concentration, in controlling the nucleation site, diffusion path, and growth pattern of the Pt atoms. When the faces of a cubic seed are capped by Br-, Pt atoms preferentially nucleate from corners and then diffuse to edges and faces for the creation of a uniform shell. The diffusion does not occur until the Pt deposited at the corner has reached a threshold thickness. At a high concentration of the precursor, self-nucleation takes place and the Pt clusters then randomly attach to the surface of a seed for the formation of a non-uniform shell. These atomistic insights offer a general guideline for the rational synthesis of nanocrystals with diverse compositions, structures, shapes, and related properties.
TL;DR: An introduction to the chemical synthesis and optical properties of AuNCs is provided, followed by the use of radiolabeled Au NCs in tracking and quantifying their pharmacokinetics, including biodistribution, tumor uptake, and intratumoral distribution.
Abstract: Gold nanocages (AuNCs) have emerged as a novel class of multifunctional nanomaterials with an array of applications in nanomedicine, including drug delivery, controlled release, as well as disease diagnosis and treatment. Labeling AuNCs with radionuclides not only offers additional therapeutic capabilities but also makes it easy to analyze their biodistribution, monitor their uptake by the tissue or organ of interest, and optimize their performance in both diagnosis and treatment. Here, an introduction to the chemical synthesis and optical properties of AuNCs is provided in the beginning. The methods developed for their radiolabeling are then showcased, followed by the use of radiolabeled AuNCs in tracking and quantifying their pharmacokinetics, including biodistribution, tumor uptake, and intratumoral distribution. Finally, their potential applications in targeted imaging and image-guided therapy are discussed.
TL;DR: In this paper, the reduction kinetics of a colloidal synthesis has been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner.
Abstract: Improving the performance of noble-metal nanocrystals in various applications critically depends on our ability to manipulate their synthesis in a rational, robust, and controllable fashion. Different from a conventional trial-and-error approach, the reduction kinetics of a colloidal synthesis has recently been demonstrated as a reliable knob for controlling the synthesis of noble-metal nanocrystals in a deterministic and predictable manner. Here we present a brief Viewpoint on the recent progress in leveraging reduction kinetics for controlling and predicting the outcome of a synthesis of noble-metal nanocrystals. With a focus on Pd nanocrystals, we first offer a discussion on the correlation between the initial reduction rate and the internal structure of the resultant seeds. The kinetic approaches for controlling both nucleation and growth in a one-pot setting are then introduced with an emphasis on manipulation of the reduction pathways taken by the precursor. We then illustrate how to extend the strategy into a bimetallic system for the preparation of nanocrystals with different shapes and elemental distributions. Finally, the influence of speciation of the precursor on reduction kinetics is highlighted, followed by our perspectives on the challenges and future endeavors in achieving a controllable and predictable synthesis of noble-metal nanocrystals.
01 Jun 2021
TL;DR: Despite significant progress in controlling the synthesis of noble-metal nanocrystals, the purity and uniformity of many products are still plagued by the unwanted nucleation events taking place in this article.
Abstract: Despite significant progress in controlling the synthesis of noble-metal nanocrystals, the purity and uniformity of many products are still plagued by the unwanted nucleation events taking place in...
TL;DR: A facile route to the preparation of Pt nanobars with aspect ratios tunable up to 2.1 is reported by simply reducing a Pt (IV) precursor in N,N -dimethylformamide (DMF) at 160 °C in the presence of poly (vinyl pyrrolidone) (PVP).
Abstract: Noble-metal nanocrystals with anisotropic shapes have received increasing interest owing to their unique properties. Here, a facile route to the preparation of Pt nanobars with aspect ratios tunable up to 2.1 was reported by simply reducing a PtIV precursor in N,N-dimethylformamide (DMF) at 160 °C in the presence of poly(vinyl pyrrolidone) (PVP). In addition to its commonly observed roles as a solvent and a reductant, DMF could also decompose to generate CO, a capping agent capable of selectively passivating Pt{100} facets to promote the formation of nanobars. The size and aspect ratio of the nanobars could be tuned by varying the amount of PtIV precursor involved in the synthesis, as well as the concentration of PVP because of its dual roles as a stabilizer and a co-reductant. Our mechanistic study indicated that the anisotropic growth resulted from both particle coalescence and localized oxidative etching followed by preferential growth.
TL;DR: In this article, a facile method is described for generating a mineral gradient in a biodegradable polymer scaffold, achieved by swelling a composite film made of polycaprolactone (PCL) and hydroxyapatite (HAp) nanoparticles with a PCL solution.
Abstract: A facile method is described herein for generating a mineral gradient in a biodegradable polymer scaffold. The gradient is achieved by swelling a composite film made of polycaprolactone (PCL) and hydroxyapatite (HAp) nanoparticles with a PCL solution. During the swelling process, the solvent and PCL polymer chains diffuse into the composite film, generating a gradient in HAp density at their interface. The thickness of the mineral gradient can be tuned by varying the extent of swelling to match the length scale of the natural tendon-to-bone attachment (20-60 µm). When patterned with an array of funnel-shaped channels, the mineral gradient presents stem cells with spatial gradations in both biochemical cues (e.g., osteoinductivity and conductivity associated with the HAp nanoparticles) and mechanical cues (e.g., substrate stiffness) to stimulate their differentiation into a graded distribution of cell phenotypes. This new class of biomimetic scaffolds holds great promise for facilitating the regeneration of the injured tendon-to-bone attachment by stimulating the formation of a functionally graded interface.
TL;DR: In this article, a colloidal method for the in situ growth of Pt-Co nanocrystals on various commercial carbon supports was proposed, which resulted in not only variations in size and composition for the nanoparticles, but also their catalytic activity and durability.
Abstract: Carbon-supported Pt-M (M = Co, Ni, and Fe) alloy nanocrystals are widely used as catalysts toward oxygen reduction, a reaction key to the operation of proton-exchange membrane fuel cells. Here we report a colloidal method for the in situ growth of Pt-Co nanocrystals on various commercial carbon supports. The use of different carbon supports resulted in not only variations in size and composition for the nanocrystals but also their catalytic activity and durability toward oxygen reduction in acidic media. Among the nanocrystals, those grown on Vulcan XC72 and Ketjenblack EC300J showed the highest specific and mass activities in the 0.1 M HClO4 and 0.05 M H2SO4 electrolytes, respectively. Additionally, the catalysts also showed different durability depending on the strength of the interaction between the nanocrystals and the carbon support. Our analysis demonstrated that the difference in catalytic performance could be ascribed to the distinct effects of carbon support on both the synthetic and catalytic processes.
TL;DR: In this paper, a method for the facile synthesis of Pt right bipyramids (RBPs) by separating nucleation from growth and controlling the nucleation step in a continuous flow reactor is presented.
Abstract: Colloidal synthesis of metal nanocrystals with controlled shapes and internal structures calls for a tight control over both the nucleation and growth processes. Here we report a method for the facile synthesis of Pt right bipyramids (RBPs) by separating nucleation from growth and controlling the nucleation step in a continuous flow reactor. Specifically, homogeneous nucleation was thermally triggered by introducing the reaction solution into a tubular flow reactor held at an elevated temperature to generate singly-twinned seeds. At a lower temperature, the singly-twinned seeds were protected from oxidative etching to allow their slow growth and evolution into RBPs while additional nucleation of undesired seeds could be largely suppressed to ensure RBPs as the main product. Further investigation indicated that the internal structure and growth pattern of the seeds were determined by the temperatures used for the nucleation and growth steps, respectively. The Br- ions involved in the synthesis also played a critical role in the generation of RBPs by serving as a capping agent for the Pt{100} facets while regulating the reduction kinetics through coordination with the Pt(IV) ions.
TL;DR: In this paper, the surface of core-shell nanocrystals with an octahedral shape and tunable Pt shell thickness was used as a model system to elucidate their surface compositions using catalytic reactions based upon selective hydrogenation of butadiene and acetylene.
Abstract: The catalytic behaviors or properties of bimetallic catalysts are highly dependent on the surface composition, but it has been a grand challenge to acquire such information. In this work, we employ Pd@PtnL core-shell nanocrystals with an octahedral shape and tunable Pt shell thickness as a model system to elucidate their surface compositions using catalytic reactions based upon the selective hydrogenation of butadiene and acetylene. Our results indicate that the surface of the core-shell nanocrystals changed from Pt-rich to Pd-rich when they were subjected to calcination under oxygen, a critical step involved in the preparation of many industrial catalysts. The inside-out migration can be attributed to both atomic interdiffusion and the oxidation of Pd atoms during the calcination process. The changes in surface composition were further confirmed using infrared and X-ray photoelectron spectroscopy. This work offers insightful guidance for the development and optimization of bimetallic catalysts toward various reactions.