Mastering the surface strain of platinum catalysts for efficient electrocatalysis.

Platinum (Pt) has found wide use as an electrocatalyst for sustainable energy conversion systems1-3. The activity of Pt is controlled by its electronic structure (typically, the d-band centre), which depends sensitively on lattice strain4,5. This dependence can be exploited for catalyst design4,6-8, and the use of core-shell structures and elastic substrates has resulted in strain-engineered Pt catalysts with drastically improved electrocatalytic performances7,9-13. However, it is challenging to map in detail the strain-activity correlations in Pt-catalysed conversions, which can involve a number of distinct processes, and to identify the optimal strain modification for specific reactions. Here we show that when ultrathin Pt shells are deposited on palladium-based nanocubes, expansion and shrinkage of the nanocubes through phosphorization and dephosphorization induces strain in the Pt(100) lattice that can be adjusted from -5.1 per cent to 5.9 per cent. We use this strain control to tune the electrocatalytic activity of the Pt shells over a wide range, finding that the strain-activity correlation for the methanol oxidation reaction and hydrogen evolution reaction follows an M-shaped curve and a volcano-shaped curve, respectively. We anticipate that our approach can be used to screen out lattice strain that will optimize the performance of Pt catalysts-and potentially other metal catalysts-for a wide range of reactions.

Tailoring Amorphous PdCu Nanostructures for Efficient C-C Cleavage in Ethanol Electrooxidation.

The large-scale application of direct ethanol fuel cells has long been obstructed by the sluggish ethanol oxidation reaction at the anode. Current wisdom for designing and fabricating EOR electrocatalysts has been focused on crystalline materials, which result in only limited improvement in catalytic efficiency. Here, we report the amorphous PdCu (a-PdCu) nanomaterials as superior EOR electrocatalysts. The amorphization of PdCu catalysts can significantly facilitate the C-C bond cleavage, which thereby affords a C1 path faradic efficiency as high as 69.6%. Further tailoring the size and shape of a-PdCu nanocatalysts through the delicate kinetic control can result in a maximized mass activity up to 15.25 A/mgPd, outperforming most reported catalysts. Notably, accelerated durability tests indicate that both the isotropic structure and one-dimensional shape can dramatically enhance the catalytic durability of the catalysts. This work provides valuable guidance for the rational design and fabrication of amorphous noble metal-based electrocatalysts for fuel cells.

General Synthesis of Amorphous PdM (M = Cu, Fe, Co, Ni) Alloy Nanowires for Boosting HCOOH Dehydrogenation.

Noble metal-based nanomaterials with amorphous structures are promising candidates for developing efficient electrocatalysts. However, their synthesis remains a significant challenge, especially under mild conditions. In this paper, we report a general strategy for preparing amorphous PdM nanowires (a-PdM NWs, M = Fe, Co, Ni, and Cu) at low temperatures by exploiting glassy non-noble metal (M) nuclei generated by special ligand adsorption as the amorphization dictator. When evaluated as electrocatalysts toward formic acid oxidation, a-PdCu NWs can deliver the mass and specific activities as high as 2.93 A/mgPd and 5.33 mA/cm2, respectively; these are the highest values for PdCu-based catalysts reported thus far, far surpassing the crystalline-dominant counterparts and commercial Pd/C. Theoretical calculations suggest that the outstanding catalytic performance of a-PdCu NWs arises from the amorphization-induced high surface reactivity, which can efficiently activate the chemically stable C-H bond and thereby significantly facilitate the dissociation of HCOOH.

Engineering Surface Structure of Pt Nanoshells on Pd Nanocubes to Preferentially Expose Active Surfaces for ORR by Manipulating the Growth Kinetics.

Synthesis of Pt nanoshells on substrates can increase the utilization efficiency of Pt atoms and reduce the amount of Pt used in the applications. However, it is still an enormous challenge in tailoring the required crystal facets of Pt nanoshells on a given substrate. In this work, we demonstrate a facile and convenient approach capable for generating Pt octahedral islands with tunable sizes and densities on Pd nanocubes by manipulating the deposition rate. The key to this synthesis is the fine control over the deposition rate of Pt on Pd seeds. Because of the different reactivities at the surface sites, the deposition of Pt can be controlled at a certain site by carefully tuning the deposition rate. With a low concentration of reductant (8.33 mg/mL of glucose), surface diffusion dominates the process, and thus the Pt cubic shells form on Pd cubic seeds. In contrast, when a higher amount of the reductant (16.67 mg/mL of glucose) is added, the deposition starts to dominate the growth of Pt shells. In this case, the deposition would be controlled at the corners, forming eight large Pt octahedra on a cubic Pd seed. Further increasing the deposition rate can induce much higher deposition rates, in which case, the deposition of Pt would likely take place not only at the corners, but also the edge and surface sites of the seeds. Not surprisingly, this growth habit can result in the formation of high-density octahedral islands on Pd cubic seeds. With the same amount of precursor supply, the higher the densities of Pt islands, the smaller the size of the octahedral islands on Pd nanocubes. Unlike other synthetic methods, the size of the octahedral islands on Pd seeds can be even controlled to be smaller than 3 nm by controlling the amount of the Pt precursor. Considering the excellent performance of {111} facets of Pt catalysts toward ORR, the Pt nanocages with small octahedral islands on the surfaces can exhibit a high activity with a mass activity 0.68 A/mg, as high as 5.2 times of that of commercial Pt/C.

Etching-Assisted Route to Heterophase Au Nanowires with Multiple Types of Active Surface Sites for Silane Oxidation.

The construction of multiple types of active sites on the surface of a metallic catalyst can markedly enhance its catalytic activity toward specific reactions. Here, we show that heterophase gold nanowires (Au NWs) with multiple types of active surface sites can be synthesized using an etching-assisted process, yielding the highest reported turnover frequency (TOF) for Au catalysts toward the silane oxidation reaction by far. We use synchrotron powder X-ray diffraction (PXRD) and aberration-corrected (scanning) transmission electron microscopy (TEM) to show that the Au NWs contain heterophase structures, planar defects, and surface steps. Moreover, the contribution to the catalytic performance from each type of active sites was clarified. Surface steps on the Au NW catalysts, which were identified using aberration-corrected (scanning) TEM, were shown to play the most important role in enhancing the catalytic performance. By using synchrotron PXRD, it was shown that a small ratio of metastable phases within Au NWs can enhance catalytic activity by a factor of 1.35, providing a further route to improve catalytic activity. Of the three types of surface active sites, surface terminations of planar defects such as twin boundaries (TB) and stacking faults (SF) are less active than metastable phases and surface steps for Au catalysts toward the silane oxidation reaction. Such an etching-assisted synthesis of heterophase Au NWs promises to open new possibilities for catalysis, plasmonic, optics, and electrical applications.

Creation of Controllable High-Density Defects in Silver Nanowires for Enhanced Catalytic Property.

Structural defects have been proven to determine many of the materials' properties. Here, we demonstrate a unique approach to the creation of Ag nanowires with high-density defects through controllable nanoparticles coalescence in one-dimensional pores of mesoporous silica. The density of defects can be easily adjusted by tuning the annealing temperature during synthetic process. The high-density defects promote the adsorption and activation of more reactants on the surface of Ag nanowires during catalytic reactions. As a result, the as-prepared Ag nanowires exhibit enhanced activities in catalyzing dehydrogenative coupling reaction of silane in terms of apparent activation energy and turnover frequency (TOF). We show further that the silane conversion rate can be enhanced by maximizing the defect density and thus the number of active sites on the Ag nanowires, reaching a remarkable TOF of 8288 h(-1), which represents the highest TOF that has been achieved by far on Ag catalysts. This work not only proves the important role of structural defects in catalysis but also provides a new and general strategy for constructing high-density defects in metal catalysts.

Shape-controlled synthesis of Pd nanocrystals and their catalytic applications.

Palladium is a marvelous catalyst for a rich variety of reactions in industrial processes and commercial devices. Most Pd-catalyzed reactions exhibit structure sensitivity, meaning that the activity or selectivity depends on the arrangement of atoms on the surface. Previously, such reactions could only be studied in ultrahigh vacuum using Pd single crystals cut with a specific crystallographic plane. However, these model catalysts are far different from real catalytic systems owing to the absence of atoms at corners and edges and the extremely small specific surface areas for the model systems. Indeed, enhancing the performance of a Pd-based catalyst, in part to reduce the amount needed of this precious and rare metal for a given reaction, requires the use of Pd with the highest possible specific surface area. Recent advances in nanocrystal synthesis are offering a great opportunity to investigate and quantify the structural sensitivity of catalysts based on Pd and other metals. For a structure-sensitive reaction, the catalytic properties of Pd nanocrystals are strongly dependent on both the size and shape. The shape plays a more significant role in controlling activity and selectivity, because the shape controls not only the facets but also the proportions of surface atoms at corners, edges, and planes, which affect the outcomes of possible reactions. We expect catalysts based on Pd nanocrystals with optimized shapes to meet the increasing demands of industrial applications at reduced loadings and costs. In this Account, we discuss recent advances in the synthesis of Pd nanocrystals with controlled shapes and their resulting performance as catalysts for a large number of reactions. First, we review various synthetic strategies based on oxidative etching, surface capping, and kinetic control that have been used to direct the shapes of nanocrystals. When crystal growth is under thermodynamic control, the capping agent plays a pivotal role in determining the shape of a product by altering the order of surface energies for different facets through selective adsorption; the resulting product has the lowest possible total surface energy. In contrast, the product of a kinetically controlled synthesis often deviates from the thermodynamically favored structure, with notable examples including nanocrystals enclosed by high-index facets or concave surfaces. We then discuss the key parameters that control the nucleation and growth of Pd nanocrystals to decipher potential growth mechanisms and build a connection between the experimental conditions and the pathways to different shapes. Finally, we present a number of examples to highlight the use of these Pd nanocrystals as catalysts or electrocatalysts for various applications with structure-sensitive properties. We believe that a deep understanding of the shape-dependent catalytic properties, together with an ability to experimentally maneuver the shape of metal nanocrystals, will eventually lead to rational design of advanced catalysts with substantially enhanced performance.

Synthesis of rhodium concave tetrahedrons by collectively manipulating the reduction kinetics, facet-selective capping, and surface diffusion.

This paper describes a facile synthesis of Rh tetrahedrons with concave side faces by collectively manipulating the reaction kinetics, facet-selective capping, and surface diffusion of atoms. Specifically, a combination of Na3RhCl6, triethylene glycol, l-ascorbic acid, and citric acid provides the right conditions for generating the concave tetrahedrons. After the formation of small Rh tetrahedral seeds through self-nucleation, the subsequently generated Rh atoms were selectively deposited onto the corner sites to generate Rh tetrapods. At the same time, the deposited atoms could diffuse from the corners to edges to generate concave side faces because the diffusion to face sites was restrained by the citric acid adsorbed on the {111} facets. This study offers deep insight into the growth mechanism involved the formation of noble-metal nanocrystals with concave surfaces. The Rh concave tetrahedrons were encased by a mix of {111} and {110} facets, showing great potential for catalytic applications.

Facile Synthesis of PtP2 Nanocrystals as Highly Active Electrocatalysts for Methanol Oxidation.

Although significant efforts have been made in the past few decades, the development of affordable, durable, and effective electrocatalysts for direct methanol fuel cells (DMFCs) remains a formidable challenge. Herein, we present a facile and efficient phosphorization approach for synthesizing PtP2 intermetallic nanocrystals and utilize them as electrocatalysts in the methanol oxidation reaction (MOR). Impressively, the synthesized PtP2 nanocatalysts exhibit a mass activity of 2.14 mA µg-1 and a specific activity of 6.28 mA cm-2, which are 5.1 and 9.5 times higher than those achieved by the current state-of-the-art commercial Pt/C catalyst, respectively. Moreover, the PtP2 nanocatalysts demonstrate improved stability toward acidic MOR by retaining 92.1% of its initial mass activity after undergoing 5000 potential cycles, far surpassing that of the commercial Pt/C (38%). Further DMFC tests present a 2.7 times higher power density than that of the commercial Pt/C, underscoring their potential for application in methanol fuel cells. Density functional theory calculations suggest that the accelerated MOR kinetics and improved CO tolerance on PtP2 can be attributed to the attenuated binding strength of CO intermediates and the enhanced stability due to strong Pt-P interaction. To our knowledge, this is the first report identifying the MOR performance on PtP2 intermetallic nanocrystals, highlighting their potential as highly active and stable nanocatalysts for DMFCs.

Enhancing the catalytic and electrocatalytic properties of Pt-based catalysts by forming bimetallic nanocrystals with Pd.

Bimetallic nanocrystals consisting of two distinct metals such as Pd and Pt are attractive for a wide variety of catalytic and electrocatalytic applications as they can exhibit not only a combination of the properties associated with both metals but also enhancement or synergy due to a strong coupling between the two metals. With Pd as the base metal, many methods have recently been demonstrated for the synthesis of Pd-Pt bimetallic nanocrystals having a wide variety of different structures in the form of alloys, dendrites, core-shells, multi-shells, and monolayers. In this tutorial review, we begin with a brief discussion on the possible structures of Pd-Pt bimetallic nanocrystals, followed by an account of recent progress on synthetic approaches to such nanocrystals with controlled structures, shapes and sizes. In addition to the experimental procedures and mechanistic studies, a number of examples are presented to highlight the use of such bimetallic nanocrystals as catalysts or electrocatalysts for various applications with enhanced performance relative to their monometallic counterparts.

Synthesis of amorphous trimetallic PdCuNiP nanoparticles for enhanced OER.

Metal phosphides with multi-element components and amorphous structure represent a novel kind of electrocatalysts for promising activity and durability towards the oxygen evolution reaction (OER). In this work, a two-step strategy, including alloying and phosphating processes, is reported to synthesize trimetallic amorphous PdCuNiP phosphide nanoparticles for efficient OER under alkaline conditions. The synergistic effect between Pd, Cu, Ni, and P elements, as well as the amorphous structure of the obtained PdCuNiP phosphide nanoparticles, would boost the intrinsic catalytic activity of Pd nanoparticles towards a wide range of reactions. These obtained trimetallic amorphous PdCuNiP phosphide nanoparticles exhibit long-term stability, nearly a 20-fold increase in mass activity toward OER compared with the initial Pd nanoparticles, and 223 mV lower in overpotential at 10 mA cm-2. This work not only provides a reliable synthetic strategy for multi-metallic phosphide nanoparticles, but also expands the potential applications of this promising class of multi-metallic amorphous phosphides.

Synthesis and characterization of Pd@M(x)Cu(1-x) (M = Au, Pd, and Pt) nanocages with porous walls and a yolk-shell structure through galvanic replacement reactions.

This paper describes the synthesis of Pd@M(x)Cu(1-x) (M = Au, Pd, and Pt) nanocages with a yolk-shell structure through galvanic replacement reactions that involve Pd@Cu core-shell nanocubes as sacrificial templates and ethylene glycol as the solvent. Compared with the most commonly used templates based on Ag, Cu offers a much lower reduction potential (0.34 versus 0.80 V), making the galvanic reaction more easily to conduct, even at room temperature. Our structural and compositional characterizations indicated that the products were hollow inside, and each one of them contained porous M-Cu alloy walls and a Pd cube in the interior. For the Pd@Au(x)Cu(1-x) yolk-shell nanocages, they displayed broad extinction peaks extending from the visible to the near-IR region. Our mechanistic study revealed that the dissolution of the Cu shell preferred to start from the slightly truncated corners and then progressed toward the interior, because the Cu {100} side faces were protected by a surface capping layer of hexadecylamine. This galvanic approach can also be extended to generating other hollow metal nanostructures by using different combinations of Cu nanostructures and salt precursors.

Controlling the morphology of rhodium nanocrystals by manipulating the growth kinetics with a syringe pump.

Noble-metal nanocrystals with well-defined and controllable morphologies are of great importance to applications in catalysis, plasmonics, and surface-enhanced spectroscopy. Many synthetic approaches have been demonstrated for controlling the growth habit and thus morphology of metal nanocrystals, but most of them are based on a thermodynamic approach, including the use of a capping agent. While thermodynamic control has shown its power in generating nanocrystals with a myriad of different morphologies, it is ultimately limited by the obligation to minimize the surface energy of a system. As a result, it is impractical to use thermodynamic control to generate nanocrystals having high-energy facets and/or a negative curvature. Using rhodium as an example, here we demonstrate a general method based on kinetic control with a syringe pump that can be potentially extended to other noble metals and even other solid materials. For the first time, we were able to produce concave nanocubes with a large fraction of {110} facets and octapods with a cubic symmetry in high yields by simply controlling the injection rate at which the precursor was added into the reaction solution. The concave nanocubes with {110} facets and a unique cavity structure on the surface are important for a variety of applications.

Noble-metal nanocrystals with concave surfaces: synthesis and applications.

Metal nanocrystals with concave surfaces are interesting for a wide variety of applications that are related to catalysis, plasmonics, and surface-enhanced spectroscopy. This interest arises from their high-index facets, surface cavities, and sharp corners/edges. Two major challenges are associated with this novel class of nanocrystals: 1) how to generate a concave surface with negative curvature, which is not favored by thermodynamics owing to its higher energy than the convex counterpart; and 2) how to stabilize the morphology of a nanocrystal with concave structures on the surface. Recently, a number of different procedures have been developed for the synthesis of noble-metal nanocrystals with concave surfaces. This Review provides a brief account of these developments, with the aim of offering new insights into the growth mechanisms. We focus on methods based on two general strategies: 1) site-specific dissolution through etching and galvanic replacement; and 2) directionally controlled overgrowth by facet-selective capping, kinetic control, and template-directed epitaxy. Their enhanced catalytic and electrocatalytic properties are also described.

Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective?

The activity and selectivity of structure-sensitive reactions are strongly correlated with the shape and size of the nanocrystals present in a catalyst. This correlation can be exploited for rational catalyst design, especially if each type of surface atom displays a different behavior, to attain the highest activity and selectivity. In this work, uniform Pd nanocrystals with cubic (in two different sizes), octahedral, and cuboctahedral shapes were synthesized through a solution-phase method with poly(vinyl pyrrolidone) (PVP) serving as a stabilizer and then tested in the hydrogenation of 2-methyl-3-butyn-2-ol (MBY). The observed activity and selectivity suggested that two types of active sites were involved in the catalysis--those on the planes and at edges--which differ in their coordination numbers. Specifically, semihydrogenation of MBY to 2-methyl-3-buten-2-ol (MBE) occurred preferentially at the plane sites regardless of their crystallographic orientation, Pd(111) and/or Pd(100), whereas overhydrogenation occurred mainly at the edge sites. The experimental data can be fit with a kinetic modeling based on a two-site Langmuir-Hinshelwood mechanism. By considering surface statistics for nanocrystals with different shapes and sizes, the optimal catalyst in terms of productivity of the target product MBE was predicted to be cubes of roughly 3-5 nm in edge length. This study is an attempt to close the material and pressure gaps between model single-crystal surfaces tested under ultra-high-vacuum conditions and real catalytic systems, providing a powerful tool for rational catalyst design.

Nanocrystals composed of alternating shells of Pd and Pt can be obtained by sequentially adding different precursors.

This paper describes a layer-by-layer epitaxial approach to the synthesis of multishelled nanocrystals composed of alternating shells of Pd and Pt by starting with seeds made of Pd or Pt nanocrystals. The synthesis was conducted by sequentially adding PtCl(4)(2-) and PdCl(4)(2-) salt precursors into a system containing either Pd or Pt seeds (in the shape of cuboctahedrons, octahedrons, plates, or cubes) together with a weak reducing agent such as citric acid (CA). The slow reduction kinetics associated with CA played an important role in the epitaxial growth of one metal on the other, resulting in the formation of Pd-Pt multishelled nanocrystals. Owing to the capping effect of CA for {111} facets of Pd and Pt, the multishelled nanocrystals tended to be enclosed by {111} facets in the form of octahedrons or thin plates, depending on the shapes of the Pd or Pt seeds: octahedrons for cuboctahedral, cubic, or octahedral seeds, and plates for platelike seeds.

Synthesis of Pd-Pt bimetallic nanocrystals with a concave structure through a bromide-induced galvanic replacement reaction.

This article describes a systematic study of the galvanic replacement reaction between PtCl(6)(2-) ions and Pd nanocrystals with different shapes, including cubes, cuboctahedrons, and octahedrons. It was found that Br(-) ions played an important role in initiating, facilitating, and directing the replacement reaction. The presence of Br(-) ions led to the selective initiation of galvanic replacement from the {100} facets of Pd nanocrystals, likely due to the preferential adsorption of Br(-) ions on this crystallographic plane. The site-selective galvanic replacement resulted in the formation of Pd-Pt bimetallic nanocrystals with a concave structure owing to simultaneous dissolution of Pd atoms from the {100} facets and deposition of the resultant Pt atoms on the {111} facets. The Pd-Pt concave nanocubes with different weight percentages of Pt at 3.4, 10.4, 19.9, and 34.4 were also evaluated as electrocatalysts for the oxygen reduction reaction (ORR). Significantly, the sample with a 3.4 wt.% of Pt exhibited the largest specific electrochemical surface area and was found to be four times as active as the commercial Pt/C catalyst for the ORR in terms of equivalent Pt mass.

Deposition of Atomically Thin Pt Shells on Amorphous Palladium Phosphide Cores for Enhancing the Electrocatalytic Durability.

As an excellent electrocatalyst, platinum (Pt) is often deposited as a thin layer on a nanoscale substrate to achieve high utilization efficiency. However, the practical application of the as-designed catalysts has been substantially restricted by the poor durability arising from the leaching of cores. Herein, by employing amorphous palladium phosphide (a-Pd-P) as substrates, we develop a class of leaching-free, ultrastable core-shell Pt catalysts with well-controlled shell thicknesses and surface structures for fuel cell electrocatalysis. When a submonolayer of Pt is deposited on the 6 nm nanocubes, the resulting Pd@a-Pd-P@PtSML core-shell catalyst can deliver a mass activity as high as 4.08 A/mgPt and 1.37 A/mgPd+Pt toward the oxygen reduction reaction at 0.9 V vs the reversible hydrogen electrode and undergoes 50 000 potential cycles with only ∼9% activity loss and negligible structural deformation. As elucidated by the DFT calculations, the superior durability of the catalysts originates from the high corrosion resistance of the disordered a-Pd-P substrates and the strong interfacial Pt-P interactions between the Pt shell and amorphous Pd-P layer.

Synthesis of titania nanosheets with a high percentage of exposed (001) facets and related photocatalytic properties.

Anatase TiO(2) nanosheets with highly reactive (001) facets exposed have been successfully synthesized by a facile hydrothermal route, taking advantage of a specific stabilization effect of fluorine ion on (001) facets. The percentage of highly reactive (001) facets in such TiO(2) nanosheets is very high (up to 89%). In addition, the as-prepared TiO(2) nanosheets exhibit excellent activity in the photocatalytic degradation of organic contaminants.

H2-Induced coalescence of Pt nanoparticles for the preparation of ultrathin Pt nanowires with high-density planar defects.

Construction of planar defects within a metallic catalyst can significantly improve its catalytic performance. However, it remains a huge challenge to introduce planar defects during the synthesis of metallic catalysts. In this work, we have reported an effective approach for the preparation of Pt nanowires with high-density planar defects. The success of the approach mainly relies on the attaching and merging of small Pt nanoparticles at low temperatures with the assistance of H2. By comparing the catalytic activities of Pt nanowires with high-density planar defects and commercial Pt/C catalysts toward methanol oxidation reactions, we show that the existence of planar defects can markedly enhance the electrocatalytic performance of the Pt nanowires. The Pt nanowires of 2.0 nm in diameter show a factor of 6.1 enhancement in specific activity and a factor of 5.4 enhancement in mass activity, respectively, for this reaction, compared to the commercial Pt/C catalyst. The method developed in this work could be an effective route to introduce planar defects within Pt catalysts, endowing them with much enhanced catalytic properties.