Atomistic insights into the nucleation and growth of platinum on palladium nanocrystals.

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.

Author Correction: Bismuthene for highly efficient carbon dioxide electroreduction reaction.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Bismuthene for highly efficient carbon dioxide electroreduction reaction.

Bismuth (Bi) has been known as a highly efficient electrocatalyst for CO2 reduction reaction. Stable free-standing two-dimensional Bi monolayer (Bismuthene) structures have been predicted theoretically, but never realized experimentally. Here, we show the first simple large-scale synthesis of free-standing Bismuthene, to our knowledge, and demonstrate its high electrocatalytic efficiency for formate (HCOO-) formation from CO2 reduction reaction. The catalytic performance is evident by the high Faradaic efficiency (99% at -580 mV vs. Reversible Hydrogen Electrode (RHE)), small onset overpotential (<90 mV) and high durability (no performance decay after 75 h and annealing at 400 °C). Density functional theory calculations show the structure-sensitivity of the CO2 reduction reaction over Bismuthene and thicker nanosheets, suggesting that selective formation of HCOO- indeed can proceed easily on Bismuthene (111) facet due to the unique compressive strain. This work paves the way for the extensive experimental investigation of Bismuthene in many different fields.

Single-atom gold oxo-clusters prepared in alkaline solutions catalyse the heterogeneous methanol self-coupling reactions.

In an effort to obtain the maximum atom efficiency, research on heterogeneous single-atom catalysts has intensified recently. Anchoring organometallic homogeneous catalysts to surfaces creates issues with retaining mononuclearity and activity, while the several techniques developed to prepare atomically dispersed precious metals on oxide supports are usually complex. Here we report a facile one-pot synthesis of inorganometallic mononuclear gold complexes formed in alkaline solutions as robust and versatile single-atom gold catalysts. The complexes remain intact on impregnation onto supports or after drying in air to give a crystalline powder. They can be used to interrogate the nuclearity of the catalytically active gold site for reactions known to be catalysed by oxidized gold species. We show that the [Au1-Ox]- cluster directs the heterogeneous coupling of two methanol molecules to methyl formate and hydrogen with a 100% selectivity below 180 °C. The reaction is industrially important as well as the key step in methanol steam reforming on gold catalysts.

Understanding the Thermal Stability of Palladium-Platinum Core-Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory.

Core-shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core-shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core-shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core-shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. The opposite trend for alloying of the core-shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.

Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra.

Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wave density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200-400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. The mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.

Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction.

Engineering the elemental composition of metal nanocrystals offers an effective strategy for the development of catalysts or electrocatalysts with greatly enhanced activity. Herein, we report the synthesis of Pt-Ag alloy nanocages with an outer edge length of 18 nm and a wall thickness of about 3 nm. Such nanocages with a composition of Pt19Ag81 could be readily prepared in one step through the galvanic replacement reaction between Ag nanocubes and a Pt(II) precursor. After 10 000 cycles of potential cycling in the range of 0.60-1.0 V as in an accelerated durability test, the composition of the nanocages changed to Pt56Ag44, together with a specific activity of 1.23 mA cm-2 toward oxygen reduction, which was 3.3 times that of a state-of-the-art commercial Pt/C catalyst (0.37 mA cm-2) prior to durability testing. Density functional theory calculations attributed the increased activity to the stabilization of the transition state for breaking the O-O bond in molecular oxygen. Even after 30 000 cycles of potential cycling, the mass activity of the nanocages only dropped from 0.64 to 0.33 A mg-1Pt, which was still about two times that of the pristine Pt/C catalyst (0.19 A mg-1Pt).

Synthesis and Characterization of Ru Cubic Nanocages with a Face-Centered Cubic Structure by Templating with Pd Nanocubes.

Nanocages have received considerable attention in recent years for catalytic applications owing to their high utilization efficiency of atoms and well-defined facets. Here we report, for the first time, the synthesis of Ru cubic nanocages with ultrathin walls, in which the atoms are crystallized in a face-centered cubic (fcc) rather than hexagonal close-packed (hcp) structure. The key to the success of this synthesis is to ensure layer-by-layer deposition of Ru atoms on the surface of Pd cubic seeds by controlling the reaction temperature and the injection rate of a Ru(III) precursor. By selectively etching away the Pd from the Pd@Ru core-shell nanocubes, we obtain Ru nanocages with an average wall thickness of 1.1 nm or about six atomic layers. Most importantly, the Ru nanocages adopt an fcc crystal structure rather than the hcp structure observed in bulk Ru. The synthesis has been successfully applied to Pd cubic seeds with different edge lengths in the range of 6-18 nm, with smaller seeds being more favorable for the formation of Ru shells with a flat, smooth surface due to shorter distance for the surface diffusion of the Ru adatoms. Self-consistent density functional theory calculations indicate that these unique fcc-structured Ru nanocages might possess promising catalytic properties for ammonia synthesis compared to hcp Ru(0001), on the basis of strengthened binding of atomic N and substantially reduced activation energies for N2 dissociation, which is the rate-determining step for ammonia synthesis on hcp Ru catalysts.

Semi-empirical correlation for binary interaction parameters of the Peng-Robinson equation of state with the van der Waals mixing rules for the prediction of high-pressure vapor-liquid equilibrium.

Peng-Robinson equation of state is widely used with the classical van der Waals mixing rules to predict vapor liquid equilibria for systems containing hydrocarbons and related compounds. This model requires good values of the binary interaction parameter kij . In this work, we developed a semi-empirical correlation for kij partly based on the Huron-Vidal mixing rules. We obtained values for the adjustable parameters of the developed formula for over 60 binary systems and over 10 categories of components. The predictions of the new equation system were slightly better than the constant-kij model in most cases, except for 10 systems whose predictions were considerably improved with the new correlation.