Browse
Submit Data
Databases
API
Help

Dataset Information

10 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Kinetic diffusion-controlled synthesis of twinned intermetallic nanocrystals for CO-resistant catalysis.

ABSTRACT: Intermetallic catalysts are of immense interest, but how heterometals diffuse and related interface structure remain unclear when there exists a strong metal-support interaction. Here, we developed a kinetic diffusion-controlled method and synthesized intermetallic Pt₂Mo nanocrystals with twin boundaries on mesoporous carbon (Pt₂Mo/C). The formation of small-sized twinned intermetallic nanocrystals is associated with the strong Mo-C interaction-induced slow Mo diffusion and the heterogeneity of alloying, which is revealed by an in situ aberration-corrected transmission electron microscope (TEM) at high temperature. The twinned Pt₂Mo/C constitutes a promising CO-resistant catalyst for highly selective hydrogenation of nitroarenes. Theoretical calculations and environmental TEM suggest that the weakened CO adsorption over Pt sites of Pt₂Mo twin boundaries and their local region endows them with high CO resistance, selectivity, and reusability. The present strategy paves the way for tailoring the interface structure of high-melting point Mo/W-based intermetallic nanocrystals that proved to be important for the industrially viable reactions.

SUBMITTER: Wang K

PROVIDER: S-EPMC9217091 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Diffusion dynamics controlled colloidal synthesis of highly monodisperse InAs nanocrystals.

Project description:Highly monodisperse colloidal InAs quantum dots (QDs) with superior optoelectronic properties are promising candidates for various applications, including infrared photodetectors and photovoltaics. Recently, a synthetic process involving continuous injection has been introduced to synthesize uniformly sized InAs QDs. Still, synthetic efforts to increase the particle size of over 5 nm often suffer from growth suppression. Secondary nucleation or interparticle ripening during the growth accompanies the inhomogeneity in size as well. In this study, we propose a growth model for the continuous synthetic processing of colloidal InAs QDs based on molecular diffusion. The experimentally validated model demonstrates how precursor solution injection reduces monomer flux, limiting particle growth during synthesis. As predicted by our model, we control the diffusion dynamics by tuning reaction volume, precursor concentration, and injection rate of precursor. Through diffusion-dynamics-control in the continuous process, we synthesize the InAs QDs with a size over 9.0-nm (1Smax of 1600 nm) with a narrow size distribution (12.2%). Diffusion-dynamics-controlled synthesis presented in this study effectively manages the monomer flux and thus overcome monomer-reactivity-originating size limit of nanocrystal growth in solution.

| S-EPMC8140152 | biostudies-literature

A universal route with fine kinetic control to a family of penta-twinned gold nanocrystals.

Project description:Some of the major difficulties hindering the synthesis of different types of colloidal nanocrystals are their complex synthetic methods and the lack of a universal growth mechanism in one system. Herein, we propose a general strategy of kinetically controlled seed-mediated growth to synthesize a family of penta-twinned gold nanocrystals. Specifically, different kinds of penta-twinned nanocrystals (truncated penta-twinned decahedra, truncated bipyramids, bipyramids, truncated bipyramids with tips, star-like penta-twinned nanocrystals, decahedra with concave edges, and decahedra) with tunable sizes and high purity were readily achieved in one system solely by tailoring the deposition kinetics of adatoms on different sites of decahedral seeds. The controllable deposition kinetics can be realized by changing the ratio of reductant/gold precursors (R), which dictates whether horizontal or vertical features along the 5-fold axis direction of Au decahedral seeds are produced. Additionally, the selective growth of a second metal (silver) on penta-twinned gold seeds can be reached through minor modification of R, which opens a new avenue for mechanistic investigation by visualizing the seed localization within the final particles. The present work demonstrates a general paradigm for the kinetic growth of penta-twinned crystals and would be extended to the synthesis of other families of nanocrystals.

| S-EPMC8494040 | biostudies-literature

Understanding the formation of multiply twinned structure in decahedral intermetallic nanoparticles.

Project description:The structure of monometallic decahedral multiply twinned nanoparticles (MTPs) has been extensively studied, whereas less is known about intermetallic MTPs, especially the mechanism of formation of multiply twinned structures, which remains to be understood. Here, by using aberration-corrected scanning transmission electron microscopy, a detailed structural study of AuCu decahedral intermetallic MTPs is presented. Surface segregation has been revealed on the atomic level and the multiply twinned structure was studied systematically. Significantly different from Au and Cu, the intermetallic AuCu MTP adopts a solid-angle deficiency of -13.35°, which represents an overlap instead of a gap (+7.35° gap for Au and Cu). By analysing and summarizing the differences and similarities among AuCu and other existing monometallic/intermetallic MTPs, the formation mechanism has been investigated from both energetic and geometric perspectives. Finally, a general framework for decahedral MTPs has been proposed and unknown MTPs could be predicted on this basis.

| S-EPMC6503919 | biostudies-literature

Electrospinning Synthesis of Carbon-Supported Pt3Mn Intermetallic Nanocrystals and Electrocatalytic Performance towards Oxygen Reduction Reaction.

Project description:To realize the large-scale application of fuel cells, it is still a great challenge to improve the performance and reduce the cost of cathode catalysts towards oxygen reduction reaction (ORR). In this work, carbon-supported ordered Pt3Mn intermetallic catalysts were prepared by thermal annealing electrospun polyacrylonitrile nanofibers containing Platinum(II) acetylacetonate/ Manganese(III) acetylacetonate. Compared with its counterparts, the ordered Pt3Mn intermetallic obtained at 950 °C exhibits a more positive half-potential and higher kinetic current density during the ORR process. Benefiting from their defined stoichiometry and crystal structure, the Mn atoms in Pt3Mn intermetallic can modulate well the geometric and electronic structure of surface Pt atoms, endowing Pt3Mn catalyst with an enhanced ORR catalytic activity. Moreover, it also has a better catalytic stability and methanol tolerance than commercial Pt/C catalyst. Our study provides a new strategy to fabricate a highly active and durable Pt3Mn intermetallic electrocatalyst towards ORR.

| S-EPMC7559926 | biostudies-literature

Room-temperature superionic-phase nanocrystals synthesized with a twinned lattice.

Project description:The engineering of nanoscale features enables the properties of solid-state materials to be tuned. Here, we show the tunable preparation of cuprous sulfide nanocrystals ranging in internal structures from single-domain to multi-domain. The synthetic method utilizes in-situ oxidation to grow nanocrystals with a controlled degree of copper deficiency. Copper-deficient nanocrystals spontaneously undergo twinning to a multi-domain structure. Nanocrystals with twinned domains exhibit markedly altered crystallographic phase and phase transition characteristics as compared to single-domain nanocrystals. In the presence of twin boundaries, the temperature for transition from the ordered phase to the high-copper-mobility superionic phase is depressed. Whereas the superionic phase is stable in the bulk only above ca. 100?°C, cuprous sulfide nanocrystals of ca. 7?nm diameter and a twinned structure are stable in the superionic phase well below ambient temperature. These findings demonstrate twinning to be a structural handle for nanoscale materials design and enable applications for an earth-abundant mineral in solid electrolytes for Li-S batteries.

| S-EPMC6650484 | biostudies-literature

Synergic Catalysis: the Importance of Intermetallic Separation in Co(III)K(I) Catalysts for Ring Opening Copolymerizations.

Project description:Dinuclear polymerization catalysts can show high activity and control. Understanding how to design for synergy between the metals is important to improving catalytic performances. Three heterodinuclear Co(III)K(I) catalysts, featuring very similar coordination chemistries, are prepared with different intermetallic separations. The catalysts are compared for the ring-opening copolymerization (ROCOP) of propene oxide (PO) with CO2 or with phthalic anhydride (PA). The catalyst with a fixed, wide intermetallic separation, LwideCoK(OAc)2 (Co-K = 8.06 Å), shows very high activity for PO/PA ROCOP, but is inactive for PO/CO2 ROCOP. On the other hand, the catalyst with a fixed, narrow intermetallic separation, LshortCoK(OAc)2 (Co-K, 3.59 Å), shows high activity for PO/CO2 ROCOP, but is much less active for PO/PA ROCOP. A bicomponent catalyst system, comprising a monometallic complex LmonoCoOAc used with an equivalent of KOAc[18-crown-6], shows high activity for both PO/CO2 and PO/PA ROCOP, provided the catalyst concentration is sufficiently high, but underperforms at low catalyst loadings. It is proposed that the two lead catalysts, LwideCoK(OAc)2 and LshortCoK(OAc)2, operate by different mechanisms for PO/PA and PO/CO2 ROCOP. The new wide separation catalyst, LwideCoK(OAc)2, shows some of the best performances yet reported for PO/PA ROCOP, and suggests other catalysts featuring larger intermetallic separations should be targeted for epoxide/anhydride copolymerizations.

| S-EPMC11345820 | biostudies-literature

Strain effect in Pd@PdAg twinned nanocrystals towards ethanol oxidation electrocatalysis.

Project description:The strain effect is a critical knob to tune the catalytic performance and has received unprecedented research interest recently. However, it is difficult to distinguish the strain effect from the synergistic effect, especially in alloyed catalysts. Here we have synthesized Pd@PdAg icosahedra and {111} truncated bi-pyramids with only different surface strains between them as electrocatalysts for the ethanol oxidation reaction (EOR). Due to the same exposed facets and compositions of the two electrocatalysts, their EOR performances are mainly determined by the surface strains of PdAg alloys. These two electrocatalysts provide a perfect model to investigate the role of the strain effect in tuning the EOR performance. It is indicated that Pd@PdAg {111} truncated bi-pyramids with a surface strain of 0.3% show better catalytic activity and durability than Pd@PdAg icosahedra with a surface strain of 2.1% including commercial Pd/C. Density functional theory (DFT) calculations reveal that the lowered d-band center of 0.3% strained PdAg alloys relative to 2.1% strained ones reduced the adsorption energy of the acetate-evolution key intermediate *CH3CO, thereby promoting the enhancement in the catalytic performance of Pd@PdAg nanocrystals for the EOR. Electrochemical analysis further verifies this demonstration on the key role of the strain effect in PdAg alloys for tuning catalytic performance.

| S-EPMC9419203 | biostudies-literature

Diffusion modifies the connectivity of kinetic schemes for multisite binding and catalysis.

Project description:The simplest way to describe the influence of the relative diffusion of the reactants on the time course of bimolecular reactions is to modify or renormalize the phenomenological rate constants that enter into the rate equations of conventional chemical kinetics. However, for macromolecules with multiple inequivalent reactive sites, this is no longer sufficient, even in the low concentration limit. The physical reason is that an enzyme (or a ligand) that has just modified (or dissociated from) one site can bind to a neighboring site rather than diffuse away. This process is not described by the conventional chemical kinetics, which is only valid in the limit that diffusion is fast compared with reaction. Using an exactly solvable many-particle reaction-diffusion model, we show that the influence of diffusion on the kinetics of multisite binding and catalysis can be accounted for by not only scaling the rates, but also by introducing new connections into the kinetic scheme. The rate constants that describe these new transitions or reaction channels turn out to have a transparent physical interpretation: The chemical rates are scaled by the appropriate probabilities that a pair of reactants, which are initially in contact, bind rather than diffuse apart. The theory is illustrated by application to phosphorylation of a multisite substrate.

| S-EPMC3856809 | biostudies-other

Supported Intermetallic PdZn Nanoparticles as Bifunctional Catalysts for the Direct Synthesis of Dimethyl Ether from CO-Rich Synthesis Gas.

Project description:The single-step syngas-to-dimethyl ether (STD) process entails economic and technical advantages over the current industrial two-step process. Pd/ZnO-based catalysts have recently emerged as interesting alternatives to currently used Cu/ZnO/Al2 O3 catalysts, but the nature of the active site(s), the reaction mechanism, and the role of Pd and ZnO in the solid catalyst are not well established. Now, Zn-stabilized Pd colloids with a size of 2 nm served as the key building blocks for the methanol active component in bifunctional Pd/ZnO-γ-Al2 O3 catalysts. The catalysts were characterized by combining high-pressure operando X-ray absorption spectroscopy and DFT calculations. The enhanced stability, longevity, and high dimethyl ether selectivity observed makes Pd/ZnO-γ-Al2 O3 an effective alternative system for the STD process compared to Cu/ZnO/γ-Al2 O3 .

| S-EPMC6856832 | biostudies-literature

Nucleation and growth of TiAl<sub>3</sub> intermetallic phase in diffusion bonded Ti/Al Metal Intermetallic Laminate.

Project description:A novel nucleation and growth phenomenon for TiAl3 intermetallic phase in Ti/Al diffusion couple is proposed based on diffusion kinetics. The interdiffusion and intrinsic diffusion co-efficients are calculated to make evident of dominant diffusion of Al towards Ti in Ti/Al diffusion couple obtained by solid state diffusion bonding. It was surprising to observe that the diffusion rate of Al was around 20 times higher than Ti with the formation of Kirkendall pores near the Al/TiAl3 interface. With such dominant diffusion of Al towards Ti, the nucleation and growth of TiAl3 intermetallic phase in Ti/Al couple happens mainly at the Ti/TiAl3 interface rather than Al/TiAl3 interface which is evident by the presence of very fine nearly nano-sized TiAl3 nuclei/grains near the Ti/TiAl3 interface. Even though the intermetallic phase is expected to nucleate at Al/TiAl3 interface, the relatively larger TiAl3 grains near that interface depicts grain growth with minimal nucleation. The theoretical calculations on diffusion parameters are in accordance with experimental observations of TiAl3 intermetallic growth phenomenon in Ti/Al system.

| S-EPMC6235842 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data