Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 87
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
J Am Chem Soc ; 144(36): 16378-16388, 2022 Sep 14.
Artigo em Inglês | MEDLINE | ID: mdl-36047705

RESUMO

Liquid crystals (LCs), when supported on reactive surfaces, undergo changes in ordering that can propagate over distances of micrometers, thus providing a general and facile mechanism to amplify atomic-scale transformations on surfaces into the optical scale. While reactions on organic and metal substrates have been coupled to LC-ordering transitions, metal oxide substrates, which offer unique catalytic activities for reactions involving atmospherically important chemical species such as oxidized sulfur species, have not been explored. Here, we investigate this opportunity by designing LCs that contain 4'-cyanobiphenyl-4-carboxylic acid (CBCA) and respond to surface reactions triggered by parts-per-billion concentrations of SO2 gas on anatase (101) substrates. We used electronic structure calculations to predict that the carboxylic acid group of CBCA binds strongly to anatase (101) in a perpendicular orientation, a prediction that we validated in experiments in which CBCA (0.005 mol %) was doped into an LC (4'-n-pentyl-4-biphenylcarbonitrile). Both experiment and computational modeling further demonstrated that SO3-like species, produced by a surface-catalyzed reaction of SO2 with H2O on anatase (101), displace CBCA from the anatase surface, resulting in an orientational transition of the LC. Experiments also reveal the LC response to be highly selective to SO2 over other atmospheric chemical species (including H2O, NH3, H2S, and NO2), in agreement with our computational predictions for anatase (101) surfaces. Overall, we establish that the catalytic activities of metal oxide surfaces offer the basis of a new class of substrates that trigger LCs to undergo ordering transitions in response to chemical species of relevance to atmospheric chemistry.


Assuntos
Cristais Líquidos , Compostos de Bifenilo , Ácidos Carboxílicos , Catálise , Cristais Líquidos/química , Nitrilas , Óxidos de Enxofre , Titânio
2.
ACS Sens ; 7(9): 2545-2555, 2022 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-35998611

RESUMO

We report how analysis of the spatial and temporal optical responses of liquid crystal (LC) films to targeted gases, when performed using a machine learning methodology, can advance the sensing of gas mixtures and provide important insights into the physical processes that underlie the sensor response. We develop the methodology using O3 and Cl2 mixtures (representative of an important class of analytes) and LCs supported on metal perchlorate-decorated surfaces as a model system. Although O3 and Cl2 both diffuse through LC films and undergo redox reactions with the supporting metal perchlorate surfaces to generate similar initial and final optical states of the LCs, we show that a three-dimensional convolutional neural network can extract feature information that is encoded in the spatiotemporal color patterns of the LCs to detect the presence of both O3 and Cl2 species in mixtures and to quantify their concentrations. Our analysis reveals that O3 detection is driven by the transition time over which the brightness of the LC changes, while Cl2 detection is driven by color fluctuations that develop late in the optical response of the LC. We also show that we can detect the presence of Cl2 even when the concentration of O3 is orders of magnitude greater than the Cl2 concentration. The proposed methodology is generalizable to a wide range of analytes, reactive surfaces, and LCs and has the potential to advance the design of portable LC monitoring devices (e.g., wearable devices) for analyzing gas mixtures using spatiotemporal color fluctuations.


Assuntos
Cristais Líquidos , Gases , Cristais Líquidos/química , Metais , Redes Neurais de Computação , Percloratos
3.
Nano Lett ; 22(9): 3591-3597, 2022 05 11.
Artigo em Inglês | MEDLINE | ID: mdl-35439017

RESUMO

Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here, we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of face-centered cubic (fcc)-Pd nanoplate templates with 12 nm plates giving fcc-Ru while 18-26 nm plates result in hexagonal closed-packed (hcp)-Ru. Although Ru overlayers with a metastable fcc- (high in bulk energy) or stable hcp-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp- (high in surface energy) and smooth fcc-facets (low in surface energy), respectively, on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The Pd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions.


Assuntos
Nanopartículas , Oxirredução , Fenômenos Físicos
4.
Proc Natl Acad Sci U S A ; 119(13): e2119883119, 2022 03 29.
Artigo em Inglês | MEDLINE | ID: mdl-35312369

RESUMO

SignificanceWe present a groundbreaking advance in completely nonprecious hydrogen fuel cell technologies achieving a record power density of 200 mW/cm2 with Ni@CNx anode and Co-Mn cathode. The 2-nm CNx coating weakens the O-binding energy, which effectively mitigates the undesirable surface oxidation during hydrogen oxidation reaction (HOR) polarization, leading to a stable fuel cell operation for Ni@CNx over 100 h at 200 mA/cm2, superior to a Ni nanoparticle counterpart. Ni@CNx exhibited a dramatically enhanced tolerance to CO relative to Pt/C, enabling the use of hydrogen gas with trace amounts of CO, critical for practical applications. The complete removal of precious metals in fuel cells lowers the catalyst cost to virtually negligible levels and marks a milestone for practical alkaline fuel cells.

5.
Chem Rev ; 122(6): 6117-6321, 2022 03 23.
Artigo em Inglês | MEDLINE | ID: mdl-35133808

RESUMO

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.


Assuntos
Fontes de Energia Elétrica , Prótons , Hidrogênio/química , Oxigênio/química , Água
6.
J Am Chem Soc ; 144(6): 2556-2568, 2022 02 16.
Artigo em Inglês | MEDLINE | ID: mdl-35108015

RESUMO

Palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure-catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH0.706. On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. This work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.

7.
Mater Horiz ; 8(7): 2050-2056, 2021 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-34846482

RESUMO

The development of responsive soft materials with tailored functional properties based on the chemical reactivity of atomically precise inorganic interfaces has not been widely explored. In this communication, guided by first-principles calculations, we design bimetallic surfaces comprised of atomically thin Pd layers deposited onto Au that anchor nematic liquid crystalline phases of 4'-n-pentyl-4-biphenylcarbonitrile (5CB) and demonstrate that the chemical reactivity of these bimetallic surfaces towards Cl2 gas can be tuned by specification of the composition of the surface alloy. Specifically, we use underpotential deposition to prepare submonolayer to multilayers of Pd on Au and employ X-ray photoelectron and infrared spectroscopy to validate computational predictions that binding of 5CB depends strongly on the Pd coverage, with ∼0.1 monolayer (ML) of Pd sufficient to cause the liquid crystal (LC) to adopt a perpendicular binding mode. Computed heats of dissociative adsorption of Cl2 on PdAu alloy surfaces predict displacement of 5CB from these surfaces, a result that is also confirmed by experiments revealing that 1 ppm Cl2 triggers orientational transitions of 5CB. By decreasing the coverage of Pd on Au from 1.8 ± 0.2 ML to 0.09 ± 0.02 ML, the dynamic response of 5CB to 1 ppm Cl2 is accelerated 3X. Overall, these results demonstrate the promise of hybrid designs of responsive materials based on atomically precise interfaces formed between hard bimetallic surfaces and soft matter.

8.
Adv Mater ; 33(49): e2103801, 2021 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34623694

RESUMO

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.

9.
Science ; 373(6562): 1518-1523, 2021 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-34554810

RESUMO

Defects may display high reactivity because the specific arrangement of atoms differs from crystalline surfaces. We demonstrate that high-temperature steam pretreatment of palladium catalysts provides a 12-fold increase in the mass-specific reaction rate for carbon-hydrogen (C­H) activation in methane oxidation compared with conventional pretreatments. Through a combination of experimental and theoretical methods, we demonstrate that an increase in the grain boundary density through crystal twinning is achieved during the steam pretreatment and oxidation and is responsible for the increased reactivity. The grain boundaries are highly stable during reaction and show specific rates at least two orders of magnitude higher than other sites on the palladium on alumina (Pd/Al2O3) catalysts. Theoretical calculations show that strain introduced by the defective structure can enhance C­H bond activation. Introduction of grain boundaries through laser ablation led to further rate increases.

10.
Nat Commun ; 12(1): 3215, 2021 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-34078886

RESUMO

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.

11.
Materials (Basel) ; 14(5)2021 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-33668152

RESUMO

Soft matter that undergoes programmed macroscopic responses to molecular analytes has potential utility in a range of health and safety-related contexts. In this study, we report the design of a nematic liquid crystal (LC) composition that forms through dimerization of carboxylic acids and responds to the presence of vapors of organoamines by undergoing a visually distinct phase transition to an isotropic phase. Specifically, we screened mixtures of two carboxylic acids, 4-butylbenzoic acid and trans-4-pentylcyclohexanecarboxylic acid, and found select compositions that exhibited a nematic phase from 30.6 to 111.7 °C during heating and 110.6 to 3.1 °C during cooling. The metastable nematic phase formed at ambient temperatures was found to be long-lived (>5 days), thus enabling the use of the LC as a chemoresponsive optical material. By comparing experimental infrared (IR) spectra of the LC phase with vibrational frequencies calculated using density functional theory (DFT), we show that it is possible to distinguish between the presence of monomers, homodimers and heterodimers in the mixture, leading us to conclude that a one-to-one heterodimer is the dominant species within this LC composition. Further support for this conclusion is obtained by using differential scanning calorimetry. Exposure of the LC to 12 ppm triethylamine (TEA) triggers a phase transition to an isotropic phase, which we show by IR spectroscopy to be driven by an acid-base reaction, leading to the formation of ammonium carboxylate salts. We characterized the dynamics of the phase transition and found that it proceeds via a characteristic spatiotemporal pathway involving the nucleation, growth, and coalescence of isotropic domains, thus amplifying the atomic-scale acid-base reaction into an information-rich optical output. In contrast to TEA, we determined via both experiment and computation that neither hydrogen bonding donor or acceptor molecules, such as water, dimethyl methylphosphonate, ethylene oxide or formaldehyde, disrupt the heterodimers formed in the LC, hinting that the phase transition (including spatial-temporal characteristics of the pathway) induced in this class of hydrogen bonded LC may offer the basis of a facile and chemically selective way of reporting the presence of volatile amines. This proposal is supported by exploratory experiments in which we show that it is possible to trigger a phase transition in the LC by exposure to volatile amines emitted from rotting fish. Overall, these results provide new principles for the design of chemoresponsive soft matter based on hydrogen bonded LCs that may find use as the basis of low-cost visual indicators of chemical environments.

12.
Angew Chem Int Ed Engl ; 60(18): 10384-10392, 2021 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-33600031

RESUMO

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.

14.
Acc Chem Res ; 54(1): 1-10, 2021 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-33275422

RESUMO

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, electronics, and biomedicine. Most of these nanocrystals are kinetically controlled products greatly deviated from the equilibrium state defined by thermodynamics. When subjected to elevated temperatures, their arrangements of atoms are expected to undergo various physical transformations, inducing changes to the shape, morphology (hollow vs solid), spatial distribution of elements (segregated vs alloyed/intermetallic), internal structure (twinned vs single-crystal), and crystal phase. In order to optimize the performance of these nanocrystals in various applications, there is a pressing need to understand and improve their thermal stability.By integrating in situ heating with transmission electron microscopy or X-ray diffraction, we have investigated the physical transformations of various types of noble-metal nanocrystals in real time. We have also explored the atomistic detail responsible for a physical transformation using first-principles calculations, providing insightful guidance for the development of noble-metal nanocrystals with augmented thermal stability. Specifically, solid nanocrystals were observed to transform into pseudospherical particles favored by thermodynamics by reducing the surface area while eliminating the facets high in surface energy. For nanocrystals of relatively large in size, a single-crystal lattice was more favorable than a twinned structure. When switching to core-shell nanocrystals, the elevation in temperature caused changes to the elemental distribution in addition to shape transformation. The compositional stability of a core-shell nanocrystal was found to be strongly dependent on the shape and thus the type of facet expressed on the surface. For hollow nanocrystals such as nanocages and nanoframes, their thermal stabilities were typically inferior to the solid counterparts, albeit their unique structure and large specific surface area are highly desired in applications such as catalysis. When a metastable crystal structure was involved, phase transition was also observed at a temperature close to that responsible for shape or compositional change. We hope 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. Such an understanding may eventually lead to the development of effective methods for retarding or even preventing some of the transformations.

15.
Chem Rev ; 121(2): 1007-1048, 2021 01 27.
Artigo em Inglês | MEDLINE | ID: mdl-33350813

RESUMO

The unprecedented ability of computations to probe atomic-level details of catalytic systems holds immense promise for the fundamentals-based bottom-up design of novel heterogeneous catalysts, which are at the heart of the chemical and energy sectors of industry. Here, we critically analyze recent advances in computational heterogeneous catalysis. First, we will survey the progress in electronic structure methods and atomistic catalyst models employed, which have enabled the catalysis community to build increasingly intricate, realistic, and accurate models of the active sites of supported transition-metal catalysts. We then review developments in microkinetic modeling, specifically mean-field microkinetic models and kinetic Monte Carlo simulations, which bridge the gap between nanoscale computational insights and macroscale experimental kinetics data with increasing fidelity. We finally review the advancements in theoretical methods for accelerating catalyst design and discovery. Throughout the review, we provide ample examples of applications, discuss remaining challenges, and provide our outlook for the near future.

16.
J Am Chem Soc ; 143(1): 149-162, 2021 01 13.
Artigo em Inglês | MEDLINE | ID: mdl-33370094

RESUMO

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 facile synthesis of Pd-Cu Janus nanocrystals with controlled shapes through site-selected growth by reducing the Cu(II) precursor with glucose in the presence of hexadecylamine and Pd icosahedral seeds. Specifically, at a slow reduction rate, the Cu atoms nucleate and grow from one vertex of the icosahedral seed to form a penta-twinned Janus nanocrystal in the shape of a pentagonal bipyramid or decahedron. At a fast reduction rate, in contrast, the Cu atoms can directly nucleate from or diffuse to the edge of the icosahedral seed for the generation of a singly twinned Janus nanocrystal in the shape of a truncated bitetrahedron. The segregation of two elements and the presence of twin boundaries on the surface make the Pd-Cu Janus nanocrystals effective catalysts for the electrochemical reduction of CO2. An onset potential as low as -0.7 VRHE (RHE: reversible hydrogen electrode) was achieved for C2+ products in 0.5 M KHCO3 solution, together with a faradaic efficiency approaching 51.0% at -1.0 VRHE. Density functional theory and Pourbaix phase diagram studies demonstrated that the high CO coverage on the Pd sites (either metallic or hydride form) during electrocatalysis enabled the spillover of CO to the Cu sites toward subsequent C-C coupling, promoting the formation of C2+ species. This work offers insights for the rational fabrication of bimetallic nanocrystals featuring desired compositions, shapes, and twin structures for catalytic applications.

17.
Nat Commun ; 11(1): 4369, 2020 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-32868769

RESUMO

The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.

18.
Acc Chem Res ; 53(9): 1893-1904, 2020 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-32869965

RESUMO

Microkinetic modeling based on density functional theory (DFT) derived energetics is important for addressing fundamental questions in catalysis. The quantitative fidelity of microkinetic models (MKMs), however, is often insufficient to conclusively infer the mechanistic details of a specific catalytic system. This can be attributed to a number of factors such as an incorrect model of the active site for which DFT calculations are performed, deficiencies in the hypothesized reaction mechanism, inadequate consideration of the surface environment under reaction conditions, and intrinsic errors in the DFT exchange-correlation functional. Despite these limitations, we aim at developing a rigorous understanding of the reaction mechanism and of the nature of the active site for heterogeneous catalytic chemistries under reaction conditions. By achieving parity between experimental and modeling outcomes through robust parameter estimation and by ensuring coverage-consistency between DFT calculations and MKM predictions, it is possible to systematically refine the mechanistic model and, thereby, our understanding of the catalytic active site in situ.Our general approach consists of developing ab initio informed MKM for a given active site and then re-estimating the energies of the transition and intermediate states so that the model predictions match quantities measured in reaction kinetics experiments. If (i) model-experiment parity is high, (ii) the adjustments to the DFT-derived energetics for a given model of the active site are rationalized within the errors of standard DFT exchange-correlation functionals, and (iii) the resultant MKM predicts surface coverages that are consistent with those assumed in the DFT calculations used to initialize the MKM, we conclude that we have correctly identified the active site and the reaction mechanism. If one or more of these requirements are not met, we iteratively refine our model by updating our hypothesis for the structure of the active site and/or by incorporating coverage effects, until we obtain a high-fidelity coverage-self-consistent MKM whose final kinetic and thermodynamic parameters are within error of the values derived from DFT.Using the catalytic reaction of formic acid (FA, HCOOH) decomposition over transition-metal catalysts as an example, here we provide an account of how we applied this algorithm to study this chemistry on powder Au/SiC and Pt/C catalysts. For the case of Au catalysts, on which the FA decomposition occurred exclusively through the dehydrogenation reaction (HCOOH → CO2+H2), our approach was used to iteratively refine the model starting from the (111) facet until we found that specific ensembles of Au atoms present in sub-nanometer clusters can describe the active site for this catalysis. For the case of Pt catalysts, wherein both dehydrogenation (HCOOH → CO2 + H2) and dehydration (HCOOH → CO + H2O) reactions were active, our approach identified that a partially CO*-covered (111) surface serves as the active site and that CO*-assisted steps contributed substantially to the overall FA decomposition activity. Finally, we suggest that once the active site and the mechanism are conclusively identified, the model can subsequently serve as a high-quality basis for designing specific goal-oriented experiments and improved catalysts.

20.
Nat Mater ; 19(11): 1207-1214, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32690912

RESUMO

A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...