Surface Diffusion Rate Research Articles

Rational design of α-MnO2@TiO2 composites for high-performance zinc ions batteries

Aqueous zinc ions batteries (AZIBs) have attracted widespread interest due to their remarkable energy density, non-toxicity, environmental friendliness and low cost. However, the application of MnO2 cathode materials for AZIBs is limited owing to the dissolution of Mn2+, structural collapse and intrinsic poor conductivity. Herein, α-MnO2@TiO2 composites were synthesized via simple hydrothermal and calcination approaches. Some smaller TiO2 were coated on the MnO2 nanorods to form the protective layer. The TiO2 protective layer not only prevents the dissolution of Mn2+ and structural collapse of MnO2, but also enhances the conductivity of the material due to the presence of Ti3+ defects, which increased electrode materials wettability, specific surface area and diffusion rate of Zn2+. In addition, the coating TiO2 causes surface adsorbed oxygen and surface binding defects in α-MnO2@TiO2, and increases surface reactivity and electrochemically active sites, which provides abundant channels and available insertion electrochemically active sites for H+/Zn2+ transport. As a result, α-MnO2@TiO2–2 delivers a high specific capacity of 182.90 mAh g−1 at 1 A g−1 after 600 cycles and outstanding rate capacity of 127.91 mAh g−1 at 5 A g−1. This work provides an idea for exploring high-performance cathode materials for AZIBs.

Bonding Behavior and Quality of Pressureless Ag Sintering on (111)-Oriented Nanotwinned Cu Substrate in Ambient Air.

(111)-oriented nanotwinned Cu ((111)nt-Cu) has shown its high surface diffusion rate and better oxidation resistance over common polycrystalline Cu (C-Cu). The application of (111)nt-Cu as an interface metallization layer in Ag-sintered technology under the role of oxygen was investigated in this work, and its connecting behavior was further clarified by comparing it with C-Cu. As the sintering temperature decreasing from 300 to 200 °C, the shear strength on the (111)nt-Cu substrate was still greater than 55 MPa after sintering for 10 min. The fracture surface correspondingly changed from the interface of Ag/die to mixed fracture mode, involving the interface of the Ag/Cu substrate and Ag/die. The existence of copper oxide provided a tight connection between Ag and the (111)nt-Cu substrate at all of the studied temperatures. Although lots of small dispersed voids were seen at the interface between copper oxide and (111)nt-Cu at 300 °C, these impurity-induced voids would not necessarily be a failure position and could be improved by adjusting the sintering temperature and time; for example, 200 °C/10 min or heating to 300 °C, and then start cooling at the same time. The microstructure of Ag-Cu joint on (111)nt-Cu behaved better than that on C-Cu. The thinner copper oxide layer and the higher connection ratio of the interface between copper oxide and Ag were still found on the (111)nt-Cu connection's structure. The poor connection between copper oxide and Ag on C-Cu easily became the failure interface. By controlling the thickness of copper oxide and the content of impurity-induced voids, the use of (111)nt-Cu in advanced-packaging could be improved to a new level.

Competitive transport and adsorption of CO2/H2O in the graphene nano-slit pore: A molecular dynamics simulation study

The study of pore structure, surface sites, and the competitive adsorption and mass transfer of CO2, particularly in conjunction with H2O, in porous solid materials is crucial for developing CO2 capture materials with superior performance and achieving carbon emission reduction goals. This paper presents the development and investigation of amino-modified graphene lamellae pore models using standard number of particles, volume, and temperature system integrated molecular dynamics simulations in a non-equilibrium state. The findings reveal that CO2 adsorption on the pore surface of graphene lamellae occurs in a two-layered manner, influenced by van der Waals and electrostatic forces. The adsorption capacity of the initial layer at a constant temperature is contingent upon the material’s adsorption area, while the site density determines the second layer’s adsorption capacity. Increasing the site density from 0/Å2 to 0.008/Å2 enhances the number of CO2 molecules in the second layer by approximately 35.6 %, though it significantly reduces their diffusion rate. Additionally, changes in temperature and pore size predominantly affect the diffusion rate and CO2 adsorption capacity. The study also explores the competitive adsorption dynamics of H2O molecules with CO2 in the pore channels. It was observed that at low temperatures, H2O molecules predominantly undergo surface diffusion, occupying the pore channel surfaces and thus impacting CO2 adsorption. At a CO2:H2O ratio of 1:1, H2O molecules cover 54.1 % of the adsorption area and may form clusters that obstruct the pore channels, thereby hindering CO2 diffusion. Calculations of surface diffusion rates for H2O molecular clusters at various CO2/H2O ratios indicate that smaller clusters exhibit higher diffusion rates. The computational approach employed in this study demands minimal resources and enables swift calculations, offering a new theoretical model for optimizing adsorbent design, enhancing CO2 capture efficiency, and exploring novel adsorbent materials.

Open Cross-gap Gold Nanocubes with Strong, Large-Area, Symmetric Electromagnetic Field Enhancement for On-Particle Molecular-Fingerprint Raman Bioassays.

Plasmonic nanoparticles with an externally open nanogap can localize the electromagnetic (EM) field inside the gap and directly detect the target via the open nanogap with surface-enhanced Raman scattering (SERS). It would be beneficial to design and synthesize the open gap nanoprobes in a high yield for obtaining uniform and quantitative signals from randomly oriented nanoparticles and utilizing these particles for direct SERS analysis. Here, we report a facile strategy to synthesize open cross-gap (X-gap) nanocubes (OXNCs) with size- and EM field-tunable gaps in a high yield. The site-specific growth of Au budding structures at the corners of the AuNC using the principle that the Au deposition rate is faster than the surface diffusion rate of the adatoms allows for a uniform X-gap formation. The average SERS enhancement factor (EF) for the OXNCs with 2.6 nm X-gaps was 1.2 × 109, and the EFs were narrowly distributed within 1 order of magnitude for ∼93% of the measured OXNCs. OXNCs consistently displayed strong EM field enhancement on large particle surfaces for widely varying incident light polarization directions, and this can be attributed to the symmetric X-gap geometry and the availability of these gaps on all 6 faces of a cube. Finally, the OXNC probes with varying X-gap sizes have been utilized in directly detecting biomolecules with varying sizes without Raman dyes. The concept, synthetic method, and biosensing results shown here with OXNCs pave the way for designing, synthesizing, and utilizing plasmonic nanoparticles for selective, quantitative molecular-fingerprint Raman sensing and imaging applications.

Hydrothermal synthesis of LiMn0.79Fe0.2Mg0.01PO4/C composite cathode materials using different Li3PO4 precursors

Doping and particle size controlling are two important approaches to improve the electrochemical performance of LiMnxFe1−xPO4 cathode materials. By employing a straightforward hydrothermal method and utilizing cost-effective lithium phosphate (Li3PO4) as the precursor, we successfully synthesized high Mn-content LiMn0.79Fe0.2Mg0.01PO4/C composites. The results reveal that the minute amount of Mg substantially enhances the electrochemical performance. In the subsequent mechanism study using Li3PO4 precursors with different particle size, we found that the nucleation process, dependent on specific surface area and diffusion rate, is likely to play a critical role for the size and morphology of formed LiMn0.79Fe0.2Mg0.01PO4. LiMn0.79Fe0.2Mg0.01PO4/C (LMFP-1), synthesized from initially smaller-sized and less agglomerated Li3PO4 (LPO-1), exhibited the most diminutive average particle size coupled with the highest specific surface area, which further facilitated electrolyte interfacial interaction and promoted Li+ diffusion kinetics. At 1C, LMFP-1 displayed a specific capacity of 110.7 mAh g−1, with 97.07% capacity retention after 200 cycles. This study provides pivotal insights for the synthesis of high-performance LiMnxFe1−xPO4 materials.

Experimental Investigation of Additional Loss Associated With Incoming Wakes in Low-Pressure Turbine Cascades

Abstract The present paper aims to experimentally investigate the influence of wake-passing frequency, Reynolds number, and suction surface diffusion rate on the additional loss due to incoming wakes to the profile loss in the low-pressure turbine (LPT) cascades and discuss a design guide for reducing the additional loss. Using a moving-bar mechanism, the unsteady effects of incoming wakes were measured in a low-speed linear turbine cascade facility. The wake-passing frequency was varied by adjusting the moving-bar speed. The different airfoils with different surface velocity distributions were tested to examine the effect of suction surface diffusion rate. For each test case in an unsteady flow condition, the additional loss due to incoming wakes was derived by subtracting the profile loss from the measured total pressure loss across the cascade. Here, the profile loss was estimated by using the friction drag force, which was calculated by the measured surface velocity distribution, and the pressure drag force, which was calculated by the measured surface pressure distribution and the predicted base pressure. The resultant additional loss includes all kinds of losses associated with incoming wakes, such as mixing loss of incoming wakes enhanced in the blade passage and unsteady interaction loss between incoming wakes and surface boundary layers. It was demonstrated that in an unsteady flow condition, a substantial performance improvement was obtained in the entire Reynolds number range by applying the surface velocity distribution with no laminar separation to a low-solidity blade row.

Measurement of Surface Diffusion at Electrochemical Interfaces Using in Situ Linear Optical Diffraction

Surface diffusion processes play an important role in many reactions at electrode surfaces and are of relevance to electrocatalysis, electrodeposition, and many other areas. Such processes have therefore been extensively studied on solids under vacuum conditions with a variety of different methods. In sharp contrast, only few studies exist to measure surface diffusion in electrochemical environment due to the lack of suitable methodology. We aim on partially filling this gap by introducing the all-optical in situ LOD methodology, which allows to measure surface diffusion rates over a wide range and thus overcomes limitations of established methods that are mostly restricted to slow diffusion rates. The method is based on the generation of a periodic spatial modulation of adsorbates using two interfering laser pulses. The subsequent equilibration of this pattern and thus the diffusion rate of adsorbates is probed by the linear optical diffraction (LOD) signal from a second laser.First proof-of-principle measurements were performed on sulfur diffusion on the Pt(111) electrode. For this purpose, the optical and electrochemical properties of this systems were investigated first, including studies of the optical reflectance change induced by chemisorbed sulfur (Sad) and investigations of the Sad oxidation mechanism. The subsequent studies of Sad surface diffusion revealed potential and coverage dependent diffusion rates which were at least an order of magnitude faster than under vacuum conditions. Supported by numerical simulations, the implications of strong adsorbate-adsorbate interaction combined with different grating modulation depths to the temporal evolution of the LOD signal were demonstrated and data accuracy and pitfalls of the method were discussed.Kattwinkel and Magnussen, ACS Meas. Sci. Au, in press (2023), https://doi.org/10.1021/acsmeasuresciau.2c00066Kattwinkel and Magnussen, Electrochimica Acta 434, 141297 (2022), https://doi.org/10.1016/j.electacta.2022.141297

Influence of polymers on oxaprozin dissolution kinetics and mechanisms

In this work, the influences of polymers (HPMC E3, PEG 6000, PVP K25, PVP K30), temperature, stirring speed and polymer mass fraction on the oxaprozin (OXA) dissolution profiles were measured by a United States Pharmacopeia (USP) Ⅱ dissolution apparatus. The two-step chemical potential gradient model combined with the interfacial steady-state mass transfer model as well as PC-SAFT (perturbed-chain statistical associating fluid theory) were used to analyze the dissolution mechanism of OXA under different conditions. The presence of polymer could promote the surface reaction of OXA while temperature and stirring speed have different influences on the surface reaction and diffusion. The diffusion boundary layer thickness δ of OXA tablets increases with the increase of temperature and decreases with the increase of stirring speed. Based on the obtained surface reaction rate constant ks and diffusion rate constant kd, the dissolution profiles with high accuracy compared with the experimental data.

Study of Asphalt Behavior on Pre-Wet Aggregate Surface Based on Molecular Dynamics Simulation and Surface Energy Theory

The improvement of the performance of asphalt mixtures has been studied by scholars. This research proposes a new asphalt–mineral interface formation method, which is a pre-wet bitumen–mineral mixture. The formation process of the pre-wet asphalt–mineral interface was simulated by molecular dynamics simulation software. The diffusion coefficient, concentration distribution, and interfacial energy of the asphalt on the surface of the pre-wet mineral material and non-pre-wet mineral material were compared and analyzed. The simulation results show that the mineral surface diffusion rate of the asphalt after pre-wetting is increased by more than 50%, and the concentration in the X, Y, and Z directions is reduced by 0.8%, 4.6%, and 7.8%, respectively. At the same time, the interface energy between the bitumen and the pre-wet mineral was increased by more than 8%. The results of the molecular dynamics model are verified based on the surface energy theory and contact angle test. The experimental results show that the contact angle of the asphalt is smaller and the diffusion performance is better after pre-wetting. At the same time, the interface adhesion work between the asphalt and wet mineral surface increased by 4.3% in a dry environment, and the peeling work decreased by 41.1% in a water environment. Therefore, the author believes that the pre-wetting technology of the asphalt mixture has a certain feasibility and practicability.

(Keynote) Electrode Stimulation: Ohmic Microscopy and the Monopolar Electrode

In a recent communication (1), we described a novel method of controlling the electrostatic potential in the solution neighboring a working electrode, we have dubbed the monopolar electrode , ME, polarized at a constant potential, EME, using a potentiostat. This tactic involved passing current between a second or stimulating electrode , SE, placed in front, and at a relatively small distance from the ME, and a distant auxiliary electrode, AE. Depending on the polarity of the current flowing through the SE, the electrostatic potential just outside the ME could be modified so as to increase or decrease the surface overpotential, and, thus modulate the rates of redox reactions at the ME|electrolyte interface. This presentation will review critical aspects of ohmic microscopy, and illustrate with two examples the electrode stimulation effect, using a ring disk electrode, RRDE, in which current flowing through the disk acting as the SE, is employed to induce reactions on the ring, acting as the ME, namely: i. the oxidation of adsorbed carbon monoxide on Pt using a Pt|glassy carbon RRDE and ii. the reduction of selenite to elemental Se on Au in aqueous 0.1 M HClO4 using a Au|Au RRDE. In both these cases, the stimulation current was generated by scanning the potential of SE within its double layer region, so as to minimize any changes in the actual composition of the solution adjacent to the ME, while monitoring the current flowing through the ME, IME . Under these conditions, the electrostatic potential in solution follows the primary current density. The efficiency of the stimulation process was determined by coulometric analysis of the CO oxidation current and in the case of selenite via a coulometric analysis of the current due to the oxidation of elemental Se produced by the reduction of selenite. The stimulation efficiency, in this latter case, could be accurately determined from a coulometric analysis of the peak for Se oxidation observed by subsequently scanning the ME linearly toward positive potentials to yield selenite. Excellent quantitative agreement was obtained between IME and EME as a function of Idisk and theoretical simulations employing COMSOL using parameters extracted from independent measurements performed under otherwise identical experimental conditions. This overall approach will open new prospects for gaining insight into the rates of surface diffusion and other interfacial dynamics phenomena.AcknowledgementsThis work was supported by a grant from NSF, CHE-1412060 References Han, Q.; Georgescu, N. S.; Gibbons, J.; Scherson, D. Acta 2019, 325, 134957.

A Chemist's View on Electronic and Steric Effects of Surface Ligands on Plasmonic Metal Nanostructures.

ConspectusPlasmonic metal nanostructures have been extensively developed over the past few decades because of their ability to confine light within the surfaces and manipulate strong light-matter interactions. The light energy stored by plasmonic nanomaterials in the form of surface plasmons can be utilized to initiate chemical reactions, so-called plasmon-induced catalysis, which stresses the importance of understanding the surface chemistry of the plasmonic materials. Nevertheless, only physical interpretation of plasmonic behaviors has been a dominant theme, largely excluding chemical intuitions that facilitate understanding of plasmonic systems from molecular perspectives. To overcome and address the lack of this complementary understanding based on molecular viewpoints, in this Account we provide a new concept encompassing the well-developed physics of plasmonics and the corresponding surface chemistry while reviewing and discussing related references. Inspired by Roald Hoffmann's descriptions of solid-state surfaces based on the molecular orbital picture, we treat molecular interfaces of plasmonic metal nanostructures as a series of metal-ligand complexes. Accordingly, the effects of the surface ligands can be described by bisecting them into electronic and steric contributions to the systems. By exploration of the quality of orbital overlaps and the symmetry of the plasmonic systems, electronic effects of surface ligands on localized surface plasmon resonances (LSPRs), surface diffusion rates, and hot-carrier transfer mechanisms are investigated. Specifically, the propensity of ligands to donate electrons in a σ-bonding manner can change the LSPR by shifting the density of states near the Fermi level, whereas other types of ligands donating or accepting electrons in a π-bonding manner modulate surface diffusion rates by affecting the metal-metal bond strength. In addition, the formation of metal-ligand bonds facilitates direct hot-carrier transfer by forming a sort of molecular orbital between a plasmonic structure and ligands. Furthermore, effects of steric environments are discussed in terms of ligand-ligand and ligand-surface nonbonding interactions. The steric hindrance allows for controlling the accessibility of the surrounding chemical species toward the metal surface by modulating the packing density of ligands and generating repulsive interactions with the surface atoms. This unconventional approach of considering the plasmonic system as a delocalized molecular entity could establish a basis for integrating chemical intuition with physical phenomena. Our chemist's outlook on a molecular interface of the plasmonic surface can provide insights and avenues for the design and development of more exquisite plasmonic catalysts with regio- and enantioselectivities as well as advanced sensors with unprecedented chemical controllability and specificity.

First-principles investigation of the electronic and Li-ion diffusion properties of LiFePO4 by graphene surface modification

The structural, electronic and Li-ion diffusion properties of LiFePO4 (010) surface modified by graphene have been investigated by first-principles calculation under the DFT + U framework. The calculated formation energy indicates that the LiFePO4 (010) surface modified with graphene is energetically favourable. It is found that strong C–Fe and C–O covalent bonds are formed at the modified interface, and the band gap of LiFePO4 modified with graphene is narrowed, indicating better electronic conductive properties. The energy barrier for the diffusion of Li-ion along the b-channel perpendicular to the (010) surface is calculated using the method of finding the transition state. The results show that the energy barrier of the modified system is reduced, indicating that the surface modification of LiFePO4 by graphene can improve the surface diffusion rate of Li-ions.

First-principles investigation of the electronic and Li-ion diffusion properties of C and B doped LiFePO4 (0 1 0) surface

The electronic structure and Li-ion diffusion properties of the surface of LiFePO4 (010) doped with C and B elements were investigated using a first-principles approach based on density universal function theory. Calculations of the formation energy show that the surface defect energy decreases after the dopant replaces the oxygen, which is in accordance with the thermodynamic stability criteria. The difference in charge density indicates that the doped atoms on the modified surface form stronger covalent bonds with adjacent Fe atoms, while the density of states study shows that the introduction of C and B elements narrows the forbidden band of LiFePO4 and exhibits better electronic conductivity. In addition, we calculate the energy barrier for the diffusion of Li-ions along the b-channel of the (010) surface using a transition state search method. The results show that the doped system possesses a lower energy barrier, which suggests that the doping of C and B elements reduces the limitation of Li-ion migration to the surface and increases the Surface diffusion rate. At the same time, we find that element B performs better than element C in improving surface conductivity and Li-ion surface diffusion .

Wavelength-switchable ultraviolet light-emitting diodes.

Dual-wavelength ultraviolet light-emitting diodes (UV-LEDs) exhibiting two discrete emission peaks of comparable intensities are reported in this work. Furthermore, this is the first report where complete switching between these two peaks was achieved by simply changing the duty cycle of the pulsed-mode excitation. While earlier reports on dual-wavelength emission were based on complex multi-stage devices, our device layer-structure was nominally similar to single-wavelength LEDs, and the special properties were realized solely through the use of specifically designed AlGaN alloys. The molecular beam epitaxy (MBE) method was chosen for this work, which can operate at significantly wider growth-parameter ranges than other more commonly used techniques. The dual-wavelength nature of our LEDs was brought about by the deliberate incorporation of nanometer-scale alloy fluctuations in the quantum well based active regions by modulating the relative surface diffusion rates of Ga/Al adatoms. The wavelength selectivity was linked to the variation in thermally assisted carrier delocalization, transport, and subsequent recombination processes in regions of different compositional inhomogeneities.

Simultaneous removal of anionic and cationic dyes from wastewater with biosorbents from banana peels

AbstractUntreated banana peel (BP) is able to adsorb efficiently cationic dyes like methylene blue (MB) but weakly anionic dyes like orange G (OG). One way to enhance the sorption capacity for both dyes is to convert BP into activated carbon (BPAC) after thermochemical treatment. Among the various BPACs tested, the highest sorption capacity for both dyes was achieved when BP was modified with NaOH and pyrolyzed at 700°C (BPAC‐NaOH‐700). The pore structure of adsorbents was analyzed with scanning‐electron‐microscopy (SEM), nitrogen sorption isotherms, and mercury intrusion porosimetry (MIP), and the meso‐ and micro‐pore size distribution of BPAC‐NaOH‐700 was the narrowest one with the smallest mean value and the highest specific surface area. Equilibrium tests in batch mode were fitted with the extended Langmuir and Freundlich isotherms and used to estimate thermodynamic properties. The MB and OG sorption dynamics onto BPAC‐NaOH‐700 was approximated with the multi‐compartment model, and the external and internal mass‐transfer coefficients were estimated. The maximum sorption capacity of BPAC‐NaOH‐700 was found to be equal to 323 mg/g for MB and 76 mg/g for OG, both higher than the corresponding values for BP, and fully consistent with the high values of its surface area ( = 530 m2/g) and total pore volume ( = 1.81 cm3/g). The synergistic interaction for the sorption of both dyes onto BPAC‐NaOH‐700 was associated with a push‐pull mechanism, while the selective sorption of MB onto BPAC‐NaOH‐700 was attributed to the very slow rates of OG pore and surface diffusion in meso‐ and micro‐porosity, respectively. The adsorption was exothermic for BP, and endothermic for OG.

Measurement of Surface Diffusion at the Electrochemical Interface by In Situ Linear Optical Diffraction.

A new in situ method for measuring the surface diffusion rates of adsorbates on electrode surfaces in electrolyte solution is presented. The method is based on the generation of a periodic spatial modulation of the adsorbate coverage via interfering laser pulses and subsequent monitoring of the diffusion-induced decay of this pattern using the optical diffraction signal of a second laser. Proof-of-principle measurements of the surface diffusion of adsorbed sulfur on Pt(111) electrodes in 0.1 M H2SO4 indicate potential- and coverage-dependent diffusion constants that are significantly higher than those of sulfur on Pt(111) under vacuum conditions.

Collectively exhaustive electrochemical hydrogen evolution reaction of polymorphic cobalt selenides derived from organic surfactants modified Co-MOFs

Finding and exploring non-noble metal-based electrocatalysts for the promising power-to-hydrogen fuel technology through water splitting reactions is highly emerging. Herein, we report the preparation of cobalt-based metal-organic frameworks (Co-MOFs) using an oleylamine (OLA) and 1-dodecanethiol (DDT)-modified trimesic acid (TMA), and cobalt precursor. Then, the electrocatalytically active cobalt selenides were derived from the Co-MOFs by a water-organic solvent mixture-assisted single-step selenization process. Interestingly, the cobalt selenide obtained from the DDT-modified Co-MOF shows collectively exhaustive hydrogen evolution reaction (HER) performance with very small overpotentials of ∼161 and ∼206 mV to achieve 10 and 50 mA cm−2, respectively, due to the phase mixing characteristics of cobalt selenide and the synergistic interaction. The fast reaction kinetics were identified at the DDT-Co selenide electrode surface as confirmed by observing the lower charge-transport/interfacial resistance and Tafel slope value due to the high surface coverage of adsorbed hydrogen (Hads) atoms, evidenced by high interfacial chemical capacitance value, as a result of the high electrical conductivity and large electrochemically accessible active sites. The calculated activation energy (Ea) of HER further reveals a low kinetic energy barrier in the HER on the DDT-Co selenide, indicating high intrinsic catalytic activity due to the fast surface diffusion rate of Hads. Furthermore, the obtained cathodic transfer coefficient (αc) value strongly suggested that the HER on the surface of DDT-Co selenide (αc = 2) proceeds in the Langmuir-Hinshelwood reaction mechanism and follows the Volmer-Tafel pathway. The present work provides valuable insights into the modification of Co-MOFs and their impact on HER catalytic activity of cobalt selenide, and also the mechanistic investigation of HER based on electrochemical impedance spectroscopy analysis.

Nanoporous Copper Ribbons Prepared By Chemical Dealloying of a Melt-Spun Zn-Cu Alloy

Dealloying process is a powerful and versatile method to fabricate three-dimensional nanoporous (np) materials for applications in electrochemical synthesis, sensors, and catalysis. In the last years, several morphologies of np-copper and their dealloying mechanisms have been reported in alkaline and acidic media.[1-4] For instance, the nature of anions such as chloride and phosphate strongly influence the ligament size of np-Cu. The effects of several experimental parameters to control the structural and chemical properties of np-Cu materials via dealloying are not fully understood to date.In our work, Zn80Cu20 alloy ribbons prepared by melt-spinning were dealloyed by free corrosion in 0.1 M HCl and 1.3 M NaOH solutions. Both the surface and cross-section of the obtained np-Cu ribbons were comprehensively characterized by SEM, EDX, STEM, XRD, and XPS. Our results show a clear relation between dealloying conditions (pH, kind of electrolyte and reaction time) and structural parameters (ligament size and chemical composition) for np-Cu ribbons. The ligament size is strongly coupled with the residual Zn content prepared by dealloying in acidic environment. In contrast, the ligaments produced in alkaline media are much smaller, whereas the residual Zn content can be tuned in a broad range without changes in ligament size. For the first time, we point out the distribution of residual Zn within single ligaments of np-Cu. We suggest that the Cu surface atoms diffuse and capture the Zn atoms which are located in the near-subsurface during dealloying. Therefore, the Zn-rich regions seem to be relicts of the master alloy. We have also evaluated the time-resolved evolution of porosity within the ribbons via cross-section analysis. Despite the relatively thick melt-spun ribbons (35 ± 3 μm), kinetics of a bicontinuous ligament-pore structure are controlled by the interfacial process instead of the diffusion of corrosive electrolyte solution in and out of the porous layers, referred to as long-range mass transport. Surface diffusivities of Cu at 25 °C were determined to be 1.4 × 10−18 and 9.4 × 10−21 m2 s−1 in 0.1 M HCl and 1.3 M NaOH, respectively. Therefore, the high Cu surface diffusion rate in the presence of chloride ions enables an enhanced dealloying front propagation into the ribbons, and also coarsening of the ligaments to form larger ligament. On the contrary, the slow surface diffusion rate of Cu (hydr)oxide in 1.3 M NaOH solution strongly limits the dealloying process and forms smaller ligaments. Moreover, dealloying temperature strongly influences the surface diffusivity of Cu, leading to a strong relationship between dealloying temperature and the np-Cu structure. The electrochemically active surface area of np-Cu ribbons was determined by double layer capacity method. The catalytic properties of the np-Cu ribbons were then evaluated for organic electro-synthesis of cyclic carbonates from CO2 and epoxide. The yield of cyclic carbonate could be improved by using np-Cu ribbons for the activation of CO2.Based on our results, we provide deeper insights to the formation processes of np-Cu ribbons with tunable ligament size and Zn content in various electrolyte environments and its application as electrode material for electro-synthesis of cyclic carbonates formation from CO2 and epoxide.

Effect of the Potentiostatic and Potentiodynamic Dealloying on the Structure and Chemical Distribution of Ag Atoms in Au-Enriched Nanoparticles

Recently, nanoporous gold (np-Au) prepared by dealloying has emerged as an efficient and durable catalyst for electrochemical oxidation of small alcohols. [1] An additional increase of surface-to-volume ratio by nano-sizing of AuxAg1-x master alloy might improve the catalytic methanol oxidation reaction (MOR). Only few research groups have recently shown that the morphology, structure and elemental distribution of dealloyed nanoparticles (NPs) depend on the various parameters such as initial particle size and composition.[2-4] Starting from AuxAg1-x alloy NPs, it is, however, unclear how the different dealloyed Au-rich NP motifs such as core-shell, hollow or porous NPs and the Ag distribution influence the catalytic MOR performance.In this work, we have investigated the effects of potentiodynamic and potentiostatic dealloying methods on the structure and chemical distribution of the residual Ag atoms for dealloyed Au-rich NPs. First, two size types of Ag-rich AuxAg1-x alloy NPs were prepared by one pot colloidal route and wet impregnation route. Larger Au23Ag77 NPs (size of 77 ± 26 nm) form a homogeneous disordered alloy, while the Au14Ag86 NPs with a size of 12 ± 5 nm show a strong enrichment of Ag atoms at the particle surface, referred to as core-shell arrangement. Subsequently, the as-prepared NPs with two sizes (12 nm and 77 nm) were electrochemically dealloyed using a potentiodynamic (cyclic voltammetry, CV) or potentiostatic (chronoamperometry, CA) method in 0.1 M HClO4. We observed that the CV method leads to the formation of pores inside the initial 77 nm NPs. Very interestingly, high-resolution STEM-EDX shows the appearance of Ag-rich regions near to the pore network of these dealloyed NPs. Unlike, after the dealloying by CV method the initial 12 nm NPs are still dense and solid, forming a thin Au-rich particle shell. After the exposure to air, the internal Ag atoms tend to segregate to the particle surface. In the CA method, we pointed out that the applied anodic potential has a strong influence of the surface diffusion behavior of the remaining Au atoms. Below a critical potential of 1.3 V vs. RHE, the dealloying process is kinetically hindered by the passivation of Au surface atoms. This critical potential in the CA method is strongly different to the critical dissolution potential of Ag atoms for AgxAu1-x NPs obtained from the CV profile (around 1.05 V vs. RHE). However, when the applied potential is larger than the critical potential, e.g. 1.6 V vs. RHE, the difference in the obtained structure and composition of dealloyed 77 nm NPs is negligible between potentiodynamic and potentiostatic approaches. On the other hand, the potentiostatic dealloying at 1.6 V vs. RHE leads to higher surface content of residual Ag for dealloyed NPs with 12 nm compared to potentiodynamic. This increased enrichment of the residual Ag atoms near the particle surface is also supported by XPS.In summary, we correlate the structural parameters (initial particle size, composition/distribution) of dealloyed AgxAu1-x NPs with the electrochemical dealloying methods (potentiostatic vs. potentiodynamic). Tailoring the surface diffusion rate of the Au atoms and the Ag distribution helps to improve the catalytic performance for MOR.

Biased self-diffusion on Cu surface due to electric field gradients

Under strong electric fields, an arc of strong current flowing through plasma can link two metal surfaces even in ultra high vacuum. Despite decades of research, the chain of events leading to vacuum arc breakdowns is hitherto unknown. Previously we showed that a tall and sharp Cu nanotip exposed to strong electric fields heats up by field emission currents and eventually melts, evaporating neutral atoms that can contribute to plasma buildup. In this work, we investigate by means of molecular dynamics (MD) simulations whether surface diffusion biased by the presence of an electric field gradient can provide sufficient mass transport of atoms toward the top of the nanotip to maintain supply of neutrals for feeding plasma. To reach the necessary timescales and to add electric field in MD, we utilized a novel combination of collective variable-driven hyperdynamics acceleration and coupling to a finite element mesh. In our simulations, we observed biased self-diffusion on Cu surfaces, that can contribute to the continuous replenishment of particle-emitting nanotips. This mechanism implies a need to reduce the rate of surface diffusion in devices that are susceptible to vacuum arcs. Finding suitable alloys or surface treatments that hinder the observed biased diffusion could guide the design of future devices, and greatly improve their efficiency.