Polycrystalline Au Research Articles

(Invited) Evaluating Protocols for Real-Time Electrochemical CO2 Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

The electrocatalytic carbon dioxide reduction reaction (CO2RR) has the potential to convert carbon dioxide to higher value fuels and chemicals, offering a pathway for carbon neutral (or negative) synthesis of carbon monoxide, ethylene, and several other compounds. A common challenge for CO2RR research is driving the selective CO2RR over the competing hydrogen evolution reaction (HER). This key performance metric is quantified by the catalyst’s faradaic efficiency (FE): the number of electrons that go toward producing a specific product divided by the total number of electrons passed during electrolysis.FE is often determined by gas and liquid chromatography. However, these methods have long response times (minutes to hours) and therefore prevent selectivity analysis in real-time. Instead, rotating ring disk electrodes (RRDE) have emerged as a rapid and sensitive method for quantitative CO2RR selectivity measurements with negligible time delays. To date, work has focused on a polycrystalline Au RRDE, especially for bench scale mechanistic studies. The Au disk electrode catalyzes both CO2RR and HER, while the concentric Au ring electrode senses the CO produced at the disk and oxidizes it back to CO2. By comparing the ring and disk currents, FECO and FEHER can be determined using the subtraction method.However, comparison across several works have reported a wide range for FECO values, 60-83%, despite identical conditions: CO2 saturated 0.1 M NaHCO3 (pH = 6.8), Edisk = -0.6 V vs RHE, and rotation at 2500 rpm [A. Goyal, et al., J. Am. Chem. Soc., 142, 4154–4161 (2020); R. E. Vos and M. T. M. Koper, ChemElectroChem, 9, e202200239 (2022)]. This work investigates the possible causes of this poor reproducibility in RRDE selectivity measurements by comparing protocols with different electrochemical methods, reagent purities, and glassware cleaning procedures. Most notably, we observed rapid loss of selectivity toward CO production during chronoamperometry measurements. Lastly, we propose operational bounds for RRDE selectivity measurements on Au under CO2RR conditions and provide our perspective on next steps for developing this into a robust analytical technique.

Theoretical model for analysis of elastic constants in orthotropic materials considering shear stress

Nowadays, a general theoretical model to describe the mechanical behavior of anisotropic or orthotropic materials is still an open challenge. In this study, we propose a new theoretical model to determine the elastic constants of these materials considering the shear components of the stress tensor. To analyze the consistency of new approach in biaxial stress state on thin films, we used data reported in the literature, based in the $\sin^2 \psi$ technique. For the first time, the shear modulus value equal to $G_{xz} = 0.3 GPa$, for a polycrystalline Au thin film, was calculated, in addition to other elastic constants. Finally, we demonstrate that the new proposal theoretical model considering shear stress can be useful to determine elastic constants in orthotropic materials from experimentally measured data.

Iridium oxide-modified reference screen-printed electrodes for point-of-care portable electrochemical cortisol detection

Cortisol is a well-known stress biomarker; this study focuses on using electrochemical immuno-sensing to measure the concentration of cortisol selectively and sensitively in artificial samples. Anti-cortisol antibodies have been immobilised on polycrystalline Au electrodes via strong covalent thiol bonds, fabricating an electrochemical bio-immunosensor for cortisol detection. IrOx was then anodically electrodeposited as a reference electrode on a commercial screen-printed electrode and electrochemical impedance spectrometry (EIS) studies were used to correlate the electrochemical response to cortisol concentration and the induced changes in charge transfer resistance (Rct). A linear relationship between the Rct and the logarithm of cortisol concentration was found in concentrations ranging from 1 ng/mL to 1 mg/mL with limit of detection at 11.85 pg/mL (32.69 pM). The modification of the reference electrode with iridium oxide has greatly improved the reproducibility of the screen-printed electrode. The sensing system can provide a reliable and sensitive detection approach for cortisol measurements.

Mechanistic Aspects of Selenate Reduction on CU(UPD) on AU Electrodes

Recent findings in our laboratories have shown that copper1and cadmium2 underpotential deposited on polycrystalline Au electrodes, can mediate the reduction of in 0.1 M HClO4 aqueous solutions, to yield irreversibly adsorbed elemental Se allowing its detection down to the nM range. Current efforts are focused on gaining a better understanding of the the factors that govern this unique electrocatalytic phenomenon by employing a combination of electrochemical, microgravimetric, and optical techniques, using Cu as the UPD species. Correlations have been sought between the rates of this process and the coverage of Cu(UPD), the concentration of and, to a more limited extent, the applied potential in 0.1 M HClO4 solutions. Experimental conditions were selected to unveil the functional dependence of the kinetics on each of the aforementioned factors, while keeping the others constant, in solutions both quiescent and in the presence of convective flow. A number of interesting observations were made based on the data collected. In particular, shown in Panel C, Fig. 1, are plots of the charge associated with the oxidation of adsorbed Cu and Se, QCu and QSe, respectively (see Panel C), obtained from the area under the peaks shaded in light blue and yellow in Panels A and B, Fig, 1, respectively, vs (see below). These data were recorded during linear potential scans following polarization of the electrode at Ehold = 0.325 V for various times, thold (see Panels A-C, Fig. 1), where the linear character of the data in solutions is consistent with Cu(UPD) proceeding under strict diffusion control. As indicated by the QSe data, the electrode displayed electrocatalytic activity for reduction only for QCu > ca. 80 μC cm2-. Additional insight was obtained from measurements of the electrode weight as a function of using a quartz crystal microbalance (see Panel D, Fig.1), which yielded evidence for adsorption only for QCu > ca. 80 μC cm2-, pointing to the formation of a surface-bound adduct, as a necessary step for reduction to ensue. On this basis, we propose that for QCu > ca. 80 μC cm2 the mechanism for reduction involves, as a first step, the reversible formation of the adduct, Eq. (1) followed by its irreversible reduction, generating adsorbed elemental Se, Cu|Se(ads), Eq. (2).Atomically resolved images of Cu(UPD) on Au(111) obtained with a scanning tunneling microscope for the closely related sulfate ion, strongly suggest that the active site involved adsorption on the empty Au sites of the so-called √3´x√3 superstructure (see Insert in Panel A, Fig. 1). A similar conclusion was drawn based on measurements performed with rotating Cu ring-polycrystalline Au disk electrodes, RRDE, at constant Cu(UPD) coverage and applied potential for various solution compositions. Quantitative analyses of all the data, which included numerical simulations, yielded kf/kr, and kET values in the range (2.4 – 3.23) ´ 106 cm3 mol-1 and (2.5 – 9) ´ 10-3 s-1, respectively. Acknowledgments Support for this work was provided by NSF CHEM 1808592

Kinetics of selenate reduction mediated by underpotentially deposited Cu on polycrystalline Au electrodes in aqueous perchloric acid

The reduction of selenate, SeO42−(aq),in 0.1 M HClO4 solutions, induced by underpotential deposition, UPD, of Cu on polycrystalline Au electrodes was investigated using the rotating ring-disk electrode, RRDE, technique. Design and implementation of electrode potential-rotation rate protocols made it possible to determine the rates of SeO42−(aq)reduction as a function of Cu coverage, θCu, as determined by the Bruckenstein method (Swathirajan et al. J. Phys. Chem.1982,86, 2480–2485). In agreement with the results reported recently for Au(111) film electrodes (Strobl et al. Electrochimica Acta2024,493, 144,298), the reaction was found to proceed only for θCu above a critical value, i.e. ca. 0.39, in this case, and the mechanism is consistent with an initial reversible formation of adsorbed Cu|SeO42−(ads),followed by its subsequent irreversible reduction, to yield a yet to be identified species denoted as Cu|Se(ads), as the rate determining step. Best fits of the kinetic model yielded values of the equilibrium constant for adduct formation, K, and first order rate constant for adduct reduction, kET, in the range (2.4 – 45) × 106 cm3 mol−1 and (0.55 – 30) × 10−3 s−1, respectively, which are close to those found for Au(111). This unique electrocatalytic effect has been attributed to a shift in the potential of zero charge of the bare substrate toward more negative values, induced by the metal UPD, which promotes the adsorption of the oxyanion at potentials more negative than those found for the bare substrate, making it possible to access overpotentials large enough for its further reduction to ensue.

Simultaneous Mapping of Electrocatalytic Activity and Selectivity via Hybrid Scanning Electrochemical Probe Microscopy.

Nanoscale scanning electrochemical probe microscopy started to elucidate the heterogeneity of electrocatalytic activity at electrode surfaces. However, understanding the heterogeneity in product selectivity, another crucial aspect of interfacial reactivity, remains challenging. Herein, we introduce a method combining scanning electrochemical microscopy (SECM) and scanning electrochemical cell microscopy (SECCM) to enable the spatially resolved mapping of both activity and selectivity in electrocatalysis. A dual-channel nanopipette probe was developed: one channel for activity mapping and the other for product detection with a high collection efficiency (>95%) and sensitivity. Simultaneous mapping of activity and selectivity in the oxygen reduction reaction (ORR) is demonstrated. Combined with colocalized crystal orientation mapping, we uncover the local electrocatalytic performance of ORR at different facets on polycrystalline Pt and Au. The high-resolution selectivity mapping enabled by our method with colocalized structural characterization can provide structure-activity-selectivity relationships that are often unavailable in ensemble measurement, holding promise for understanding key structural motifs controlling interfacial reactivity.

Selenate reduction mediated by underpotentially deposited Cu on the low index faces of Au in aqueous perchloric acid

Underpotential deposited Cu on the low index faces of single crystal Au electrodes has been found to promote the reduction of selenate, SeO42−(aq),in 0.1 M HClO4 solutions, a behavior analogous to that reported earlier in our laboratory for polycrystalline Au (Strobl et al. J. Electrochem. Soc.2016,163 (13), H1066). Sequential potential step-linear scan voltammetry data collected for Au(111) film electrodes in solutions containing Cu2+(aq) in the μM range afforded evidence that the onset for the electrocatalytic activity occurs for Cu(UPD) coverages, θCu ≈ 0.18, the same value at which complementary microgravimetric data displayed a clear increase in mass. On this basis, a reaction mechanism has been proposed involving the initial reversible formation of an adsorbed adduct, we denote as Cu|SeO42−(ads), followed by a first order irreversible reduction to yield a yet to be identified species, which we denote as Cu|Se(ads), as the rate determining step. Support for this reaction scheme was obtained from numerical solutions of the coupled differential equations that govern the time evolution of Cu|SeO4−(ads) and Cu|Se(ads), yielding best agreement with the experimental data for values of the equilibrium constant for adduct formation and the adduct reduction rate constant of 2.5 × 106 cm3 mol−1, and 9.1 × 10−3 s−1, respectively. This unique electrocatalytic effect has been attributed to a shift in the potential of zero charge of the bare Au substrates induced by Cu(UPD), which promotes the adsorption of HSeO4−(aq) at potentials more negative than those found for the bare substrates, allowing access to overpotentials high enough for its activation and further reduction to ensue.

The Electrocatalytic Activity of Au Electrodes Changes Significantly in Various Na+/K+ Supporting Electrolyte Mixtures

The potential of maximum entropy (PME) is an indicator of extreme disorder at the electrode/electrolyte interface and can predict changes in catalytic activity within electrolytes of varying compositions. The laser‐induced current transient technique is employed to evaluate the PME for Au polycrystalline (Aupc) electrodes immersed in Ar‐saturated cation electrolyte mixtures containing potassium and sodium ions at pH = 8. Five cation ratios (0.5 M K2SO4:0.5 M Na2SO4 = 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0) are explored, considering earlier studies that unveil cation‐dependent shifts at near‐neutral pH. Moreover, for all electrolyte compositions, electrochemical impedance spectroscopy is utilized to determine the double‐layer capacitance (CDL), the minimum of which should be close to the potential of zero charge (PZC). By correlating cation molar ratios with the PMEs and PZCs, the impact on the model oxygen reduction reaction (ORR) activity, assessed via the rotating disk electrode method, is analyzed. The results demonstrate a linear relationship between electrolyte cation mixtures and PME, while ORR activity exhibits an exponential trend. This observation validates the PME–activity link hypothesis, underscoring electrolyte components’ pivotal role in tailoring interfacial properties for electrocatalytic systems. These findings introduce a new degree of freedom for designing optimal electrocatalytic systems by adjusting various electrolyte components.

Unveiling Nanoscale Heterogeneities at the Bias-Dependent Gold-Electrolyte Interface.

Electrified solid-liquid interfaces (SLIs) are extremely complex and dynamic, affecting both the dynamics and selectivity of reaction pathways at electrochemical interfaces. Enabling access to the structure and arrangement of interfacial water in situ with nanoscale resolution is essential to develop efficient electrocatalysts. Here, we probe the SLI energy of a polycrystalline Au(111) electrode in a neutral aqueous electrolyte through in situ electrochemical atomic force microscopy. We acquire potential-dependent maps of the local interfacial adhesion forces, which we associate with the formation energy of the electric double layer. We observe nanoscale inhomogeneities of interfacial adhesion force across the entire map area, indicating local differences in the ordering of the solvent/ions at the interface. Anion adsorption has a clear influence on the observed interfacial adhesion forces. Strikingly, the adhesion forces exhibit potential-dependent hysteresis, which depends on the local gold grain curvature. Our findings on a model electrode extend the use of scanning probe microscopy to gain insights into the local molecular arrangement of the SLI in situ, which can be extended to other electrocatalysts.

In-situ and operando Grazing Incidence XAS: a novel set-up and its application to model Pd electrodes for alcohols oxidation

Abstract In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems.

Potential Dependent Reorientation Controlling Activity of a Molecular Electrocatalyst.

The activity of molecular electrocatalysts depends on the interplay of electrolyte composition near the electrode surface, the composition and morphology of the electrode surface, and the electric field at the electrode-electrolyte interface. This interplay is challenging to study and often overlooked when assessing molecular catalyst activity. Here, we use surface specific vibrational sum frequency generation (VSFG) spectroscopy to study the solvent and potential dependent activation of Mo(bpy)(CO)4, a CO2 reduction catalyst, at a polycrystalline Au electrode. We find that the parent complex undergoes potential dependent reorientation at the electrode surface when a small amount of N-methyl-2-pyrrolidone (NMP) is present. This preactivates the complex, resulting in greater yields at less negative potentials, of the active electrocatalyst for CO2 reduction.

High-resolution MHz time- and angle-resolved photoemission spectroscopy based on a tunable vacuum ultraviolet source.

The time- and angle-resolved photoemission spectroscopy (trARPES) allows for direct mapping of the electronic band structure and its dynamic response on femtosecond timescales. Here, we present a new ARPES system, powered by a new fiber-based femtosecond light source in the vacuum ultraviolet range, accessing the complete first Brillouin zone for most materials. We present trARPES data on Au(111), polycrystalline Au, Bi2Se3, and TaTe2, demonstrating an energy resolution of 21meV with a time resolution of <360fs, at a high repetition rate of 1MHz. The system is integrated with an extreme ultraviolet high harmonic generation beamline, enabling an excellent tunability of the time-bandwidth resolution.

Merging of Bi-Modality of Ultrafast Laser Processing: Heating of Si/Au Nanocomposite Solutions with Controlled Chemical Content.

Ultrafast laser processing possesses unique outlooks for the synthesis of novel nanoarchitectures and their further applications in the field of life science. It allows not only the formation of multi-element nanostructures with tuneable performance but also provides various non-invasive laser-stimulated modalities. In this work, we employed ultrafast laser processing for the manufacturing of silicon-gold nanocomposites (Si/Au NCs) with the Au mass fraction variable from 15% (0.5 min ablation time) to 79% (10 min) which increased their plasmonic efficiency by six times and narrowed the bandgap from 1.55 eV to 1.23 eV. These nanostructures demonstrated a considerable fs laser-stimulated hyperthermia with a Au-dependent heating efficiency (~10-20 °C). The prepared surfactant-free colloidal solutions showed good chemical stability with a decrease (i) of zeta (ξ) potential (from -46 mV to -30 mV) and (ii) of the hydrodynamic size of the nanoparticles (from 104 nm to 52 nm) due to the increase in the laser ablation time from 0.5 min to 10 min. The electrical conductivity of NCs revealed a minimum value (~1.53 µS/cm) at 2 min ablation time while their increasing concentration was saturated (~1012 NPs/mL) at 7 min ablation duration. The formed NCs demonstrated a polycrystalline Au nature regardless of the laser ablation time accompanied with the coexistence of oxidized Au and oxidized Si as well as gold silicide phases at a shorter laser ablation time (<1 min) and the formation of a pristine Au at a longer irradiation. Our findings demonstrate the merged employment of ultrafast laser processing for the design of multi-element NCs with tuneable properties reveal efficient composition-sensitive photo-thermal therapy modality.

Observation and Characterization of Vibrationally Active Surface Species Accessed with Nonthermal Nitrogen Plasmas.

Polycrystalline Ni, Pd, Cu, Ag, and Au foils exposed to nonthermal plasma (NTP)-activated N2 are found to exhibit a vibrational feature near 2200 cm-1 in polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS) observations that are not present in the same materials exposed to N2 under nonplasma conditions. The feature is similar to that reported elsewhere and is typically assigned to chemisorbed N2. We employ a combination of temperature-dependent experiments, sequential dosing, X-ray photoelectron spectroscopy, isotopic labeling, and density functional theory calculations to characterize the feature. Results are most consistent with a triatomic species, likely NCO, with the C and O likely originating from ppm-level impurities in the ultrahigh-purity (UHP) Ar and/or N2 gas cylinders. The work highlights the potential for nonthermal plasmas to access adsorbates inaccessible thermally as well as the potential contributions of ppm-level impurities to corrupt the interpretation of plasma catalytic chemistry.

Toward Eco‐Friendly E‐Waste Recycling: New Perspectives on Ozone‐Assisted Gold Leaching

Global demand for more effective methods to reclaim gold from electronic waste (E‐waste) has never been greater. Alternatives to hydrometallurgical methods, such as cyanide, are still limited. This work examines utilizing ozone and chlorides to recycle Au from E‐waste. It is started with a fundamental investigation of Au dissolution processes on the extended surface of Au polycrystalline and Au nanoparticulated electrodes. An online electrochemical scanning flow cell coupled with inductively coupled plasma mass spectrometry quantifies the rates and amounts of Au leaching. Identical‐location scanning electron microscopy (IL‐SEM) further correlates dissolution events with electrode morphological changes. It is demonstrated that ozone in the electrolyte imposes an anodic potential on the electrode, leading to anodic Au dissolution. Passivation disappears when small amounts of chlorides are added to the electrolyte, significantly enhancing the leaching yield. IL‐SEM images of gold nanoparticles (NPs) before and after exposure to ozone reveal heterogeneity in NP size‐dependent dissolution, showing higher dissolution for smaller particles. An effective Au leaching procedure is further demonstrated in a lab‐scale reactor using real E‐waste where almost complete recovery of Au is achieved. This research suggests that with engineering optimization in reactor applications based on ozone‐stimulated gold, dissolution can pave the way for environmentally friendly gold recycling.

(Invited) Probing the Oxygen Reduction and Hydrazine Oxidation Reactions Using Transient Amperometric Techniques

The kinetics of electrochemical reactions affected by mass transfer is often investigated by rotating disc electrode (RDE) and rotating ring disc electrodes. However, these hydrodynamic techniques require electrodes that can be shaped into a disk or catalysts that can be drop casted on the surface of a disk electrode. Instead, transient amperometric techniques such as chronoamperometry and sampled current voltammetry (SCV) hold potential to investigate the kinetics of reactions without such requirements.In SCV, a series of chronoamperograms are recorded for a range of target potentials, and the current sampled at a fixed time or over a range of time scales. Sampled current voltammograms are obtained by plotting the selected currents vs the target potentials. 1-3 As we demonstrated recently with ferri/ferrocyanide ions and with oxygen reduction reaction (ORR) on Pt polycrystalline disk electrode, proper selection of the sampling times leads to the same mass transfer coefficients as in the RDE, and so the obtained SCV are equivalent to the linear sweep voltammograms recorded with a RDE. 4 Moreover, the kinetically controlled current can be extracted from the current transients, by plotting the inverse of the current vs the square root of time and by extrapolating to infinitely short times (large mass transfer coefficients). Tafel analysis can then be conducted. 4 In this talk, we will first present how these transient amperometric techniques were used to investigate the oxygen reduction on Au (001) thin films with different thicknesses grown on insulating MgO (001) substrates. 5 It will be shown that SCV is sensitive to the structure and to themosaicity of the thin films, and thus suitable to establish reactivity structure relationships. Then, we will show some of our recent work on the hydrazine oxidation on Au and Pt polycrystalline surfaces. 6 References [1] A. J. V and L. R. Faulkner, Electrochemical methods: Fundamentals and Applications; Wiley, 2001.[2] S.C. Perry and G. Denuault, Phys. Chem. Chem. Phys. 17, 30005 (2015).[3] L. Mignard, M. Denoual, O. Lavastre, D. Floner and F. Geneste, J. Electroanal. Chem., 689, 83 (2013).[4] C. O. Soares, O. Rodríguez, G. Buvat, G., M. Duca, S. Garbarino, D. Guay, G. Denuault and A. C. Tavares, Electrochim. Acta, 362, 136946 (2020).[5] C. O. Soares, G. Buvat, Y. G. Hernández, S. Garbarino, M. Duca, A. Ruediger, G. Denuault, A. C. Tavares and D. Guay, ACS Catal 12, 1664 (2022).[6] D. Kashyap, C. O. Soares, A. C. Tavares, G. Denuault, D. Guay, in preparation. Acknowledgements This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC, Strategic Partnership program). Cybelle Oliveira Soares acknowledges the FRQNT funding by means of the PBEEE merit scholarship and an internship received from the Engineered Nickel Catalysts for Electrochemical Clean Energy project administered from Queen’s University and supported by Grant No RGPNM 477963-2015 under the NSERC Discovery Frontiers Program.

Redox Behavior of Arsenic (III) and Copper (II) Mixtures on Ultraflat Au (111) Thin Film Electrodes

The electrochemical behavior of arsenic on gold (Au) electrodes surfaces is of great interest as As is well-recognized as a highly toxic and relatively ubiquitous ground water species. The United States Environmental Protection Agency (USEPA) and World Health Organization (WHO) drinking water standards for arsenic are 10 PPB, or 𝜇g L-1 [1]. These minute ion concentrations necessitate the use of analytical methods with high sensitivity and a low susceptibility to cross interferences. Electrochemical stripping voltammetry is a well-established electroanalytical method for arsenic ions [2]. Polycrystalline gold electrodes are often used due to their high redox stability and relatively low overpotential for hydrogen evolution. We recently explored the use of ultra-flat, thin film, Au(111) electrodes to replace polycrystalline Au for As stripping voltammetry. Previous studies on oriented single crystals showed relatively narrow stripping peaks with greatly improved peak to background ratios on the (111) surfaces [3]. We observed comparatively similar or better stripping behavior on the Au(111) thin film electrodes with correspondingly far less gold usage per electrode. Unfortunately, copper is a known interference for arsenic stripping electroanalysis, with a strong affinity for UPD deposition on gold. We therefore studied the deposition behavior of Cu on Au(111) thin film electrodes and the co- deposition of Cu and As on the Au(111) thin film electrodes to evaluate cross interference effects. Copper redox behavior in 0.5M H2SO4 was characterized by cyclic voltammetry, electro- deposition and linear stripping voltammetry (LSV) measurements. Strong Cu UPD behavior was observed on Au(111) thin films with sharper, better defined redox peaks than polycrystalline electrodes. Arsenic and Cu ions were also co-deposited over a wide range of Cu (II) and As (III) concentrations. Complex redox behavior was observed with strong indications of Cu-As alloy formation. This was confirmed via angle resolved, X-ray Photoemission Spectroscopy (XPS) measurements. Our results also indicate that the electrodeposition efficiency during LSV of As is increased by the co-deposition of Cu. The results of this study have important implications for understanding the nature of Cu (II) interference with electrochemical detection of trace As (III) in water.[1] USEPA. National Secondary Drinking Water Regulations. 2009. https://www.epa.gov/sdwa/drinking-water- regulations-and-contaminants (accessed.[2] USEPA. METHOD 7063: ARSENIC IN AQUEOUS SAMPLES AND EXTRACTSBY ANODIC STRIPPING VOLTAMMETRY (ASV). 1996.[3] Casuse-Driovínto, T. Q.; Rizo, R.; Benavidez, A.; Brearley, A. J.; Cerrato, J. M.; Garzon, F. H.; Herrero, E.; Feliu, J. M. Increased Sensitivity and Selectivity for As(III) Detection at the Au(111) Surface: Single Crystals and Ultraflat Thin Films Comparison. The Journal of Physical Chemistry C 2022, 126 (48), 20343-20353. DOI: 10.1021/acs.jpcc.2c05541.

Phase-field crystal simulation of the evolution of voids in polycrystalline Au–Al bonds with elastic interaction and the Kirkendall effect

In this paper, the modified phase-field crystal (MPFC) model is employed to study the evolution of Kirkendall voids in polycrystalline Au–Al bonds under mechanical loading. The MPFC model can simulate the structural evolution of deformed pure nanocrystalline materials considering instantaneous elastic interactions. Therefore, coupling a concentration field evolved by the Cahn-Hilliard equation with a density field evolved by the existing MPFC model makes it possible to study the phase transformation of a binary system in the presence of mechanical deformation. Using this modified model, we focus on the morphology evolution of the voids in Au–Al bonds under different mechanical loadings. The semi-implicit Fourier spectral algorithm is applied to solve the six-order coupling dynamics equations. The Kirkendall porosity of the diffusion couple is computed and analyzed. The effects of quasi-static and cyclic axial tensile loads on the morphology of voids, and porosity of the system are investigated. It is found that the morphology of Kirkendall voids that result from applying a quasi-static load is different from those that result from applying a cyclic load.

A New Method for Urea Synthesis under Environmental Conditions Based on Nucleophilic Addition Reaction During Electrochemical CO2 Reduction

AbstractUrea (H2NCONH2) is a commercially indispensable chemical as a fertilizer and starting material for the manufacture of many other products. Currently, commercial urea can be prepared with an energy‐consuming process by combining liquid ammonia (NH3) and liquid carbon dioxide (CO2) under high‐temperature and high‐pressure conditions. An alternative approach for synthesis of urea may involve electrochemical synthesis reactions that occur under aqueous and ambient conditions. Here, we propose synthesis of urea via nucleophilic addition reaction during an electrochemical CO2 reduction process in NH4HCO3‐containing electrolytes. The urea formation at a rate of 0.11 mmol g−1 h−1 was achieved on a polycrystalline Au electrode (area: 1 cm2) at a potential of −1.4 V (vs. saturated calomel electrode). Furthermore, the detailed investigations including in‐situ spectroscopic analysis and isotopic labeling characterization reveal the capability of producing urea could be mainly attributed to a spontaneous reaction between the NH3 molecule and the CO2⋅− intermediate. This study promotes the exploration of electrochemical synthesis of high‐value‐added products.

Electrochemical investigations and antimicrobial activity of Au nanoparticles photodeposited on titania nanoparticles

Titanium oxide nanopowder (TiO2 NPs) was synthesized via anodization in 0.7 M perchloric acid then annealed in nitrogen at 450 °C for 3 h to prepared the Titanium Oxide Nitrogen annealed nanoparticles (TiO2 NPs-N2) powder as catalytic support. Using a photodeposition process, gold was added with isopropanol as a sacrificial donor and H[AuCl4] acid, producing gold nanoparticles on nitrogen-annealed titanium oxide nanoparticles (Au-NPs on TiO2-NPs-N2). The mass loading of Au NPs was 2.86 × 10−4 (g/cm2). TEM images of Au NPs on TiO2-NPs-N2 suggest circular particles with a tendency to agglomerate. Cyclic voltammetry (CV) was used to investigate the electrocatalytic performance of the Au NPs/TiO2-NPs-N2 catalysts in ferrocyanide, KOH, and H2SO4, and the results were compared to those of a polycrystalline Au electrode that is readily accessible in the market. In KOH, H2SO4, and (2 M KOH + 0.1 M glycerol) solutions, the Au NPs/TiO2-NPs-N2 electrode displayed a startlingly high electrocatalytic performance. Using CV, the electrocatalytic oxygen reduction reaction (ORR) of Au NPs/TiO2-NPs-N2 and Au-NPs against glycerol oxidation in basic media was studied. The results indicated that Au NPs/TiO2-NPs-N2 is a promising support material for improving the electrocatalytic activity for acidic and basic oxidation. The electrode made of Au NPs/TiO2-NTs-N2 has steady electrocatalytic activity and may be reused repeatedly. TiO2 NPs and Au NPs/TiO2NPs-N2 showed satisfactory antibacterial activity against some human pathogenic bacteria using the disc diffusion method.