Selectivity-Enhanced Electroreduction of CO2 to CO at Novel Ru-Linked-GO Nanohybrids: the Role of Nanoarchitecture.

Recently, global-scale efforts have been conducted for the electroreduction of CO2 as a potentially beneficial pathway for the conversion of greenhouse gases to useful chemicals and renewable fuels. This study focuses on the development of selective and sustainable electrocatalysts for the reduction of aqueous CO2 to CO. A RuIIcomplex [Ru(tptz)(ACN)Cl2] (RCMP) (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine, ACN = acetonitrile) was prepared as a molecular electrocatalyst for the CO2 reduction reaction in an aqueous solution. Density functional theory-calculated frontier molecular orbitals suggested that the tptz ligand plays a key role in dictating the electrocatalytic reactions. The RCMP electrocatalyst was grafted onto the graphene oxide (GO) surface both noncovalently (GO/RCMP) and covalently (GO-RCMP). The field emission scanning electron microscopy and elemental distribution analyses revealed the homogeneous distribution of the complex onto the GO sheet. The photoluminescence spectra confirmed accelerated charge-transfer in both nanohybrids. Compared to the bare complex, the GO-RCMP and GO/RCMP nanohybrids showed enhanced electrocatalytic activity, achieving >95% and 90% Faradaic efficiencies for CO production at more positive onset potentials, respectively. The GO-RCMP nanohybrid demonstrated outstanding electrocatalytic activity with a current of ∼84 µA. The study offers a perspective on outer- and inner-sphere electron-transfer mechanisms for electrochemical energy conversion systems.

Boosting Oxygen Reduction at Pt(111)|Proton Exchange Ionomer Interfaces through Tuning the Microenvironment Water Activity.

A proton exchange ionomer is one of the most important components in membrane electrode assemblies (MEAs) of polymer electrolyte membrane fuel cells (PEMFCs). It acts as both a proton conductor and a binder for nanocatalysts and carbon supports. The structure and the wetting conditions of the MEAs have a great impact on the microenvironment at the three-phase interphases in the MEAs, which can significantly influence the electrode kinetics such as the oxygen reduction reaction (ORR) at the cathode. Herein, by using the Pt(111)|X ionomer interface as a model system (X = Nafion, Aciplex, D72), we find that higher drying temperature lowers the onset potential for sulfonate adsorption and reduces apparent ORR current, while the current wave for OHad formation drops and shifts positively. Surprisingly, the intrinsic ORR activity is higher after properly correcting the blocking effect of Pt active sites by sulfonate adsorption and the poly(tetrafluoroethylene) (PTFE) skeleton. These results are well explained by the reduced water activity at the interfaces induced by the ionomer/PTFE, according to the mixed potential effect. Implications for how to prepare MEAs with improved ORR activity are provided.

CO2 reduction on adatom decorated platinum stepped surfaces.

The rate of CO formation from CO2 reduction on Pt(111) vicinal surfaces containing (100) steps, Pt(S)[n(111) × (100)], has been investigated using cyclic voltammetry. To obtain further information about the different roles of terrace and step atoms in this reaction, selective modification of step sites with either bismuth or copper has been performed. In this way, two different mechanistic regimes have been differentiated, depending on the potential range. In the high potential region, between 0.2 and 0.4 V RHE, CO2 is activated on steps and proceeds to the formation of adsorbed CO even when there is no hydrogen adsorbed on the terrace. We suggest that protonation of the activated CO2 uses protons from the solution. In this potential range, the activity decreases after the selective blockage of step sites with bismuth, while the deposition of copper on steps increases the activity. Contrarily, in the low potential region, below 0.2 V RHE, the presence of copper on the steps does not increase the amount of CO formed from CO2 reduction. In fact, the amount of CO formed attains the same saturation value with or without copper. In addition, the CO formed in this potential region remains adsorbed near step sites as shown in the voltammetric profile. We rationalize these observations considering that, in this potential region, activated CO2 reacts with adsorbed hydrogen and the reactions stop when hydrogen near the steps is depleted.

Autonomous electrochemical system for ammonia oxidation reaction measurements at the International Space Station.

An autonomous electrochemical system prototype for ammonia oxidation reaction (AOR) measurements was efficiently done inside a 4'' x 4'' x 8'' 2U Nanoracks module at the International Space Station (ISS). This device, the Ammonia Electrooxidation Lab at the ISS (AELISS), included an autonomous electrochemical system that complied with NASA ISS nondisclosure agreements, power, safety, security, size constrain, and material compatibility established for space missions. The integrated autonomous electrochemical system was tested on-ground and deployed to the International Space Station as a "proof-of-concept" ammonia oxidation reaction testing space device. Here are discussed the results of cyclic voltammetry and chronoamperometry measurements done at the ISS with a commercially available channel flow-cell with eight screen-printed electrodes, including Ag quasi-reference (Ag QRE) and carbon counter electrodes. Pt nanocubes in Carbon Vulcan XC-72R were used as the catalyst for the AOR and 2 µL drop of Pt nanocubes/ Carbon Vulcan XC-72R, 20 wt%, ink was placed on the carbon working electrodes and allowed to dry in air. After the AELISS was prepared for launch to the ISS, a 4 days delayed (2 days in the space vehicle Antares and 2 days space transit to the ISS) cause a slight shift on the Ag QRE potential. Nevertheless, the AOR cyclic voltametric peak was observed in the ISS and showed ca. 70% current density decrease due to the buoyancy effect in agreement with previous microgravity experiments done at the zero-g aircraft.

Spectroelectrochemical Studies of CTAB Adsorbed on Gold Surfaces in Perchloric Acid.

The behaviour of CTAB adsorbed on polycrystalline gold electrodes has been studied using a combination of spectroelectrochemical methods. The results indicate that the formation of the layer is the consequence of the precipitation of the CTAB micelles on the electrode surface as bromide ions, which stabilize the micelles, are replaced by perchlorate anions. This process leads to the formation of CTA+ layers in which perchlorate ions are intercalated, in which the adlayer suffers a continuous rearrangement that leads to the formation of micro-dominions of different types of hydrogen-bonded water populations throughout the adlayer. After prolonged cycling, a stable situation is reached. Under these conditions, water molecules permeate through the adlayer toward the electrode surface at potentials positive of the potential of zero charge, due to the repulsion between the CTA+ layer and the positive charge of the electrode.

Inverse kinetic isotope effects in the oxygen reduction reaction at platinum single crystals.

Although the oxygen reduction reaction (ORR) involves multiple proton-coupled electron transfer processes, early studies reported the absence of kinetic isotope effects (KIEs) on polycrystalline platinum, probably due to the use of unpurified D2O. Here we developed a methodology to prepare ultra-pure D2O, which is indispensable for reliably investigating extremely surface-sensitive platinum single crystals. We find that Pt(111) exhibits much higher ORR activity in D2O than in H2O, with potential-dependent inverse KIEs of ~0.5, whereas Pt(100) and Pt(110) exhibit potential-independent inverse KIEs of ~0.8. Such inverse KIEs are closely correlated to the lower *OD coverage and weakened *OD binding strength relative to *OH, which, based on theoretical calculations, are attributed to the differences in their zero-point energies. This study suggests that the competing adsorption between *OH/*OD and *O2 probably plays an important role in the ORR rate-determining steps that involve a chemical step preceding an electrochemical step (CE mechanism).

Investigating the presence of adsorbed species on Pt steps at low potentials.

The study of the OH adsorption process on Pt single crystals is of paramount importance since this adsorbed species is considered the main intermediate in many electrochemical reactions of interest, in particular, those oxidation reactions that require a source of oxygen. So far, it is frequently assumed that the OH adsorption on Pt only takes place at potentials higher than 0.55 V (versus the reversible hydrogen electrode), regardless of the Pt surface structure. However, by CO displacement experiments, alternating current voltammetry, and Raman spectroscopy, we demonstrate here that OH is adsorbed at more negative potentials on the low coordinated Pt atoms, the Pt steps. This finding opens a new door in the mechanistic study of many relevant electrochemical reactions, leading to a better understanding that, ultimately, can be essential to reach the final goal of obtaining improved catalysts for electrochemical applications of technological interest.

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

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.

Interfacial Water Structure as a Descriptor for Its Electro-Reduction on Ni(OH)2-Modified Cu(111).

The hydrogen evolution reaction (HER) has been crucial for the development of fundamental knowledge on electrocatalysis and electrochemistry, in general. In alkaline media, many key questions concerning pH-dependent structure-activity relations and the underlying activity descriptors remain unclear. While the presence of Ni(OH)2 deposited on Pt(111) has been shown to highly improve the rate of the HER through the electrode's bifunctionality, no studies exist on how low coverages of Ni(OH)2 influence the electrocatalytic behavior of Cu surfaces, which is a low-cost alternative to Pt. Here, we demonstrate that Cu(111) modified with 0.1 and 0.2 monolayers (ML) of Ni(OH)2 exhibits an unusual non-linear activity trend with increasing coverage. By combining in situ structural investigations with studies on the interfacial water orientation using electrochemical scanning tunneling microscopy and laser-induced temperature jump experiments, we find a correlation between a particular threshold of surface roughness and the decrease in the ordering of the water network at the interface. The highly disordered water ad-layer close to the onset of the HER, which is only present for 0.2 ML of Ni(OH)2, facilitates the reorganization of the interfacial water molecules to accommodate for charge transfer, thus enhancing the rate of the reaction. These findings strongly suggest a general validity of the interfacial water reorganization as an activity descriptor for the HER in alkaline media.

Detection of Superoxide Anion Oxygen Reduction Reaction Intermediate on Pt(111) by Infrared Reflection Absorption Spectroscopy in Neutral pH Conditions.

In this work, in situ external infrared reflection absorption spectroscopy (IRRAS) is successfully employed for the detection of intermediate species in the oxygen reduction reaction (ORR) mechanism on a flat and well-defined Pt surface. Superoxide anion species (O2-) are detected on the Pt(111) surface in an O2-saturated solution with a NaF/HClO4 mixture with pH 5.5 by the observation of a O-O vibration band at ca. 1080 cm-1. The observation of O2- without the use of any other additional method of signal enhancement is possible because in these experimental conditions O2- is the main ORR-generated intermediate and its reactivity is limited in this pH. This leads to the accumulation of O2- near the Pt surface, facilitating its identification.

Cation Effects on Interfacial Water Structure and Hydrogen Peroxide Reduction on Pt(111).

The interface between the Pt(111) surface and several MeF/HClO4 (Me+ = Li+, Na+, or Cs+) aqueous electrolytes is investigated by means of cyclic voltammetry and laser-induced temperature jump experiments. Results point out that the effect of the electrolyte on the interfacial water structure is different depending on the nature of the metal alkali cation, with the values of the potential of maximum entropy (pme) following the order pme (Li+) < pme (Na+) < pme (Cs+). In addition, the hydrogen peroxide reduction reaction is studied under these conditions. This reaction is inhibited at low potentials as a consequence of the build up of negative charges on the electrode surface. The potential where this inhibition takes place (E inhibition) follows the same trend as the pme. These results evidence that the activity of an electrocatalytic reaction can depend to great extent on the structure of the interfacial water adlayer and that the latter can be modulated by the nature of the alkali metal cation.

Role of OH Intermediates during the Au Oxide Electro-Reduction at Low pH Elucidated by Electrochemical Surface-Enhanced Raman Spectroscopy and Implicit Solvent Density Functional Theory.

Molecular understanding of the electrochemical oxidation of metals and the electro-reduction of metal oxides is of pivotal importance for the rational design of catalyst-based devices where metal(oxide) electrodes play a crucial role. Operando monitoring and reliable identification of reacting species, however, are challenging tasks because they require surface-molecular sensitive and specific experiments under reaction conditions and sophisticated theoretical calculations. The lack of molecular insight under operating conditions is largely due to the limited availability of operando tools and to date still hinders a quick technological advancement of electrocatalytic devices. Here, we present a combination of advanced density functional theory (DFT) calculations considering implicit solvent contributions and time-resolved electrochemical surface-enhanced Raman spectroscopy (EC-SERS) to identify short-lived reaction intermediates during the showcase electro-reduction of Au oxide (AuOx) in sulfuric acid over several tens of seconds. The EC-SER spectra provide evidence for temporary Au-OH formation and for the asynchronous adsorption of (bi)sulfate ions at the surface during the reduction process. Spectral intensity fluctuations indicate an OH/(bi)sulfate turnover period of 4 s. As such, the presented EC-SERS potential jump approach combined with implicit solvent DFT simulations allows us to propose a reaction mechanism and prove that short-lived Au-OH intermediates also play an active role during the AuOx electro-reduction in acidic media, implying their potential relevance also for other electrocatalytic systems operating at low pH, like metal corrosion, the oxidation of CO, HCOOH, and other small organic molecules, and the oxygen evolution reaction.

Activation Energy of Hydrogen Adsorption on Pt(111) in Alkaline Media: An Impedance Spectroscopy Study at Variable Temperatures.

The hydrogen evolution reaction is one of the most studied processes in electrochemistry, and platinum is by far the best catalyst for this reaction. Despite the importance of this reaction on platinum, detailed and accurate kinetic measurements of the steps that lead to the main reaction are still lacking, particularly because of the fast rate of the reaction. Hydrogen adsorption on Pt(111) has been taken as a benchmark system in a large number of computational studies, but reliable experimental data to compare with the computational studies is very scarce. To gain further knowledge on this matter, a temperature study of the hydrogen adsorption reaction has been carried out to obtain kinetic information for this process on Pt(111) in alkaline solution. This was achieved by measuring electrochemical impedance spectra and cyclic voltammograms in the range of 278 ≤ T ≤ 318 (K) to obtain the corresponding surface coverage by adsorbed species and the faradaic charge transfer resistance. From this data, the standard rate constant has been extracted with a kinetic model assuming a Frumkin-type isotherm, resulting in values of 2.60 × 10-7 ≤ k0 ≤ 1.68 × 10-6 (s-1). The Arrehnius plot gives an activation energy of 32 kJ mol-1. Comparisons are made with values calculated by computational methods and reported values for the overall HER, giving a reference frame to support future studies on hydrogen catalysis.

Revisiting the Atomistic Structures at the Interface of Au(111) Electrode-Sulfuric Acid Solution.

Knowledge of atomistic structures at solid/liquid interfaces is essential to elucidate interfacial processes in chemistry, physics, and materials sciences. The (√3 × âˆš7) structure associated with a pair of sharp reversible current spikes in the cyclic voltammogram on a Au(111) electrode in sulfuric acid solution represents one of the most classical ordered structures at electrode/electrolyte interfaces. Although more than 10 adsorption configurations have been proposed in the past four decades, the atomistic structure remains ambiguous and is consequently an open problem in electrochemistry and surface science. Herein, by combining high-resolution electrochemical scanning tuning microscopy, electrochemical infrared and Raman spectroscopies, and, in particular, the newly developed quantitative computational method for electrochemical infrared and Raman spectra, we unambiguously reveal that the adstructure is Au(111)(√3 × âˆš7)-(SO4···w2) with a sulfate anion (SO4*) and two structured water molecules (w2*) in a unit cell, and the crisscrossed [w···SO4···w]n and [w···w···]n hydrogen-bonding network comprises the symmetric adstructure. We further elucidate that the electrostatic potential energy dictates the proton affinity of sulfate anions, leading to the potential-tuned structural transformations. Our work enlightens the structural details of the inner Helmholtz plane and thus advances our fundamental understanding of the processes at electrochemical interfaces.

Structure effects on electrocatalysts. Oxygen reduction on Te-modified Pt(111) surfaces: Site-blocking vs electronic effects.

In this work, the oxygen reduction reaction (ORR) on tellurium-modified Pt(111) surfaces has been studied. Adsorption of Te adatoms on Pt(111) progressively shifts toward less positive values of both the ORR reaction onset and the half-wave potential in 0.1M HClO4 for 0 < θTe < 0.25. However, at θTe > 0.25, the ORR activity increases relative to the one at θTe < 0.25, but remains lower than that on clean Pt(111). Results were analyzed in light of simulations of kinetic currents as a function of θTe, calculated by employing a simple mean field model including both site blocking and electronic effects. Inside this framework, experimental data are best explained by considering that oxygenated Te species inhibit the ORR by either negatively modifying adsorption energies of reaction intermediates or combined site-blocking and electronic effects. A redox ORR catalysis due to redox properties of Te adatoms is discarded. Contrarily, in 0.05M H2SO4, a positive catalytic effect has been found, interpreted in terms of a competitive adsorption-desorption mechanism involving the replacement of adsorbed sulfate by Te adatoms. On the other hand, despite the strong site-blocking effect on Hads and OHads adsorption by Te adatoms, it appears that the reduced Te-Pt(111) adlayer does not inhibit the reaction, suggesting different active sites for Hads and OHads adsorption and for the rate-determining step of the ORR mechanism.

Monitoring of CO Binding Sites on Stepped Pt Single Crystal Electrodes in Alkaline Solutions by in Situ FTIR Spectroscopy.

The site geometry preference of CO binding on stepped Pt single crystals in alkaline solution was investigated by in situ FTIR spectroscopy. The surfaces of the Pt single crystals consisted of different width (111) terraces, interrupted by (110) or (100) monatomic steps. Experiments carried out with CO adsorbed exclusively on the top of the steps revealed that only linearly bonded CO formed on the (110) steps, while two CO binding geometries (linear and bridge) were observed on the (100) steps. On one hand, for CO adsorbed only on the steps, the positions of the bands corresponding to linearly bonded CO were similar, regardless of the density of steps, suggesting the existence of an interaction between COads only along the line of the steps. On the other hand, for full CO coverage, the CO stretching frequencies and the geometry of bound CO were sensitive to the width of the (111) terraces and the step orientations. Consequently, the CO binding sites favored linearly bonded CO for surfaces consisting of shorter (111) terraces and (110) steps. Bridge-bonded CO was favored on surfaces consisting of shorter (111) terraces interrupted by (100) steps. In order to understand the origin of the preference of CO binding sites, the results were compared to the corresponding behavior in acid media, which revealed that, in addition to the effect inherent to the Pt surface, the charge on the metal side in an aqueous environment should be taken into consideration. The analysis suggested that the CO adlayers formed at full coverage in acidic and alkaline media had different structures. On the other hand, the structure of the layer of CO adsorbed only at the steps was independent of pH.

Coherent Bragg imaging of 60†nm Au nanoparticles under electrochemical control at the NanoMAX beamline.

Nanoparticles are essential electrocatalysts in chemical production, water treatment and energy conversion, but engineering efficient and specific catalysts requires understanding complex structure-reactivity relations. Recent experiments have shown that Bragg coherent diffraction imaging might be a powerful tool in this regard. The technique provides three-dimensional lattice strain fields from which surface reactivity maps can be inferred. However, all experiments published so far have investigated particles an order of magnitude larger than those used in practical applications. Studying smaller particles quickly becomes demanding as the diffracted intensity falls. Here, in situ nanodiffraction data from 60 nm Au nanoparticles under electrochemical control collected at the hard X-ray nanoprobe beamline of MAX IV, NanoMAX, are presented. Two-dimensional image reconstructions of these particles are produced, and it is estimated that NanoMAX, which is now open for general users, has the requisites for three-dimensional imaging of particles of a size relevant for catalytic applications. This represents the first demonstration of coherent X-ray diffraction experiments performed at a diffraction-limited storage ring, and illustrates the importance of these new sources for experiments where coherence properties become crucial.

Surface Structure Characterization of Shape and Size Controlled Pd Nanoparticles by Cu UPD: A Quantitative Approach.

The search for new surface sensitive probes that characterize the surface structure of shape and size-controlled nanoparticles is an interesting topic to properly understand the correlations between electrocatalytic properties and surface structure at the nanoscale. Herein, we report the use of Cu UPD to characterize, not only qualitatively but also quantitatively, the surface structure of different Pd nanoparticles with controlled particle shape and size. Thus, Pd nanoparticles with cubic, octahedral and rhombic dodecahedral shapes, that is, with preferential {100}, {111}, and {110} surface structures, respectively, were prepared. In addition, cubic Pd nanoparticles with different particles sizes and spherical (2-3 nm) Pd nanoparticles were also synthesized. Based on the Cu UPD results on Pd single crystals, a new approach is proposed to qualitatively and quantitatively determine the percentages of {100}, {111}, and {110} surface domains present at the surface of the different shape and size controlled Pd nanoparticles. The results reported clearly show the benefits of this Cu UPD to get detailed information of the surface structure of the nanoparticles according to their particle shape and size.

Interfacial Study of Nickel-Modified Pt(111) Surfaces in Phosphate-Containing Solutions: Effect on the Hydrogen Evolution Reaction.

The surface modification of electrodes attracts great interest in electrocatalysis. It has often been observed that deposition of foreign adatoms on the surface of an electrode can originate a significant enhancement in the catalytic activity. For example, it has been reported that nickel deposits on Pt surfaces improve the rate of the hydrogen evolution reaction (HER, Nature Energy 2017, 2, 17031). During the deposition process of such metal adlayers, the pH and the nature of the ions in the electrolyte play an important role. Phosphate species are typically used to prepare buffer solutions in a wide range of pH. Therefore, electrolytes containing phosphate species are used in a large number of applications. However, the effect of phosphate on platinum surface modification with nickel deposits has not been studied yet. In this work, new data about the interaction of phosphate with nickel adatoms deposited on Pt(111) at pH 5 is investigated using cyclic voltammetry and infrared spectroscopy. The results show that, when nickel is in solution, the phosphate ions are adsorbed at lower potentials than in the absence of nickel. In addition, Laser-Induced Temperature Jump Technique demonstrates that nickel facilitates the adsorption of phosphate because of a shift of the potential of zero charge (pzc) toward negative potentials. This increases the magnitude of the positive electric field on the electrode surface, at a given potential E>pzc, facilitating the adsorption of anions. CO displacement technique has been also employed to obtain additional information about co-adsorbed phosphate on nickel adlayers. Finally, the HER has been studied at pH 5 in the presence of nickel, with and without phosphate in the bulk solution.