Faraday Discussions最新文献

A general theory of coupled ion–electron transfer (CIET) is presented, which unifies Marcus kinetics of electron transfer (ET) with Butler–Volmer kinetics of ion transfer (IT). In the limit of large reorganization energy, the theory predicts normal Marcus kinetics of “electron-coupled ion transfer” (ECIT). In the limit of large ion transfer energies, the theory predicts Butler–Volmer kinetics of “ion-coupled electron transfer” (ICET), where the charge transfer coefficient and exchange current are connected to microscopic properties of the electrode/electrolyte interface. In the ICET regime, the reductive and oxidative branches of Tafel’s law are predicted to hold over a wide range of overpotentials, bounded by the ion-transfer energies for oxidation and reduction, respectively. The probability distribution of transferring electron energies in CIET smoothly interpolates between a shifted Gaussian distribution for ECIT (as in the Gerischer–Marcus theory of ET) to an asymmetric, fat-tailed Meixner distribution centered at the Fermi level for ICET. The latter may help interpret asymmetric line shapes in x-ray photo-electron spectroscopy (XPS) and Auger electron spectroscopy (AES) for metal surfaces in terms of shake-up relaxation of the ionized atom and its image polaron by ICET. In the limit of large overpotentials, the theory predicts a transition to inverted Marcus ECIT, leading to a universal reaction-limited current for metal electrodes, dominated by barrierless quantum transitions. Uniformly valid, closed-form asymptotic approximations are derived that smoothly transition between the limiting rate expressions for ICET and ECIT for metal electrodes, using simple but accurate mathematical functions. The theory is applied to lithium intercalation in lithium iron phosphate (LFP) and found to provide a consistent description of the observed current dependence on overpotential, temperature and concentration. CIET theory thus provides a critical bridge between quantum electrochemistry and electrochemical engineering, which may find many other applications and extensions.

Gradients of voltage, pressure, temperature, and salinity can transport objects in micro- and nanofluidic systems by well-known mechanisms. This paper explores the dynamics of particles in a viscosity gradient with numerical simulations. The different stochastic rules used to integrate the random motion of Brownian particles affect the steady-state distribution of particles in a diffusivity gradient. Importantly, the simulations illuminate the important role that the boundary conditions play, disallowing a steady-state flux when the boundary conditions mimic those of a closed container, but allowing flux when they mimic electrodes. These results provide an interpretation for measurements of a steady ionic current flowing between electrodes separated by a nanofluidic channel with a liquid viscosity gradient.

In many practical applications, ions are the primary charge carrier and must move through either semipermeable membranes or through pores, which mimic ion channels in biological systems. In analogy to electronic devices, the “iontronic” ones use electric fields to induce the charge motion. However, unlike the electrons that move through a conductor, motion of ions is usually associated with simultaneous solvent flow. A study of electroosmotic flow through narrow pores is an outstanding challenge that lies at the interface of non-equilibrium statistical mechanics and fluid dynamics. In this paper, we will review recent works that use dissipative particle dynamics simulations to tackle this difficult problem. We will also present a classical density functional theory (DFT) based on the hypernetted-chain approximation (HNC), which allows us to calculate the velocity of electroosmotic flows inside nanopores containing 1 : 1 or 2 : 1 electrolyte solution. The theoretical results will be compared with simulations. In simulations, the electrostatic interactions are treated using the recently introduced pseudo-1D Ewald summation method. The zeta potentials calculated from the location of the shear plane of a pure solvent are found to agree reasonably well with the Smoluchowski equation. However, the quantitative structure of the fluid velocity profiles deviates significantly from the predictions of the Smoluchowski equation in the case of charged pores with 2 : 1 electrolyte. For low to moderate surface charge densities, the DFT allows us to accurately calculate the electrostatic potential profiles and the zeta potentials inside the nanopores. For pores with 1 : 1 electrolyte, the agreement between theory and simulation is particularly good for large ions, for which steric effects dominate over the ionic electrostatic correlations. The electroosmotic flow is found to depend very strongly on the ionic radii. In the case of pores containing 2 : 1 electrolyte, we observe a reentrant transition in which the electroosmotic flow first reverses and then returns to normal as the surface change density of the pore is increased.

The activation of dinitrogen as a fundamental step in reactions to produce nitrogen compounds, including ammonia and nitrates, has a cornerstone role in chemistry. Bringing together research from disparate fields where this can be achieved sustainably, this Faraday Discussion seeks to build connections between approaches that can stimulate further advances. In this paper we set out to provide an overview of these different approaches and their commonalities. We explore experimental aspects including the positive role of increasing nitrogen pressure in some fields, as well as offering perspectives on when ¹⁵N₂ experiments might, and might not, be necessary. Deconstructing the nitrogen reduction reaction, we attempt to provide a common framework of energetic scales within which all of the different approaches and their components can be understood. On sustainability, we argue that although green ammonia produced from a green-H₂-fed Haber–Bosch process seems to fit the bill, there remain many real-world contexts in which other, sustainable, approaches to this vital reaction are urgently needed.

We report on a combined experimental and theoretical investigation of the N(²D) + C₆H₆ (benzene) reaction, which is of relevance in the aromatic chemistry of the atmosphere of Titan. Experimentally, the reaction was studied (i) under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy (E_c) of 31.8 kJ mol⁻¹ to determine the primary products, their branching fractions (BFs), and the reaction micromechanism, and (ii) in a continuous supersonic flow reactor to determine the rate constant as a function of temperature from 50 K to 296 K. Theoretically, electronic structure calculations of the doublet C₆H₆N potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction mechanism. The reaction is found to proceed via barrierless addition of N(²D) to the aromatic ring of C₆H₆, followed by formation of several cyclic (five-, six-, and seven-membered ring) and linear isomeric C₆H₆N intermediates that can undergo unimolecular decomposition to bimolecular products. Statistical estimates of product BFs on the theoretical PES were carried out under the conditions of the CMB experiments and at the temperatures relevant for Titan’s atmosphere. In all conditions the ring-contraction channel leading to C₅H₅ (cyclopentadienyl) + HCN is dominant, while minor contributions come from the channels leading to o-C₆H₅N (o-N-cycloheptatriene radical) + H, C₄H₄N (pyrrolyl) + C₂H₂ (acetylene), C₅H₅CN (cyano-cyclopentadiene) + H, and p-C₆H₅N + H. Rate constants (which are close to the gas kinetic limit at all temperatures, with the recommended value of 2.19 ± 0.30 × 10⁻¹⁰ cm³ s⁻¹ over the 50–296 K range) and BFs have been used in a photochemical model of Titan’s atmosphere to simulate the effect of the title reaction on the species abundances as a function of the altitude.

The efficient synthesis of ammonia using carbon-footprint-free hydrogen under mild conditions is a grand challenge in chemistry today. To achieve this objective, novel concepts are needed for the activation process and catalyst. This article briefly reviews catalytic activation of N₂ for ammonia synthesis under mild conditions. The features of the various activation methods reported so far are summarized, looking chronologically back at progress in heterogeneous catalysts since the use of iron oxide for the Haber–Bosch process, and finally the technical challenges to be overcome are described. Establishing low work functions for the support materials of the metal catalysts is one key to reducing the activation barrier to dissociate N₂. Surfaces of electride materials that preserve the character of the bulk are shown to be useful for this purpose. The requirements of desired catalysts are high efficiency at low temperatures, Ru-free compositions, and chemical robustness in the ambient atmosphere.

Nitrogen fixation has a rich history within the inorganic chemistry community. In recent years attention has (re)focused on developing electrocatalytic systems capable of mediating the nitrogen reduction reaction (N₂RR). Well-defined molecular catalyst systems have much to offer in this context. This personal perspective summarizes recent progress from our laboratory at Caltech, pulling together lessons learned from a number of studies we have conducted, placing them within the broader context of thermodynamic efficiency and selectivity for the N₂RR. In particular, proton-coupled electron transfer (PCET) provides an attractive strategy to achieve enhanced efficiency for the multi-electron/proton reduction of N₂ to produce NH₃ (or NH₄⁺), and electrocatalytic PCET (ePCET) via an ePCET mediator affords a promising means of mitigating HER such that the N₂RR can be achieved in a catalytic fashion.

Optical methods for monitoring electrochemical reactions at an interface are advantageous because of their table-top setup and ease of integration into reactors. Here we apply EDL-modulation microscopy to one of the main components of amperometric measurement devices: a microelectrode. We present experimental measurements of the EDL-modulation contrast from the tip of a tungsten microelectrode at various electrochemical potentials inside a ferrocene-dimethanol Fe(MeOH)₂ solution. Using the combination of the dark-field scattering microscope and the lock-in detection technique, we measure the phase and amplitude of local ion-concentration oscillations in response to an AC potential as the electrode potential is scanned through the redox-activity window of the dissolved species. We present the amplitude and phase map of this response, as such this method can be used to study the spatial and temporal variations of the ion-flux due to an electrochemical reaction close to metallic and semiconducting objects of general geometry. We discuss the advantages and possible extensions of using this microscopy method for wide-field imaging of ionic currents.

Applying a novel action spectroscopic technique in a 4 K cryogenic ion-trap instrument, the molecule c-C₃H₂D⁺ has been investigated by high-resolution rovibrational and pure rotational spectroscopy for the first time. In total, 126 rovibrational transitions within the fundamental band of the ν₁ symmetric C–H stretch were measured with a band origin centred at 3168.565 cm⁻¹, which were used to predict pure rotational transition frequencies in the ground vibrational state. Based on these predictions, 16 rotational transitions were observed between 90 and 230 GHz by using a double-resonance scheme. These new measurements will enable the first radio-astronomical search for c-C₃H₂D⁺.

Ion interactions with interfaces and transport in confined spaces, where electric double layers overlap, are essential in many areas, ranging from crevice corrosion to understanding and creating nano-fluidic devices at the sub 10 nm scale. Tracking the spatial and temporal evolution of ion exchange, as well as local surface potentials, in such extreme confinement situations is both experimentally and theoretically challenging. Here, we track in real-time the transport processes of ionic species (LiClO₄) confined between a negatively charged mica surface and an electrochemically modulated gold surface using a high-speed in situ sensing Surface Forces Apparatus. With millisecond temporal and sub-micrometer spatial resolution we capture the force and distance equilibration of ions in the confinement of D ≈ 2–3 nm in an overlapping electric double layer (EDL) during ion exchange. Our data indicate that an equilibrated ion concentration front progresses with a velocity of 100–200 μm s⁻¹ into a confined nano-slit. This is in the same order of magnitude and in agreement with continuum estimates from diffusive mass transport calculations. We also compare the ion structuring using high resolution imaging, molecular dynamics simulations, and calculations based on a continuum model for the EDL. With this data we can predict the amount of ion exchange, as well as the force between the two surfaces due to overlapping EDLs, and critically discuss experimental and theoretical limitations and possibilities.