Electrochemical Synthesis of Sound: Hearing the Electrochemical Double Layer.

Electrochemical double layers (EDLs) govern the operation of batteries, fuel cells, electrochemical sensors, and electrolyzers. However, their invisible nature makes their properties and function difficult to conceptualize, creating an impediment to the broader understanding of double-layer function required for future technologies in energy storage and chemical synthesis. To render the behavior of electrochemical interfaces more intuitive, we made the rearrangement of interfacial components audible by employing the EDL as a variable element in a relaxation oscillator circuit. Connecting the circuit to a speaker generated an audible output corresponding to the change in potential resulting from EDL rearrangement. Variations in the applied voltage, electrolyte concentration and identity, as well as in the electrode material, yielded audible frequency variations that provide an intuitive understanding of EDL behavior. We expect that hearing the trends in behavior will provide a helpful and alternative method for understanding molecular movement at the electrochemical interface.

Mind the Interface: The Role of Adsorption in Electrocatalysis.

In the field of electrocatalysis, significant emphasis has been placed on developing electrode materials to enable critical energy storage reactions and sustainable chemical synthesis. However, the electrode is just one part of a complex interfacial environment that controls substrate adsorption and reactivity. In the presence of a liquid electrolyte and an electrochemical interface, adsorption processes behave substantially differently than those in the gas phase. Understanding these adsorption processes, which play an important role in all electrocatalytic reactions, is critical for the design of effective electrocatalysts. In this Perspective, we discuss the current understanding of electrochemical adsorption and its implications for catalyst design.

Insight into the Role of Entropy in Promoting Electrochemical CO2 Reduction by Imidazolium Cations.

The electroreduction of CO2 plays an important role in achieving a net-zero carbon economy. Imidazolium cations can be used to enhance the rate of CO2 reduction reactions, but the origin of this promotion remains poorly understood. In this work, we show that in the presence of 1-ethyl-3-methylimidazolium (EMIM+), CO2 reduction on Ag electrodes occurs with an apparent activation energy near zero, while the applied potential influences the rate through the pre-exponential factor. Our findings suggest that the CO2 reduction rate is controlled by the initial state entropy, which depends on the applied potential through the organization of cations at the electrochemical interface. Further characterization shows that the C2-proton of EMIM+ is consumed during the reaction, leading to the collapse of the cation organization and a decrease in the catalytic performance. Our results have important implications for understanding the effect of potential on reaction rates, as they indicate that the common picture based on vibrational activation of electron transfer reactions is insufficient for describing the impact of potential in complex systems, such as CO2 reduction in the presence of imidazolium cations.

Electrocatalytic Scission of Unactivated C(sp3)-C(sp3) Bonds through Real-Time Manipulation of Surface-Bound Intermediates.

Electrocatalysis plays a critical role in future technologies for energy storage and sustainable synthesis, but the scope of reactions achievable using electricity remains limited. Here, we demonstrate an electrocatalytic approach to cleave the C(sp3)-C(sp3) bond in ethane at room temperature over a nanoporous Pt catalyst. This reaction is enabled by time-dependent electrode potential sequences, combined with monolayer-sensitive in situ analysis, which allows us to gain independent control over ethane adsorption, oxidative C-C bond fragmentation, and reductive methane desorption. Importantly, our approach allows us to vary the electrode potential to promote the fragmentation of ethane after it is bound to the catalyst surface, resulting in unprecedented control over the selectivity of this alkane transformation reaction. Steering the transformation of intermediates after adsorption constitutes an underexplored lever of control in catalysis. As such, our findings widen the parameter space for catalytic reaction engineering and open the door to future sustainable synthesis and electrocatalytic energy storage technologies.

Competition between H and CO for Active Sites Governs Copper-Mediated Electrosynthesis of Hydrocarbon Fuels.

The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO2 . Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface-affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH4 and H2 production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate-limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis.

All Solution-Processed, Hybrid Organic-Inorganic Photocathode for Hydrogen Evolution.

Nowadays, the efficient, stable, and scalable conversion of solar energy into chemical fuels represents a great scientific, economic, and ethical challenge. Amongst the available candidate technologies, photoelectrochemical water-splitting potentially has the most promising technoeconomic trade-off between cost and efficiency. However, research on semiconductors and photoelectrode architectures suitable for H2 evolution has focused mainly on the use of fabrication techniques and inorganic materials that are not easily scalable. Here, we report for the first time an all solution-processed approach for the fabrication of hybrid organic/inorganic photocathodes based on organic semiconductor bulk heterojunctions that exhibit promising photoelectrochemical performance. The sequential deposition of inorganic material, charge-selective contacts, visible-light sensitive organic polymers, and earth-abundant, nonprecious catalyst by spin coating leads to state-of-the-art photoelectrochemical parameters, comprising a high onset potential [+0.602 V vs reversible hydrogen electrode (RHE)] and a positive maximum power point (+0.222 V vs RHE), a photocurrent density as high as 5.25 mA/cm2 at 0 V versus RHE, an incident photon-to-current conversion efficiency at 0 V versus RHE of above 35%, and 100% faradaic efficiency for hydrogen production. The demonstrated all solution-processed hybrid photoelectrodes represent an eligible candidate for the scalable and low-cost solar-to-H2 conversion technology that embodies the feasibility requirements for large area, plant-scale applications.

Molecular Engineering of Potent Sensitizers for Very Efficient Light Harvesting in Thin-Film Solid-State Dye-Sensitized Solar Cells.

Dye-sensitized solar cells (DSSCs) have shown significant potential for indoor and building-integrated photovoltaic applications. Herein we present three new D-A-π-A organic sensitizers, XY1, XY2, and XY3, that exhibit high molar extinction coefficients and a broad absorption range. Molecular modifications of these dyes, featuring a benzothiadiazole (BTZ) auxiliary acceptor, were achieved by introducing a thiophene heterocycle as well as by shifting the position of BTZ on the conjugated bridge. The ensuing high molar absorption coefficients enabled the fabrication of highly efficient thin-film solid-state DSSCs with only 1.3 µm mesoporous TiO2 layer. XY2 with a molar extinction coefficient of 6.66 × 10(4) M(-1) cm(-1) at 578 nm led to the best photovoltaic performance of 7.51%.

New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO2 on a Silver Electrode.

The electrochemical reduction of CO2 to CO is a reaction of central importance for sustainable energy conversion and storage. Herein, structure-activity relationships of a series of imidazolium-based cocatalysts for this reaction are described, which demonstrate that the C4- and C5-protons on the imidazolium ring are vital for efficient catalysis. Further investigation of these findings led to the discovery of new imidazolium salts, which show superior activity as cocatalysts for the reaction, i.e., CO is selectively produced at significantly lower overpotentials with nearly quantitative faradaic yields for CO.

Cu2O Nanowire Photocathodes for Efficient and Durable Solar Water Splitting.

Due to its abundance, scalability, and nontoxicity, Cu2O has attracted extensive attention toward solar energy conversion, and it is the best performing metal oxide material. Until now, the high efficiency devices are all planar in structure, and their photocurrent densities still fall well below the theoretical value of 14.5 mA cm(-2) due to the incompatible light absorption and charge carrier diffusion lengths. Nanowire structures have been considered as a rational and promising approach to solve this issue, but due to various challenges, performance improvements through the use of nanowires have rarely been achieved. In this work, we develop a new synthetic method to grow Cu2O nanowire arrays on conductive fluorine-doped tin oxide substrates with well-controlled phase and excellent electronic and photonic properties. Also, we introduce an innovative blocking layer strategy to enable high performance. Further, through material engineering by combining a conformal nanoscale p-n junction, durable protective overlayer, and uniform catalyst decoration, we have successfully fabricated Cu2O nanowire array photocathodes for hydrogen generation from solar water splitting delivering unprecedentedly high photocurrent densities of 10 mA cm(-2) and stable operation beyond 50 h, establishing a new benchmark for metal oxide based photoelectrodes.

Covalent Immobilization of a Molecular Catalyst on Cu2O Photocathodes for CO2 Reduction.

Sunlight-driven CO2 reduction is a promising way to close the anthropogenic carbon cycle. Integrating light harvester and electrocatalyst functions into a single photoelectrode, which converts solar energy and CO2 directly into reduced carbon species, is under extensive investigation. The immobilization of rhenium-containing CO2 reduction catalysts on the surface of a protected Cu2O-based photocathode allows for the design of a photofunctional unit combining the advantages of molecular catalysts with inorganic photoabsorbers. To achieve large current densities, a nanostructured TiO2 scaffold, processed at low temperature, was deposited on the surface of protected Cu2O photocathodes. This led to a 40-fold enhancement of the catalytic photocurrent as compared to planar devices, resulting in the sunlight-driven evolution of CO at large current densities and with high selectivity. Potentiodynamic and spectroelectrochemical measurements point toward a similar mechanism for the catalyst in the bound and unbound form, whereas no significant production of CO was observed from the scaffold in the absence of a molecular catalyst.

Low-Temperature Atomic Layer Deposition of Crystalline and Photoactive Ultrathin Hematite Films for Solar Water Splitting.

We developed a low-temperature atomic layer deposition route to deposit phase pure and crystalline hematite (α-Fe2O3) films at 230 °C without the need for postannealing. Homogenous and conformal deposition with good aspect ratio coverage was demonstrated on a nanostructured substrate and analyzed by transmission electron microscopy. These as-deposited α-Fe2O3 films were investigated as photoanodes for photoelectrochemical water oxidation and found to be highly photoactive. Combined with a TiO2 underlayer and a low-cost Ni(OH)2 catalyst, hematite films of less than 10 nm in thickness reached photocurrent densities of 0.3 mA cm(-2) at 1.23 V vs RHE and a photocurrent onset potential of less than 0.9 V vs RHE, previously unseen for films this thin and without high temperature annealing. In a thickness-dependent photoelectrochemical analysis, we identified a hematite thickness of only 10 nm to yield the highest internal quantum efficiency when using a suitable underlayer such as TiO2 that induces doping of the hematite film and reduces electron/hole recombination at the back contact. We find that, at high bias potentials, photocurrent density and quantum efficiency proportionally increase with light absorption in films thinner than 10 nm and are limited by the space charge layer width in thicker films. Thus, we propose to apply hematite films of 10 nm in thickness for future developments on suitable nanostructured conductive scaffolds that can now be extended to organic scaffolds due to our low-temperature process.

Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics.

Artificial photosynthesis, mimicking nature in its efforts to store solar energy, has received considerable attention from the research community. Most of these attempts target the production of H2 as a fuel and our group recently demonstrated solar-to-hydrogen conversion at 12.3% efficiency. Here, in an effort to take this approach closer to real photosynthesis, which is based on the conversion of CO2, we demonstrate the efficient reduction of CO2 to carbon monoxide driven solely by simulated sunlight using water as the electron source. Employing series-connected perovskite photovoltaics and high-performance catalyst electrodes, we reach a solar-to-CO efficiency exceeding 6.5%, which represents a new benchmark in sunlight-driven CO2 conversion. Considering hydrogen as a secondary product, an efficiency exceeding 7% is observed. Furthermore, this study represents one of the first demonstrations of extended, stable operation of perovskite photovoltaics, whose large open-circuit voltage is shown to be particularly suited for this process.

Solution transformation of Cu2O into CuInS2 for solar water splitting.

Though Cu2O has demonstrated high performance as a photocathode for solar water splitting, its band gap is too large for efficient use as the bottom cell in tandem configurations. Accordingly, copper chalcopyrites have recently attracted much attention for solar water splitting due to their smaller and tunable band gaps. However, their fabrication is mainly based on vacuum evaporation, which is an expensive and energy consuming process. Here, we have developed a novel and low-cost solution fabrication method, and CuInS2 was chosen as a model material due to its smaller band gap compared to Cu2O and relatively simple composition. The nanostructured CuInS2 electrodes were synthesized at low temperature in crystalline form by solvothermal treatment of electrochemically deposited Cu2O films. Following the coating of overlayers and decoration with Pt catalyst, the as-fabricated CuInS2 electrode demonstrated water splitting photocurrents of 3.5 mA cm(-2) under simulated solar illumination. To the best of our knowledge, this is the highest performance yet reported for a solution-processed copper chalcopyrite electrode for solar water splitting. Furthermore, the electrode showed good stability and had a broad incident photon-to-current efficiency (IPCE) response to wavelengths beyond 800 nm, consistent with the smaller bandgap of this material.

Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts.

Although sunlight-driven water splitting is a promising route to sustainable hydrogen fuel production, widespread implementation is hampered by the expense of the necessary photovoltaic and photoelectrochemical apparatus. Here, we describe a highly efficient and low-cost water-splitting cell combining a state-of-the-art solution-processed perovskite tandem solar cell and a bifunctional Earth-abundant catalyst. The catalyst electrode, a NiFe layered double hydroxide, exhibits high activity toward both the oxygen and hydrogen evolution reactions in alkaline electrolyte. The combination of the two yields a water-splitting photocurrent density of around 10 milliamperes per square centimeter, corresponding to a solar-to-hydrogen efficiency of 12.3%. Currently, the perovskite instability limits the cell lifetime.

Carbon nanotubes as electronic interconnects in solid acid fuel cell electrodes.

Carbon nanotubes have been explored as interconnects in solid acid fuel cells to improve the link between nanoscale Pt catalyst particles and macroscale current collectors. The nanotubes were grown by chemical vapor deposition on carbon paper substrates, using nickel nanoparticles as the catalyst, and were characterized using scanning electron microscopy and Raman spectroscopy. The composite electrode material, consisting of CsH2PO4, platinum nanoparticles, and platinum on carbon-black nanoparticles, was deposited onto the nanotube-overgrown carbon paper by electrospraying, forming a highly porous, fractal structure. AC impedance spectroscopy in a symmetric cell configuration revealed a significant reduction of the electrode impedance as compared to similarly prepared electrodes without carbon nanotubes.