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Electrochemical CO reduction can serve as a sequential step in the transformation of CO2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product.

Electrochemical CO[Formula: see text] reduction is a potential route to the sustainable production of valuable fuels and chemicals. Here, we perform CO[Formula: see text] reduction experiments on Gold at neutral to acidic pH values to elucidate the long-standing controversy surrounding the rate-limiting step. We find the CO production rate to be invariant with pH on a Standard Hydrogen Electrode scale and conclude that it is limited by the CO[Formula: see text] adsorption step. We present a new multi-scale modeling scheme that integrates ab initio reaction kinetics with mass transport simulations, explicitly considering the charged electric double layer. The model reproduces the experimental CO polarization curve and reveals the rate-limiting step to be *COOH to *CO at low overpotentials, CO[Formula: see text] adsorption at intermediate ones, and CO[Formula: see text] mass transport at high overpotentials. Finally, we show the Tafel slope to arise from the electrostatic interaction between the dipole of *CO[Formula: see text] and the interfacial field. This work highlights the importance of surface charging for electrochemical kinetics and mass transport.

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO2 due to their wide electrochemical stability window, low volatility, and high CO2 solubility. There is environmental and economic interest in the direct utilization of the captured CO2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO2, eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO2 with aqueous electrolytes presents limited CO2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO2, often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation. [ABSTRACT FROM AUTHOR]

The presently increasing global population demands increased food production. Consequently, phosphate – an indispensable fertilizer component – will be needed in ever greater amounts. Current levels of mining of phosphate's most important constituent element, phosphorus (P), are unsustainable, and P rock is predicted to soon be completely depleted. Because P is a non‐renewable resource, techniques to recover and reuse waste phosphate are necessary. Large amounts of unused phosphate exist in both municipal and agricultural wastewater streams, as well as in sewage sludge. Approaches to recovering phosphate from these sources fall into three main categories: biological, chemical, and electrochemical. Biological phosphate recovery has seen some plant‐scale use, but significant drawbacks including the complication of operation have prevented it from becoming widespread. The most common method of phosphate recovery, chemical phosphate recovery, has been applied at scale with success due to the stability and reliability of the process. However, disadvantages such as the exorbitant amounts of alkali dosing required to maintain the high pH necessary for phosphate precipitation leave room for improvement. In recent years, electrochemical phosphate recovery has gained traction because of its potential to overcome the weaknesses of traditional chemical approaches by utilizing water electrolysis to induce a high pH without the need for an added base. But before plant‐scale electrochemical methods can be considered economically viable, the steep energy requirements of water electrolysis must be mitigated through the development of improved electrocatalysts or circumvented through the discovery and application of new electrochemical processes to generate hydroxyl ions needed to induce a high pH. In this review, the three broad categories of phosphate recovery techniques are discussed and an outlook on the future of electrocatalysis for phosphate recovery is presented. Particularly, the requirements for improved and Earth‐abundant electrocatalysts are considered alongside a critical discussion of the possibility of a decentralized network of onsite wastewater treatment facilities powered by renewable electricity. [ABSTRACT FROM AUTHOR]

Electrochemical CO reduction can serve as a sequential step in the transformation of CO2 into multicarbon fuels and chemicals. In this study, we provide insights on how to steer selectivity for CO reduction almost exclusively toward a single multicarbon oxygenate by carefully controlling the catalyst composition and its surrounding reaction conditions. Under alkaline reaction conditions, we demonstrate that planar CuAg electrodes can reduce CO to acetaldehyde with over 50% Faradaic efficiency and over 90% selectivity on a carbon basis at a modest electrode potential of -0.536 V vs. the reversible hydrogen electrode. The Faradaic efficiency to acetaldehyde was further enhanced to 70% by increasing the roughness factor of the CuAg electrode. Density functional theory calculations indicate that Ag ad-atoms on Cu weaken the binding energy of the reduced acetaldehyde intermediate and inhibit its further reduction to ethanol, demonstrating that the improved selectivity to acetaldehyde is due to the electronic effect from Ag incorporation. These findings will aid in the design of catalysts that are able to guide complex reaction networks and achieve high selectivity for the desired product. [ABSTRACT FROM AUTHOR]

Coupling of Earth-abundant hydrogen evolution catalysts to photoabsorbers is crucial for the production of hydrogen fuel using sunlight. In this work, we demonstrate the use of magnetron sputtering to deposit Mo2C as an efficient hydrogen evolution reaction catalyst onto surface-protected amorphous silicon (a-Si) photoabsorbers. The a-Si/Mo2C photocathode evolves hydrogen under simulated solar illumination in strongly acidic and alkaline electrolytes. Onsets of photocurrents are observed at potentials as positive as 0.85 V vs RHE. Under AM 1.5G (1 sun) illumination, the photocathodes reach current densities of -11.2 mA cm-2 at the reversible hydrogen potential in 0.1 M H2SO4 and 1.0 M KOH. The high photovoltage and low-cost of the Mo2C/a-Si assembly make it a promising photocathode for solar hydrogen production. [ABSTRACT FROM AUTHOR]