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Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO2 (eCO2R); yet further improvements are required for their wide-scale deployment in carbon mitigation efforts. Here, we systematically investigate a family of dilute Cu-based alloys to explore their viability as active and selective catalysts for eCO2R through a combined theoretical–experimental approach. Using a quantum–classical modeling approach that accounts for dynamic solvation effects, we assess the stability and activity of model single-atom catalysts under eCO2R conditions. Our calculations identify that the presence of eCO2R intermediates, such as CO*, H*, and OH*, may dynamically influence the local catalyst surface composition. Additionally, we identify through binding energy descriptors of the CO*, CHO*, and OCCO* dimer intermediates that certain elements, such as group 13 elements (B, Al, and Ga), enhance the selectivity of C2+ species relative to pure Cu by facilitating CO dimerization. The theoretical work is corroborated by preliminary testing of eCO2R activity and selectivity of candidate dilute Cu-based alloy catalyst films prepared by electron beam evaporation in a zero-gap gas diffusion electrode-based reactor. Of all studied alloys, dilute CuAl was found to be the most active and selective toward C2+ products like ethylene, consistent with the theoretical predictions. We attribute the improved performance of dilute CuAl alloys to more favorable dimerization reaction energetics of bound CO species relative to that on pure Cu. In a broader context, the results presented here demonstrate the power of our simulation framework in terms of rational catalyst design. [ABSTRACT FROM AUTHOR]

Aqueous supercapacitors are among the most promising materials for clean and renewable energy storage; however, their utilization for applications is limited by their low specific energy arising from issues due to water splitting. Herein, water splitting-inactive electrode materials of mesoporous carbon were fabricated through the dehalogenation of polyvinylidene fluoride (PVDF) by sodium ethoxide (EtONa). The as-generated EtOH and NaF were demonstrated to facilitate the formation of hierarchical porous carbon based on the bubble and templating effects. Due to full dehalogenation, the resulting carbon materials acquired high contents of carbon without unfavorable alien dopants. The resulting porous, dehalogenated, carbon materials were applied as electrode materials for an aqueous supercapacitor neutral electrolyte. The significantly suppressed water-splitting activity has been addressed in the electrochemical system. Therefore, the open circuit voltage (OCV) could be safely expanded to 2.0 V. Over 94.0% of the capacitance was also maintained after cycling 5000 times at 5.0 A g−1. Our strategy that utilizes water-splitting inactive electrode materials to expand the working window of an aqueous supercapacitor may enable the design of materials for aqueous supercapacitors with higher OCVs over 2.0 V. [ABSTRACT FROM AUTHOR]

An amorphous Co-doped MoS2 coated highly crystalline pyrite-phase CoS2 hierarchical nanoarray exhibits ultrahigh activity towards acidic hydrogen evolution with a low onset potential (∼44 mV) and a small overpotential of ∼110.5 mV for driving the current density of ∼10 mA cm−2, ascribed to its novel hierarchical structure and the Co doping caused synergistic effects. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) are a family of high-profile layer materials with tunable metal species and interlayer spacing, and herein the LDHs are first investigated as bifunctional electrocatalysts. It is found that trinary LDH containing nickel, cobalt, and iron (NiCoFe-LDH) shows a reasonable bifunctional performance, while exploiting a preoxidation treatment can significantly enhance both oxygen reduction reaction and oxygen evolution reaction activity. This phenomenon is attributed to the partial conversion of Co2+ to Co3+ state in the preoxidation step, which stimulates the charge transfer to the catalyst surface. The practical application of the optimized material is demonstrated with a small potential hysteresis (800 mV for a reversible current density of 20 mA cm−2) as well as a high stability, exceeding the performances of noble metal catalysts (commercial Pt/C and Ir/C). The combination of the electrochemical metrics and the facile and cost-effective synthesis endows the trinary LDH as a promising bifunctional catalyst for a variety of applications, such as next-generation regenerative fuel cells or metal-air batteries. [ABSTRACT FROM AUTHOR]

Fluorine-doped hierarchical porous single-crystal rutile TiO2 nanorods have been synthesized through a silica template method, in which F− ions acts as both n-type dopants and capping agents to make the isotropic growth of the nanorods. The combination of high crystallinity, abundant surface reactive sites, large porosity, and improved electronic conductivity leads to an excellent photoelectrochemical activity. The photoanode made of F-doped porous single crystals displays a remarkably enhanced solar-to-hydrogen conversion efficiency (≈0.35 % at −0.33 V vs. Ag/AgCl) under 100 mW cm−2 of AM=1.5 solar simulator illumination that is ten times of the pristine solid TiO2 single crystals. [ABSTRACT FROM AUTHOR]

In this work, we report a facile and nontoxic one-pot hydrothermal method for synthesizing F-doped rutile single crystalline TiO2 with tuneable solar absorption. The optical band gap of the catalyst can be easily manipulated from 3.05 to 2.58 eV via altering the initial F : Ti molar ratio of reaction precursors. The photoanodes made of rutile TiO2 single crystals with appropriate F-doping concentration show excellent photoelectrocatalytic activity towards water oxidation under ultraviolet and visible light illumination. The best photoelectrocatalytic performance under UV irradiation can be obtained by F-doped TiO2 with an initial F : Ti molar ratio of 0.1, which is almost 15 times higher than that of un-doped TiO2. Further, the F-doped TiO2 photoanodes also exhibit superior photoelectrocatalytic activity under visible irradiation, and the best performance can be achieved by F-doped TiO2 photoanode with an initial F : Ti molar ratio of 0.05. The superior photoelectrocatalytic activity could be attributed to the highly n-type dopant introduced by fluorine, which significantly tunes the electrical conductivities and band structures of the resulting TiO2 photoanodes, and thus the photoelectrocatalytic activities under both UV and visible irradiation. Different techniques have been employed to characterize the electrical conductivity, charge carrier density and band structures of the F-doped rutile TiO2 films, such as photoelectrochemical method, electrical impedance spectroscopy (EIS) measurements, Mott–Schottky plots and XPS valence band spectra. [ABSTRACT FROM AUTHOR]

Semiconductor nanowires are promising for photovoltaic applications, but, so far, nanowire-based solar cells have had lower efficiencies than planar cells made from the same materials, even allowing for the generally lower light absorption of nanowires. It is not clear, therefore, if the benefits of the nanowire structure, including better charge collection and transport and the possibility of enhanced absorption through light trapping, can outweigh the reductions in performance caused by recombination at the surface of the nanowires and at p-n junctions. Here, we fabricate core-shell nanowire solar cells with open-circuit voltage and fill factor values superior to those reported for equivalent planar cells, and an energy conversion efficiency of ?5.4%, which is comparable to that of equivalent planar cells despite low light absorption levels. The device is made using a low-temperature solution-based cation exchange reaction that creates a heteroepitaxial junction between a single-crystalline CdS core and single-crystalline Cu2S shell. We integrate multiple cells on single nanowires in both series and parallel configurations for high output voltages and currents, respectively. The ability to produce efficient nanowire-based solar cells with a solution-based process and Earth-abundant elements could significantly reduce fabrication costs relative to existing high-temperature bulk material approaches. [ABSTRACT FROM AUTHOR]

• Scalable fabrication of nanoporous copper powders through ball milling and dealloying. • Nanoporous copper powder catalysts for electrochemical CO 2 reduction in a commercially relevant MEA electrolyzer. • Peak ethylene Faradaic efficiency of 34% at 75-100 mA/cm2 with a hydrogen Faradaic efficiency below 30%. • Bridges the gap between lab-scale ECR catalyst development and the need of an emerging ECR industry. Electrochemical CO 2 reduction (ECR) is a promising technology to close the anthropic CO 2 circle using renewable energy to achieve carbon neutrality. Future commercialization of ECR will require the development of new catalyst synthesis routes that will allow significant upscaling of catalyst production from current research-level milligram quantities to the kilogram scale and beyond while maintaining the activity and selectivity demonstrated at the research level. In this work, we report on generating and testing submicron-sized nanoporous copper (npCu) particles by using a scalable approach consisting of ball milling brittle Cu-based intermetallics followed by dealloying to add nanoporosity for high surface area. The resulting npCu particles have been tested in an industry-relevant large area (25 cm2) electrolyzer platform and showed Faraday efficiencies (FE) for ethylene up to 34 % at current densities of 75−100 mA/cm2 while keeping FE for hydrogen less than 30 %. Our results demonstrate that a combination of ball milling and dealloying is a promising approach to generate large quantities of high activity and high surface area npCu particles for ECR at an industry-relevant scale. [ABSTRACT FROM AUTHOR]