Embedding Covalency into Metal Catalysts for Efficient Electrochemical Conversion of CO_2

CO_2 conversion is an essential technology to develop a sustainable carbon economy for the present and the future. Many studies have focused extensively on the electrochemical conversion of CO_2 into various useful chemicals. However, there is not yet a solution of sufficiently high enough efficiency and stability to demonstrate practical applicability. In this work, we use first-principles-based high-throughput screening to propose silver-based catalysts for efficient electrochemical reduction of CO_2 to CO while decreasing the overpotential by 0.4–0.5 V. We discovered the covalency-aided electrochemical reaction (CAER) mechanism in which p-block dopants have a major effect on the modulating reaction energetics by imposing partial covalency into the metal catalysts, thereby enhancing their catalytic activity well beyond modulations arising from d-block dopants. In particular, sulfur or arsenic doping can effectively minimize the overpotential with good structural and electrochemical stability. We expect this work to provide useful insights to guide the development of a feasible strategy to overcome the limitations of current technology for electrochemical CO_2 conversion

Solution-processed near-infrared Cu(In,Ga)(S,Se)(2) photodetectors with enhanced chalcopyrite crystallization and bandgap grading structure via potassium incorporation

Although solution-processed Cu(In,Ga)(S,Se)(2) (CIGS) absorber layers can potentially enable the low-cost and large-area production of highly stable electronic devices, they have rarely been applied in photodetector applications. In this work, we present a near-infrared photodetector functioning at 980 nm based on solution-processed CIGS with a potassium-induced bandgap grading structure and chalcopyrite grain growth. The incorporation of potassium in the CIGS film promotes Se uptake in the bulk of the film during the chalcogenization process, resulting in a bandgap grading structure with a wide space charge region that allows improved light absorption in the near-infrared region and charge carrier separation. Also, increasing the Se penetration in the potassium-incorporated CIGS film leads to the enhancement of chalcopyrite crystalline grain growth, increasing charge carrier mobility. Under the reverse bias condition, associated with hole tunneling from the ZnO interlayer, the increasing carrier mobility of potassium-incorporated CIGS photodetector improved photosensitivity and particularly external quantum efficiency more than 100% at low light intensity. The responsivity and detectivity of the potassium-incorporated CIGS photodetector reach 1.87 A W-1 and 6.45 x 10(10) Jones, respectively, and the - 3 dB bandwidth of the device extends to 10.5 kHz under 980 nm near-infrared light

Achieving tolerant CO₂ electro-reduction catalyst in real water matrix

In order to achieve practical application of electrochemical CO₂ conversion technologies, the development of durable catalyst in real water matrix is essential because the use of catalysts only showing high performance within a well-refined environment cannot guarantee their feasibility in realistic conditions. Here, we report a design strategy for a catalyst, which shows excellent tolerance to deactivation factors, using a carbon-based material under more practical condition implemented by real tap water. Screening analyses on various components in tap water elucidated that the impurity group, which can be deposited on the catalyst surface and impede the active sites, such as copper, zinc, and especially iron are the main factors responsible for deactivation. Based on these findings, the structural modified nitrogen-doped carbon nanotube (denoted as ball mill N-CNT) was adopted as a catalyst design to secure durability. Consequently, the ball mill N-CNT revealed tolerance to the disclosed deactivation factors and showed stable performance during unprecedented long-time of 120 h in tap water media

Scanning tunneling microscopic studies of SiO2 thin film supported metal nano-clusters

This dissertation is focused on understanding heterogeneous metal catalysts supported on oxides using a model catalyst system of SiO2 thin film supported metal nano-clusters. The primary technique applied to this study is scanning tunneling microscopy (STM). The most important constituent of this model catalyst system is the SiO2 thin film, as it must be thin and homogeneous enough to apply electron or ion based surface science techniques as well as STM. Ultra-thin SiO2 films were successfully synthesized on a Mo(112) single crystal. The electronic and geometric structure of the SiO2 thin film was investigated by STM combined with LEED, Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The relationship between defects on the SiO2 thin film and the nucleation and growth of metal nano-clusters was also investigated. By monitoring morphology changes during thermal annealing, it was found that the metal-support interaction is strongly dependent on the type of metal as well as on the defect density of the SiO2 thin film. Especially, it was found that oxygen vacancies and Si impurities play an important role in the formation of Pd-silicide. By substituting Ti atoms into the SiO2 thin film network, an atomically mixed TiO2-SiO2 thin film was synthesized. Furthermore, these Ti atoms play a role as heterogeneous defects, resulting in the creation of nucleation sites for Au nano-clusters. A marked increase in Au cluster density due to Ti defects was observed in STM. A TiO2-SiO2 thin film consisting of atomic Ti as well as TiOx islands was also synthesized by using higher amounts of Ti (17 %). More importantly, this oxide surface was found to have sinter resistant properties for Au nano-clusters, which are desirable in order to make highly active Au nano-clusters more stable under reaction conditions

Theoretical insights into selective electrochemical conversion of carbon dioxide.

Electrochemical conversion of CO2 and water to valuable chemicals and fuels is one of the promising alternatives to replace fossil fuel-based processes in realizing a carbon-neutral cycle. For practical application of such technologies, suppressing hydrogen evolution reaction and facilitating the activation of stable CO2 molecules still remain major challenges. Furthermore, high production selectivity toward high-value chemicals such as ethylene, ethanol, and even n-propanol is also not easy task to achieve. To settle these challenges, deeper understanding on underlying basis of reactions such as how intermediate binding affinities can be engineered at catalyst surfaces need to be discussed. In this review, we briefly outline recent strategies to modulate the binding energies of key intermediates for CO2 reduction reactions, based on theoretical insights from density functional theory calculation studies. In addition, important design principles of catalysts and electrolytes are also provided, which would contribute to the development of highly active catalysts for CO2 electroreduction

Theoretical insights into selective electrochemical conversion of carbon dioxide

Abstract Electrochemical conversion of CO2 and water to valuable chemicals and fuels is one of the promising alternatives to replace fossil fuel-based processes in realizing a carbon–neutral cycle. For practical application of such technologies, suppressing hydrogen evolution reaction and facilitating the activation of stable CO2 molecules still remain major challenges. Furthermore, high production selectivity toward high-value chemicals such as ethylene, ethanol, and even n-propanol is also not easy task to achieve. To settle these challenges, deeper understanding on underlying basis of reactions such as how intermediate binding affinities can be engineered at catalyst surfaces need to be discussed. In this review, we briefly outline recent strategies to modulate the binding energies of key intermediates for CO2 reduction reactions, based on theoretical insights from density functional theory calculation studies. In addition, important design principles of catalysts and electrolytes are also provided, which would contribute to the development of highly active catalysts for CO2 electroreduction

UV-Curable Polymer-QD Flexible Films as the Downconversion Layer for Improved Performance of Cu(In,Ga)Se2Solar Cells

The downconversion process effectively traps high-energy photons of ultraviolet light and converts them into low-energy photons for utilization in solar cells. In this work, transparent, highly emissive, ultraviolet (UV)-curable nitrogen-functionalized graphene quantum dot-dispersed Norland Optical Adhesive (NOA) nanocomposite (herein denoted as poly-QD film) flexible films were applied as luminescent downconversion (LDC) layers to boost the efficiency of copper indium gallium selenide solar cells. The N-graphene quantum dots (GQDs) were embedded into clear, colorless UV-curable NOA polymer matrices via the clickreaction of thiol-ene components under UV light at room temperature. The best poly-QD film showed a high emission peak of >500 nm and improved external quantum efficiency in the high-energy solar spectrum, resulting in the highest efficiency of ∼9.70% (compared to 8.77% for bare cells), which triggered an ∼10.60% relative performance increment compared to bare copper indium gallium selenide (CIGS) solar cells. Hence, the overall CIGS solar cell performance enhancement caused mainly by Jsc improvement of ∼9.06% (relative enhancement) due to efficient trapping of short-wavelength photons. As-prepared poly-QD films were applied as LDC layers, which significantly boost quantum efficiency in short-wavelength spectra. © 2020 American Chemical Society.1

Electrochemical beta-Selective Hydrocarboxylation of Styrene Using CO2 and Water

The carboxylation of hydrocarbons using CO2 as a one-carbon building block is an attractive route for the synthesis of carboxylic acids and their derivatives. Until now, chemical carboxylation catalyzed by organometallic nucleophiles and reductants has been generally adopted particularly for the precise selectivity control of carboxylation sites. As another approach, electrochemical carboxylation has been attempted but these carboxylation reactions are limited to only a few pathways. In the case of styrene, dicarboxylation at the alpha- and beta-positions is mostly observed with electrochemical carboxylation while site-selective hydrocarboxylations are hardly achieved. In this study, electrochemical beta-selective hydrocarboxylation of styrene using CO2 and water is developed, in which the site selectivity can be precisely controlled between beta-hydrocarboxylation and dicarboxylation without the aid of homogeneous catalysts. In this platform, water is used as proton source in the beta-hydrocarboxylation of styrene where its addition results in significant enhancement of the selectivity toward beta-hydrocarboxylation. This work provides insights into new strategies for site-selectivity-controllable carboxylation with CO2 using an electrochemical platform.N