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Plasmonic chiral nanostructures provide a novel route for extraordinary optical properties, such as light polarization control and enhancing chiroptical signals of molecules. The symmetry of chiral nanostructures, such as helices, gyroids, and irregular tetrahedrons, is strongly correlated to chiroptical responses; therefore, it is an important design parameter. In a previous study, a synthetic strategy is demonstrated for 432‐symmetric chiral gold nanoparticles by breaking the mirror symmetry of a 4/m3¯$\overline 3 $ 2/m‐symmetric crystal structure on a high‐index surface. Herein, the aim is to extend the chiral symmetry of gold nanoparticles and their chiroptical responses. The symmetry of gold nanoparticles can be modulated by inducing single or multiple twin planes in seed nanoparticles. The 32‐symmetric chiral gold nanoplates, referred to as 32 helicoids, are successfully synthesized using 3 2/m‐symmetric triangular and hexagonal plates. The growth mechanism of the 32 helicoids, which results in two different characteristic morphologies, is analyzed. The 32 helicoids are significantly important owing to their optical activity over a wide range from the visible to the near‐infrared region. This investigation provides an insight that symmetry control of the nanomorphology can represent an important research direction in chiral plasmonic applications. [ABSTRACT FROM AUTHOR]

Finding a novel method to generate a chiral plasmonic material has been highlighted in the last decades for its unique light‐matter interactions. Recently, an aqueous based peptide directed synthesis of chiral plasmonic gold nanoparticle with exceptional chiroptic response has been reported. Especially, the facile and precise control of chirality using biomolecules allows potential expansion of chiral metamaterial synthesis. In this work, we show a significant enhancement of chiroptic response by simultaneous introduction of multiple bio‐molecular chiral modifiers, glutathione and homooligonucleotide containing thymine. Compared to previously synthesized single chiral plasmonic nanoparticles using only glutathione molecules, further addition of an oligonucleotide into the growth solution induces a two‐fold increase of dissymmetric factor. We believe that the presented synthetic method proposes an effective route of chiral metamaterial morphology and property control for versatile applications. [ABSTRACT FROM AUTHOR]

An electrokinetic analysis of electrochemical CO2 reduction reactions provides information about the decoupled involvement of electron–proton transfer from the Tafel slope and reaction order analyses. Conventionally, a one-electron transfer to CO2 and a chemical proton transfer from HCO3− have been considered to be typical rate-limiting steps. These suggested reaction mechanisms are justified under several assumptions: (1) the bicarbonate ion is a major proton donor, (2) the gaseous CO2 is a carbon source, (3) the reaction mechanism is unaffected by the applied potentials outside the Tafel region, etc. However, recent electrokinetic studies combined with in situ and isotopic experiments raise a question that the above conventional assumptions may not always be valid. Furthermore, there are unresolved issues between the mechanisms suggested by electrokinetic studies. In this review, reported reaction mechanisms of the CO2 reduction reaction are summarized with CO and HCOO− formation as model reaction systems. The reaction pathways are also discussed with a theoretical consideration. A deep investigation into the mechanisms reveals the complex feature of reaction pathways and the difficulty in suggesting the mechanism solely from an electrokinetic analysis. [ABSTRACT FROM AUTHOR]

In manufacturing C-N bond-containing compounds, it is an important challenge to alternate the conventional methodologies that utilize reactive substrates, toxic reagents, and organic solvents. In this study, we developed an electrochemical method to synthesize a C-N bond-containing molecule avoiding the use of cyanides and amines by harnessing nitrate (NO 3 - ) as a nitrogen source in an aqueous electrolyte. In addition, we utilized oxalic acid as a carbon source, which can be obtained from electrochemical conversion of CO 2. Thus, our approach can provide a route for the utilization of anthropogenic CO 2 and nitrate wastes, which cause serious environmental problems including global warming and eutrophication. Interestingly, the coreduction of oxalic acid and nitrate generated reactive intermediates, which led to C-N bond formation followed by further reduction to an amino acid, namely, glycine. By carefully controlling this multireduction process with a fabricated Cu-Hg electrode, we demonstrated the efficient production of glycine with a faradaic efficiency (F.E.) of up to 43.1 % at -1.4 V vs. Ag/AgCl (current density≈90 mA cm -2 )., (© 2021 Wiley-VCH GmbH.)

Chirality is a basic property of nature and has great importance in photonics, biochemistry, medicine, and catalysis. This importance has led to the emergence of the chiral inorganic nanostructure field in the last two decades, providing opportunities to control the chirality of light and biochemical reactions. While the facile production of 3D nanostructures has remained a major challenge, recent advances in nanocrystal synthesis have provided a new pathway for efficient control of chirality at the nanoscale by transferring molecular chirality to the geometry of nanocrystals. Interestingly, this discovery stems from a purely crystallographic outcome: chirality can be generated on high-Miller-index surfaces, even for highly symmetric metal crystals. This is the starting point herein, with an overview of the scientific history and a summary of the crystallographic definition. With the advance of nanomaterial synthesis technology, high-Miller-index planes can be selectively exposed on metallic nanoparticles. The enantioselective interaction of chiral molecules and high-Miller-index facets can break the mirror symmetry of the metal nanocrystals. Herein, the fundamental principle of chirality evolution is emphasized and it is shown how chiral surfaces can be directly correlated with chiral morphologies, thus serving as a guide for researchers in chiral catalysts, chiral plasmonics, chiral metamaterials, and photonic devices., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO 2 reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO 2 conversion and, ultimately, achieve a carbon-neutral cycle., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrocatalytic conversion of CO 2 into a long-chain hydrocarbon represents an important research direction in adding value to CO 2 -based chemicals and realizing its practical application. Long-chain hydrocarbons may change the current fossil fuel-based industry in that those chemicals have a similar energy density as gasoline, high compatibility with the current infrastructure, and low hydroscopicity for pipeline distribution. However, most of the electrocatalysts produce C 1 , C 2 , and C 3 chemicals, and methods for producing long-chain hydrocarbons are not available thus far. Interestingly, nature utilizes many enzymes to generate long-chain hydrocarbons using C 2 building blocks and suggests key mechanisms, inspiring new perspective in the design of electrocatalysts. In this Perspective, we present case studies to demonstrate how CO 2 and its reductive derivatives interact with the electrode surface during C-C bond formation and introduce how these issues are addressed in biological systems. We end this Perspective by outlining possible strategies to translate the natural mechanism into a heterogeneous electrode.