This paper reviews recent progress made in identifying electrocatalysts for carbon dioxide (CO2) reduction to produce low-carbon fuels, including CO, HCOOH/HCOO−, CH2O, CH4, H2C2O4/HC2O4−, C2H4, CH3OH, CH3CH2OH and others. The electrocatalysts are classified into several categories, including metals, metal alloys, metal oxides, metal complexes, polymers/clusters, enzymes and organic molecules. The catalyts' activity, product selectivity, Faradaic efficiency, catalytic stability and reduction mechanisms during CO2 electroreduction have received detailed treatment. In particular, we review the effects of electrode potential, solution–electrolyte type and composition, temperature, pressure, and other conditions on these catalyst properties. The challenges in achieving highly active and stable CO2 reduction electrocatalysts are analyzed, and several research directions for practical applications are proposed, with the aim of mitigating performance degradation, overcoming additional challenges, and facilitating research and development in this area.

A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels

Nanoscale materials are increasingly found in consumer goods, electronics, and pharmaceuticals. While these particles interact with the body in myriad ways, their beneficial and/or deleterious effects ultimately arise from interactions at the cellular and subcellular level. Nanoparticles (NPs) can modulate cell fate, induce or prevent mutations, initiate cell–cell communication, and modulate cell structure in a manner dictated largely by phenomena at the nano–bio interface. Recent advances in chemical synthesis have yielded new nanoscale materials with precisely defined biochemical features, and emerging analytical techniques have shed light on nuanced and context-dependent nano-bio interactions within cells. In this review, we provide an objective and comprehensive account of our current understanding of the cellular uptake of NPs and the underlying parameters controlling the nano-cellular interactions, along with the available analytical techniques to follow and track these processes.

/pdf/cellular-uptake-of-nanoparticles-journey-inside-the-cell-3icse0401r.pdf

Cellular uptake of nanoparticles: journey inside the cell.

Structure and nanostructure in ionic liquids.

The electrochemical reduction of CO2 has gained significant interest recently as it has the potential to trigger a sustainable solar-fuel-based economy. In this Perspective, we highlight several heterogeneous and molecular electrocatalysts for the reduction of CO2 and discuss the reaction pathways through which they form various products. Among those, copper is a unique catalyst as it yields hydrocarbon products, mostly methane, ethylene, and ethanol, with acceptable efficiencies. As a result, substantial effort has been invested to determine the special catalytic properties of copper and to elucidate the mechanism through which hydrocarbons are formed. These mechanistic insights, together with mechanistic insights of CO2 reduction on other metals and molecular complexes, can provide crucial guidelines for the design of future catalyst materials able to efficiently and selectively reduce CO2 to useful products.

Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide

Recent advances in wet chemical synthesis and biomolecular functionalization of gold nanoparticles have led to a dramatic expansion of their potential biomedical applications, including biosensorics, bioimaging, photothermal therapy, and targeted drug delivery. As the range of gold nanoparticle types and their applications continues to increase, human safety concerns are gaining attention, which makes it necessary to better understand the potential toxicity hazards of these novel materials. Whereas about 80 reports on the in vivo biodistribution and in vitrocell toxicity of gold nanoparticles are available in the literature, there is lack of correlation between both fields and there is no clear understanding of intrinsic nanoparticle effects. At present, the major obstacle is the significant discrepancy in experimental conditions under which biodistribution and toxicity effects have been evaluated. This critical review presents a detailed analysis of data on the in vitro and in vivo biodistribution and toxicity of most popular gold nanoparticles, including atomic clusters and colloidal particles of diameters from 1 to 200 nm, gold nanoshells, nanorods, and nanowires. Emphasis is placed on the systematization of data over particle types and parameters, particle surface functionalization, animal and cell models, organs examined, doses applied, the type of particle administration and the time of examination, assays for evaluating gold particle toxicity, and methods for determining the gold concentration in organs and distribution of particles over cells. On the basis of a critical analysis of data, we arrive at some general conclusions on key nanoparticle parameters, methods of particle surface modification, and doses administered that determine the type and kinetics of biodistribution and toxicity at cellular and organismal levels (197 references).

Biodistribution and toxicity of engineered gold nanoparticles: a review of in vitro and in vivo studies

Catalytic Electrochemical Reduction of CO2 in Ionic Liquid EMIMBF3Cl

The ionic conductivity, relative viscosity, and solution enthalpy of LiNTF2 and NaNTF2 solutions in ionic liquid BMINTF2 have been measured. We observed that the conductivity decreased and the viscosity increased when the Li+ and Na+ salts were dissolved in BMINTF2. We also observed that the dissolution is an exothermic process with a solution enthalpy of approximately −18.07 ± 4.61 kJ/mol. The experimental results indicate that the Li+ ion may associate with multiple NTF2− anions in the BMINTF2 solution to form a solvated complex.

Conductivity, Viscosity, and Dissolution Enthalpy of LiNTF2 in Ionic Liquid BMINTF2

In this paper we report a label-free detection method of unmodified DNA using polypyrrole as an immobilization matrix by impedance measurement. A probe and a target complementary DNA sequence specific for the bacterial pathogen, Bacillus cereus are used. Impedance measurements are performed without using additional redox probes. The effects of hybridization and non-specific binding are compared when the Probe DNA molecules were immobilized by two different methods: electrochemical adsorption and entrapment. 
The probe DNA immobilized using electrochemical adsorption yielded better hybridization signals compared to that immobilized using the entrapment method. Control experiments were also performed to prove the specificity of the biosensor in the presence of non complementary DNA. Negligible unspecific binding with the immobilized probe was observed with the electrochemically adsorbed probe, whereas the entrapped probe responded to the non complementary target. The performance of the DNA sensor was characterized using both cyclic voltammetry and impedance spectroscopy techniques and proved to be effective in terms of specificity of hybridization events.

/pdf/comparison-between-dna-immobilization-techniques-on-a-redox-ankcmr16q2.pdf

Comparison Between DNA Immobilization Techniques on a Redox Polymer Matrix

The ferrocene/ferrocenium (Fc/Fc+) redox couple has been deemed one of the best candidates of the standard electrochemical reference for redox reactions in ionic liquids (ILs). To fully reveal the redox reaction mechanism in the IL condensed phase, solvation, as a prerequisite, apparently needs to be understood. As a preliminary attempt to study the solvation of Fc/Fc+ in imidazolium-based ILs, using model complexes, systematic investigations of the intrinsic pair-wise interactions between the solute and solvent ions in the gas phase are performed with B97-D, a dispersion-corrected density functional method. B97-D is carefully benchmarked with available experimental values and high-level ab initio quantum mechanical results for Fc/Fc+ alone and the solvated structures. Present calculations demonstrate dramatically different solvation features for Fc vs. Fc+, e.g., Fc forms direct stable interactions with both solvent cations and anions with binding energies of −11 to −14 kcal mol−1. As an interesting observation, no π-stacking interactions are captured between the imidazolium ring of the solvent cation and the cyclopentadienyl motif of the solute. However, due to the strong electrostatic interactions, Fc+ can only be solvated by solvent anions in the first solvation shell with much stronger binding energies of −72 to −86 kcal mol−1. Binding energies, structures, and electrostatic potentials are all characterized. The electronic structures are further analyzed with the Natural Bond Orbital method. The theoretical calculation results help explain several experimental observations obtained earlier or in the present work, including solubility, diffusion coefficient, and solution conductivity. Due to the involvement of the aromatic structures, the current study also sheds valuable light on π-interactions, in general.

Theoretical investigations of ferrocene/ferrocenium solvation in imidazolium-based room-temperature ionic liquids

Protic ionic liquids (PILs) are promising alternatives to water for swelling Nafion as a fuel cell proton exchange membrane (PEM). PILs can significantly improve the high-temperature performance of a PEM. The proton dissociation and solvation mechanisms in a PIL, which are keys to understanding the proton transportation and conductivity, have not been fully explored. In this paper, we used FTIR, Raman, and electronic spectroscopy with computational simulation techniques to explore the spectroscopic properties of bis(trifluoromethanesulfonyl)imide (HTFSI) solutions in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) ionic liquid at concentrations from ∼0.1 to as high as ∼1.0 M. Solution conductivities were measured at room temperature and elevated temperatures up to ∼65 °C. The solution structure and properties depend on the concentration of HTFSI. At lower concentration, around 0.1 M, the HTFSI solution has higher conductivity than pure BMITFSI. However, the conductivity decreases ...

Conductivity and Spectroscopic Investigation of Bis(trifluoromethanesulfonyl)imide Solution in Ionic Liquid 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide

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