In situ Raman reveals the critical role of Pd in electrocatalytic CO2 reduction to CH4 on Cu-based catalysts.

Electrocatalytic CO2 reduction reaction (CO2RR) for CH4 production presents a promising strategy to address carbon neutrality, and the incorporation of a second metal has been proven effective in enhancing catalyst performance. Nevertheless, there remains limited comprehension regarding the fundamental factors responsible for the improved performance. Herein, the critical role of Pd in electrocatalytic CO2 reduction to CH4 on Cu-based catalysts has been revealed at a molecular level using in situ surface-enhanced Raman spectroscopy (SERS). A "borrowing" SERS strategy has been developed by depositing Cu-Pd overlayers on plasmonic Au nanoparticles to achieve the in situ monitoring of the dynamic change of the intermediate during CO2RR. Electrochemical tests demonstrate that Pd incorporation significantly enhances selectivity toward CH4 production, and the Faradaic efficiency (FE) of CH4 is more than two times higher than that for the catalysts without Pd. The key intermediates, including *CO2-, *CO, and *OH, have been directly identified under CO2RR conditions, and their evolution with the electrochemical environments has been determined. It is found that Pd incorporation promotes the activation of both CO2 and H2O molecules and accelerates the formation of abundant active *CO and hydrogen species, thus enhancing the CH4 selectivity. This work offers fundamental insights into the understanding of the molecular mechanism of CO2RR and opens up possibilities for designing more efficient electrocatalysts.

Robust Organic Radical Molecular Junctions Using Acetylene Terminated Groups for C-Au Bond Formation.

Organic paramagnetic and electroactive molecules are attracting interest as core components of molecular electronic and spintronic devices. Currently, further progress is hindered by the modest stability and reproducibility of the molecule/electrode contact. We report the synthesis of a persistent organic radical bearing one and two terminal alkyne groups to form Au-C σ bonds. The formation and stability of self-assembled monolayers and the electron transport through single-molecule junctions at room temperature have been studied. The combined analysis of both systems demonstrates that this linker forms a robust covalent bond with gold and a better-defined contact when compared to traditional sulfur-based linkers. Density functional theory and quantum transport calculations support the experimental observation highlighting a reduced variability of conductance values for the C-Au based junction. Our findings advance the quest for robustness and reproducibility of devices based on electroactive molecules.

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry.

A novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved.

Transport Matters: Boosting CO2 Electroreduction in Mixtures of [BMIm][BF4 ]/Water by Enhanced Diffusion.

Room-temperature ionic liquids (RTILs) are promising new electrolytes for efficient carbon dioxide reduction. However, due to their high viscosity, the mass transport of CO2 in RTILs is typically slow, at least one order of magnitude slower than in aqueous systems. One possibility to improve mass transport in RTILs is to decrease their viscosity through dilution with water. Herein, defined amounts of water are added to 1-butyl-3methylimidazolium tetrafluoroborate ([BMIm][BF4 ]), which is a hydrophilic RTIL. Electrochemical measurements on quiescent and hydrodynamic systems both indicate enhanced CO2 electroreduction. This enhancement has its origin in thermodynamic/kinetic effects (the addition of water increases the availability of H+ , which is a reaction partner of CO2 electroreduction) and in an increased rate of transport due to lower viscosity. Electrochemically determined diffusion coefficients for CO2 in [BMIm][BF4 ]/water systems agree well with values determined by NMR spectroscopy.

Single Graphene Layer on Pt(111) Creates Confined Electrochemical Environment via Selective Ion Transport.

Graphene is a promising candidate for an ideal membrane material. Its ultralow (one-atomic) thickness potentially provides high permeation and at the same time high selectivity. Here, it is shown that these properties can be used to create a confined, two-dimensional electrochemical environment between a graphene layer and a single-crystal Pt(111) surface. The well-defined fingerprint voltammetric characteristics of Pt(111) provide an immediate information about the penetration and intercalation of ions into the confined space. These processes are shown to be highly selective.

A redox-active radical as an effective nanoelectronic component: stability and electrochemical tunnelling spectroscopy in ionic liquids.

A redox-active persistent perchlorotriphenylmethyl (PTM) radical chemically linked to gold exhibits stable electrochemical activity in ionic liquids. Electrochemical tunnelling spectroscopy in this medium demonstrates that the PTM radical shows a highly effective redox-mediated current enhancement, demonstrating its applicability as an active nanometer-scale electronic component.

Break junction under electrochemical gating: testbed for single-molecule electronics.

Molecular electronics aims to construct functional molecular devices at the single-molecule scale. One of the major challenges is to construct a single-molecule junction and to further manipulate the charge transport through the molecular junction. Break junction techniques, including STM break junctions and mechanically controllable break junctions are considered as testbed to investigate and control the charge transport on a single-molecule scale. Moreover, additional electrochemical gating provides a unique opportunity to manipulate the energy alignment and molecular redox processes for a single-molecule junction. In this review, we start from the technical aspects of the break junction technique, then discuss the molecular structure-conductance correlation derived from break junction studies, and, finally, emphasize electrochemical gating as a promising method for the functional molecular devices.

In Situ Monitoring of Electrooxidation Processes at Gold Single Crystal Surfaces Using Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy.

Identifying the intermediate species in an electrocatalytic reaction can provide a great opportunity to understand the reaction mechanism and fabricate a better catalyst. However, the direct observation of intermediate species at a single crystal surface is a daunting challenge for spectroscopic techniques. In this work, electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) is utilized to in situ monitor the electrooxidation processes at atomically flat Au(hkl) single crystal electrode surfaces. We systematically explored the effects of crystallographic orientation, pH value, and anion on electrochemical behavior of intermediate (AuOH/AuO) species. The experimental results are well correlated with our periodic density functional theory calculations and corroborate the long-standing speculation based on theoretical calculations in previous electrochemical studies. The presented in situ electrochemical SHINERS technique offers a unique way for a real-time investigation of an electrocatalytic reaction pathway at various well-defined noble metal surfaces.

Electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy: correlating structural information and adsorption processes of pyridine at the Au(hkl) single crystal/solution interface.

Electrochemical methods are combined with shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) for a comprehensive study of pyridine adsorption on Au(111), Au(100) and Au(110) single crystal electrode surfaces. The effects of crystallographic orientation, pyridine concentration, and applied potential are elucidated, and the formation of a second pyridine adlayer on Au(111) is observed spectroscopically for the first time. Electrochemical and SHINERS results correlate extremely well throughout this study, and we demonstrate the potential of EC-SHINERS for thorough characterization of processes occurring on single crystal surfaces. Our method is expected to open up many new possibilities in surface science, electrochemistry and catalysis. Analytical figures of merit are discussed.

Electrochemical CO2 Reduction - A Critical View on Fundamentals, Materials and Applications.

The electrochemical reduction of CO(2) has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO(2) in water, the maximum CO(2) reduction current which could be drawn falls in the range of 0.01-0.02 A cm(-2). This is at least an order of magnitude lower current density than the requirement to make CO(2)-electrolysis a technically and economically feasible option for transformation of CO(2) into chemical feedstock or fuel thereby closing the CO(2) cycle. This work attempts to give a short overview on the status of electrochemical CO(2) reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

DNA-Grafted Supramolecular Polymers: Helical Ribbon Structures Formed by Self-Assembly of Pyrene-DNA Chimeric Oligomers.

The controlled arraying of DNA strands on adaptive polymeric platforms remains a challenge. Here, the noncovalent synthesis of DNA-grafted supramolecular polymers from short chimeric oligomers is presented. The oligomers are composed of an oligopyrenotide strand attached to the 5'-end of an oligodeoxynucleotide. The supramolecular polymerization of these oligomers in an aqueous medium leads to the formation of one-dimensional (1D) helical ribbon structures. Atomic force and transmission electron microscopy show rod-like polymers of several hundred nanometers in length. DNA-grafted polymers of the type described herein will serve as models for the development of structurally and functionally diverse supramolecular platforms with applications in materials science and diagnostics.

Electrochemical control of single-molecule conductance by Fermi-level tuning and conjugation switching.

Controlling charge transport through a single molecule connected to metallic electrodes remains one of the most fundamental challenges of nanoelectronics. Here we use electrochemical gating to reversibly tune the conductance of two different organic molecules, both containing anthraquinone (AQ) centers, over >1 order of magnitude. For electrode potentials outside the redox-active region, the effect of the gate is simply to shift the molecular energy levels relative to the metal Fermi level. At the redox potential, the conductance changes abruptly as the AQ unit is oxidized/reduced with an accompanying change in the conjugation pattern between linear and cross conjugation. The most significant change in conductance is observed when the electron pathway connecting the two electrodes is via the AQ unit. This is consistent with the expected occurrence of destructive quantum interference in that case. The experimental results are supported by an excellent agreement with ab initio transport calculations.

Promising anchoring groups for single-molecule conductance measurements.

The understanding of the charge transport through single molecule junctions is a prerequisite for the design and building of electronic circuits based on single molecule junctions. However, reliable and robust formation of such junctions is a challenging task to achieve. In this topical review, we present a systematic investigation of the anchoring group effect on single molecule junction conductance by employing two complementary techniques, namely scanning tunneling microscopy break junction (STM-BJ) and mechanically controllable break junction (MCBJ) techniques, based on the studies published in the literature and important results from our own work. We compared conductance studies for conventional anchoring groups described earlier with the molecular junctions formed through π-interactions with the electrode surface (Au, Pt, Ag) and we also summarized recent developments in the formation of highly conducting covalent Au-C σ-bonds using oligophenyleneethynylene (OPE) and an alkane molecular backbone. Specifically, we focus on the electron transport properties of diaryloligoyne, oligophenyleneethynylene (OPE) and/or alkane molecular junctions composed of several traditional anchoring groups, (dihydrobenzo[b]thiophene (BT), 5-benzothienyl analogue (BTh), thiol (SH), pyridyl (PY), amine (NH2), cyano (CN), methyl sulphide (SMe), nitro (NO2)) and other anchoring groups at the solid/liquid interface. The qualitative and quantitative comparison of the results obtained with different anchoring groups reveals structural and mechanistic details of the different types of single molecular junctions. The results reported in this prospective may serve as a guideline for the design and synthesis of molecular systems to be used in molecule-based electronic devices.

Special aspects of total hip arthroplasty in patients with proximal femur pseudarthrosis.

Introduction: The rate of proximal femur fractures (PFF) in the structure of musculoskeletal system injuries among all fractures of long bones ranges from 3.9 to 18%. According to Russian Ministry of Health 2020 data, the incidence of femoral fractures in Russia was up to 61 cases per 100,000 population (90,000 per year); and femoral neck fractures incidence was 4 times higher among people over 75 years of age. The choice of surgical technique and the fixator used depend on many factors, such as fracture location and its nature, the age of the patient, comorbidities, and the quality of bone tissue. Internal osteosynthesis, is the current treatment method of choice for extra-articular proximal femur fracture, but every treatment method has its limitations. a significant number of complications caused by technical errors, vicious union or nonunion with the subsequent development of false joints, the development of femoral head aseptic necrosis, which leads to coxarthrosis and persistent pain syndrome. To solve the above-described problems, it is necessary to use a conversion surgery - total hip replacement. Objectives: long-term analysis of the results of total hip replacement in patients with proximal femur pseudarthrosis. Methods: The study was based on clinical and laboratory data analysis and on the results of total hip arthroplasty (THA) in 45 patients aged 56-84 years (mean age 68.3), including 32 (71.1%) women and 13 (26.1%) men. 12 patients initially received conservative treatment, and 33 patients received initial surgical treatment using various metal osteosynthesis procedures. The time from osteosynthesis or from the moment of injury to admission to the hospital for hip arthroplasty ranged from 12 to 30 months. All patients, before conversion arthroplasty and after discharge, were repeatedly invited to the clinical diagnostic department for a clinical examination and for assessment using rating scales. 3, 6 and 12 months after the surgery, pain syndrome and patient quality of life were assessed using the following questionnaire scales: Harris Hip Score, MOS SF-36, VAS. The maximum follow-up period ranged from 12 to 60 months. Results: Based on the results obtained, patients of all 4 groups after conversion arthroplasty noted a significant quality of life improvement, a decrease in pain severity and functional results improvement. This was probably due to the presence of a severe limitation of range of movements in the joint, intense pain, absence of support ability of the extremity, as well as low operative efficacy expectations.In 1 (2%) patient, acute PJI was diagnosed in the early postoperative period, followed by sepsis and death.In 4 patients (9%) the result was considered unsatisfactory. At 1 year of follow-up after surgery, they complained of pain and claudication in the operated joint.3 (6%) patients underwent reduction of dislocation. Conclusions: Strict adherence to the recommended treatment algorithm for patients with proximal femur pseudarthrosis made it possible to achieve good treatment results in 90% of surgically treated patients. An important step in the treatment of this patients is a careful preoperative planning with thorough assessment of bone tissue quality and muscles condition in the proximal femur area, allowing to choose the optimal endoprosthesis components.

A new approach to the studies of submicron particle suspensions based on the effect of pressure in capillary zone electrophoresis.

A new approach based on the effect of pressure in CZE is suggested for acceleration of particle migration in electrophoretic runs resulting in reduction of the analysis time. It provides conditions for studying fast processes in suspensions. The effect of pressure on the migration of silica spheres with average diameters of 100, 150, and 390 nm was studied by CZE at an applied voltage of 25 kV. The particle hydrodynamic behavior was also investigated under the same capillary dimensions and BGE composition. The total particle mobility (excluding the average flow rate) was found to increase with increasing the pressure applied and particle size. The particle migration mechanism explaining the effect of pressure on particle velocity was shown to be almost the same as in wide-bore hydrodynamic chromatography. It is based on changing radial distribution of particle concentration along the capillary cross section depending on particle diffusivity. On the basis of this mechanism appearance of a zone of negatively charged particles in electropherograms ahead of the marker peak can be explained.

Formation of two-dimensional supramolecular polymers by amphiphilic pyrene oligomers.

Reading the bands: Amphiphilic pyrene trimers self-assemble into two-dimensional, supramolecular polymers in aqueous medium. Folding and aggregation processes are accompanied by simultaneous development of J- and H-bands and significant changes in the fluorescence properties. The formation of sheet-like nano-structures is confirmed by AFM.

Effective perspiration is essential to uphold the stability of zero-gap MEA-based cathodes used in CO2 electrolysers.

The application of gas diffusion electrodes (GDEs) for the electrochemical reduction of CO2 to value-added products creates the possibility of achieving current densities of a few hundred mA cm-2. To achieve stable operation at such high reaction rates remains, however, a challenging task, due to the flooding of the GDE. In order to mitigate flooding in a zero-gap membrane-electrode assembly (MEA) configuration, paths for effective electrolyte perspiration inside the GDE structure have to be kept open during the electrolysis process. Here we demonstrate that apart from the operational parameters of the electrolysis and the structural properties of the supporting gas diffusion layers, also the chemical composition of the applied catalyst inks can play a decisive role in the electrolyte management of GDEs used for CO2 electroreduction. In particular, the presence of excess amounts of polymeric capping agents (used to stabilize the catalyst nanoparticles) can lead to a blockage of micropores, which hinders perspiration and initiates the flooding of the microporous layer. Here we use a novel ICP-MS analysis-based approach to quantitatively monitor the amount of perspired electrolyte that exits a GDE-based CO2 electrolyser, and we show a direct correlation between the break-down of effective perspiration and the appearance of flooding-the latter ultimately leading to a loss of electrolyser stability. We recommend the use of an ultracentrifugation-based approach by which catalyst inks containing no excess amount of polymeric capping agents can be formulated. Using these inks, the stability of electrolyses can be ensured for much longer times.

Conformationally controlled electron delocalization in n-type rods: synthesis, structure, and optical, electrochemical, and spectroelectrochemical properties of dicyanocyclophanes.

A series of dicyanobiphenylcyclophanes 1-6 with various π-backbone conformations and characteristic n-type semiconductor properties is presented. Their synthesis, optical, structural, electrochemical, spectroelectrochemical, and packing properties are investigated. The X-ray crystal structures of all n-type rods allow the systematic correlation of structural features with physical properties. In addition, the results are supported by quantum mechanical calculations based on density functional theory. A two-step reduction process is observed for all n-type rods, in which the first step is reversible. The potential gap between the reduction processes depends linearly on the cos(2) value of the torsion angle φ between the π-systems. Similarly, optical absorption spectroscopy shows that the vertical excitation energy of the conjugation band correlates with the cos(2) value of the torsion angle φ. These correlations demonstrate that the fixed intramolecular torsion angle φ is the dominant factor determining the extent of electron delocalization in these model compounds, and that the angle φ measured in the solid-state structure is a good proxy for the molecular conformation in solution. Spectroelectrochemical investigations demonstrate that conformational rigidity is maintained even in the radical anion form. In particular, the absorption bands corresponding to the SOMO-LUMO+i transitions are shifted bathochromically, whereas the absorption bands corresponding to the HOMO-SOMO transition are shifted hypsochromically with increasing torsion angle φ.

Oxo-functionalised mesoionic NHC nickel complexes for selective electrocatalytic reduction of CO2 to formate.

Strategies for the conversion of CO2 to valuable products are paramount for reducing the environmental risks associated with high levels of this greenhouse gas and offer unique opportunities for transforming waste into useful products. While catalysts based on nickel as an Earth-abundant metal for the sustainable reduction of CO2 are known, the vast majority produce predominantly CO as a product. Here, efficient and selective CO2 reduction to formate as a synthetically valuable product has been accomplished with novel nickel complexes containing a tailored C,O-bidentate chelating mesoionic carbene ligand. These nickel(ii) complexes are easily accessible and show excellent catalytic activity for electrochemical H+ reduction to H2 (from HOAc in MeCN), and CO2 reduction (from CO2-saturated MeOH/MeCN solution) with high faradaic efficiency to yield formate exclusively as an industrially and synthetically valuable product from CO2. The most active catalyst precursor features the 4,6-di-tert-butyl substituted phenolate triazolylidene ligand, tolerates different proton donors including water, and reaches an unprecedented faradaic efficiency of 83% for formate production, constituting the most active and selective Ni-based system known to date for converting CO2 into formate as an important commodity chemical.

A General and Facile Approach for the Electrochemical Reduction of Carbon Dioxide Inspired by Deep Eutectic Solvents.

Deep eutectic solvents (DESs) were applied to the electrochemical CO2 reduction reaction (CO2 RR). Choline-based DESs represent a non-toxic and inexpensive alternative to room-temperature ionic liquids (RTILs) as additives to the system or as electrolyte. Following the study on choline-based DESs this approach was generalized and simple and organic-soluble systems were devised based on the combination of organic chloride salts with ethylene glycol (EG), allowing the chlorides to be readily used as cocatalysts in the CO2 RR. This approach negates the need for anion exchange and, because the chloride salt is usually the least expensive one, substantially reduces the cost of the electrolyte and opens the way for high-throughput experimentation.