Heat Capacity of Indium or Gallium Sesqui-Chalcogenides.

The chalcogenides of p-block elements constitute a significant category of materials with substantial potential for advancing the field of electronic and optoelectronic devices. This is attributed to their exceptional characteristics, including elevated carrier mobility and the ability to fine-tune band gaps through solid solution formation. These compounds exhibit diverse structures, encompassing both three-dimensional and two-dimensional configurations, the latter exemplified by the compound In2Se3. Sesqui-chalcogenides were synthesized through the direct reaction of highly pure elements within a quartz ampoule. Their single-phase composition was confirmed using X-ray diffraction, and the morphology and chemical composition were characterized using scanning electron microscopy. The compositions of all six materials were also confirmed using X-ray photoelectron spectroscopy and Raman spectroscopy. This investigation delves into the thermodynamic properties of indium and gallium sesqui-chalcogenides. It involves low-temperature heat capacity measurements to evaluate standard entropies and Tian-Calvet calorimetry to elucidate the temperature dependence of heat capacity beyond the reference temperature of 298.15 K, as well as the enthalpy of formation assessed from DFT calculations.

Applications of Atomic Layer Deposition in Design of Systems for Energy Conversion.

There is a huge demand for clean energy conversion in all industries. The clean energy production processes include electrocatalytic and photocatalytic conversion of water to hydrogen, carbon dioxide reduction, nitrogen conversion to ammonia, and oxygen reduction reaction and require novel cheap and efficient photo- and electrocatalysts and their scalable methods of fabrication. Atomic layer deposition is a thin film deposition method that allows to deposit thin layers of catalysts on virtually any surface of any shape, size, and porosity in an even and easy to control manner. Here the state of the art in applications of atomic layer deposition in the clean energy production and the opportunities it represents for the whole field of the photo- and electrocatalysis for a sustainable future are reviewed.

Two-Dimensional Functionalized Germananes as Photoelectrocatalysts.

Succeeding graphene, monoelemental two-dimensional (2D) materials such as germanene and silicene, coined as "Xenes", have attracted vast scientific and technological interests. Adding covalently bonded hydrogen on both sides of germanene leads to germanane (i.e., hydrogen-terminated germanene, GeH). Further, the covalent functionalization of germanane allows the tuning of its physical and chemical properties. Diverse variants of germananes have been synthesized, but current research is primarily focused on their fundamental properties. As a case in point, their applications as photo- and electrocatalysts in the field of modern energy conversion have not been explored. Here, we prepare 2D germanene-based materials, specifically germanane and germananes functionalized by various alkyl chains with different terminal groups-germanane with methyl, propyl, hydroxypropyl, and 2-(methoxycarbonyl)ethyl-and investigate their structural, morphological, optical, electronic, and electrochemical properties. The bond geometries of the functionalized structures, their formation energies, and band gap values are investigated by density functional theory calculations. The functionalized germananes are tested as photoelectrocatalysts in the hydrogen evolution reaction (HER) and photo-oxidation of water. The performance of the germananes is influenced by the functionalized groups, where the germanane with -CH2CH2CH2OH termination records the lowest HER overpotentials and with -H termination reaches the highest photocurrent densities for water oxidation over the entire visible spectral region. These positive findings serve as an overview of organic functionalization of 2D germananes that can be expanded to other "Xanes" for targeted tuning of the optical and electronic properties for photo- and electrochemical energy conversion applications.

Six-Degree-of-Freedom Steerable Visible-Light-Driven Microsubmarines Using Water as a Fuel: Application for Explosives Decontamination.

Micro/nanomotors are capable of a wide variety of tasks related, i.e., to biomedical or environmental applications. Light-driven semiconductor-based micromotors are especially appealing, as they can split surrounding water via light irradiation, and therefore, they can move infinitely. However, their motion is typically limited to in-plane motion with four degrees of freedom (4DoF) or even pseudo-1D motion with 2DoF. Herein, magnetically steerable tubular TiO2 /Fe3 O4 /CdS micromotors, termed microsubmarines, with 6DoF motion, based on a fuel-free design where surrounding water acts as fuel upon visible light irradiation, are presented, with an average velocity of 7.9 µm s-1 . Besides, the generation of radicals via such water splitting aids the photocatalytic chemicals degradation with the potential to use solar radiation. A light-induced self-electrophoretic mechanism is responsible for the self-propulsion and can be used to predict the motion direction based on the structure and composition. Finally, the TiO2 /Fe3 O4 /CdS microsubmarines are tested in a proof-of-concept application of high-energy explosive, e.g., picric acid, photocatalytic degradation, with the best performance owing to the versatility of 6DoF motion, the surface coating with amorphous TiO2 layer, and UV light. The results can help optimize light-active micromotor design for potential national security and environmental application, hydrogen evolution, and target cargo delivery.

A Maze in Plastic Wastes: Autonomous Motile Photocatalytic Microrobots against Microplastics.

An extremely high quantity of small pieces of synthetic polymers, namely, microplastics, has been recently identified in some of the most intact natural environments, e.g., on top of the Alps and Antarctic ice. This is a "scary wake-up call", considering the potential risks of microplastics for humans and marine systems. Sunlight-driven photocatalysis is the most energy-efficient currently known strategy for plastic degradation; however, attaining efficient photocatalyst-plastic interaction and thus an effective charge transfer in the micro/nanoscale is very difficult; that adds up to the common challenges of heterogeneous photocatalysis including low solubility, precipitation, and aggregation of the photocatalysts. Here, an active photocatalytic degradation procedure based on intelligent visible-light-driven microrobots with the capability of capturing and degrading microplastics "on-the-fly" in a complex multichannel maze is introduced. The robots with hybrid powers carry built-in photocatalytic (BiVO4) and magnetic (Fe3O4) materials allowing a self-propelled motion under sunlight with the possibility of precise actuation under a magnetic field inside the macrochannels. The photocatalytic robots are able to efficiently degrade different synthetic microplastics, particularly polylactic acid, polycaprolactone, thanks to the generated local self-stirring effect in the nanoscale and enhanced interaction with microplastics without using any exterior mechanical stirrers, typically used in conventional systems. Overall, this proof-of-concept study using microrobots with hybrid wireless powers has shown for the first time the possibility of efficient degradation of ultrasmall plastic particles in confined complex spaces, which can impact research on microplastic treatments, with the final goal of diminishing microplastics as an emergent threat for humans and marine ecosystems.

Rhenium Doping of Layered Transition-Metal Diselenides Triggers Enhancement of Photoelectrochemical Activity.

The ever decreasing sources of fossil fuels have launched extensive research of alternative materials that might play a key role in their replacement. Therefore, the scientific community continuously investigates the possibilities of maximizing the working capacity of such materials in order to fulfill energy challenges in the near future. In this context, doping of the semiconducting materials is a versatile strategy to trigger their physicochemical properties as well their electrochemical performance. Herein, the impact of rhenium doping toward photoelectrochemical activity of MoSe2 and WSe2 was studied. Our results indicate that rhenium as a dopant contributes to better overall electrochemical performance, that is, an easier electron transfer of these materials compared to pristine compounds. Additionally, the photoelectrochemical measurements revealed that the doping with rhenium generated an enhancement of the photocurrent response of MoSe2 as well as WSe2 under UV light illumination.

Near-Atomic-Thick Bismuthene Oxide Microsheets for Flexible Aqueous Anodes: Boosted Performance upon 3D → 2D Transition.

Aqueous batteries provide safety, but they usually suffer from low energy and short lifetimes, limiting their use for large-scale energy storage. Two-dimensional materials with infinite lateral dimensions have inherent properties such as high surface area and remarkable power density and cycling stability that are shown to be critical for the next generation of energy storage systems. Here, ultrathin bismuthene oxide with a large aspect ratio is studied as an anode material for rechargeable aqueous metal-ion batteries. The metal oxides are prepared via a novel electrochemical system allowing for a smooth, high-quality transition of bismuthene to bismuthene oxide in a short time. This anodic system is shown to overcome major limiting factors of such batteries, including low capacity and irreversible and unstable redox reactions in aqueous electrolytes. The essential energy storage properties of two-dimensional (2D) microsheets, without the addition of conductive additives and binders, are compared with those of the corresponding three-dimensional (3D) structures. Notably, the battery performance of 2D microsheets is significantly better than that of nanoparticles from all examined aspects, including power density and potential and cycling stability, while exhibiting a capacity density close to their theoretical value. Moreover, 2D microsheets have shown impressive mechanical flexibility related to the ultrathin thickness of individual microsheets and strong interaction between them after film deposition. Combining the excellent energy storage properties of bismuthene oxide, the simple electrode preparation procedure, the inherent flexing characteristic, and the nontoxicity of both the battery material and the electrolyte makes this 2D material an exceptional candidate for large-scale wearable green electronics.

Bismuthene Metallurgy: Transformation of Bismuth Particles to Ultrahigh-Aspect-Ratio 2D Microsheets.

Ultrathin bismuth exhibits promising performance for topological insulators due to its narrow band gap and intrinsic strong spin-orbit coupling, as well as for energy-related applications because of its electronic and mechanical properties. However, large-scale production of 2D sheets via liquid-phase exfoliation as an established large-scale method is restricted by the strong interaction between bismuth layers. Here, a sonication method is utilized to produce ultrahigh-aspect-ratio bismuthene microsheets. The studies on the mechanism excludes the exfoliation of the layered bulk bismuth and formation of the microsheets is attributed to the melting of spherical particles (r = 1.5 µm) at a high temperature-generated under the ultrasonic tip-followed by a recrystallization step producing uniformly-shaped ultrathin microsheets (A = 0.5-2 µm2 , t: ≈2 nm). Notably, although the preparation is performed in oxygenated aqueous solution, the sheets are not oxidized, and they are stable under ambient conditions for at least 1 month. The microsheets are used to construct a vapor sensor using electrochemical impedance spectroscopy as detection technique. The device is highly selective, and it shows long-term stability. Overall, this project exhibits a reproducible method for large-scale preparation of ultrathin bismuthene microsheets in a benign environment, demonstrating opportunities to realize devices based on bismuthene.

Prospects for Functionalizing Elemental 2D Pnictogens: A Study of Molecular Models.

Despite the intense amount of attention and huge potential of 2D-layered pnictogens for applications in chemistry, physics, and materials science, there has yet to be a robust strategy developed to systematically functionalize them to tailor their properties. This is due to a number of factors, including practical instability toward ambient conditions, difficulty in characterizing modified materials, and also more inherent reactivity issues. Here, avenues for functionalization are discussed using examples of molecular models from the wider literature, along with their possible advantages and likely pitfalls. Finally, a critical appraisal of the current field and its future is offered.

Cross-Bridged Cyclam with Phosphonate and Phosphinate Pendant Arms: Chelators for Copper Radioisotopes with Fast Complexation.

Cross-bridged cyclam derivatives bearing two phosphonate (H4L1), bis(phosphinate) (H4L2), or phosphinate (H2L3) pendant arms were synthesized and studied with respect to their application as copper radioisotope carriers in nuclear medicine. The ligands show high macrocycle basicity (pK1 > 14) and high Cu(II) complex stability (log K = 20-24). The complexation and dissociation kinetics of the Cu(II) complexes were studied by ultraviolet-visible spectroscopy. Phosphonate Cu(II)-H4L1 and bis(phosphinate) Cu(II)-H4L2 complexes form very quickly, reaching quantitative formation within 1 s at pH ∼6 and millimolar concentrations. Conversely, the formation of the phosphinate complex Cu(II)-H2L3 is much slower (9 min at pH ∼6) due to the low stability of the out-of-cage reaction intermediate. All studied complexes are highly kinetically inert, showing half-lives of 120, 11, and 111 h for Cu(II)-H4L1, Cu(II)-H4L2, and Cu(II)-H2L3 complexes, respectively, in 1 M HClO4 at 90 °C. The high thermodynamic stability, fast formation, and extreme kinetic inertness of Cu(II) complexes indicate that phosphonate and bis(phosphinate) derivatives are promising ligands for nuclear medicine.

Layered black phosphorus as a reducing agent - decoration with group 10 elements.

Black phosphorus is prone to surface oxidation under ambient conditions. This attribute is often seen as a negative property of this interesting material. However, its proneness to oxidation - thus the reductive properties - can also be employed in modification of its surface and in preparation of composite materials. Here we describe the process of decoration of BP particles with nickel, palladium and platinum in form of a phosphide or in metallic form, respectively. The deposits have forms of films or nanoparticles and the reported method represents a general way of modifying the surface of black phosphorus with metals or their respective compounds for desired applications.

Alkali Metal Arenides as a Universal Synthetic Tool for Layered 2D Germanene Modification.

The rediscovery of graphene in 2004 has started an enormous chase in the research of 2D materials. A new family of layered 2D materials consisting of the 14th group elements beyond carbon has already been reported. Here, a new methodology in germanene chemistry is presented using germanane (Ge6 H6 ) as a stable and easily accessible starting material for effective synthesis of novel germanene derivatives. The modification procedure utilizing strong bases-alkali metal arenides-for deprotonation of germanane and its subsequent functionalization with p-nitrobenzyl bromide is described. Functionalization of germanene is confirmed by FT-IR, Raman, and XPS spectroscopy as well as by X-ray diffraction analysis.

Preserving Fine Structure Details and Dramatically Enhancing Electron Transfer Rates in Graphene 3D-Printed Electrodes via Thermal Annealing: Toward Nitroaromatic Explosives Sensing.

Additive manufacturing (AM) represents one of the nine pillars of the new industrial revolution. Owing to the enthusiastic utilization of this technology by the wider professional and amateur communities, AM is becoming a driving force in the manufacturing sector due to its fast expansion and the availability of cheap and robust 3D printers. The 3D printing, especially the fused deposition modeling (FDM) method, has previously been utilized to fabricate carbon/polylactic acid (PLA) electrodes for electrochemical setups. Such electrodes require activation from their pristine state for improved conductivity, so far achieved by chemical treatment. Herein, a new simple physical thermal annealing method to activate graphene-based PLA electrodes is presented. The graphene/PLA electrodes are fabricated via FDM 3D printing using a commercial graphene-polymer composite conductive filament and subjected to thermal and chemical activation with a subsequent electrochemical pre-treatment. The thermally annealed electrodes exhibit faster electron transfer than the chemically activated or non-treated electrodes in the inner sphere redox probe ferro/ferricyanide. The thermally activated graphene/PLA electrodes are also successfully employed as a low-cost alternative to nitroaromatic explosive sensors. This chemical-free activation method is a facile, fast, and simple route to activate conductive carbon/PLA 3D prints, which increases the electric conductivity and preserves the fine details of the printed objects, making this activation method relevant to a broad range of applied fields utilizing conductive polymer composites.

Chemotactic Micro- and Nanodevices.

Preparation of autonomous chemotactic micro- and nanomachines represents one of the most difficult challenges of modern materials science. To construct a device mimicking the behavior of many microorganisms, which evolved their chemotactic abilities during the millennia of evolution, places extreme demands on the imagination and abilities of researchers. However, with the chemotactic devices in hand, many novel and interesting applications of micromachines could be implemented. The introduction of an autonomous navigation, independent of the external control with electric, magnetic, or electromagnetic field is crucial for applications in environmental remediation and might be advantageous in medical applications. This Minireview summarizes the development in the field of chemotactic micro- and nanomachines, describes the trends in their construction, and compares the different approaches to their construction considering the areas of possible application of the devices.

Fluorographene and Graphane as an Excellent Platform for Enzyme Biocatalysis.

The application of enzymes is a crucial issue for current biotechnological application in pharmaceutical, as well as food and cosmetic industry. Effective platforms for enzyme immobilization are necessary for their industrial use in various biosynthesis procedures. Such platforms must provide high yield of immobilization and retain high activity at various conditions for their large-scale applications. Graphene derivatives such as hydrogenated graphene (graphane) and fluorographene can be applied for enzyme immobilization with close to 100 % yield that can result to activities of the composites significantly exceeding activity of free enzymes. The hydrophobic properties of graphene stoichiometric derivatives allowed for excellent non-covalent bonding of enzymes and their use in various organic solvents. The immobilized enzymes retain their high activities even at elevated temperatures. These findings show excellent application potential of enzyme biocatalysts immobilized on graphene stoichiometric derivatives.

Products of Degradation of Black Phosphorus in Protic Solvents.

Deterioration of the surface of black phosphorus (BP) caused by ambient atmosphere is an undesired process, limiting broader use of BP in many areas. The mechanism of BP degradation was explained theoretically, and the oxidized materials were thoroughly characterized experimentally. However, the surface analysis techniques introduce only a limited insight into the real state of the material. Here, we report a thorough analysis of the composition of mixtures obtained after a prolonged exposure of suspensions of BP to atmospheric oxygen with the aim to further disclosure the processes involved in the decomposition process. The results are compared with the predicted structures of the oxidized material and confirm the results of the theoretical calculations. The comparison of reactivity of BP with reactivity of white phosphorus under similar conditions concludes a similar distribution of the products in both cases.

Mechanism of Surface Alkylation of a Gold Aerogel with Tetra-n-butylstannane-d36: Identification of Byproducts.

The formation of self-assembled monolayers on surfaces is often likely to be accompanied by the formation of byproducts, whose identification holds clues to the reaction mechanism but is difficult due to the minute amounts produced. We now report a successful identification of self-assembly byproducts using gold aerogel with a large specific surface area, a procedure likely to be applicable generally. Like a thin gold layer on a flat substrate, the aerogel surface is alkylated with n-butyl-d9 groups upon treatment with a solution of tetra-n-butylstannane-d36 under ambient conditions. The reaction byproducts accumulate in the mother liquor in amounts sufficient for GC-MS analysis. In chloroform solvent, they are butene-d8, butane-d10, octane-d18, and tributylchlorostannane-d27. In hexane, they are the same except that tributylchlorostannane-d27 is replaced with hexabutyldistannane-d54. The results are compatible with an initial homolytic dissociation of a C-Sn bond on the gold surface, followed by known radical processes.

Fluorographene Modified by Grignard Reagents: A Broad Range of Functional Nanomaterials.

Fluorographene is the youngest stoichiometric derivative of graphene; hence, its reactivity is only poorly explored. Compared to graphene, the significantly higher reactivity of C-F bonds makes this material a suitable platform for a large number of chemical modifications. Fluorographene is also the only member of the halographene family that can be prepared in the stoichiometric composition (C1 F1 ). Herein, the chemical modification of fluorographene with Grignard reagents, which are well known in organic synthesis for the formation of new C-C bonds, is presented. The reaction with alkyl magnesium bromides led to successful modification of fluorographene with ethyl, vinyl, ethynyl and propargyl groups. Chemical characterisation showed the presence of covalently bonded functional groups in a high concentration exceeding one functional group per C6 motif. The reactivity of Grignard reagents with fluorographene decreased from ethyl to ethynyl. The terminal carbon-carbon triple bonds were used for click reactions with organic azides leading to the formation of triazole rings. These findings open up a broad spectrum of opportunities for simple and robust modification of graphene by chemical reactions proceeding at room temperature under mild conditions. These results have major application potential in sensing, biomedical and energy-related applications.

Metal Complexes with Very Large Dipole Moments: the Anionic Carborane Nitriles 12-NC-CB11X11(-) (X = H, F, CH3) as Ligands on Pt(II) and Pd(II).

The anionic nitriles 1-R-12-NC-CB11H10(-) (R = H, CH3, I, COOH), 12-NC-1-H-CB11Me10(-), and 12-NC-1-H-CB11F10(-) were prepared, and three of them were examined for complex formation with (Et3P)2Pt(II) and (Et3P)2Pd(II). Several stable internally charge-compensated zwitterionic complexes were obtained and characterized. RI-BP86/SV(P) calculations suggest that their dipole moments exceed 20 D. An attempt to measure the dipole moments in solution failed due to insufficient solubility in solvents of low polarity.

Thermodynamic and kinetic study of scandium(III) complexes of DTPA and DOTA: a step toward scandium radiopharmaceuticals.

Diethylenetriamine-N,N,N',N'',N''-pentaacetic acid (DTPA) and 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) scandium(III) complexes were investigated in the solution and solid state. Three (45)Sc NMR spectroscopic references suitable for aqueous solutions were suggested: 0.1 M Sc(ClO4)3 in 1 M aq. HClO4 (δSc =0.0 ppm), 0.1 M ScCl3 in 1 M aq. HCl (δSc =1.75 ppm) and 0.01 M [Sc(ox)4](5-) (ox(2-) = oxalato) in 1 M aq. K2C2O4 (δSc =8.31 ppm). In solution, [Sc(dtpa)](2-) complex (δSc = 83 ppm, Δν = 770 Hz) has a rather symmetric ligand field unlike highly unsymmetrical donor atom arrangement in [Sc(dota)](-) anion (δSc = 100 ppm, Δν = 4300 Hz). The solid-state structure of K8[Sc2(ox)7]⋅13 H2O contains two [Sc(ox)3](3-) units bridged by twice "side-on" coordinated oxalate anion with Sc(3+) ion in a dodecahedral O8 arrangement. Structures of [Sc(dtpa)](2-) and [Sc(dota)](-) in [(Hguanidine)]2[Sc(dtpa)]⋅3 H2O and K[Sc(dota)][H6 dota]Cl2⋅4 H2O, respectively, are analogous to those of trivalent lanthanide complexes with the same ligands. The [Sc(dota)](-) unit exhibits twisted square-antiprismatic arrangement without an axial ligand (TSA' isomer) and [Sc(dota)](-) and (H6 dota)(2+) units are bridged by a K(+) cation. A surprisingly high value of the last DOTA dissociation constant (pKa =12.9) was determined by potentiometry and confirmed by using NMR spectroscopy. Stability constants of scandium(III) complexes (log KScL 27.43 and 30.79 for DTPA and DOTA, respectively) were determined from potentiometric and (45)Sc NMR spectroscopic data. Both complexes are fully formed even below pH 2. Complexation of DOTA with the Sc(3+) ion is much faster than with trivalent lanthanides. Proton-assisted decomplexation of the [Sc(dota)](-) complex (τ1/2 =45 h; 1 M aq. HCl, 25 °C) is much slower than that for [Ln(dota)](-) complexes. Therefore, DOTA and its derivatives seem to be very suitable ligands for scandium radioisotopes.