3D Printing of Self-Healing Materials.

This review article presents a comprehensive overview of the latest advances in the field of 3D printable structures with self-healing properties. Three-dimensional printing (3DP) is a versatile technology that enables the rapid manufacturing of complex geometric structures with precision and functionality not previously attainable. However, the application of 3DP technology is still limited by the availability of materials with customizable properties specifically designed for additive manufacturing. The addition of self-healing properties within 3D printed objects is of high interest as it can improve the performance and lifespan of structural components, and even enable the mimicking of living tissues for biomedical applications, such as organs printing. The review will discuss and analyze the most relevant results reported in recent years in the development of self-healing polymeric materials that can be processed via 3D printing. After introducing the chemical and physical self-healing mechanism that can be exploited, the literature review here reported will focus in particular on printability and repairing performances. At last, actual perspective and possible development field will be critically discussed.

Microbial Fuel Cells as Effective Tools for Energy Recovery and Antibiotic Detection in Water and Food.

This work demonstrates that microbial fuel cells (MFCs), optimized for energy recovery, can be used as an effective tool to detect antibiotics in water-based environments. In MFCs, electroactive biofilms function as biocatalysts by converting the chemical energy of organic matter, which serves as the fuel, into electrical energy. The efficiency of the conversion process can be significantly affected by the presence of contaminants that act as toxicants to the biofilm. The present work demonstrates that MFCs can successfully detect antibiotic residues in water and water-based electrolytes containing complex carbon sources that may be associated with the food industry. Specifically, honey was selected as a model fuel to test the effectiveness of MFCs in detecting antibiotic contamination, and tetracycline was used as a reference antibiotic within this study. The results show that MFCs not only efficiently detect the presence of tetracycline in both acetate and honey-based electrolytes but also recover the same performance after each exposure cycle, proving to be a very robust and reliable technology for both biosensing and energy recovery.

Morphology Effects on Electro- and Photo-Catalytic Properties of Zinc Oxide Nanostructures.

Environmental problems are among the most pressing issues in the modern world, including the shortage of clean drinking water partially caused by contamination from various industries and the excessive emission of CO2 primarily from the massive use of fossil fuels. Consequently, it is crucial to develop inexpensive, effective, and environmentally friendly methods for wastewater treatment and CO2 reduction, turning them into useful feedstocks. This study explores a unique method that addresses both challenges by utilizing ZnO, which is recognized as one of the most active semiconductors for photocatalysis, as well as a cost-effective electrocatalyst for the CO2 reduction reaction (CO2RR). Specifically, we investigate the influence of the morphology of various ZnO nanostructures synthesized via different low-cost routes on their photocatalytic properties for degrading the rhodamine-B dye (RhB) and on their electrocatalytic performance for the CO2RR. Our results show that the ZnO lamella morphology achieves the best performance compared to the nanorod and nanoparticle structures. This outcome is likely attributed to the lamella's higher aspect ratio, which plays a critical role in determining the structural, optical, and electrical properties of ZnO.

Optimizing the Performance of Low-Loaded Electrodes for CO2-to-CO Conversion Directly from Capture Medium: A Comprehensive Parameter Analysis.

Gas-fed reactors for CO2 reduction processes are a solid technology to mitigate CO2 accumulation in the atmosphere. However, since it is necessary to feed them with a pure CO2 stream, a highly energy-demanding process is required to separate CO2 from the flue gasses. Recently introduced bicarbonate zero-gap flow reactors are a valid solution to integrate carbon capture and valorization, with them being able to convert the CO2 capture medium (i.e., the bicarbonate solution) into added-value chemicals, such as CO, thus avoiding this expensive separation process. We report here a study on the influence of the electrode structure on the performance of a bicarbonate reactor in terms of Faradaic efficiency, activity, and CO2 utilization. In particular, the effect of catalyst mass loading and electrode permeability on bicarbonate electrolysis was investigated by exploiting three commercial carbon supports, and the results obtained were deepened via electrochemical impedance spectroscopy, which is introduced for the first time in the field of bicarbonate electrolyzers. As an outcome of the study, a novel low-loaded silver-based electrode fabricated via the sputtering deposition technique is proposed. The silver mass loading was optimized by increasing it from 116 µg/cm2 to 565 µg/cm2, thereby obtaining an important enhancement in selectivity (from 55% to 77%) and activity, while a further rise to 1.13 mg/cm2 did not provide significant improvements. The tremendous effect of the electrode permeability on activity and proficiency in releasing CO2 from the bicarbonate solution was shown. Hence, an increase in electrode permeability doubled the activity and boosted the production of in situ CO2 by 40%. The optimized Ag-electrode provided Faradaic efficiencies for CO close to 80% at a cell voltage of 3 V and under ambient conditions, with silver loading of 565 µg/cm2, the lowest value ever reported in the literature so far.

Carboxymethyl cellulose nanocolloids anchored Pd(0) nanoparticles (CMC@Pd NPs): synthesis, characterization, and catalytic application in transfer hydrogenation.

Herein, we report on the preparation of novel colloidal system based on carboxymethyl cellulose (CMC) and Pd nanoparticles (CMC@Pd NPs) via an ecofriendly auto-reduction process under mild conditions. In the first step, the follow-up of reduction and preparation of CMC anchored palladium nanoparticles (Pd NPs) in aqueous solution was carried out using UV-Vis spectroscopy. Thereafter, the monodispersed colloids were fully characterized by advanced analytical, structural, and morphological techniques. Based on Scherrer equation, the as-synthesized CMC@Pd NPs crystallite size was about 10.88 nm. Accordingly, the detailed microscopic study revealed CMC nanocolloids anchored uniform distribution of Pd NPs and the presence of CMC nanofilm as protective monolayer. To the best of our knowledge, the observed nanoscale properties are reported for the first time for CMC-M system. The performance of the as-synthesized CMC@Pd nanocolloids was first investigated in the reduction of 4-nitrophenol, as a model substrate, to 4-aminophenol using NaBH4 as a hydrogen source. Moreover, the catalytic reduction of various nitroarenes bearing electron withdrawing or donating substituents was carried out and monitored by UV-Vis spectroscopy. The chemo- and regioselectivity of the catalytic reduction in presence of CMC@Pd NPs were also studied. Consequently, the prepared CMC@Pd nanocolloids exhibit remarkable activity, good heterogeneity, and higher reusability and stability for the catalytic reduction reaction under mild conditions.

Highly Dispersed Few-Nanometer Chlorine-Doped SnO2 Catalyst Embedded in a Polyaniline Matrix for Stable HCOO- Production in a Flow Cell.

With the spread of alternative energy plants, electrolysis processes are becoming the protagonists of the future industrial generation. The technology readiness level for the electrochemical reduction of carbon dioxide is still low and is largely based on precious metal resources. In the present work, tin ions are anchored on a polyaniline matrix, via a sonochemical synthesis, forming a few atomic layers of chlorine-doped SnO2 with a total loading of tin atom load of only 7 wt %. This catalyst is able to produce formate (HCOO-) with great selectivity, exceeding 72% of Faradaic efficiency in the first hour of testing in 1 M KHCO3 electrolyte, with a current density of more than 50 mA cm-2 in a 2 M KHCO3 electrolyte flow cell setup. Catalyst stability tests show a stable production of HCOO- during 6 h of measurement, accumulating an overall TONHCOO- of more than 10,000 after 16 h of continuous formate production. This strategy is competitive in drastically reducing the amount of metal required for the overall catalysis.

Electrochemical Reduction of CO2 With Good Efficiency on a Nanostructured Cu-Al Catalyst.

Carbon monoxide (CO) and formic acid (HCOOH) are suggested to be the most convenient products from electrochemical reduction of CO2 according to techno-economic analysis. To date, tremendous advances have been achieved in the development of catalysts and processes, which make this research topic even more interesting to both academic and industrial sectors. In this work, we report nanostructured Cu-Al materials that are able to convert CO2 to CO and HCOOH with good efficiency. The catalysts are synthesized via a green microwave-assisted solvothermal route, and are composed of Cu2O crystals modified by Al. In KHCO3 electrolyte, these catalysts can selectively convert CO2 to HCOOH and syngas with H2/CO ratios between 1 and 2 approaching one unit faradaic efficiency in a wide potential range. Good current densities of 67 and 130 mA cm-2 are obtained at -1.0 V and -1.3 V vs. reversible hydrogen electrode (RHE), respectively. When switching the electrolyte to KOH, a significant selectivity up to 20% is observed for C2H4 formation, and the current densities achieve 146 and 222 mA cm-2 at -1.0 V and -1.3 V vs. RHE, respectively. Hence, the choice of electrolyte is critically important as that of catalyst in order to obtain targeted products at industrially relevant current densities.

Recent Advances in the Lithium Recovery from Water Resources: From Passive to Electrochemical Methods.

The ever-increasing amount of batteries used in today's society has led to an increase in the demand of lithium in the last few decades. While mining resources of this element have been steadily exploited and are rapidly depleting, water resources constitute an interesting reservoir just out of reach of current technologies. Several techniques are being explored and novel materials engineered. While evaporation is very time-consuming and has large footprints, ion sieves and supramolecular systems can be suitably tailored and even integrated into membrane and electrochemical techniques. This review gives a comprehensive overview of the available solutions to recover lithium from water resources both by passive and electrically enhanced techniques. Accordingly, this work aims to provide in a single document a rational comparison of outstanding strategies to remove lithium from aqueous sources. To this end, practical figures of merit of both main groups of techniques are provided. An absence of a common experimental protocol and the resulting variability of data and experimental methods are identified. The need for a shared methodology and a common agreement to report performance metrics are underlined.

Effect of Thermal Stabilization on PAN-Derived Electrospun Carbon Nanofibers for CO2 Capture.

Carbon capture is amongst the key emerging technologies for the mitigation of greenhouse gases (GHG) pollution. Several materials as adsorbents for CO2 and other gases are being developed, which often involve using complex and expensive fabrication techniques. In this work, we suggest a sound, easy and cheap route for the production of nitrogen-doped carbon materials for CO2 capture by pyrolysis of electrospun poly(acrylonitrile) (PAN) fibers. PAN fibers are generally processed following specific heat treatments involving up to three steps (to get complete graphitization), one of these being stabilization, during which PAN fibers are oxidized and stretched in the 200-300 °C temperature range. The effect of stabilization temperature on the chemical structure of the carbon nanofibers is investigated herein to ascertain the possible implication of incomplete conversion/condensation of nitrile groups to form pyridine moieties on the CO2 adsorption capacity. The materials were tested in the pure CO2 atmosphere at 20 °C achieving 18.3% of maximum weight increase (equivalent to an uptake of 4.16 mmol g-1), proving the effectiveness of a high stabilization temperature as route for the improvement of CO2 uptake.

Zn- and Ti-Doped SnO2 for Enhanced Electroreduction of Carbon Dioxide.

The electrocatalytic reduction of CO2 into useful fuels, exploiting rationally designed, inexpensive, active, and selective catalysts, produced through easy, quick, and scalable routes, represents a promising approach to face today's climate challenges and energy crisis. This work presents a facile strategy for the preparation of doped SnO2 as an efficient electrocatalyst for the CO2 reduction reaction to formic acid and carbon monoxide. Zn or Ti doping was introduced into a mesoporous SnO2 matrix via wet impregnation and atomic layer deposition. It was found that doping of SnO2 generates an increased amount of oxygen vacancies, which are believed to contribute to the CO2 conversion efficiency, and among others, Zn wet impregnation resulted the most efficient process, as confirmed by X-ray photoelectron spectroscopy analysis. Electrochemical characterization and active surface area evaluation show an increase of availability of surface active sites. In particular, the introduction of Zn elemental doping results in enhanced performance for formic acid formation, in comparison to un-doped SnO2 and other doped SnO2 catalysts. At -0.99 V versus reversible hydrogen electrode, the total faradaic efficiency for CO2 conversion reaches 80%, while the partial current density is 10.3 mA cm-2. These represent a 10% and a threefold increases for faradaic efficiency and current density, respectively, with respect to the reference un-doped sample. The enhancement of these characteristics relates to the improved charge transfer and conductivity with respect to bare SnO2.

Microwave-Assisted Synthesis of Nitrogen and Sulphur Doped Graphene Decorated with Antimony Oxide: An Effective Catalyst for Oxygen Reduction Reaction.

In this study, we report on the facile synthesis of a novel electrocatalysts for the oxygen reduction reaction (ORR), based on reduced graphene oxide (RGO), functionalized with metallic and non-metallic elements. In particular, thanks to a fast one-pot microwave-assisted procedure, we induced, in the RGO graphene lattice, a combined doping with nitrogen and sulphur, and the simultaneous decoration with antimony oxide nanocrystals. The multi-doped-decorated material shows enhanced catalytic performance towards ORR, with respect to common nitrogen- or sulphur-doped carbon-based materials. The presence of co-doping is confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy analysis. The detailed electrochemical characterization shows the simultaneous effects of dopant atoms on the catalytic behavior. In particular, the importance of nitrogen and sulphur atoms in driving the oxygen absorption, together with the role of antimony in enhancing the electrochemical performance toward the ORR, are discussed.

Rapid prototyping of 3D Organic Electrochemical Transistors by composite photocurable resin.

Rapid Prototyping (RP) promises to induce a revolutionary impact on how the objects can be produced and used in industrial manufacturing as well as in everyday life. Over the time a standard technique as the 3D Stereolithography (SL) has become a fundamental technology for RP and Additive Manufacturing (AM), since it enables the fabrication of the 3D objects from a cost-effective photocurable resin. Efforts to obtain devices more complex than just a mere aesthetic simulacre, have been spent with uncertain results. The multidisciplinary nature of such manufacturing technique furtherly hinders the route to the fabrication of complex devices. A good knowledge of the bases of material science and engineering is required to deal with SL technological, characterization and testing aspects. In this framework, our study aims to reveal a new approach to obtain RP of complex devices, namely Organic Electro-Chemical Transistors (OECTs), by SL technique exploiting a resin composite based on the conductive poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) and the photo curable Poly(ethylene glycol) diacrylate (PEGDA). A comprehensive study is presented, starting from the optimization of composite resin and characterization of its electrochemical properties, up to the 3D OECTs printing and testing. Relevant performances in biosensing for dopamine (DA) detection using the 3D OECTs are reported and discussed too.

Binder Free and Flexible Asymmetric Supercapacitor Exploiting Mn3O4 and MoS2 Nanoflakes on Carbon Fibers.

Emerging technologies, such as portable electronics, have had a huge impact on societal norms, such as access to real time information. To perform these tasks, portable electronic devices need more and more accessories for the processing and dispensation of the data, resulting in higher demand for energy and power. To overcome this problem, a low cost high-performing flexible fiber shaped asymmetric supercapacitor was fabricated, exploiting 3D-spinel manganese oxide Mn3O4 as cathode and 2D molybdenum disulfide MoS2 as anode. These asymmetric supercapacitors with stretched operating voltage window of 1.8 V exhibit high specific capacitance and energy density, good rate capability and cyclic stability after 3000 cycles, with a capacitance retention of more than 80%. This device has also shown an excellent bending stability at different bending conditions.

TEM Nanostructural Investigation of Ag-Conductive Filaments in Polycrystalline ZnO-Based Resistive Switching Devices.

Memristive devices based on a resistive switching mechanism are considered very promising for nonvolatile memory and unconventional computing applications, even though many details of the switching mechanisms are not yet fully understood. Here, we report a nanostructural study by means of high-resolution transmission electron microscopy and spectroscopy techniques of a Ag/ZnO/Pt memristive device. To ease the localization of the filament position for its characterization, we propose to use the guiding effect of regular perturbation arrays obtained by FIB technology to assist the filament formation. HRTEM and EDX were used to identify the composition and crystalline structure of the so-obtained conductive filaments and surrounding regions. It was determined that the conducting paths are composed mainly of monocrystalline Ag, which remains polycrystalline in some circumstances, including the zone where the switching occurs and at secondary filaments created at the grain boundaries of the polycrystalline ZnO matrix. We also observed that the ZnO matrix shows a degraded quality in the switching zone, while it remains unaltered in the rest of the memristive device.

Coupled Copper-Zinc Catalysts for Electrochemical Reduction of Carbon Dioxide.

A catalyst plays a key role in the electrochemical reduction of CO2 to valuable chemicals and fuels. Hence, the development of efficient and inexpensive catalysts has attracted great interest from both the academic and industrial communities. In this work, low-cost catalysts coupling Cu and Zn are designed and prepared with a green microwave-assisted route. The Cu to Zn ratio in the catalysts can be easily tuned by adjusting the precursor solutions. The obtained Cu-Zn catalysts are mainly composed of polycrystalline Cu particles and monocrystalline ZnO nanoparticles. The electrodes with optimized Cu-Zn catalysts show enhanced CO production rates of approximately 200 µmol h-1 cm-2 with respect to those with a monometallic Cu or ZnO catalyst under the same applied potential. At the bimetallic electrodes, ZnO-derived active sites are selective for CO formation and highly conductive Cu favors electron transport in the catalyst layer as well as charge transfer at the electrode/electrolyte interface.

Electrospun Nanofibers: from Food to Energy by Engineered Electrodes in Microbial Fuel Cells.

Microbial fuel cells (MFCs) are bio-electrochemical devices able to directly transduce chemical energy, entrapped in an organic mass named fuel, into electrical energy through the metabolic activity of specific bacteria. During the last years, the employment of bio-electrochemical devices to study the wastewater derived from the food industry has attracted great interest from the scientific community. In the present work, we demonstrate the capability of exoelectrogenic bacteria used in MFCs to catalyze the oxidation reaction of honey, employed as a fuel. With the main aim to increase the proliferation of microorganisms onto the anode, engineered electrodes are proposed. Polymeric nanofibers, based on polyethylene oxide (PEO-NFs), were directly electrospun onto carbon-based material (carbon paper, CP) to obtain an optimized composite anode. The crucial role played by the CP/PEO-NFs anodes was confirmed by the increased proliferation of microorganisms compared to that reached on bare CP anodes, used as a reference material. A parameter named recovered energy (Erec) was introduced to determine the capability of bacteria to oxidize honey and was compared with the Erec obtained when sodium acetate was used as a fuel. CP/PEO-NFs anodes allowed achieving an Erec three times higher than the one reached with a bare carbon-based anode.

Photofabrication of polymeric biomicrofluidics: New insights into material selection.

We propose a versatile method to evaluate the suitability of polymers for the fabrication of microfluidic devices for biomedical applications, based on the concept that the selection and the design of convenient materials should involve different properties depending on the final microfluidic application. Here polymerase chain reaction (PCR) is selected as biological model and target microfluidic reaction. A class of photocured siloxanes is introduced as device building polymers and copolymerization is adopted as strategy to finely tune and optimize the final material properties. All-polymeric flexible devices are easily fabricated exploiting the rapidity of the photopolymerization reaction: they resist to thermal cycles without leakage or de-bonding (i.e., without separation of different chip parts made of the same material bonded together), show very limited water swelling and permeability, are bioinert and prevent the inhibition of the biochemical reaction. PCR is thus successfully conducted in the photocured microfluidic devices made with a specifically designed siloxane copolymer.

Scaling Organic Electrochemical Transistors Down to Nanosized Channels.

The perspective of downscaling organic electrochemical transistors (OECTs) in the nanorange is approached by depositing poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) on electrodes with a nanogap designed and fabricated by electromigration induced break junction (EIBJ) technique. The electrical response of the fabricated devices is obtained by acquiring transfer characteristics in order to clarify the specific main characteristics of OECTs with sub-micrometer-sized active channels (nanogap-OECTs). On the basis of their electrical response to different scan times, the nanogap-OECT shows a maximum transconductance unaffected upon changing scan times in the time window from 1 s to 100 µs, meaning that fast varying signals can be easily acquired with unchanged amplifying performance. Hence, the scaling down of the channel size to the nanometer scale leads to a geometrical paradigm that minimizes effects on device response due to the cationic diffusion into the polymeric channel. A comprehensive study of these features is carried out by an electrochemical impedance spectroscopy (EIS) study, complemented by a quantitative analysis made by equivalent circuits. The propagation of a redox front into the polymer bulk due to ionic diffusion also known as the "intercalation pseudocapacitance" is identified as a limiting factor for the transduction dynamics.

PDMS/Polyimide Composite as an Elastomeric Substrate for Multifunctional Laser-Induced Graphene Electrodes.

Laser-induced graphene (LIG) emerged as one of the most promising materials for flexible functional devices. However, the attempts to obtain LIG onto elastomeric substrates never succeed, hindering its full exploitation for stretchable electronics. Herein, a novel polymeric composite is reported as a starting material for the fabrication of graphene-based electrodes by direct laser writing. A polyimide (PI) powder is dispersed into the poly(dimethylsiloxane) (PDMS) matrix to achieve an easily processable and functional elastomeric substrate, allowing the conversion of the polymeric surface into laser-induced graphene (LIG). The mechanical and electrical properties of the proposed material can be easily tuned by acting on the polyimide powder concentration. The reported procedure takes advantage from the simple casting process, typical of silicone elastomer, allowing to produce electrodes conformable to any kind of shape and surface as well as complex three-dimensional structures. Electrochemical capacitors and strain gauges are selected as flexible prototypes to demonstrate the multifunctional properties of the obtained LIG on the PDMS/PI composite substrate.

Self-limited single nanowire systems combining all-in-one memristive and neuromorphic functionalities.

The ability for artificially reproducing human brain type signals' processing is one of the main challenges in modern information technology, being one of the milestones for developing global communicating networks and artificial intelligence. Electronic devices termed memristors have been proposed as effective artificial synapses able to emulate the plasticity of biological counterparts. Here we report for the first time a single crystalline nanowire based model system capable of combining all memristive functions - non-volatile bipolar memory, multilevel switching, selector and synaptic operations imitating Ca2+ dynamics of biological synapses. Besides underlying common electrochemical fundamentals of biological and artificial redox-based synapses, a detailed analysis of the memristive mechanism revealed the importance of surfaces and interfaces in crystalline materials. Our work demonstrates the realization of self-assembled, self-limited devices feasible for implementation via bottom up approach, as an attractive solution for the ultimate system miniaturization needed for the hardware realization of brain-inspired systems.