Search

Green hydrogen production from water is one attractive route to non-fossil fuel and a potential source of clean energy. Hydrogen is not only a zero-carbon energy source but can also be utilized as an efficient storage of electrical energy generated through various other sources, such as wind and solar. Cost-effective and environmentally benign direct hydrogen production through neutral water (∼pH 7) reduction is particularly challenging due to the low concentration of protons. There is currently a major need for easy-to-prepare, robust, as well as active electrode materials. Herein we report three new molecular electrodes that were prepared by anchoring commercially available, and environmentally benign cobalt-containing electrocatalysts with three different ligand frameworks (porphyrin, phthalocyanine, and corrin) on a structurally modified graphite foil surface. Under the studied reaction conditions (over 7 h at 22°C), the electrode with Co-porphyrin is the most efficient for the water reduction with starting ∼740 mV onset potential (OP) (vs. RHE, current density 2.5 mA/cm2) and a Tafel slope (TS) of 103 mV/dec. It is followed by the molecular electrodes having Co-phthalocyanine [825 mV (OP), 138 mV/dec (TS)] and Vitamin-B12 (Co-corrin moiety) [830 mV (OP), 194 mv/dec (TS)]. A clear time-dependent improvement (>200 mV over 3 h) in the H2 production overpotential with the Co-porphyrin-containing cathode was observed. This is attributed to the activation due to water coordination to the Co-center. A long-term chronopotentiometric stability test shows a steady production of hydrogen from all three cathode surfaces throughout seven hours, confirmed using an H2 needle sensor. At a current density of 10 mA/cm2, the Co-porphyrin-containing electrode showed a TOF value of 0.45 s−1 at 870 mV vs. RHE, whereas the Co-phthalocyanine and Vitamin-B12-containing electrodes showed 0.37 and 0.4 s−1 at 1.22 V and 1.15 V (vs. RHE), respectively.

This work focuses on the production of methane through the photocatalytic reduction of carbon dioxide using Pt-doped CdS/TiO2 heterostructures. The photocatalysts were prepared using P25 commercial titania and CdS synthesized through a solvothermal methodology, followed by the impregnation of Pt onto the surface to enhance the physicochemical properties of the resulting photocatalysts. The pure and heterostructure-based materials were characterized using X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible spectroscopy (UV-Vis), ultraviolet photoelectron spectroscopy (UPS), and photoluminescence spectroscopy (PL). The obtained results show the successful synthesis of the heterostructure impregnated with Pt. Moreover, the observed key role of CdS and Pt nanoparticles in the final semiconductor is to reduce the electron-hole pair recombination rate by acting as an electron sink, which slows down the recombination process and increases the photocatalyst efficiency. Thus, Pt-doped CdS/TiO2 heterostructures with the best observed composition presents better catalytic activity than P25 titania with methane production values being 460 and 397 µmol CH4/g·h, respectively.

While carbon in itself appears as simple an element as it could possibly get, the undeniable truth is that carbon materials represent a plethora of possibilities both from the perspective of their structure and their applications. While we may believe that carbon is “just another element”, one should never forget that its special ability to coordinate through different hybridizations with apparent ease grants the element properties that no other element may even match. Taking this one step further into the materials realm opens up numerous avenues in terms of materials dimensionality, surface and bulk functionalization, or degree of structural order just to mention a few examples. If these properties are translated into the properties and applications field, the results are just as impressive, with new applications and variants appearing with growingly larger frequency. This has resulted in over a million scientific papers published in the last decade in which the term “carbon” was used either in the title, abstract or keywords. When the search is narrowed down to the field “title” alone, the results drop to just over 318.000 scientific papers. These are figures that no other element in the periodic table can equal, which is a clear indicative that the story of carbon materials is still under constant evolution and development. This review will present an overview of the works published in the Frontiers in Carbon-based materials section during its 10 years of life that reflect the advancements achieved during the last decade in the field of carbon materials.

Defect-containing carbon nanotube materials were prepared by subjecting two commercial multiwalled carbon nanotubes (MWCNTs) of different purities to purification (HCl) and oxidative conditions (HNO3) and further heat treatment to remove surface oxygen groups. The as-prepared carbon materials were physicochemically characterized to observe changes in their properties after the different treatments. TEM microscopy shows morphological modifications in the MWCNTs after the treatments such as broken walls and carbon defects including topological defects. This leads to both higher surface areas and active sites. The carbon defects were analysed by Raman spectroscopy, but the active surface area (ASA) and the electrochemical active surface area (EASA) values showed that not all the defects are equally active for oxygen reduction reactions (ORRs). This suggests the importance of calculating either ASA or EASA in carbon materials with different structures to determine the activity of these defects. The as-prepared defect-containing multiwalled carbon nanotubes exhibit good catalytic performance due to the formation of carbon defects active for ORR such as edge sites and topological defects. Moreover, they exhibit good stability and methanol tolerances. The as-prepared MWCNTs sample with the highest purity is a promising defective carbon material for ORR because its activity is only related to high concentrations of active carbon defects including edge sites and topological defects.

The present review revisits representative studies addressing the development of efficient Pd-based carbon-supported heterogeneous catalysts for two important reactions, namely, the production of hydrogen from formic acid and the hydrogenation of carbon dioxide into formic acid. The HCOOH-CO2 system is considered a promising couple for a hydrogen storage system involving an ideal carbon-neutral cycle. Significant advancements have been achieved in the catalysts designed to catalyze the dehydrogenation of formic acid under mild reaction conditions, while much effort is still needed to catalyze the challenging CO2 hydrogenation reaction. The design of Pd-based carbon-supported heterogeneous catalysts for these reactions encompasses both the modulation of the properties of the active phase (particle size, composition, and electronic properties) and the modification of the supports by means of the incorporation of nitrogen functional groups. These approaches are herein summarized to provide a compilation of the strategies followed in recent studies and to set the basis for a hydrogen storage system attained using the HCOOH-CO2 couple.

The aim of this work is to establish the Oxygen Reduction Reaction (ORR) activity of self-standing electrospun carbon fiber catalysts obtained from different metallic salt/lignin solutions. Through a single-step electrospinning technique, freestanding carbon fiber (CF) electrodes embedded with various metal nanoparticles (Co, Fe, Pt, and Pd), with 8–16 wt% loadings, were prepared using organosolv lignin as the initial material. These fibers were formed from a solution of lignin and ethanol, into which the metallic salt precursors were introduced, without additives or the use of toxic reagents. The resulting non-woven cloths were thermostabilized in air and then carbonized at 900 °C. The presence of metals led to varying degrees of porosity development during carbonization, improving the accessibility of the electrolyte to active sites. The obtained Pt and Pd metal-loaded carbon fibers showed high nanoparticle dispersion. The performance of the electrocatalyst for the oxygen reduction reaction was assessed in alkaline and acidic electrolytes and compared to establish which metals were the most suitable for producing carbon fibers with the highest electrocatalytic activity. In accordance with their superior dispersion and balanced pore size distribution, the carbon fibers loaded with 8 wt% palladium showed the best ORR activity, with onset potentials of 0.97 and 0.95 V in alkaline and acid media, respectively. In addition, this electrocatalyst exhibits good stability and selectivity for the four-electron energy pathway while using lower metal loadings compared to commercial catalysts.

Debt compensation is a process via which various entities (companies, people, etc.) propose the payment of their mutual debts by compensating them according to the credits they may have in their favor. The aim is to establish the financial information of a company so that its debts can somehow be satisfied by its credits, breaking the vicious cycle of debts that cannot be paid. To this end, this financial information is retrieved from the business information system of a company, encompassing how much is owed and to which companies. From the retrieved information, this paper describes the implementation of an automatic system that allows calculating not only the debt cycles involving different companies, but also how these cycles can be effectively solved using blockchain technology thanks to the use of smart contracts. Blockchain technology can have a great impact for companies in this kind of application, guaranteeing the security and traceability of transactions among companies, which are two well-appreciated features from a financial auditing point of view.

Among various electrochemical reactions to produce fuels and chemicals, glycerol electrolysis to co-produce hydrogen and lactic acid has received great attention. However, studies have shown the benchmark Pt based catalysts are insufficient in selectively catalysing the glycerol to lactic acid transformation, resulting in a low yield of lactic acid. Here we report a study on glycerol electrolysis with anion-exchange membrane electrode assembly electrolyser. The reaction conditions including mass transport, temperature, current density and KOH concentration were optimised, among which temperature played a significant role in facilitating the reaction rate and thermodynamics. With the optimised condition a multicomponent Pt/C-zeolite electrocatalyst system (Pt/C-CBV600) was developed and tested, which is capable to increase the lactic acid selectivity to 57.3% from the 33.8% with standalone Pt/C. Although the detailed mechanism required further investigation, it is hypothesised that the CBV600 zeolite with abundant Lewis acid surface sites can effectively bind the dihydroxyacetone intermediate, and drive the reaction towards pyruvaldehyde heterogeneously, the key step to form lactic acid.

The Stipa tenacissima S. is an endemic species of the Western Mediterranean countries, which grows on the semi-arid grounds of North Africa and South Spain. This biomass offers an abundant, renewable, and low-cost precursor for the production of activated carbon (AC). In that context, ACs were prepared by chemical activation of Stipa tenacissima leaves (STL) using phosphoric acid (H3PO4). The effects of activation temperature and impregnation ratio on the textural and chemical surface properties of the prepared activated carbons were investigated. Activation temperatures of 450 and 500 °C turned out to be the most suitable to produce activated carbons with well-developed porous textures. The best results in terms of developed surface area (1503 m2/g) and micropore volume (0.59 cm3/g) were observed for an STLs to phosphoric acid ratio of 1:2 and a carbonization temperature of 450 °C. The adsorption capacity of the optimal activated carbon was found to be 110 mg/g for the atenolol drug. The adsorption equilibrium was well explained by the pseudo-second-order model and Langmuir isotherm. This study showed that the chemical activation method using H3PO4 as an activating agent was suitable for developing STL-based activated carbon prepared for the removal of atenolol drug in an aqueous solution and compared with commercial activated carbon supplied by Darco.

Various carbon materials were used as support of polyvinylpyrrolidone (PVP)-capped Pd nanoparticles for the synthesis of catalysts for the production of hydrogen from formic acid dehydrogenation reaction. Among investigated, MWCNT-supported catalysts were the most promising, with a TOF of 1430 h−1 at 80°C. The presence of PVP was shown to play a positive role by increasing the hydrophilicity of the materials and enhancing the interface contact between the reactant molecules and the catalytic active sites.

Schwarzites have a three-dimensional sp2 carbon structure with negative Gaussian curvatures. They can be synthesized through the deposition of carbon by chemical vapor deposition on a zeolite template and may be formed by increasing the amount of carbon. In this research, the amount of carbon deposition was increased by shortening the length of the diffusion pathways of the template through the use of nano-sized zeolite Y (nano-FAU). It was found that significantly larger quantities of carbon could be deposited inside the pores of nano-FAU (40 nm), compared to the micro-sized zeolite Y (300 nm). It is thus confirmed that by shortening the diffusion pathways enables more carbon to infiltrate into the center of the template before the pore channels are blocked, which leads to larger carbon depositions. A low acetylene gas concentration (15% vol in N2) and a prolonged period for chemical vapor deposition (6 h) is preferable for effectively loading carbon into the template. The obtained carbon replica exhibits the ordered structure derived from zeolite Y with an unprecedented 72 carbon atoms per supercage, of which a model with a structure similar to schwarzite was proposed.

The increasing worldwide energy consumption has contributed to both the vast growth of greenhouse emissions from carbon-containing fuels-based sources (coal, petroleum, etc.) and the depletion of the aforementioned sources. Given this scenario, the development of inexpensive and high-performing energy storage devices, which have the least possible environmental impact, is needed. At this point, electrochemical capacitors (ECs) or supercapacitors are a particular alternative or complementary option to batteries and fuel cells (FCs). ECs present high power output and long cycle life, but little power density compared to conventional or Lithium-ion batteries. Therefore, ECs are going to play a pivotal role, not only in portable electronic devices, but also to provide power density in hybrid electric vehicles. Many efforts have been focused on improving the energy output of ECs, although its enhancement keeping the high power density is still the cornerstone of most investigations. Many studies have been conducted toward the development of electrode materials such as metal oxides, conducting polymers or novel carbons. Nevertheless, they have shown important shortcomings to be implemented (i.e., high cost, low electrical conductivity, poor stability, etc.). Recent studies put the spotlight on nitrogen-containing carbon materials as candidates to improve the ECs performance in terms of energy. Optimizing the ECs configuration (asymmetric and hybrid) is another approach reported to tackle the challenge. Additionally, it is important to mention that the design of carbon materials obtained from inexpensive precursors lately attracted the attention of the research community. This review compiles works performed in our research group over the last years. The effect of nitrogen groups present in the carbon network on the capacitance will be reported and the study of asymmetric configuration to enhance de energy density will be discussed, either opening the potential window or by increasing the capacitance. Moreover, a lignin-based ECs will be described as an environmentally friendly approach. Finally, perspective and conceivable research guidelines in order to hurdle the challenges proposed to implement the carbon materials in the field of ECs will be addressed.

Different functionalized Multi-Wall Carbon Nanotube and gold nanoparticles (AuNPs) were synthesized as biosensor electrodes. These materials have been applied to the detection of the Prostate Specific Antigen (PSA). The synthesis of AuNPs was carried out using polyvinylpyrrolidone (PVP) as protecting agent. The PVP/Au molar ratio (0.5 and 50) controls the nanoparticle size distribution, obtaining a wide and narrow distribution with an average diameter of 9.5 and 6.6 nm, respectively. Nanoparticle size distribution shows an important effect in the electrochemical performance of the biosensor, increasing the electrochemical active surface area (EASA) and promoting the electron-transfer from the redox probe (Ferrocene/Ferrocenium) to the electrode. Furthermore, a narrow and small nanoparticle size distribution enhances the amount of antibodies immobilized on the transducer material and the performance during the detection of the PSA. Significant results were obtained for the quantification of PSA, with a limit of detection of 1 ng·ml−1 and sensitivities of 0.085 and 0.056 μA·mL·ng−1 for the two transducer materials in only 5 min of detection.

Chemical hydrogen storage stands as a promising option to conventional storage methods. There are numerous hydrogen carrier molecules that afford satisfactory hydrogen capacity. Among them, ammonia borane has attracted great interest due to its high hydrogen capacity. Great efforts have been devoted to design and develop suitable catalysts to boost the production of hydrogen from ammonia borane, which is preferably attained by Ru catalysts. The present review summarizes some of the recent Ru-based heterogeneous catalysts applied in the hydrolytic dehydrogenation of ammonia borane, paying particular attention to those supported on carbon materials and oxides.

High-quality performance of catalysts is increasingly required to meet industry exigencies. However, chemical synthesis is often insufficient to maximize the potential properties of the catalysts. On the other hand, electrochemical synthesis has arisen as a promising alternative to overcome these limitations and provide precise control in the preparation of catalysts. In this sense, this work involved the well-controlled electrochemical synthesis of a catalyst based on platinum nanoparticle deposition on carbon nanotubes using only electrochemical treatments. Thin films of functionalized carbon nanotubes were cast onto the surface of a glassy carbon electrode using potential pulsed electrodeposition, resulting in a better distribution of the carbon nanotubes on the electrode when comparing with traditional methods. Then, platinum nanoparticles were electrodeposited on the carbon nanotube-modified electrode. To check the performance of the catalyst and the relevance of the electrochemical synthesis treatments, the samples were analyzed as electrocatalysts towards methanol electrooxidation, showing an important improvement in the catalytic activity in comparison with electrodes that were prepared by traditional methodologies.

LaMn1−xCoxO3 perovskites were synthesized by a modified sol-gel method which incorporates EDTA. These materials’ electrochemical activity towards both oxygen reduction (ORR) and oxygen evolution reactions (OER) was studied. The cobalt substitution level determines some physicochemical properties and, particularly, the surface concentration of Co and Mn’s different oxidation states. As a result, the electroactivity of perovskite materials can be tuned using their composition. The presence of cobalt at low concentration influences the catalytic activity positively, and better bifunctionality is attained. As in other perovskites, their low electrical conductivity limits their applicability in electrochemical devices. It was found that the electrochemical performance improved significantly by physically mixing with a mortar the active materials with two different carbon black materials. The existence of a synergistic effect between the electroactive component and the carbon material was interpreted in light of the strong carbon–oxygen–metal interaction. Some mixed samples are promising electrocatalysts towards both ORR and OER.

Nitrogen functionalization of a highly microporous activated carbon (SBET > 3000 m2/g), to be used as electrode of electric double layer capacitor (EDLC), was carried out by different methods based on organic chemistry protocols at low temperature and selective thermal post-treatments under inert atmosphere. The combination of both methods allowed the production of carbon materials with very similar surface area (2400–3000 m2/g) and different surface chemistry. The nitrogen functionalization by chemical methods produce the attachment of 4 at. % N (XPS) by consumption of oxygen functional groups. The thermal treatments rearrange the surface chemistry by decreasing and converting both nitrogen and oxygen moieties. The effect of surface chemistry on the performance of these materials as electrodes for symmetric supercapacitors was analyzed in organic electrolyte (1M TEMABF4/propylene carbonate). The devices showed high gravimetric capacitance (37–40 F/g) and gravimetric energy density (31–37 Wh/kg). The electrochemical stability of the EDLC was evaluated by a floating test under severe conditions of voltage and temperature. The results evidence an improvement of the durability of nitrogen-doped activated carbons modified by chemical treatments due to the decrease of detrimental oxygen functionalities and the generation of nitrogen groups with higher electrochemical stability.

The production of H2 from the so-called Liquid Organic Hydrogen Carriers (LOHC) has recently received great focus as an auspicious option to conventional hydrogen storage technologies. Among them, formic acid, the simplest carboxylic acid, has recently emerged as one of the most promising candidates. Catalysts based on Pd nanoparticles are the most fruitfully investigated, and, more specifically, excellent results have been achieved with bimetallic PdAg-based catalytic systems. The enhancement displayed by PdAg catalysts as compared to the monometallic counterpart is ascribed to several effects, such as the formation of electron-rich Pd species or the increased resistance against CO-poisoning. Aside from the features of the metal active phases, the properties of the selected support also play an important role in determining the final catalytic performance. Among them, the use of carbon materials has resulted in great interest by virtue of their outstanding properties and versatility. In the present review, some of the most representative investigations dealing with the design of high-performance PdAg bimetallic heterogeneous catalysts are summarised, paying attention to the impact of the features of the support in the final ability of the catalysts towards the production of H2 from formic acid.

Biographene was successfully produced in water from graphite flakes by a simple, rapid, and efficient methodology based on a bioexfoliation technology. The methodology consisted in the application of a lipase, with a unique mechanism of interaction with hydrophobic surfaces, combined with a previous mechanical sonication, to selectively generate lipase-graphene sheets conjugates in water at room temperature. The adsorption of the lipase on the graphene sheets permits to keep the sheets separated in comparison with other methods. It was possible to obtain more than 80% of graphene (in the form of multi-layer graphene) from low-cost graphite and with less damage compared to commercial graphene oxide (GO) or reduced GO. Experimental analysis demonstrated the formation of multi-layer graphene (MLG) mainly using lipase from Thermomyces Lanuginosus (TLL).

While it has been proved that multiple scattering in the microwave frequencies has to be accounted for in precipitation retrieval algorithms, the effects of the random arrangements of drops in space has seldom been investigated. The fact is, a single rain drop size distribution (RDSD) corresponds with many actual 3D distributions of those rain drops and each of those may a priori absorb and scatter radiation in a different way. Each spatial configuration is equivalent to any other in terms of the RDSD function, but not in terms of radiometric characteristics, both near and far from field, because of changes in the relative phases among the particles. Here, using the T-matrix formalism, we investigate the radiometric variability of two ensembles of 50 different 3D, stochastically-derived configurations from two consecutive measured RDSDs with 30 and 31 drops, respectively. The results show that the random distribution of drops in space has a measurable but apparently small effect in the scattering calculations with the exception of the asymmetry factor.

The elimination of volatile organic compounds (VOCs) at low concentration is a subject of great interest because these compounds are very harmful for the environment and human health. In this work, we have developed a synthesis methodology of TiO2 that allows obtaining meso-macroporous materials with hierarchical porosity and with high thermal stability for their application as photocatalysts in the removal of VOCs, specifically propene. The materials synthesized in this work were characterized by Scanning electron microscope (SEM), Transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Thermogravimetric Analysis (TG), and nitrogen adsorption. It is observed that the samples calcined at 250 °C and 500 °C present a high photoactivity for the photooxidation of propene, which is similar to the benchmark material P25 (commercial TiO2). Moreover, the textural properties are better than those for P25, indicating that the samples are interesting for the preparation of photocatalysts with different conformations, such as in the form of coatings and fillings in different size scales.

Since the discovery of MCM-41, the interpretation of its structure and porous texture has evolved from a simple model of straight parallel mesopores to a much more complex model with a rough surface. The physisorption of nitrogen at 77.3 K and 87.5 K and of carbon dioxide at 273 K was carried out on both MCM-41 and a precipitated silica (PSIL). This silica was prepared for comparison purposes under identical conditions to those for MCM-41 but without the use of the surfactant. The adsorption characteristics of both materials for both adsorptives were indistinguishable at low adsorption pressures independent of the adsorption temperature employed, suggesting similarities in parts of their porosity (i.e. excluding mesoporosity). We propose that, in addition to its well-acknowledged mesoporosity, MCM-41 includes considerable surface roughness and/or heterogeneities similar to that shown by microporous silica. This surface structure appears to have adsorption characteristics indistinguishable from classical microporosity, and may also be an important feature of this material which is very often not taken into consideration in most of its applications.