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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.

In the present work, multifunctional electrocatalysts formed by palladium nanoparticles (Pd NPs) loaded on Fe or Cu-containing composite supports, based on carbon nitride (C3N4) and super-activated carbon with a high porosity development (SBET 3180 m2/g, VDR 1.57 cm3/g, and VT 1.65 cm3/g), were synthesised. The presence of Fe or Cu sites favoured the formation of Pd NPs with small average particle size and a very narrow size distribution, which agreed with Density Functional Theory (DFT) calculations showing that the interaction of Pd clusters with C3N4 flakes is weaker than with Cu- or Fe-C3N4 sites. The electroactivity was also dependent on the composition and, as suggested by preliminary DFT calculations, the Pd-Cu catalyst showed lower overpotential for hydrogen evolution reaction (HER) while bifunctional oxygen reduction reaction/ oxygen evolution reaction (ORR/OER) behaviour was superior in Pd-Fe sample. The Pd-Fe electrocatalyst was studied in a zinc-air battery (ZAB) for 10 h, showing a performance similar to a commercial Pt/C + RuO2 catalyst with a high content of precious metal. This study demonstrates the synergistic effect between Pd species and transition metals and shows that transition metals anchored on C3N4-based composite materials promote the electroactivity of Pd NPs in HER, ORR and OER due to the interaction between both species.

Graphene oxide (GO) has been electrochemically synthesized by chronoamperometry and using a three-electrode system. Iron, manganese and cobalt phthalocyanines (FePc, MnPc and CoPc, respectively) have been incorporated to GO. These materials were characterized both physicochemically (X-ray Photoelectron Spectroscopy (XPS), UV–Vis, elemental analysis and Raman spectroscopy), morphologically (Transmission Electron Microscopy, TEM) and electrochemically (cyclic voltammetry). Electrochemical studies included the oxygen reduction reaction (ORR) and Zn-air battery performance using the synthesized electrocatalysts. In addition, graphene oxide buckypapers (GOBs) have been fabricated and evaluated as self-supporting electrodes for the Zn-air battery. Both GO/FePc and FePc supported on GOB (GOB/FePc), with a Fe content lower than 0.5 wt%, were subjected to Zn-air battery discharging tests. Both GO/FePc and GOB/FePc show comparable performance to the commercial Pt-based electrocatalyst using a much lower amount of metal.

Multilayer graphene (MLG), obtained by mild sonication of graphite in NMP, was functionalised via 1,3-dipolar cycloaddition with azomethine ylides generated by thermal 1,2-prototropy from various imino esters. The microwave-assisted functionalisation took place in five hours at 100 °C. The resulting MLG, containing substituted proline-based amine functional groups, was characterized using XPS and showed a nitrogen loading three times that obtained for the same transformation performed for five days using convection-assisted heating. The preparation of the imino ester containing a bipyridine unit at the arylidene position allowed for the preparation of the corresponding functionalised MLG, which incorporated the ruthenium atom to achieve a heterogeneous MLG-Ru complex. This supported complex was tested, as a proof of concept, as a photocatalyst of the aerobic oxidative hydroxylation of 4-methoxyphenylboronic acid.

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are key electrochemical reactions for the development of rechargeable Zn-air batteries. However, due to the high cost of commercial noble metal-based catalysts and their limited bifunctionality, it is necessary the design of new electrocatalysts. In this study, stable electrocatalysts have been synthesized through a hydrothermal method and further low-temperature thermal treatment. The materials consist of La stabilized low crystallinity Mn and Co metal (hydro-)oxides. The electrocatalytic performance of these materials has been compared with counterparts calcined at higher temperatures. The findings demonstrate that materials synthesized at lower temperatures and with low crystallinity exhibit superior electrocatalytic activity for both ORR and OER. Moreover, the research highlights the favorable influence of the lanthanum cation, which enhances changes of surface morphology and oxidation states of other cations (Mn and Co). Additionally, the positive contribution of the carbon component to electrochemical activity and electrical conductivity has been elucidated. The best electrocatalyst was studied in a rechargeable Zn-air battery with a durability of up to 120 hours. They exhibited better stability and performance than the commercial Pt/C + RuO2 catalyst currently used.

Hydrogen storage by cryoadsorption on porous materials has the advantages of low material cost, safety, fast kinetics, and high cyclic stability. The further development of this technology requires reliable data on the H2 uptake of the adsorbents, however, even for activated carbons the values between different laboratories show sometimes large discrepancies. So far no reference material for hydrogen cryoadsorption is available. The metal-organic framework ZIF-8 is an ideal material possessing high thermal, chemical, and mechanical stability that reduces degradation during handling and activation. Here, we distributed ZIF-8 pellets synthesized by extrusion to 9 laboratories equipped with 15 different experimental setups including gravimetric and volumetric analyzers. The gravimetric H2 uptake of the pellets was measured at 77 K and up to 100 bar showing a high reproducibility between the different laboratories, with a small relative standard deviation of 3–4 % between pressures of 10–100 bar. The effect of operating variables like the amount of sample or analysis temperature was evaluated, remarking the calibration of devices and other correction procedures as the most significant deviation sources. Overall, the reproducible hydrogen cryoadsorption measurements indicate the robustness of the ZIF-8 pellets, which we want to propose as a reference material.

In the search of versatile electrocatalysts for the electrochemical reduction of carbon dioxide (CO2RR), different transition metal phthalocyanines (MPc, where M=Fe, Co, Ni and Cu) have been immobilized by an easy and scalable wet impregnation on carbon nanotubes (CNTs) in the form of buckypaper (BP). Both the nature of the metal and the surface chemistry of the carbon support were found to play a pivotal role in determining their CO2RR efficiency and selectivity. We disclose here a potentiodynamic strategy for the controlled surface modification of BP with N- and P-containing polymeric species as a simple heterogenization strategy for molecular catalysts, enabling to easily tune their electrocatalytic performance. Syngas (mixture of H2 and CO) was obtained as the main product from CO2RR using FePc, CoPc and NiPc as electrocatalysts on functionalized (BPf) or non-modified BP. In contrast, CuPc was found to mainly catalyze the hydrogen evolution reaction (HER), with small amounts of formate as the only CO2RR product. It is possible to modulate the H2/CO ratio in the final product through the appropriate selection of the metal in MPc, the modification of the coordination environment by the controlled functionalization of the carbon support and the adjustment of the operating conditions. In particular, H2/CO ratios in a range between 0.17 and 1.28 have been obtained with good stability during electrolysis. Among all the MPc studied, CoPc surfaced as the most promising candidate for the reduction of CO2 to CO and H2 production, a finding substantiated by computational studies highlighting the positive impact of phosphate ligands on CoPc. This strategy outlines the starting line of a potential route toward the controlled generation of CO2RR-related products.

Environmentally friendly polymers such as cellulose acetate (CA) and chitosan (CS) were used to obtain electrospun fibers for Cu2+, Pb2+, and Mo6+ capture. The solvents dichloromethane (DCM) and dimethylformamide (DMF) allowed the development of a surface area of 148 m2 g−1 for CA fibers and 113 m2 g−1 for cellulose acetate/chitosan (CA/CS) fibers. The fibers were characterized by IR-DRIFT, SEM, TEM, CO2 sorption isotherms at 273 K, Hg porosimetry, TGA, stress-strain tests, and XPS. The CA/CS fibers had a higher adsorption capacity than CA fibers without affecting their physicochemical properties. The capture capacity reached 102 mg g−1 for Cu2+, 49.3 mg g−1 for Pb2+, and 13.1 mg g−1 for Mo6+. Furthermore, optimal pH, adsorption times qt, and C0 were studied for the evaluation of kinetic models and adsorption isotherms. Finally, a proposal for adsorbate-adsorbent interactions is presented as a possible capture mechanism where, in the case of Mo6+, a computational study is presented. The results demonstrate the potential to evaluate the fibers in tailings wastewater from copper mining.

Due to the need for decarbonization in energy generation, it is necessary to develop electrocatalysts for the oxygen reduction reaction (ORR), a key process in energy generation systems such as fuel cells and metal–air batteries. Perovskite–carbon material composites have emerged as active and stable electrocatalysts for the ORR, and the interaction between both components is a crucial aspect for electrocatalytic activity. This work explores different mixing methods for composite preparation, including mortar mixing, ball milling, and hydrothermal and thermal treatments. Hydrothermal treatment combined with ball milling resulted in the most favorable electrocatalytic performance, promoting intimate and extensive contact between the perovskite and carbon material and improving electrocatalytic activity. Employing X-ray photoelectron spectroscopy (XPS), an increase in the number of M-O-C species was observed, indicating enhanced interaction between the perovskite and the carbon material due to the adopted mixing methods. This finding was further corroborated by temperature-programmed reduction (TPR) and temperature-programmed desorption (TPD) techniques. Interestingly, the ball milling method results in similar performance to the hydrothermal method in the zinc–air battery and, thus, is preferable because of the ease and straightforward scalability of the preparation process.

The use of sacrificial agents in photocatalysis is a powerful resource to enhance the performance of photoactive materials. Despite its importance, the effect of the amount of sacrificial agent is not properly described in the literature. In this paper, we have focused on the role of EtOH in the photoreduction of CO2 to CH4 using Cu-P25 photocatalysts in a flow reactor. We found that the production of CH4 increased with the concentration of EtOH, achieving an outstanding CH4 production yield of 235 µmol/(g·h) for a flow of 0.25 µmol/min of EtOH in the gas stream, hinting at the important role of the sacrificial agent in the reaction. The catalytic results together with the characterization of the materials highlight the need to achieve a minimum surface coverage of EtOH on the surface of the catalyst to control the reaction pathway. The adsorption of EtOH is a key factor in boosting the catalytic activity of the best-performing catalyst and producing CH4 from CO2 photoreduction and C2H4O from the photooxidation of EtOH, obtaining two easily separable interesting products for industrial applications in one reaction.

A mesoporous material was synthesized using silica extracts from fly ash and its properties were studied. Subsequently, it was functionalized with carbamoylmethylphosphine oxide (CMPO) to capture La3+ and Ce3+. The developed mesoporous material was obtained by the sol-gel method and was called Si-MMS (siliceous mesoporous materials), subsequently functionalized with APTMS (1-(2-aminoethyl)-3-aminopropyl trimethoxysilane) in a reflux system, which led to the synthesis of Si-MMS-APTMS. This derivative was modified with carbonyldiimidazole (CDI) and diethylphosphonoacetic acid, which finally resulted in the synthesis of Si-MMS-CMPO as the final product. The materials were characterized by DRIFT, XRD, SEM-EDS, TEM, XPS, elemental analysis and nitrogen isotherms at −196 °C, confirming that the synthesis and subsequent modification of the mesoporous structure was successful. Adsorption studies in batch systems indicated that the optimal pH for La3+ was 6, the Langmuir isotherm model and the non-linear Sips models were perfectly fitted and the best fitting kinetics is the Elovich model. For Ce3+ the optimal pH was 7.5, the non-linear Sips isotherm fit the best and the non-linear Pseudo-second order kinetics was the mechanism that best represents the adsorption. The maximum experimental adsorption capacity qe of La3+ was 17.00 mg g−1 and for Ce3+ was 30.09 mg g−1. In both cases, the rapid adsorption suggests an open porous matrix that facilitates the formation of chelates between the adsorbates and the phosphoryl group -PO32-.

In this work, highly efficient carbon-supported Pd-based catalysts for formic acid dehydrogenation were synthesized by a straightforward wet impregnation-reduction method. The carbon support was obtained from a biomass residue (almond shell) prepared via H3PO4-assisted hydrothermal carbonization (HTC) and thermal activation. This carbon support was doped with nitrogen groups to study the effect on the electronic properties and catalytic performance of the catalysts. Investigating the formation of PdAg alloys with varying Pd:Ag molar ratios resulted in catalysts exhibiting enhanced catalytic activity compared to monometallic Pd counterparts. Notably, the Pd1Ag0.5/NAS catalyst displayed outstanding catalytic performance, achieving an initial TOF of 1716 h-1 (calculated in the first 3 minutes of reaction and expressed per mole of Pd) and maintaining substantial activity over 6 consecutive reaction cycles. This work elucidates the successful synthesis of effective catalysts, emphasizing the influence of nitrogen doping and PdAg alloy composition on catalytic behavior and stability.

La, Mn and Co-based materials with diverse compositions encapsulated in N-doped carbon materials were synthesized by an in-situ sol-gel method. The as-prepared materials were physically activated with CO2 giving as a result composites with excellent performance for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The composites were characterized by different physicochemical techniques revealing the importance of porosity created by CO2 activation. This crucial step increases the number of accessible active sites such as Co-Nx-C sites, Co/MnO heterointerfaces and graphitic N groups. Moreover, the formation of La2O2CO3 was detected to enhance electrical conductivity and electrochemical performance and it is active for ORR. Although the composite containing La, Mn and Co has less concentration of the highly active sites, its small particle size favour a better distribution of these sites. The Co-containing composites were tested as air-electrodes in a Zn-air battery and compared to commercial electrocatalysts. All composites showed a better operation in terms of higher cyclability and higher energy density which is a consequence of metal nanostructures encapsulation in N-doped porous carbon shells. Interestingly, the pure Co-based composite showed an outstanding performance related to the high concentration of the Co-Nx-C active sites that provide high activity and stability.

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.