Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene

Metal-free catalysts based on nitrogen-doped porous carbons were designed and synthesized from mixtures of melamine as nitrogen and carbon sources and calcium citrate as carbon source and porogen system. Considering the physicochemical and textural properties of the prepared carbons, a melamine/citrate ratio of 2:1 was selected to study the effect of the pyrolysis temperature. It was observed that a minimum pyrolysis temperature of 750 ◦C is required to obtain a carbonaceous structure. However, although there is a decrease in the nitrogen amount at higher pyrolysis temperatures, a gradual development of the porosity is produced from 750 ◦C to 850 ◦C. Above that temperature, a deterioration of the carbon porous structure is produced. All the prepared carbon materials, with no need for a further activation treatment, were active in the hydrogenation reaction of 1-chloro-4-nitrobenzene. A full degree of conversion was reached with the most active catalysts obtained from 2:1 melamine/citrate mixtures pyrolyzed at 850 ◦C and 900 ◦C, which exhibited a suitable compromise between the N-doping level and developed mesoporosity that facilitates the access of the reactants to the catalytic sites. What is more, all the materials showed 100% selectivity for the hydrogenation of the nitro group to form the corresponding chloro-aniline.Financial support from the Ministry of Science and Innovation (Spain, PID2019-108453GB-C21) and Generalitat Valenciana (Spain, CIPROM/2021/022) is gratefully acknowledged

N-Doped Activated Carbons from Polypyrrole – Effect of Steam Activation Conditions

Polypyrrole (PPy) has been prepared by oxidative polymerization of pyrrole and used as a raw material for the preparation of N-doped activated carbons. Thus, PPy has been pyrolyzed at 900 °C and then activated with steam under different activation conditions (time and temperature). This has allowed for the preparation of activated carbons with different porosity development and nitrogen content, as well as distinctive distribution of nitrogen species. It has been observed that the presence of nitrogen functionalities favors water adsorption at low relative pressures but, at relative pressures higher than 0.5 it is determined by the porosity development.Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID2019-108453GB-C21) is gratefully acknowledged. Open access funding enabled and organized by Projekt DEAL

Doped activated carbons obtained from nitrogen and sulfur-containing polymers as metal-free catalysts for application in nitroarenes hydrogenation

Activated carbons doped with nitrogen and/or sulfur have been obtained by pyrolysis followed of steam activation of a sulfur containing polymer (polythiophene) and two nitrogen-containing polymers (polyaniline and polypyrrole). These polymers were synthesized by oxidative chemical polymerization in aqueous media of their corresponding monomers. The influence of the steam activation on the textural properties and surface chemistry of the carbons has been evaluated and their catalytic activity has been determined in the hydrogenation reaction of 1-chloro-4-nitrobenzene. The degree of conversion in the reaction depends on the development of adequate porosity in the activated carbon (which is determined by the activation conditions) together with the presence of heteroatoms that act as active catalytic sites, with S showing considerably greater effectiveness than N. A compromise between an acceptable level of doping with sulfur and an adequate porosity is necessary, which has been achieved in a carbon obtained from polythiophene pyrolyzed at 900 °C and steam activated at 800 °C for 4 h, with a specific surface area of 742 m2/g and S content of 1.71 at%.Financial support from Spain Ministry of Science and Innovation (PID2019-108453GB-C21) is gratefully acknowledged

Conducting Polymer–TiO2 Hybrid Materials: Application in the Removal of Nitrates from Water

Materials able to produce the reduction of nitrate from water without the need of a metal catalyst and with avoiding the use of gaseous hydrogen have been developed by combining the synergistic properties of titania and two conducting polymers. Polymerization of aniline and pyrrol on titanium dioxide in the presence of two different oxidants/dopants (iron trichloride or potassium persulfate) has been evaluated. The resulting hybrid materials have good thermal stability imparted by the titania counterpart, and a considerable conductivity provided by the conducting polymers. The capability of the hybrid materials of reducing aqueous nitrate has been assessed and compared to the catalytic hydrogenation of nitrate using a platinum catalyst supported on these hybrid synthesized materials. The mechanism of nitrate abatement implies adsorption of nitrate on the polymer by ion exchange with the dopant anion, followed by the reduction of nitrate. The electron transfer from titania to the conducting polymer in the hybrid material favors the reductive ability of the polymer, in such a way that nitrate is selectively reduced with a very low production of undesirable side products. The obtained results show that the activity and selectivity of the catalytic reduction of nitrate with dihydrogen in the presence of a platinum catalyst supported on the hybrid materials are considerably lower than those of the metal-free nanocomposites.Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) and Ministry of Economy and Competitivity (MAT2016-80285-P) is gratefully acknowledged. E.S. acknowledges the Spanish MINECO and AEI/FEDER (ref CTQ2015-74494-JIN) and the University of Alicante (ref UATALENTO16-03)

Green synthesis of polypyrrole-supported metal catalysts: application to nitrate removal in water

Pt and Pt/Sn catalysts supported on polypyrrole (PPy) have been prepared using Ar plasma to reduce the metal precursors dispersed on the polymer. The PPy support was synthesized by chemical polymerization of pyrrole with FeCl3·6H2O, this leading to the conducting form of the polymer (conductimetric measurements). The Ar plasma treatment produced a partial reduction of platinum ions, anchored as platinum chloro-complexes to the PPy chain, into metallic platinum. A homogeneous distribution of Pt and Sn nanoparticles was observed by TEM. Activity of the PPy-supported catalysts was evaluated in the reduction of aqueous nitrate with H2 at room temperature. Nitrate concentration in water below the maximum acceptable level of 50 mg L−1 was achieved with all catalysts. However, considering not only efficiency in nitrate reduction, but also minimized concentrations of undesired nitrite and ammonium, the monometallic Pt catalyst seems to be the most promising one.Financial support from Generalitat Valenciana, Spain (PROMETEO/2009/002 – FEDER and PROMETEOII/2014/004) is gratefully acknowledged. Support by PEst-C/EQB/LA0020/2013, financed by FEDER through COMPETE – Programa Operacional Factores de Competitividade, and by FCT – Fundação para a Ciência e a Tecnologia; NORTE-07-0162-FEDER-000050, financed by QREN, ON2 and FEDER is acknowledged by LCM group. O. S. G. P. Soares acknowledges the grant received from FCT (SFRH/BPD/97689/2013)

Hydrogenation of 4-nitrochlorobenzene catalysed by cobalt nanoparticles supported on nitrogen-doped activated carbon

The hydrogenation of nitroarenes to produce the corresponding amines using dihydrogen as reducing agent has an important industrial role, since it allows to obtain important added-value products. This reaction needs the help of a catalyst to proceed. Many catalysts have been already tested and studied. Most of them are based on noble metals supported on metal oxides. These catalysts perform well, but they are expensive and thus, alternative systems are needed. In this context, cobalt-based catalysts have emerged as adequate alternatives, despite cobalt nanoparticles per se are not very active for this reaction. A way to improve the catalytic activity of cobalt nanoparticles is by supporting them on a support with functional groups that are able to change their intrinsic properties and to enhance their catalytic properties. In this sense, N-containing carbons are promising candidates to be used as support, since nitrogen functionalities may modify the catalytic properties of cobalt. In this work, cobalt nanoparticles supported on N-doped activated carbons have been prepared and studied as catalysts for the hydrogenation of 1-chloro-4-nitrobencene to the corresponding chloro-aniline. It is demonstrated that the catalytic activity is enhanced by the presence of nitrogen species in the support. When the temperature of the catalyst activation treatment (reduction under flowing hydrogen) is increased, the catalytic activity increases drastically in the presence of nitrogen functionalities on the support. The catalysts have been characterised by transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction, X-ray photoelectron spectroscopi (XPS) and N2 adsorption at 77 K. It has been found that the enhanced catalytic activity was due to two different factors, namely the interaction of the cobalt particles with the nitrogen functional groups (forming Co4N), and the development of mesopores in the support during the activation process that increases the accessibility of reactants to the active sites.Authors acknowledge financial support by MINECO (Spain) through the projects MAT2017-86992-R and MAT2016-80285-P and the European Union for the project “eForFuel”, grant agreement 763911. J. C. S. R. would like to thank the Spanish Ministry of Science and Innovation for financial support through the Ramón y Cajal Program, Grant: RYC-2015-19230 J. C. S. R. would also like to thank Junta de Andalucía for financial support through the projects PY18-RE-0012 and IE18_0047_FUNDACIÓN LOYOLA

Effect of cold Ar plasma treatment on the catalytic performance of Pt/CeO2 in water-gas shift reaction (WGS)

The effect of Ar plasma treatment on the catalytic performance of Pt/CeO2 has been studied. The catalyst was activated using different procedures separately or in combination: calcination, reduction under pure H2 and cold Ar plasma treatment. The resulting materials were characterized by X-ray photoelectron spectroscopy, X-ray adsorption near edge structure and temperature-programmed reduction with H2. The resulting materials were tested in the water-gas shift reaction (WGS). It has been found that the combination of calcination, plasma and hydrogen treatments leads to a very active catalyst for WGS. Furthermore, the catalyst structure–performance relationship has been assessed. The plasma treatment generated electron-enriched Pt particles which show a very strong interaction with the ceria support. This favoured CO chemisorption and increased the reducibility of the support, which takes part in the WGS the reaction by favouring water splitting.Financial support from Generalitat Valenciana (project PROMETEOII/2014/004) and MINECO (Project MAT2013-45008-P) is gratefully acknowledged. EVRF also thanks MINECO for his Ramon y Cajal fellow RYC-2012-11427 and the following project MAT2016-81732-ERC

Surfactant-assisted synthesis of conducting polymers. Application to the removal of nitrates from water

Three different conducting polymers, polythiophene (PT), polypirrol (PPY) and polyaniline (PANI) have been synthesized via oxidative chemical polymerization in aqueous media, in such a way that the synthesis protocol did not involve any toxic solvents. They have been tested in the abatement of nitrates from an aqueous solution without the need of any metal catalyst. The N-containing polymers (PANI and PPy) were able to remove nitrates to a level that accomplishes the European legislation requirements; however, the nature of each polymer greatly influenced the process mechanism. Whereas ion exchange between Cl- and SO42- counter-ions in the polymer and NO3- from water is the main responsible for the effective nitrate removal in PANI, as assessed by FTIR and XPS analyses, the nitrate removal mechanism on PPy is based in an electron transfer from the polymer to nitrate through N sites located in the pyrrolic ring. On the other hand, PT was not able to exchange nitrate unless it was synthesized with FeCl3 as oxidant/dopant and an anionic surfactant (sodium dodecyl sulfate -SDS-) is used. In that case, the electrostatic attraction between sulfate (OSO3-) groups from the surfactant and Fe3+ ions from FeCl3 produced the anchoring of Cl- to the oxidized PT growing chain, this favoring ion exchange with nitrate in the aqueous solution, followed by a redox process.Financial support from Generalitat Valenciana, Spain (PROMETEOII/2014/004) is gratefully acknowledged

Highly N2-Selective Activated Carbon-Supported Pt-In Catalysts for the Reduction of Nitrites in Water

The catalytic reduction of nitrites over Pt-In catalysts supported on activated carbon has been studied in a semi-batch reactor, at room temperature and atmospheric pressure, and using hydrogen as the reducing agent. The influence of the indium content on the activity and selectivity was evaluated. Monometallic Pt catalysts are very active for nitrite reduction, but the addition of up to 1 wt% of indium significantly increases the nitrogen selectivity from 0 to 96%. The decrease in the accessible noble metal surface area reduces the amount of hydrogen available at the catalyst surface, this favoring the combination of nitrogen-containing intermediate molecules to promote the formation of N2 instead of being deeply hydrogenated into NH4+. Several activated carbon-supported Pt-In catalysts, activated under different calcination and reduction temperatures, have been also evaluated in nitrite reduction. The catalyst calcined and reduced at 400°C showed the best performance considering both the activity and the selectivity to nitrogen. This enhanced selectivity is ascribed to the formation of Pt-In alloy. The electronic properties of Pt change upon alloy formation, as it is demonstrated by XPS.This work was financially supported by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by natiunal funds through FCT/MCTES (PIDDAC). Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID 2019-108453GB-C21 and PID 2020-116998RB-I00) is gratefully acknowledged

Cosmological bounds on neutrino statistics

We consider the phenomenological implications of the violation of the Pauli exclusion principle for neutrinos, focusing on cosmological observables such as the spectrum of Cosmic Microwave Background anisotropies, Baryon Acoustic Oscillations and the primordial abundances of light elements. Neutrinos that behave (at least partly) as bosonic particles have a modified equilibrium distribution function that implies a different influence on the evolution of the Universe that, in the case of massive neutrinos, can not be simply parametrized by a change in the effective number of neutrinos. Our results show that, despite the precision of the available cosmological data, only very weak bounds can be obtained on neutrino statistics, disfavouring a more bosonic behaviour at less than 2sigma