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The composition of the catalyst layer plays an important role in the carbon dioxide reduction reaction (CO 2 RR), since it influences greatly the mass diffusion rate and the accessibility of active sites. Until now, tremendous efforts have been dedicated to the development of cathode materials with innovative characteristics, while scarce efforts have been concentrated on the study of the catalyst layer aiming at maximizing the performance of the electrodes toward the CO 2 RR. This work focuses on a full investigation of the key electrode components and their effects on the CO 2 RR performance. It is found that all key components such as Nafion binder, zinc oxide catalyst and carbon black conductor significantly affect the current density and the faradaic efficiency for carbon monoxide (CO) formation. [Display omitted] • A thorough study of the composition of a ZnO-based electrode is conducted for CO 2 RR. • All key components show significant effects on CO selectivity and production rate. • Nafion favors charge transfer while it limits electron transport and CO 2 diffusion. • Carbon black considerably increases electrical conductivity. • ZnO loading is associated with the number of active sites and their accessibility. [ABSTRACT FROM AUTHOR]

[Display omitted] • The submitted work is of great interest for the Journal Applied Energy due to its peculiar theme, the electrochemical CO 2 reduction, and for its approach in the investigation. Indeed, a complete ab initio modelling guided the experimental synthesis and testing of a molecular electrocatalyst which shows great performances for the CO2RR. • This work elucidate the possibility to activate the CO 2 through organic molecules and, moreover, shows the feasibility of this approach to be completely integrated inside a TRL 3–4 electrolysis cell. The electrochemical reduction of CO 2 to value-added products is hindered by its thermodynamic stability and by the large energy required to chemically activate the molecule. With this respect, forcing CO 2 in a non-linear geometry would induce an internal electron charge rearrangement which would facilitate further electrochemical transformations. In this work, we achieved this goal through the design of a dual function electro-organocatalyst, which exploits the ability of the imidazolate (Im-) lone pair to bind CO 2 via nucleophilic attack and then electrochemically reduce it. To give structural stability to the Im- based catalyst, the imidazoles species are incorporated into a solid structure, namely ZIF-8. Once activated by the organic Im- ligand, CO 2 is electrochemically reduced to CO when a bias is applied to ZIF-8. The catalyst proposed in our study was first devised by computer aided design based on Density functional Theory simulations and then realized in laboratory. Our results demonstrate that ZIF-8 supported on conductive CNTs presents surface Im- active sites which convert CO 2 into CO with a high faradaic efficiency (70.4 %) at −1.2 V vs reversible hydrogen electrode, by combining chemical activation with electrochemical catalysis. [ABSTRACT FROM AUTHOR]

• CO oxidation was studied by in situ Raman spectroscopy on nanostructured ceria-based materials. • In situ Raman analyses during CO oxidation allowed to monitor defect sites in operando conditions. • Cycles of reduction (CO in N 2) and oxidation (pure O 2) at 400 °C allow to study the stability of defects. • Oxygen vacancies evolved from clusters to isolated ones according to the atmosphere and temperature. • The involvement of the defect sites in structural rearrangement is fostered by easily reducible dopants. Among the factors affecting ceria activity, the defectiveness plays a key role in the case of CO oxidation. In this study, its connection with the catalytic performance was investigated via in-situ Raman spectroscopy on nanostructured pure and Cu/Mn-doped ceria, monitoring the defect sites and surface species evolution during the reaction. The accumulation of polyene-like chains, formed through CO dissociative adsorption at the catalyst surface, was observed and their disappearance was related to the catalyst light-off temperature. Moreover, the doped samples exhibited a rise of the Raman bands associated to defects after the tests, consequence of the structural rearrangements occurring during CO oxidation. Indeed, in-situ Raman measurements during reduction (CO/N 2) and oxidation cycles at 400 °C evidenced the formation of oxygen vacancy clusters in reducing atmosphere, which could reorganize not only in O 2 but also upon a temperature decrease, forming isolated vacancies and then evolving in Frenkel and extrinsic oxidized dopant-containing sites when exposed to oxygen. [ABSTRACT FROM AUTHOR]

Highly efficient, separable, and stable magnetic iron-based-photocatalysts produced from ultra-stable Y (USY) zeolite were applied, for the first time, to the photo-Fenton removal of phenol under solar light. USY Zeolite with a Si/Al molar ratio of 385 was impregnated under vacuum with an aqueous solution of Fe2+ ions and thermally treated (500–750 °C) in a reducing atmosphere. Three catalysts, Fe-USY500°C-2h, Fe-USY600°C-2h and Fe-USY750°C-2h, containing different amounts of reduced iron species entrapped in the zeolitic matrix, were obtained. The catalysts were thoroughly characterized by absorption spectrometry, X-ray powder diffraction with synchrotron source, followed by Rietveld analysis, X-ray photoelectron spectroscopy, N 2 adsorption/desorption at −196 °C, high-resolution transmission electron microscopy and magnetic measurements at room temperature. The catalytic activity was evaluated in a recirculating batch photoreactor irradiated by solar light with online analysis of evolved CO 2. Photo-Fenton results showed that the catalyst obtained by thermal treatment at 500 °C for 2 h under a reducing atmosphere (FeUSY-500°C-2h) was able to completely mineralize phenol in 120 min of irradiation time at pH = 4 owing to the presence of a higher content of entrapped nano-sized magnetite particles. The latter promotes the generation of hydroxyl radicals in a more efficient way than the Fe-USY catalysts prepared at 600 and 750 °C because of the higher Fe 3 O 4 content in ultra-stable Y zeolite treated at 500 °C. The FeUSY-500°C-2h catalyst was recovered from the treated water through magnetic separation and reused five times without any significant worsening of phenol mineralization performances. The characterization of the FeUSY-500°C-2h after the photo-Fenton process demonstrated that it was perfectly stable during the reaction. The optimized catalyst was also effective in the mineralization of phenol in tap water. Finally, a possible photo-Fenton mechanism for phenol mineralization was assessed based on experimental tests carried out in the presence of scavenger molecules, demonstrating that hydroxyl radicals play a major role. [Display omitted] • Stable catalysts were prepared by entrapping Fe species in ultra-stable Y zeolite. • The catalyst's magnetic properties allow easy separation and reuse. • Complete phenol removal is achieved by solar light-driven photo-Fenton reaction. • Phenol mineralization increases with Fe 3 O 4 content in ultra-stable Y zeolite. • Hydroxyl radicals play the main role in the removal of phenol under solar light. [ABSTRACT FROM AUTHOR]

Abstract: The synthesis of a series of azobenzene containing liquid crystalline methacrylic homopolymers, poly(4-ω-methacryloyloxy-hexyloxy-4′-ethoxyazobenzene) [Poly(M6A)], with distinct average chain lengths and low polydispersity has been achieved by Atom Transfer Radical Polymerization (ATRP) in THF solution using allyl 2-bromoisobutyrate as initiator and Cu(I)Br as catalyst. Under the adopted conditions the living centers concentration is found to be constant throughout the polymerization process and well defined chain end-groups are obtained. All the obtained polymeric samples, having average molecular mass ranging from 3300 to 14000g/mol, exhibit smectic and nematic liquid-crystalline phases on heating, with transition temperatures strongly dependent on polymerization degree, as characterized by differential scanning calorimetry and polarized optical microscopy. The photomechanical effects (i.e. the dependence of volume and density) exhibited upon trans-to-cis and cis-to-trans photoisomerization of the azobenzene mesogenic groups have been investigated by ellipsometry and related to molecular weight, with particular attention to important parameters for potential applications such as the relative variation of total volume, response time, stability and reproducibility. [Copyright &y& Elsevier]