Photocatalytic processes as a potential solution for plastic waste management

Plastics have become a critical environmental problem due to their widespread use, high physico-chemical stability and the inefficiency of wastewater treatments. Despite the efforts to reduce production and to increase reuse and recycling, the current strategies for plastic waste treatment are not suitable to handle with the growing demand of plastics and the concomitant waste in an environmentally friendly manner. Herein, we review the existing strategies for the treatment of plastic waste, highlighting photocatalytic processes as a potential solution for the degradation of plastics. The possibility of incorporating photocatalysts to plastics during the production process could enhance their light-activated biodegradability. Parallelly, photocatalysts can be employed during waste treatment processes of non-biodegradable stable plastics. The scarcely studied factors affecting plastic photocatalytic degradation, namely catalyst type, reactor configuration, and radiation source (intensity and wavelength), are discussed, highlighting the role that photocatalytic processes can play in the future of plastic management. Finally, relevant quantification methods for measuring the photo-degradation of plastics are overviewed. We believe that photocatalysis can be an environmentally friendly strategy both to increase the biodegradability of plastics and to treat plastic waste. With this novel comprehensive overview, we hope to stimulate further research and innovation in this field.Xunta de Galicia | Ref. ED481B 2019/091Universidade de Vigo/CISU

Compositional fluctuations mediated by excess of tellurium in bismuth antimony telluride nanocomposite yields high thermoelectric performance

A high thermoelectric figure of merit (ZT) in state-of-the-art bismuth antimony telluride (BST) composites was attained by an excess tellurium-assisted liquid-phase compaction approach. Herein, we report a maximum ZT of approximate to 1.4 at 500 K attained for BST bulk nanocomposites fabricated by spark plasma sintering of colloidally synthesized (Bi,Sb)(2)Te-3 platelets and Te-rich rods. The Terich nanodomains and antimony precipitation during sintering result in compositional fluctuations and atomic ordering within the BST-Te eutectic microstructure, which provides additional phonon scattering and hole contributions. The electrical transport measurement and theoretical calculations corroborate the altered free carrier density via lattice defects and atomic ordering under Te-rich conditions, resulting in a higher power factor. Microstructural studies suggest that reduction in lattice thermal conductivity is due to composite interfaces and defects in the closely packed (Bi,Sb)(2)Te-3 matrix with unevenly distributed Sband Te-rich nanodomains. This work provides an unconventional chemical synthesis route with large scalability for developing high-performance chalcogenide-based bulk nanocomposites for thermoelectric applications.- We thank the members of the Nanochemistry Research Group (http://nanochemgroup.org) at INL for insightful discussions and support. This work was supported by the Portuguese national funding agency for science, research, and technology (FCT) under the UT-BORN-PT project (UTAP-EXPL/CTE/0050/2017), strategic project UID/FIS/04650/2020, Project SATRAP (POCI-01-0145-FEDER-028108) and Advanced Computing Project CPCA/A2/4513/2020 for access to MACC-BOB HPC resources. B.A.K. acknowledges funding of this work by the Robert A. Welch Foundation (grant no. F1464). N.S.C. and T.M. acknowledge SERB, India (project no. SPO/SERB/MET/2018547) for financial support

Synergistic Computational–Experimental Discovery of Highly Selective PtCu Nanocluster Catalysts for Acetylene Semihydrogenation

Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic approach using density functional theory (DFT) to identify the best catalyst in a Cu–Pt system. The DFT results showed that with a 55 atom system at ∼1.1 Pt/Cu ratio for Pt28Cu27/Al2O3, the d-band center shifted −2.2 eV relative to the Fermi level leading to electron-saturated Pt, which allows only adsorption of ethylene via a π-bond, resulting in theoretical 99.7% SC2H4 at nearly complete XC2H2. Based on the DFT results, Pt–Cu/Al2O3 (PtCu) and Pt/Al2O3 (Pt) nanocatalysts were synthesized via cluster beam deposition (CBD), and their properties and activities were correlated with the computational predictions. For bimetallic PtCu, the electron microscopy results show the formation of alloys. The bimetallic PtCu catalyst closely mimics the DFT predictions in terms of both electronic structure, as confirmed by X-ray photoelectron spectroscopy, and catalytic activity. The alloying of Pt with Cu was responsible for the high C2H4 specific yield resulting from electron transfer between Cu and Pt, thus making PtCu a promising catalyst for SHA

Discovery of Colossal Breathing-Caloric Effect under Low Applied Pressure in the Hybrid Organic–Inorganic MIL-53(Al) Material

Financiado para publicación en acceso aberto: Universidade da Coruña/CISUG[Abstract] In this work, “breathing-caloric” effect is introduced as a new term to define very large thermal changes that arise from the combination of structural changes and gas adsorption processes occurring during breathing transitions. In regard to cooling and heating applications, this innovative caloric effect appears under very low working pressures and in a wide operating temperature range. This phenomenon, whose origin is analyzed in depth, is observed and reported here for the first time in the porous hybrid organic–inorganic MIL-53(Al) material. This MOF compound exhibits colossal thermal changes of ΔS ∼ 311 J K–1 kg–1 and ΔH ∼ 93 kJ kg–1 at room temperature (298 K) and under only 16 bar, pressure which is similar to that of common gas refrigerants at the same operating temperature (for instance, p(CO2) ∼ 64 bar and p(R134a) ∼ 6 bar) and noticeably lower than p > 1000 bar of most solid barocaloric materials. Furthermore, MIL-53(Al) can operate in a very wide temperature range from 333 K down to 254 K, matching the operating requirements of most HVAC systems. Therefore, these findings offer new eco-friendly alternatives to the current refrigeration systems that can be easily adapted to existing technologies and open the door to the innovation of future cooling systems yet to be developed.This work was financially supported by Ministerio de Economía y Competitividad MINECO and EU-FEDER (projects MAT2017-86453-R and PDC2021-121076-I00), Xunta de Galicia and IACOBUS Programme. Funding for open access fee was provided by Universidade da Coruña/CISU

Covalent organic frameworks as catalyst support: A case study of thermal, hydrothermal, and mechanical pressure stability of β-ketoenamine-linked TpBD-Me2

Covalent organic frameworks (COFs) are crystalline, ordered networks, that, due to their high surface areas and the opportunity for periodic placement of catalytically active sites, are interesting materials for catalysis. Despite the great interest in the use of COFs for this application, there is currently a lack of fundamental understanding on how catalytically relevant conditions affect the integrity of the materials. To gain insight into the stability of COFs as catalyst supports, we herein subjected a β-ketoenamine-linked COF to thermal treatment at high temperatures, to autogenous pressure in water at different temperatures, and to mechanical pressure during pelletizing, after which the materials were thoroughly characterized to gain insight into the structural changes occurring during these catalytically relevant treatments. The COF was largely stable under all hydrothermal conditions studied, highlighting the applicability of β-ketoenamine-linked COFs under aqueous and vapor conditions. On the other hand, thermal and pressure treatments led to a rapid decline in the surface area already at the lowest temperatures and pressures studied. Theoretical calculations indicated this loss to stem from interlayer rearrangement or buckling of the COF layers induced by the applied conditions. This study demonstrates the suitability of β-ketoenamine-linked COFs for use under hydrothermal conditions, and sheds light on the degradation pathways under thermal and pressure treatments, opening the path to the design of COFs with increased stability under such conditions.Fundação para a Ciência e a Tecnologia | Ref. UTA-EXPL/NPN/0055/2019Fundação para a Ciência e a Tecnologia | Ref. PTDC/QUI-OUT/2095/2021Fundação para a Ciência e a Tecnologia | Ref. PTDC/EQU-EQU/1707/2020Agencia Estatal de Investigación | Ref. RYC2020-030414-IUniversidade de Vigo/CISU

A post-synthetic modification strategy for the synthesis of pyrene-fused azaacene covalent organic frameworks

Post-synthetic modification strategy is presented to extend the π-system of covalent organic framework (COF) backbone giving access to boronic ester based pyrene-fused azaacene COFs. Optimized catalyst-free reaction conditions yield COFs post-synthetically modified with up to 33% conversion and corresponding intriguing optical properties. The presented chemistry is expected to find application in post-synthetic tailoring of the optical properties of COFs.S.P.S.F. acknowledges the FCT − Fundação para a Ciência e Tecnologia for the Ph.D. scholarship SFRH/BD/131791/2017. This work received funding from the COFforH2 project (UTA-EXPL/NPN/0055/2019) through the Portuguese Foundation for Science and Technology funds under UT Austin Portugal, Charm project (PTDC/QUI-OUT/2095/2021) through the Portuguese Foundation for Science and Technology funds, The Excellence Clusters ‘Nanosystems Initiative Munich (NIM)’, and from the Free State of Bavaria through the Research Network ‘Solar Technologies go Hybrid’.Peer reviewe

Electrocatalysis using nanomaterials

Since the turn of the millennium, the search for highly efficient electrocatalysts has been strongly directed toward nanomaterials, which exhibit an array of interesting properties due to finite-size effects. For example, nanoelectrocatalysts usually have enhanced electrical conductivity, high effective electrochemically active surface area, and tunable strength of substrate/intermediate bonding, among other useful electrochemical properties. In this chapter, we explore what makes nanoelectrocatalysts so effective. This includes an introduction to nanoscale effects in electrocatalysis followed by an overview of the electrochemical characterization techniques most typically applied to electrocatalytic nanomaterials. We then provide in-depth discussion on some of the most important electrocatalytic processes of interest, namely those reactions in which H[sbnd]H, O[dbnd]O, and C[sbnd]O bonds are broken or formed over nanoelectrocatalysts, and go on to showcase the potential of these materials to catalyze the formation of N-containing compounds

Enhanced Thermoelectric Performance in Hf-Free p-Type (Ti, Zr)CoSb Half-Heusler Alloys

High thermal conductivity and exorbitant cost of Hf has for a long time limited the prospects of half-Heusler (HH) alloys for applicability in thermoelectric (TE) energy conversion devices. This work demonstrates the implication of nanostructuring and efficacy of p-type acceptor dopant in (Ti,Zr)CoSb based HH alloys for enhancing the figure of merit (ZT) while eliminating the use of Hf. A series of (Ti,Zr)CoSb1-x(Si,Sn)(x) HH composition was synthesized using arc-melting and consolidated employing spark plasma sintering (SPS). The optimal doping of acceptor dopants, namely, Si and Sn significantly improves the power factor and strengthens the phonon scattering resulting in an enhanced TE performance with maximum ZT of 0.26 and 0.5 at 873 K, obtained for TiCoSb0.8Sn0.2 and ZrCoSb0.8Sn0.2, respectively. For further optimization, microstructural modifications by fine-tuning of the Ti to Zr ratio induces strain field effects and mass fluctuation in (Ti,Zr)CoSb0.8Sn0.2 compositions, which remarkably introduces additional phonon scattering resulting in maximum ZT similar to 0.8 at 873 K for the best performing Zr0.5Ti0.5CoSb0.8Sn0.2 compound. The current study provides a better understanding of p-type dopants in HH materials by which prospective high TE performance can be obtained in low-cost Hf-free p-type (Ti,Zr)CoSb half-Heusler alloys

Multiple emulsions as soft templates for the synthesis of multifunctional silicone porous particles

\u3cp\u3eMultiple emulsion templating is a versatile strategy for the synthesis of porous particles. The present work addresses the synthesis of multifunctional poly(dimethylsiloxane) porous particles using multiple water-in-oil-in-water emulsions as soft templates with an oil phase constituted by a crosslinkable poly(dimethylsiloxane) (PDMS) oil. Herewith, the impact of the viscosity of PDMS oil (i.e., molecular weight) on the properties of both the emulsion templates and the resulting particles was evaluated. The viscosity of PDMS oil has a strong effect on the size and polydispersity of the emulsion templates as well as on the mechanical properties of the derived particles. The elastic modulus can be tuned by mixing PDMS oils of different viscosities to form bimodal crosslinked networks. Iron oxide nanoparticles can be readily incorporated into the emulsion templates to provide additional functionalities to the silicone particles, such as magnetic separation or magnetic hyperthermia. The synthesized composite magnetic particles were found to be useful as recoverable absorbent materials (e.g., for oil spills) by taking advantage of their high buoyancy and high hydrophobicity.\u3c/p\u3