Article
Nanoscience & Nanotechnology
Xuewen Guo, Jabor Rabeah, Ruixue Sun, Dengxu Wang, Esteban Mejia
Summary: A series of hybrid porous polymers (HPPs) based on polyhedral oligomeric silsesquioxane (POSS) were synthesized and successfully used as metal-free heterogeneous photocatalysts for cross-dehydrogenative coupling reactions, showing efficient catalytic performance under visible light. The novel catalysts can be easily recovered and reused, with mechanistic investigations revealing the oxidation-reduction process during photoexcitation.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Review
Chemistry, Multidisciplinary
Johannes Grosskopf, Thorsten Bach
Summary: Upon irradiation with a suitable chiral catalyst, racemic compounds can be converted into enantiopure compounds through a process called photochemical deracemization. This review comprehensively covers the research and current developments in this field, discussing the reactions and mechanistic details underlying the presented reaction. Photochemical deracemization offers a unique opportunity to directly obtain enantiopure compounds from racemates, and short-lived intermediates play a key role in determining the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhenghui Wen, Ting Wan, Arjun Vijeta, Carla Casadevall, Laura Buglioni, Erwin Reisner, Timothy Noel
Summary: The mesoporous carbon nitride (mpg-CNx) photocatalyst enables efficient azolation of various arenes through direct oxidation, with a broad substrate scope and high photocatalytic stability. This method offers a greener and more sustainable route for the late-stage functionalization of pharmaceuticals.
Article
Chemistry, Physical
Ivano Alessandri, Irene Vassalini
Summary: This article discusses recent works on oxygen-mediated surface photoreactions, which provide an advantageous approach for addressing key issues in sustainable chemistry, circular production of feedstocks, and environmental remediation. Examples of metal and polymer recovery and recycling, metal-free oxidation of organic molecules, and the use of persistent radicals for pollution destruction and disinfection are explored, highlighting common aspects, unique features, potential, and limitations. Oxygen-mediated surface photoreactions serve as an extremely versatile tool for environmental remediation, critical raw material recycling, and sustainable feedstock production.
Article
Chemistry, Organic
Wei-Hsin Hsu, Susanne Reischauer, Peter H. Seeberger, Bartholomaus Pieber, Dario Cambie
Summary: Metallaphotoredox catalysis is a versatile synthetic platform that enables mild cross-couplings without the need for noble metals. In this study, a continuous-flow approach using a heterogeneous catalyst that combines both photo- and nickel-catalysts in one material is reported. The catalyst is embedded in a packed-bed reactor, simplifying the translation from batch to continuous flow reactions. The catalyst exhibited stability and effectiveness in the metallaphotoredox cross-coupling reactions.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Nanoscience & Nanotechnology
G. Mamba, P. J. Mafa, V. Muthuraj, A. Mashayekh-Salehi, S. Royer, T. I. T. Nkambule, S. Rtimi
Summary: In recent years, ABO(3) perovskite materials have been widely used in heterogeneous advanced oxidation processes (AOPs) for water treatment and disinfection due to their remarkable catalytic properties. This review provides an overview of the synthesis strategies, structure, and properties of ABO(3) materials, and discusses their recent applications in various AOPs, including photocatalysis, Fenton/photo-Fenton, persulphate activation, sonocatalysis/sonophotocatalysis, catalytic/photocatalytic ozonation, piezocatalysis/piezo photocatalysis, and photoelectrocatalytic oxidation. The catalytic activity of ABO(3) perovskites can be modulated through synthesis protocol, doping, heterojunction formation, and the incorporation of carbon nanomaterials. Moreover, the combination of ABO(3) materials with oxidants such as persulphate, H2O2, and O-3 enhances the activity of hybrid processes. The review also discusses the mechanisms of charge carriers' formation and transfer in ABO(3-)mediated AOPs.
MATERIALS TODAY NANO
(2022)
Review
Chemistry, Physical
Sarah Freeburne, Brock Hunter, Kirsten Bell, Christian W. Pester
Summary: Heterogeneous photocatalysis combines light chemistry with catalytic platforms to enable re-use of photocatalysts, providing economic, sustainable, safe, and user-friendly chemical syntheses. This review outlines recent developments in heterogeneous photocatalyst design and their use in mediating polymerizations. Four prevalent classes of materials, including nanoparticles, polymer networks, metal organic frameworks (MOFs), and immobilized photocatalysts on solid supports, are explored for their potential in light-mediated reversible deactivation radical polymerization.
Article
Biochemistry & Molecular Biology
Sergio Rossi, Fabian Herbrik, Simonetta Resta, Alessandra Puglisi
Summary: This paper reports the immobilization of Eosin Y onto Merrifield resin and its application in the direct photochemical arylation of furan with aryldiazonium salts. The synthesized supported photocatalyst showed high efficiency in both heterogeneous and flow reactions, with the possibility of recovery and reuse. The flow reaction demonstrated higher productivity and space-time-yield compared to batch reactions in a short reaction time.
Article
Chemistry, Physical
Nicolas Keller, Javier Ivanez, James Highfield, Agnieszka M. Ruppert
Summary: This review critically evaluates the advances in photo-/thermal synergies in catalysis, focusing on the impact of dual-mode excitation on key processes in future solar-biorefineries. It also discusses the classification of possible co-excitation synergies and the inclusion of pan-spectral absorbers in catalyst design towards process intensification.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Review
Chemistry, Physical
Fabio Julia
Summary: Despite being historically overlooked, the excited-state reactivity of 3d-metal complexes is now gaining recognition in synthetic chemistry. The emergence of photoredox catalysis has changed the perception towards photochemistry, and the utilization of outer-sphere single-electron transfer events is widely acknowledged. A new mode of photoactivation based on inner-sphere reactivity triggered by ligand-to-metal charge-transfer excited states has recently received attention. This mode, known as LMCT-activation, offers unique reactivity profiles and is particularly suitable for Earth-abundant metal complexes.
Article
Geochemistry & Geophysics
M. A. J. Brown, M. R. Patel, S. R. Lewis, J. A. Holmes, G. J. Sellers, P. M. Streeter, A. Bennaceur, G. Liuzzi, G. L. Villanueva, A. C. Vandaele
Summary: A positive vertical correlation between ozone and water ice on Mars is revealed through observation and simulation, with heterogeneous chemistry potentially impacting ozone abundance. This relationship is crucial for understanding ozone variations in the Martian atmosphere.
JOURNAL OF GEOPHYSICAL RESEARCH-PLANETS
(2022)
Article
Chemistry, Multidisciplinary
Meikun Xia, Chengliang Mao, Alan Gu, Athanasios A. Tountas, Chenyue Qiu, Thomas E. Wood, Young Feng Li, Ulrich Ulmer, Yangfan Xu, Camilo J. Viasus, Jessica Ye, Chenxi Qian, Geoffrey Ozin
Summary: This research presents an eco-friendly method for synthesizing urea from CO2 and NH3 using solar energy at room temperature, demonstrating the potential for utilizing solar energy in urea production and providing new insights for sustainable, modular plants for distributed urea production on farms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Apoorva Shetty, Vandana Molahalli, Aman Sharma, Gurumurthy Hegde
Summary: Biomass-derived carbons have unique physical and chemical properties, such as tunable surface, chemical inertness, and hydrophobicity, which make them ideal candidates to be used as heterogeneous catalysts and catalytic supports. The wide range of reactions that can be compatible with biomass-derived carbon materials includes organic transformations, electrocatalytic reactions, and photocatalytic reactions. This review discusses the uses of biomass-derived materials in the field of heterogeneous catalysis, highlighting the importance and unique properties of carbon materials derived from biomass as potential catalysts.
Review
Chemistry, Multidisciplinary
Alberto Vega-Penaloza, Javier Mateos, Xavier Companyo, Margarita Escudero-Casao, Luca Dell'Amico
Summary: Organic photocatalysts are proving to be more sustainable tools compared to metal complexes, with recent advancements in applications and structural redesign. Rational structural modification of these photocatalysts is crucial for achieving unprecedented reactivity and enhancing their catalytic performances by altering physicochemical and redox properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Beatriz Villajos, Alvaro Tolosana-Moranchel, Moises Canle, Andrea Farina, Antonio Gasco, Sara Mesa-Medina, Marisol Faraldos, Daphne Hermosilla, Ana Bahamonde
Summary: An intrinsic kinetic model based on the volumetric rate of photon absorption has been successfully validated for photocatalytic degradation, with a proposed simplified model showing excellent fitting with experimental values. The synthesized nanocomposite exhibited good stability and durability in the degradation of alachlor by photo-oxidation over six consecutive cycles of reuse.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2021)
Article
Biochemistry & Molecular Biology
Daniel R. Ramos, Paul G. Furtmueller, Christian Obinger, Moises Canle, M. Isabel Fernandez, M. Victoria Garcia, J. Arturo Santaballa
Summary: MPO is an enzyme mainly expressed in the azurophilic granules of neutrophils, and it plays a role in the defense against pathogens by catalyzing the formation of reactive oxygen species. Research shows that ionizing radiation affects MPO activity at peripheral functional groups rather than at its core structure. These findings are important for understanding the resistance mechanism of our innate anti-pathogenic defense system and for developing therapeutic strategies for autoimmune diseases.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY
(2022)
Article
Chemistry, Physical
Eduardo Humeres, Abil E. Aliev, Alessandra Smaniotto, Rafael Brognoli, Nito Angelo Debacher, Regina de F. P. M. Moreira, J. Arturo Santaballa, Moises Canle
Summary: Graphite microparticles were oxidized to graphene oxide (MPGO) and further modified to sulfur-modified graphene oxide (mMPGO). The presence of paramagnetic manganese ions in mMPGO and ring currents from graphene aromatic layers were found to affect the NMR signals of alkyl chains bound to mMPGO.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Engineering, Environmental
W. Remache, D. R. Ramos, L. Mammeri, H. Boucheloukh, Z. Marin, S. Belaidi, T. Sehili, J. A. Santaballa, M. Canle
Summary: The degradation of aqueous propranolol in a heterogeneous system with natural iron oxide and oxalic acid under near UV-Vis irradiation is investigated. The results show that the photocatalytic system is effective in removing the pollutant and the mechanism involves the formation of hydroxyl radicals.
JOURNAL OF WATER PROCESS ENGINEERING
(2022)
Article
Chemistry, Applied
S. D. Aguilar, D. R. Ramos, J. A. Santaballa, M. Canle
Summary: An innovative bulky photocatalyst for water decontamination has been developed, which combines the excellent properties of TiO2 with those of a natural clay. The photocatalyst, prepared in the form of small pellets, prevents the activity reduction usually observed in supported catalysts and can be easily reused. It showed optimum activity at a 40% clay / 60% P25 ratio and higher calcination temperatures negatively affected its performance.
Article
Chemistry, Multidisciplinary
Moises Canle, Ana M. Antao-Geraldes
Summary: A snapshot screening was conducted in an urban river to evaluate the presence and environmental risk of certain contaminants in the water and sediments. The most commonly detected contaminants were bisphenol A (BPA) and caffeine. The overall environmental risk, considering all the screened compounds together, was found to be significant. The results are discussed in relation to available literature data, and a four-color alert system is included to inform about the risk levels of specific contaminants.
APPLIED SCIENCES-BASEL
(2023)
Article
Biochemistry & Molecular Biology
Daniel R. Ramos, Paul G. Furtmueller, Christian Obinger, Angeles Pena-Gallego, Ignacio Perez-Juste, J. Arturo Santaballa
Summary: Electronic structure calculations using DFT were conducted to examine the influence of water molecules and protonation on the heme group of peroxidases in different redox and spin states. The study discusses shared geometries, spectroscopic properties, and thermodynamics of peroxidases. Computed Gibbs free energies suggest that the corresponding aquo complexes are not thermodynamically stable, supporting the five-coordinate Fe(III) center in native ferric peroxidases with a non-bonding water molecule. Protonation of the ferryl oxygen of compound II is found to be necessary and computed Gibbs free energies reveal pK(a) values of approximately 8.5-9.0 for compound II.
Article
Chemistry, Physical
Soukayna Belekbir, Mohammed El Azzouzi, Laura Rodriguez-Lorenzo, Adnane El Hamidi, Juan Arturo Santaballa, Moises Canle
Summary: One of the main challenges in photocatalysis is to find a stable and effective photocatalyst that works well under sunlight. In this study, the photocatalytic degradation of phenol in aqueous solution using TiO2-P25 impregnated with different concentrations of Co was investigated. Co(0.1%)/TiO2 showed the highest effectiveness under NUV-Vis irradiation, with approximately 96% TOC removal. UV radiation, on the other hand, only achieved 23% removal.
Article
Environmental Sciences
Marta Sanchez, Maria Isabel Fernandez, Isabel Ruiz, Moises Canle, Manuel Soto
Summary: This study evaluated the performance of a three-step lab-scale system consisting of a hybrid digester, a vertical flow constructed wetland, and a photodegradation lamp. Different arrangements of the recirculation point were tested. The system achieved excellent removal of total suspended solids (TSS) and chemical oxygen demand (COD). Additionally, the system showed significant removal of various pharmaceutical and personal care products (PPCPs), with different removal mechanisms observed in different units of the system.
Article
Green & Sustainable Science & Technology
K. Jimenez-Bautista, A. Gasco, D. R. Ramos, E. Palomo, V. Muelas-Ramos, M. Canle, D. Hermosilla, A. Bahamonde
Summary: The behavior of novel pellet-shaped bulky titania-kaolin photocatalysts in the solar-assisted photocatalytic treatment of a bio-recalcitrant pesticide mix was evaluated. The results showed promising removal of pesticides and good stability and durability of the photocatalyst. The identification of reactive species and degradation mechanisms of different pesticides were also investigated.
JOURNAL OF CLEANER PRODUCTION
(2023)
Article
Engineering, Environmental
Silvio Aguilar, Briggitte Guerrero, Angel Benitez, Daniel R. Ramos, J. Arturo Santaballa, Moises Canle, Daniel Rosado, Javier Moreno-Andres
Summary: The disinfection efficiency of novel photocatalytic macrocomposites made of Ecuadorian clay mixed with two semiconductor materials has been evaluated. The results show that these composites exhibit a significant increase in the inactivation rate of Staphylococcus aureus and Escherichia coli compared to single UVA inactivation. The specific bacterial species and material ratios affect the inactivation kinetics, with the 80% ZnO composite showing the highest efficiency at maximum loading.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2023)
Article
Biotechnology & Applied Microbiology
D. R. Ramos, M. Iazykov, M. I. Fernandez, J. A. Santaballa, M. Canle
Summary: The use of chemical-free, sunlight-driven photocatalytic units to replace traditional tertiary water treatment is often suggested. Photocatalysts are required to be cost-effective, inert, chemically stable, reusable, and easy to separate with mechanical stability. Studies have investigated how mechanical stress affects the photoactive TiO2 layer and its effectiveness in degrading phenol during photocatalytic water treatment. Various methods have been used to coat spherical glass beads with the photocatalyst TiO2, and the physicochemical characteristics of the coated beads were analyzed. The catalytic activity of the coated glass beads varied depending on the method of coating and calcination temperature, with LPD-coated glass beads generally displaying higher catalytic activity.
FRONTIERS IN CHEMICAL ENGINEERING
(2021)