L. Mascaretti, A. Dutta, Š. Kment, V. M. Shalaev, A. Boltasseva, R. Zbořil, and A. Naldoni, "Plasmon-enhanced photoelectrochemical water splitting for efficient renewable energy storage," ADVANCED MATERIALS, Article in press.
DOI: 10.1016/j.ccr.2018.09.017, IF = 21.95
P.Štarha, J.Vančo, Z.Trávníček: Platinum iodido complexes: A comprehensive overview of anticancer activity and mechanisms of action, COORDINATION CHEMISTRY REVIEWS vol. 380, pp. 103-135, 2019.
DOI: 10.1016/j.ccr.2018.09.017, IF = 14.499
Abstract: Platinum iodido complexes have long been recognized as synthetic intermediates of various platinum complexes (e.g., chlorido or carboxylato), including the world-wide used platinum-based anticancer drugs cisplatin, carboplatin and oxaliplatin. At the same time, platinum iodido complexes have been overlooked by bioinorganic chemists, because several pioneer works deemed the iodido ligand as unsuitable for the development of novel platinum-based metallotherapeutics. This was because most of platinum iodido complexes were identified as biologically and pharmacologically non-prospective as compared with the chlorido analogues. More recently, several research teams have developed various types of platinum iodido complexes as substances possessing the combination of promising chemical, physical, and especially biological properties. In particular, a number of platinum iodido complexes showed higher activity than their chlorido analogues and they exceeded even the activity of the conventional platinum-based drugs. Additionally, a lot of results have implied that relevant differences exist in the mechanism of action between platinum iodido agents, and their chlorido analogues and clinically-used platinum complexes
I.S. Pieta, A. Rathi, P. Pieta, R. Nowakowski, M. Hołdynski, M. Pisarek, A. Kaminska, M.B.Gawande, R.Zboril: Electrocatalytic methanol oxidation over Cu, Ni and bimetallic Cu-Ni nanoparticles supported on graphitic carbon nitride, APPLIED CATALYSIS B: ENVIRONMENTAL, vol. 244, pp. 272-283, 2019.
DOI: 10.1016/j.apcatb.2018.10.072, IF = 11.698
Abstract: Ni, Cu and Cu–Ni nanostructures have been fabricated and homogeneously embedded on ultrathin two-dimensional (2D) carbon nitride (g-C3N4), and the surface morphology and composition of the resulting hybrid nanostructures were studied by XRD, TEM, HRTEM-elemental mapping, Raman spectroscopy and XPS. The new hierarchical hetero-structures dropcasted on GC anodes have been visualised by SEM and their catalytic performance have been examined in methanol electrooxidation reaction (MOR) under alkaline conditions. Nanosized Ni particles dispersed finely over g-C3N4 are very active electrocatalysts with MOR onset at potential 0.35 V and charge transfer resistance 0.12 kΩ. The stability of modyfied GC electrodes, examined under chronoamperometric conditions showed that for electrode loading with 4% (wt. %) of NiO the stable current density ca. 36 A g−1 (12 A cm2) was obtained during whole experiment (up to 160 min). For all catalyst studied the curent density obtained during MOR reaction was enhanced when electrode was iluminated by UV light λ∼400 nm, and the highest value were obtained for 4% Ni/CN catalyst ca. 127 A g−1 (22 A cm2). The Cu incorporation in the hybrid material evoke loss of activity mostly due to Cu+ irreversible reduction/oxidation to Cu° and Cu2+, CuO segregation and influencing electron transfer process which results in the increasing in the redox potential. These results represent an important step towards light-enhanced electro-reactive systems and sensors in which heterojunction formation can facilitate electron-hole separation and enable more efficient energy transfer.
A.Naldoni, M. Altomare, G.Zoppellaro, N. Liu, Š.Kment, R.Zbořil, P.Schmuki: Photocatalysis with Reduced TiO2: From Black TiO2 to Cocatalyst-Free Hydrogen Production, ACS CATALYSIS, vol. 9, iss. 1, pp. 345-364, 2019.
DOI: 10.1021/acscatal.8b04068, IF = 11.384
Abstract: Black TiO2 nanomaterials have recently emerged as promising candidates for solar-driven photocatalytic hydrogen production. Despite the great efforts to synthesize highly reduced TiO2, it is apparent that intermediate degree of reduction (namely, gray titania) brings about the formation of peculiar defective catalytic sites enabling cocatalyst-free hydrogen generation. A precise understanding of the structural and electronic nature of these catalytically active sites is still elusive, as well as the fundamental structure–activity relationships that govern formation of crystal defects, increased light absorption, charge separation, and photocatalytic activity. In this Review, we discuss the basic concepts that underlie an effective design of reduced TiO2 photocatalysts for hydrogen production such as (i) defects formation in reduced TiO2, (ii) analysis of structure deformation and presence of unpaired electrons through electron paramagnetic resonance spectroscopy, (iii) insights from surface science on electronic singularities due to defects, and (iv) the key differences between black and gray titania, that is, photocatalysts that require Pt-modification and cocatalyst-free photocatalytic hydrogen generation. Finally, future directions to improve the performance of reduced TiO2 photocatalysts are outlined.
H.Barès, A.Bakandritsos, M.Medveď, J.Ugolotti, P.Jakubec, O.Tomanec, S.Kalytchuk, R.Zbořil, M.Otyepka: Bimodal role of fluorine atoms in fluorographene chemistry opens a simple way toward double functionalization of graphene, CARBON vol. 145, pp. 251-258, 2019.
DOI: 10.1016/j.carbon.2019.01.059, IF = 7.082
Abstract: Photo-triggered and double functionalization of graphene without use of aggressive photo-generated radicals is a challenging task in two-dimensional chemistry. This was here-in achieved by unravelling the bimodal role of fluorine atoms in fluorographene chemistry: (i) they rendered graphene's double bonds susceptible to reaction with a photo-activated diene and (ii) allowed nucleophilic substitution on F-bonded carbons. Theoretical calculations indicated that the presence of F atoms in the vicinity of sp2 carbon domains significantly increased bond polarization, turning the otherwise unfeasible on pristine graphene photo-cycloaddition into a very efficient functionalization strategy. Following this strategy, we prepared new graphene derivatives densely and homogeneously covered by functional groups. Furthermore, photo-induced cycloaddition following amine nucleophilic substitution on fluorographene enabled preparation of a bis-functionalized graphene derivative. The reported procedure paves the way toward unexplored graphene derivatives not attainable through known graphene chemistries, which can be utilized in many applications such as dual read-out sensors, drug delivery systems, catalysis, and energy storage.
D.D.Chronopoulos, M. Medved’, P.Błoński, Z. Nováček, P.Jakubec, O.Tomanec, A.Bakandritsos, V.Novotná, R.Zbořil, M.Otyepka: Alkynylation of graphene via the Sonogashira C–C cross-coupling reaction on fluorographene, CHEMICAL COMMUNICATIONS, vol. 55, iss. 8, pp. 1088–1091, 2019.
DOI: 10.1039/c8cc08492k, IF = 6.29
Abstract: We report successful grafting of alkynyl groups onto graphene via the Sonogashira reaction between fluorographene and terminal alkynes. Theoretical calculations revealed that fluorographene can efficiently bind and oxidize the palladium catalyst on electrophilic sites activated by fluorine atoms. This paves the way towards conductive and mechanically robust 3D covalent networks.
L. Stadler, M. Homafar, A. Hartl, S. Najafishirtari, M. Colombo, R.Zboril, P. Martin, M.B.Gawande, J. Zhi, O. Reiser: Recyclable Magnetic Microporous Organic Polymer (MOP) Encapsulated with Palladium Nanoparticles and Co/C Nanobeads for Hydrogenation Reactions, ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 7, iss. 2, pp. 2388–2399, 2019.
DOI: 10.1021/acssuschemeng.8b05222, IF = 6.14
Abstract: Microporous organic polymers (MOPs) encapsulated with palladium nanoparticles (NPs) and immobilized on magnetic Co/C nanobeads show excellent activity in hydrogenation reactions of alkenes, alkynes, and nitro arenes with turnover frequencies (TOFs) up to 3000 h–1. The magnetic core of the nanobeads ensures an easy and fast recyclability for at least six consecutive runs by applying an external magnet to recapture the catalyst. The catalytic system reported here uses cross-linked toluene as a polymer structure and is readily prepared via a cost-efficient and versatile synthesis based on commercially available starting materials. The novel catalysts combine the advantages of a heterogeneous magnetic support with MOPs that prevent NPs from agglomeration or deactivation. In addition, the advantages of palladium NPs as exceedingly active catalyst due to their high surface-area-to-volume ratio are exploited. Furthermore, the polymeric structure can easily be varied by the change of the aromatic monomer. Introducing hydroxyl groups by 2,2′-biphenol as the monomer into the MOP, the leaching of palladium and cobalt from the catalyst can be reduced to a minimum.