Review
Chemistry, Multidisciplinary
Jan-Hendrik Kruse, Marcel Langer, Iuliia Romanenko, Ivan Trentin, David Hernandez-Castillo, Leticia Gonzalez, Felix H. Schacher, Carsten Streb
Summary: Molecular metal oxides or polyoxometalates (POMs) exhibit unique properties, but their technological application is hindered by their molecular nature. Immobilizing POMs on heterogeneous substrates has become a central theme in research. Integration of POMs in soft matter matrices has led to breakthroughs in composite design. This review summarizes the progress in this emerging field, highlights challenges to be overcome, and provides insights into future directions.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Yupeng Zhao, Dandan Gao, Si Liu, Johannes Biskupek, Ute Kaiser, Rongji Liu, Carsten Streb
Summary: Efficient and stable oxygen evolution reaction (OER) catalysts based on noble-metal-free materials are crucial for energy conversion and storage. This study demonstrated the conversion of polyoxometalate (POM)-doped ZIF-67 into a stable oxygen evolution electrocatalyst through chemical etching, cation exchange, and thermal annealing steps. Characterization techniques confirmed the synthesis of POM-doped ZIF-67 derived carbon-supported metal oxides, which exhibited structural and compositional advantages leading to low overpotential (306 mV at j=10 mA center dot cm(-2)) and long-term stability under harsh OER conditions (1.0 M aqueous KOH).
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Knoll, Matthias Haenle, Alexander K. Mengele, Dieter Sorsche, Sven Rau, Carsten Streb
Summary: CLICK-chemistry is used to covalently link organic molecules with azides and alkynes. This study demonstrates the attachment of oligoaromatic organic moieties to Dawson-type polyoxometalates using CLICK-chemistry. The versatility and supramolecular chemistry of these systems are explored, and the charge-transfer behavior is found to depend on the size of the oligoaromatic pi-system.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Nanoscience & Nanotechnology
Daniel Costabel, Afshin Nabiyan, Avinash Chettri, Franz Jacobi, Magdalena Heiland, Julien Guthmuller, Stephan Kupfer, Maria Waechtler, Benjamin Dietzek-Ivansic, Carsten Streb, Felix H. Schacher, Kalina Peneva
Summary: We present a photocatalytic setup using the organic photosensitizer diiodo-BODIPY, the non-precious-metal-based hydrogen evolution reaction catalyst (NH4)2[Mo3S13], and a polyampholytic unimolecular matrix poly(dehydroalanine)-graft-poly(ethylene glycol) in water. The system exhibits remarkable performance with high turnover numbers (TON > 7300) and turnover frequencies (TOF > 450 h-1), comparable to noble-metal-containing systems. Excited-state absorption spectra confirm the formation of a long-lived triplet state of the photosensitizer in both water and organic media. This system serves as a blueprint for developing noble-metal-free hydrogen evolution reaction in water, allowing for component optimization by modifying the substituent of the photosensitizer and the composition of the catalyst.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Nikhil Arya, Tom Philipp, Simon Greiner, Michael Steiner, Christine Kranz, Montaha Anjass
Summary: The reversible electrodeposition of molecular vanadium oxide clusters and the formation of thin films are reported. The reversibility is found to be dependent on the reduction potential. The multi-electron reduction of the polyoxovanadate cluster facilitates the reversible formation of potassium vanadium oxide thin films.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Martin Laemmle, Alexander K. K. Mengele, Georgina E. E. Shillito, Stephan Kupfer, Sven Rau
Summary: In recent decades, research on artificial photocatalysis aiming to mimic natural photosynthesis has focused on reducing fossil fuel consumption through efficient solar energy harvesting. However, the instability problems of catalysts during light-driven operation are major challenges for industrial-scale implementation. This review discusses the structure-catalyst-stability relationships of di- and oligonuclear photocatalysts with different bridging ligand architectures, as well as the effects of ligands on catalytic centers and their implications for catalytic activity in intermolecular systems, providing important insights for the future design of operationally stable catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Carsten Streb
Summary: The atomically precise assembly of metal nanoparticles provides great opportunities for materials chemistry. Ring-shaped polyoxometalates have been used to stabilize Ag-30 nanoparticles with exposed surfaces.
Review
Chemistry, Multidisciplinary
Samar Batool, Marcel Langer, Stephen Nagaraju Myakala, Magdalena Heiland, Dominik Eder, Carsten Streb, Alexey Cherevan
Summary: This review summarizes prominent examples of thiomolybdate-based electro- and photocatalysis and provides a comprehensive analysis of their reactivities under homogeneous and heterogenized conditions. The study examines the active sites of thiomolybdates relevant for the hydrogen evolution reaction and discusses the shift from solution-phase to surface-supported thiomolybdates with a focus on applications in electrocatalysis and photocatalysis.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Sarah Klingler, Benedikt Bagemihl, Alexander K. Mengele, Simon Kaufhold, Pasi Myllyperkioe, Jussi Ahokas, Mika Pettersson, Sven Rau, Boris Mizaikoff
Summary: Currently, the efficient and economical utilization of photosensitizers and catalysts based on rare earth metals in artificial photosynthesis is a major concern. Although repairing inactivated catalysts is a potential solution, it remains a challenge. The study introduces an innovative in situ technique using non-invasive rotational Raman spectroscopy to accurately monitor initially evolved hydrogen and gas reaction products after active repair, providing valuable insights into the mechanism of active repair during light-driven catalysis and enabling the identification of relevant mechanistic details and innovative repair strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shujun Li, Yubin Ma, Yue Zhao, Rongji Liu, Yupeng Zhao, Xusheng Dai, Nana Ma, Carsten Streb, Xuenian Chen
Summary: The study demonstrates the activation of molecular hydrogen by polyoxometalate (POM)-based heterogeneous compounds functionalized with Platinum particles. The synergism between a hydrogen spillover mechanism and electron-proton transfer by the POM enables the selective catalytic reduction of olefins and nitroarenes with high functional group tolerance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Philipp Stehle, Daniel Rutz, Ali M. Bazzoun, Dragoljub Vrankovic, Montaha Anjass
Summary: LiDFP has been found to improve the performance of Si-containing anodes in pouch cells, with a concentration of 1 wt% being the most optimal. Higher concentrations of LiDFP lead to the formation of a more beneficial SEI film, resulting in less degradation of electrolyte components and better maintenance of the anode microstructure.
Article
Chemistry, Multidisciplinary
Meena Ghosh, Dieter Sorsche, Rezwana Binte Ahmed, Montaha Anjass
Summary: Decavanadate clusters stabilized with organic guanidinium cation exhibit improved thermal properties and stability in liquid organic electrolytes, making them promising anode materials for sodium-ion and lithium-ion batteries. Hydrogen bonding interactions between amino groups of the cation and the anion play a key role in enhancing the stability of the cluster structures. The Gdm{V10} cluster shows better rate capability and cycling stability than Tba{V10} in sodium-ion battery half-cell tests.
Article
Multidisciplinary Sciences
Stefan Repp, Moritz Remmers, Alexandra Stefanie Jessica Rein, Dieter Sorsche, Dandan Gao, Montaha Anjass, Mihail Mondeshki, Luca M. Carrella, Eva Rentschler, Carsten Streb
Summary: In this study, a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di- metal-functionalization of a prototype molecular vanadium oxide cluster is reported. Mechanistic analyses reveal that coordination of a Mg2+ ion leads to the formation of mono-functionalized compound and release of a placeholder cation. Irradiation with visible light results in one-electron reduction, exchange of the second placeholder cation, and formation/crystallization of the di-metal-functionalized compound. Furthermore, the study demonstrates the feasibility of applying this synthetic concept to other metal cations.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jonas Eichhorn, Patricia Hofmann, Benedikt Bagemihl, Carsten Streb, Sven Rau, Felix H. Schacher
Summary: In this study, molecular ruthenium (II) photosensitizers were covalently embedded within block copolymer micelles for light-driven catalysis with excellent performance in hydrogen evolution reaction (HER) using molecularly dissolved thiomolybdate clusters. The block copolymers, PS-b-P(ClHPMA-co-MMS) and PS-b-P(bpyHPMA-co-MMS), were synthesized and functionalized with ruthenium (II) polypyridyl complex, and self-assembled into ruthenium-functionalized block copolymer micelles. The colloidal system outperformed the homogeneous reference in the hydrogen evolution reaction.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Stefan Repp, Kim Lara Junginger, Dieter Sorsche, Theresa Zorn, Ann-Christin Poeppler, Yuji Kikukawa, Yoshihito Hayashi, Carsten Streb
Summary: The self-assembly of polyoxometalates (POMs), molecular metal oxides, can be controlled by internal or external templates. This study explores how the interaction between internal templates (halides, oxoanions) and external organic templates (protonated cyclene species) affects the self-assembly of a model polyoxovanadate cluster. Crystallographic analyses, spectroscopic studies, and V-51 NMR spectroscopy provide insights into the formation of an intermediate vanadate species during the process. These findings contribute to the development of template-driven synthetic chemistry of polyoxovanadates.
DALTON TRANSACTIONS
(2023)
