TOP RCPTM journal publications 2024

Y. Wang, N. Denisov, S. Qin, D. S. Gonçalves, H. Kim, B. B. Sarma and P. Schmuki, "Stable and Highly Active Single Atom Configurations for Photocatalytic H2 Generation," ADVANCED MATERIALS, Article in press, 2024.
DOI: 10.1002/adma.202400626, IF = 32.086

Abstract: The employment of single atoms (SAs), especially Pt SAs, as co-catalysts in photocatalytic H2 generation has gained significant attention due to their exceptional efficiency. However, a major challenge in their application is the light-induced agglomeration of these SAs into less active nanosized particles under photocatalytic conditions. This study addresses the stability and reactivity of Pt SAs on TiO2 surfaces by investigating various post-deposition annealing treatments in air, Ar, and Ar-H2 environments at different temperatures. It is described that annealing in an Ar-H2 atmosphere optimally stabilizes SA configurations, forming stable 2D rafts of assembled SAs ≈0.5–1 nm in diameter. These rafts not only resist light-induced agglomeration but also exhibit significantly enhanced H2 production efficiency. The findings reveal a promising approach to maintaining the high reactivity of Pt SAs while overcoming the critical challenge of their stability under photocatalytic conditions.

U. Kerketta, H. Kim, N. Denisov and P. Schmuki, "Grätzel‐Type TiO2 Anatase Layers as Host for Pt Single Atoms: Highly Efficient and Stable Photocatalytic Hydrogen Production," ADVANCED ENERGY MATERIALS, vol. 14, iss. 4, pp. 2302998, 2024.
DOI: 10.1002/aenm.202302998, IF = 29.698

Abstract: Single atoms (SAs) represent not only a new frontier in classic heterogeneous catalysis but are also increasingly investigated as co-catalysts in photocatalytic reactions. In contrast to classic catalysis, many photocatalytic platforms require only a very low SA loading density to reach a saturated photocatalytic activity. As a result, an optimized light harvesting/carrier transport combination in the supporting semiconductor becomes the key aspect for the overall photocatalytic efficiency. In this work, it is demonstrated that Grätzel type mesoporous TiO2 layers represent an ideal host for Pt single-atoms (SAs) that allow for a highly effective photocatalytic H2 generation. Using a layer with an optimized geometry, structure, as well as Pt SA loading, a photocatalytic H2 production is achieved of up to ≈2900 µL h−1 (under irradiation at λ = 365 nm and I = 65 mW cm−2) – a performance that is far superior to previous Pt SA/TiO2 structures based on TiO2 nanotubes, nanosheets, or metal organic frameworks. Moreover, such SA/substrate combination provides a highly stable H2 production over time. The present work thus introduces the use of this classic TiO2 nanostructure as the most effective host for Pt SAs and its use for highly efficient photocatalytic H2 production from aqueous solutions.

Mansi, V. Shrivastav, P. Dubey, S. Sundriyal, U. K. Tiwari and A. Deep, "Recent advances on core-shell metal-organic frameworks for energy storage applications: Controlled assemblies and design strategies," COORDINATION CHEMISTRY REVIEWS, vol. 499, pp. 215497, 2023.
DOI: 10.1016/j.ccr.2023.215497, IF = 24.833

Abstract: Core-shell metal–organic framework (CSMOF) has attracted the attention of researchers in the material science and nanotechnology research field. The structural properties of CSMOF and their derived material include extortionate specific surface area and porosity, good structural flexibility, high stability, etc. These appealing properties make CSMOF a great alternative for various practical applications. CSMOF has shown great performance as an electrode material for energy storage applications. This review is primarily focused on the factor affecting the assemblies and synthesis of core shell structures, strategy to control the assemblies, synthesis methods, and properties of different CSMOFs for energy storage devices viz. supercapacitors (SC) and batteries. After that, different CSMOF structures are compared in terms of their performance parameters for SC including specific capacitance, capacitance retention, cyclic stability, energy density, and self-discharge.On the other hand, reversible capacity, initial discharge capacity, and cyclic stability are a few performance parameters for Li-ion batteries that are also discussed for different materials.CSMOF’s applications for some other batteries like Na-ion, K-ion, Li-S, Li-Se, and Li-O2 will likewise be discussed in other sections. Eventually, the expansion and future scope of CSMOF and its derivatives are proposed for upcoming energy storage applications.

H. B. Kale, A. D. Kute, R. P. Gaikwad, P. Fornasiero, R. Zbořil and M. B. Gawande, "Synthesis and energy applications of copper-based single-atom electrocatalysts," COORDINATION CHEMISTRY REVIEWS, vol. 502, pp. 215602, 2024.
DOI: 10.1016/j.ccr.2023.215602, IF = 24.833

Abstract: Considering the current energy scenario, it is of great importance to design and develop innovative, economically feasible electrocatalysts for the various energy applications. The high cost, and low availability of noble metal-based (Pd, Pt, Ru, etc.) electrocatalysts limit their widespread implementation of electrochemical reactions. Earth-abundant copper-based single-atom electrocatalysts (Cu-based SAEs) possess desired electronic, morphological, and physicochemical properties that have been extensively deployed for the energy applications. In the context of the progress of copper-based SAEs, herein we reviewed the notable advancement in fabrication and applications of Cu-based SAEs for the production of fuels, hydrocarbons, and ammonia. We also addressed the stability of developed electrocatalysts and active sites present in the structure of single-atom copper electrocatalysts. The challenges, and potential insights into the mechanism of action are also described including the ways to enhance the overall SAEs activities by tailoring the active site chemistry on the basis of computational studies and designing the advanced synthesis strategy.

K. Ghosh, S. Ng, P. Lazar, A. K. K. Padinjareveetil, J. Michalička and M. Pumera, "2D Germanane‐MXene Heterostructures for Cations Intercalation in Energy Storage Applications," ADVANCED FUNCTIONAL MATERIALS, vol. 34, iss. 7, pp. 2308793, 2024.
DOI: 10.1002/adfm.202308793, IF = 19.924

Abstract: Heterostructures offer an exceptional possibility of combining individual 2D materials into a new material having altered properties compared to the parent materials. Germanane (GeH) is a 2D material with many favorable properties for energy storage and catalysis, however, its performance is hindered by its low electrical conductivity. To address the low electrochemical performance of GeH, a heterostructure of GeH and Ti3C2Tx is fabricated. The Ti3C2TX is a layered material belonging to the family of MXenes. The resulting heterostructure (GeMXene) at a defined mass ratio of GeH and Ti3C2Tx shows superior capacitive performance that surpasses that of both pristine materials. The effect of the size of cations and anions for intercalation into GeMXene in different aqueous salt solutions is studied. GeMXene allows only cation intercalation, which is evidenced by the gravimetric electrochemical quartz crystal microbalance (EQCM) technique. The capacitive performance of the GeMXene is compared in neutral, acidic, and alkaline electrolytes to determine the best electrochemical performance. This unleashes the potential use of GeMXene heterostructure in different electrolytes for supercapacitors and batteries. This work will pave the way to explore the heterostructures of other 2D materials such as novel MXenes and functionalized germanane for highly energy-storage efficient systems, and beyond.

B. Bartolomei, M. Sbacchi, C. Rosso, A. Günay‐Gürer, L. Zdražil, A. Cadranel, S. Kralj, D. M. Guldi and M. Prato, "Synthetic Strategies for the Selective Functionalization of Carbon Nanodots Allow Optically Communicating Suprastructures," ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 63, iss. 5, pp. e202316915, 2024.
DOI: 10.1002/anie.202316915, IF = 16.823

Abstract: AbstractThe surface of Carbon Nanodots (CNDs) stands as a rich chemical platform, able to regulate the interactions between particles and external species. Performing selective functionalization of these nanoscale entities is of practical importance, however, it still represents a considerable challenge. In this work, we exploited the organic chemistry toolbox to install target functionalities on the CND surface, while monitoring the chemical changes on the material's outer shell through nuclear magnetic resonance spectroscopy. Following this, we investigated the use of click chemistry to covalently connect CNDs of different nature en‐route towards covalent suprastructures with unprecedent molecular control. The different photophysical properties of the connected particles allowed their optical communication in the excited state. This work paves the way for the development of selective and addressable CND building blocks which can act as modular nanoscale synthons that mirror the long‐established reactivity of molecular organic synthesis.

J. H. Kim, S. Wu, L. Zdrazil, N. Denisov and P. Schmuki, "2D Metal–Organic Framework Nanosheets based on Pd‐TCPP as Photocatalysts for Highly Improved Hydrogen Evolution," ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 63, iss. 7, pp. e202319255, 2024.
DOI: 10.1002/anie.202319255, IF = 16.823

Abstract: In this report, a 2D MOF nanosheet derived Pd single-atom catalyst, denoted as Pd-MOF, was fabricated and examined for visible light photocatalytic hydrogen evolution reaction (HER). This Pd-MOF can provide a remarkable photocatalytic activity (a H2 production rate of 21.3 mmol/gh in the visible range), which outperforms recently reported Pt-MOFs (with a H2 production rate of 6.6 mmol/gh) with a similar noble metal loading. Notably, this high efficiency of Pd-MOF is not due to different chemical environment of the metal center, nor by changes in the spectral light absorption. The higher performance of the Pd-MOF in comparison to the analogue Pt-MOF is attributed to the longer lifetime of the photogenerated electron-hole pairs and higher charge transfer efficiency.

V. Hrubý, V. Šedajová, P. Jakubec, A. Bakandritsos, R. Zbořil and M. Otyepka, "Unleashing the power: Superior properties of fluorographene-derived materials for energy storage applications," POWER ELECTRONIC DEVICES AND COMPONENTS, vol. 7, pp. 100058, 2024.
DOI: 10.1016/j.pedc.2024.100058

Abstract: Fluorographene exhibits a rich chemistry and a wide range of applications in energy storage devices. This review, which is based on our lab results acquired in the last decade, explores the synthesis, properties, and performance of fluorographene-based materials in supercapacitors and batteries. Fluorographene can be prepared through mechanical or chemical delamination of graphite fluoride, allowing for scalable synthesis and further chemical processing. The chemical versatility of fluorographene enables a wide portfolio of chemical reactions, leading to a new class of graphene derivatives. Graphene acid, a product of fluorographene chemistry, exhibits excellent specific capacitance, cycling stability, and rate capability. Hybridizing graphene acid with metal-organic frameworks can achieve even higher energy and power densities. Furthermore, nitrogen-doped graphene derived from fluorographene demonstrates remarkable capacitive behavior, making it an efficient electrode material for supercapacitors. Additionally, fluorographene-based materials, such as graphene acid, graphene-sulfur hybrids, and graphene-based anodes, have exhibited outstanding performance in lithium-ion and lithium-sulfur batteries. The scalable synthesis, high performance, and versatility of fluorographene-derived materials render them attractive for practical energy storage applications. The unique properties and wide range of chemistries offered by fluorographene chemistry open new possibilities for improving advanced energy storage devices.