Dong-Hui Chen

This study explores high-entropy sulfides (HESs) as potential electrocatalysts for the hydrogen evolution reaction (HER). Novel Pa-3 and Pnma structured HESs containing Fe, Mn, Ni, Co and Mo, were synthesized via a facile mechanochemical method. Structural and chemical properties were extensively characterized using x-ray diffraction, transmission electron microscopy, energy-dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy. The electrocatalytic performance of four as-prepared HESs in alkaline electrolyte for HER reveals the remarkable outperformance compared to medium-entropy and conventional sulfides. Particularly, (Fe_0.2Mn_0.2Ni_0.2Co_0.2Mo_0.2)S₂ demonstrated outstanding activities, with minimal overpotentials (187 mV at 10 mA cm^–2) and outstanding durability under harsh alkaline conditions (a mere polarization increase ΔE = 17 mV after 14 h via chronopotentiometry). The remarkable catalytic activities can be attributed to synergistic effects resulting from the cocktail effects within the high-entropy disulfide. The introduction of Mo contributes to the formation of a layered structure, which leads to an increased surface area and thus to a superior HER performance compared to other HES and conventional sulfides. This work demonstrates the promising potential of HES and underscores that further development for catalytic applications paves the way for innovative routes to new and more efficient active materials for HER catalysis.

Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn‐based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer‐by‐layer spin‐coating using Zn acetate dihydrate and benzene‐1,4‐dicarboxylic acid (H₂BDC) and biphenyl‐4,4’‐dicarboxylic acid (H₂BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal‐to‐linker molar ratio used for fabrication. Under equimolar conditions, H₂BPDC creates a type of structure like that proposed for SURMOF‐2, whereas H₂BDC generates a different metal‐hydroxide‐organic framework. Large excess of Zn²⁺ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal‐organic thin films, such that properties can be rationally engineered and explained.

Elektron‐Phonon‐Wechselwirkungen, die in kondensierter Materie von entscheidender Bedeutung sind, werden in metallorganischen Gerüstverbindungen (MOFs) selten beobachtet. In Lanthanoid‐ oder Actinoid‐basierten Verbindungen gelingt der Nachweis dieser Wechselwirkungen typischerweise über die Analyse der Lumineszenz. Frühere Studien zu Ln‐ und Ac‐basierten MOFs bei hohen Temperaturen ergaben zusätzliche Lumineszenzsignale, die jedoch zu schwach für eine gründliche Analyse waren. Im Rahmen unserer Untersuchungen haben wir mithilfe eines Schicht‐für‐Schicht‐Verfahrens eine hochgeordnete, kristalline uranbasierte MOF‐Dünnschicht (KIT‐U‐1) hergestellt. Unter UV‐Licht zeigte diese Schicht zwei ausgeprägte „heiße Banden“, die auf eine starke Elektron‐Phonon‐Wechselwirkung hinweisen. Während bei 77 K keine Emissionsbanden sichtbar waren, erschien bei 300 K eine Emissionsbande mit der halben Intensität der Hauptbande. Überraschenderweise tauchte oberhalb von 320 K eine zweite, sogenannte heiße Bande auf, die von früheren Ergebnissen aus Seltenerd‐Verbindungen abweicht. Wir haben eine detaillierte ab initio‐Analyse mithilfe der zeitabhängigen Dichtefunktionaltheorie durchgeführt, um dieses ungewöhnliche Verhalten zu verstehen und die für die starke Elektron‐Phonon‐Kopplung verantwortliche Gitterschwingung zu identifizieren. Die heißen Emissionsbanden der KIT‐U‐1‐Schicht wurden dann dazu genutzt, ein hochempfindliches optisches Einkomponenten‐Thermometer zu entwickeln. Diese Ergebnisse belegen das Potenzial hochwertiger MOF‐Dünnschichten bei der Nutzung der einzigartigen Lumineszenz von Lanthanoiden und Actinoiden für neuartige Anwendungen.

Electron‐phonon interactions, crucial in condensed matter, are rarely seen in Metal–Organic Frameworks (MOFs). Detecting these interactions typically involves analyzing luminescence in lanthanide‐ or actinide‐based compounds. Prior studies on Ln‐ and Ac‐based MOFs at high temperatures revealed additional peaks, but these were too faint for thorough analysis. In our research, we fabricated a high‐quality, crystalline uranium‐based MOF (KIT‐U‐1) thin film using a layer‐by‐layer method. Under UV light, this film showed two distinct “hot bands,” indicating a strong electron‐phonon interaction. At 77 K, these bands were absent, but at 300 K, a new emission band appeared with half the intensity of the main luminescence. Surprisingly, a second hot band emerged above 320 K, deviating from previous findings in rare‐earth compounds. We conducted a detailed ab‐initio analysis employing time‐dependent density functional theory to understand this unusual behaviour and to identify the lattice vibration responsible for the strong electron‐phonon coupling. The KIT‐U‐1 film's hot‐band emission was then utilized to create a highly sensitive, single‐compound optical thermometer. This underscores the potential of high‐quality MOF thin films in exploiting the unique luminescence of lanthanides and actinides for advanced applications.

Easy-to-integrate, remote read-out thermometers with fast response are of huge interest in numerous application fields. In the context of optical read-out devices, sensors based on the emission of lanthanides (Eu(III), Tb(III)) are particularly promising. Here, by using a layer-by-layer (LbL) approach in the liquid-phase epitaxy process, a series of continuous, low-thickness lanthanide-MIL-103 SURMOFs were fabricated to yield highly sensitive thermometers with optical readout. These Ln-SURMOFs exhibit remarkable temperature-sensing photoluminescence behavior, which can be read out using the naked eye. High transmittance is realized as well by precisely controlling the film thickness and the quality of these Ln-SURMOF thermometers. Moreover, we demonstrate that the thermal sensitivity can be improved in the temperature regime above 120 K, by controlling the energy transfer between Tb(III) and Eu(III). This performance is achieved by employing a sophisticated supramolecular architecture, namely MOF-on-MOF heteroepitaxy.

Metal-organic frameworks (MOFs) are a class of crystalline porous coordination materials, which are assembled from inorganic nodes and organic linkers. Numerous applications, such as gas storage, molecule separation, catalysis, optical sensing, and charge transport, benefit from the outstanding properties of MOF materials. More advanced applications, e.g., in the electronics and optoelectronics area, demand homogeneous and monolithic MOF thin films. Recent studies demonstrated that surface-mounted MOFs (SURMOFs) are well suited to fulfill the requirements for the integration of MOFs into devices. As a crystalline thin-film material with tunable thickness, SURMOFs have been widely used in the optimization of chromophore stacking, electrical transport, stimuli-response, etc. The fabrication of SURMOFs is carried out employing a layer-by-layer (LbL) assembly technique, and it can yield MOF thin films with a well-defined orientation, tunable thickness, and editable crystalline heterostructure. We summarize the LbL assembly methods for SURMOF fabrication and the realization of advanced SURMOF architectures, including optical and electronic applications as well as the integration of photoactive SURMOFs and SURMOF-derived materials in technical devices. We conclude with a discussion of the challenges and prediction of the future of SURMOF materials.

For the first time, a procedure has been established for the growth of surface-anchored metal-organic framework (SURMOF) copper(II) benzene-1,4-dicarboxylate (Cu-BDC) thin films of thickness control with single molecule accuracy. For this, we exploit the novel method solution atomic layer deposition (sALD). The sALD growth rate has been determined at 4.5 Å per cycle. The compact and dense SURMOF films grown at room temperature by sALD possess a vastly superior film thickness uniformity than those deposited by conventional solution-based techniques, such as dipping and spraying while featuring clear crystallinity from 100 nm thickness. The highly controlled layer-by-layer growth mechanism of sALD proves crucial to prevent unwanted side reactions such as Ostwald ripening or detrimental island growth, ensuring continuous Cu-BDC film coverage. This successful demonstration of sALD-grown compact continuous Cu-BDC SURMOF films is a paradigm change and provides a key advancement enabling a multitude of applications that require continuous and ultrathin coatings while maintaining tight film thickness specifications, which were previously unattainable with conventional solution-based growth methods.

Metal organic frameworks (MOFs) are crystalline three-dimensional porous solids featuring a high surface area, which have attracted considerable attention in a wide range of applications e.g. in catalysis, hydrogen storage, gas separation, thermoelectric applications or as chemical sensors. Beyond solvothermal synthesis of bulk MOF crystals, growing MOFs thin films has been limited so far to rather conventional solution-based techniques. However, traditional growth methods from solution such as spin-coating, spray-coating or dip-coating generate MOFs thin films with a rather low film quality and an alarming lack of a precise film thickness control under 1 nm. This renders them unsuitable for most industrial applications and severely limits their future application potential. Atomic layer deposition (ALD) provides this capability, but is limited by the necessity to use gaseous precursors in vacuum conditions at temperatures typically above 100°C. This is incompatible with the typically high temperature sensitivity of many hybrid metal-organic compounds such as the MOFs. In this perspective, we have transferred the principles of ALD to precursors dissolved in liquid solvents. The ‘solution ALD’ (sALD) method can be implemented in a variety of microfluidic or slot-die processing devices. We have demonstrated that the principles of classical, gas-based ALD —self-limiting surface reactions— are reproduced in sALD. sALD shares the fundamental properties of standard ‘gas ALD’ (gALD), in particular the self-limiting surface chemistry and the ability to coat deep pores in a conformal manner Furthermore, sALD allows the experimentalist to design new, advantageous, reactions of known semiconductors (oxides, heavier chalcogenides), or to deposit materials otherwise inaccessible to ALD altogether, such as polymers, ionic solids, and metal-organic frameworks. They may be obtained in highly pure, crystalline form at room temperature, either as planar films or as conformal coatings of porous substrates. Based on these advances, we have been able to make the first sALD-derived films of a MOF, Cu-BDC. At any chosen thickness, sALD MOF films feature significantly lower roughness and better adhesion than those generated by the best spray-coating and dip-coating methods available currently.

By using a layer-by-layer (LbL) approach, we have fabricated lanthanide-based, monolithic metal-organic framework (MOF) thin films for optical applications. The thickness of the Ln-SURMOFs can be easily controlled, thereby maintaining its transparent properties, which makes them attractive for the field of optical coatings. Moreover, employing a hetero-epitaxy process, we demonstrated that Ln-SURMOF can be deposited on the top of other Ln-SURMOFs with different lanthanide ions, maintaining the crystallinity and orientation. The hetero-epitaxial multilayer architectures of Ln-SURMOF reduced the efficient energy transfer between different lanthanides ions and optimized the fabrication of Ln-MOF thin film with a straightforward modulation of the emission color. Meanwhile, the distance between lanthanide ions in Ln-SURMOFs was extended by replacing the linkers. These novel hetero-epitaxial Ln-SURMOF architectures, possess a bright future in the field of optics, photonics and optoelectronics.

Lanthanide-based crystalline coatings have a great potential for energy-conversion devices, but until now luminescent surface-anchored materials were difficult to fabricate. Thin films, called lanthanides surface-mounted metal–organic frameworks (SURMOFs) with tetrasubstituted halide (fluorine, chlorine, and bromine) terephthalic acid derivative linkers as a basic platform for optical devices, exhibit a high quantum yield of fluorescence visible to the naked eyes under ambient light. We show that we can tune the luminescent properties in thin films by halide substitution, which affords control over the molecular structure of the material. We rationalize the mechanism for the modulation of the photophysical properties by “antenna effect”, which controls the energy transfer and quantum yields using experimental and theoretical techniques for chelated lanthanides as a function of the type of atom substitutions at the phenyl rings and the resulting dihedral angle between phenyl rings in the linkers and carboxylate groups.