ABSTRACT Developing efficient and stable non‐precious metal electrocatalysts for hydrogen evolution reaction (HER) is of great significance for advancing water electrolysis hydrogen production technology. This paper presents a Cr‐doped Ni 3 S 2 nanosheet array catalyst prepared on nickel foam via a one‐step hydrothermal method. Experimental results show that the introduction of Cr effectively improves conductivity and accelerates interfacial electron transfer, resulting in the catalyst exhibiting excellent hydrogen evolution performance in a 1.0 M KOH electrolyte, achieving a current density of 10 mA cm −2 with only a 122 mV overpotential, and maintaining long‐term operational stability for over 20 h. Furthermore, XPS and Raman results show that Cr doping not only optimizes the electronic structure of Ni 3 S 2 but also induces the formation of a surface oxygen sulfide layer thereby promoting the dissociation of water. This study provides a new approach for designing superior hydrogen evolution catalysts by synergistically controlling electronic structure and surface reconstruction through doping engineering.

ABSTRACT Ligand‐protected metal nanoclusters have garnered considerable attention in recent years as a class of emergent nanocatalysts. Organic ligands are conventionally used to stabilize metal nanoclusters by preventing uncontrolled aggregation and disintegration. However, excessive ligand shielding will hinder the accessibility to catalytically active sites, thereby often hampering nanoclusters’ catalytic activity. Thus, constructing metal nanoclusters that are both stable and catalytically active is challenging but crucial for the discovery of efficient nanocluster catalysts. In addition to acting as conventional spectator ligands to stabilize nanoclusters and regulate their electronic structures, functional ligands may directly interact with reactants or reagents to promote the reaction or, in situ, release vacant metal sites that participate in catalysis via hemilabile coordination. This minireview outlines recent advances in metal nanocluster catalysis from a ligand perspective, focusing on the role of functional ligands in catalysis. We first provide a general overview of metal nanoclusters. Then, we delve into functional ligand‐participated metal nanocluster catalysis from the following aspects: i) Functional ligands furnishing organocatalytic sites, including Lewis basic sites or hydrogen bond donors/acceptors, in catalysis. ii) Anchoring catalytically active metal complex units onto nanoclusters using functional ligands. iii) Hemilabile ligands liberating vacant metal sites for catalysis. Finally, an outlook is provided.

ABSTRACT The catalytic upgrading of ethanol into C 2 + olefins has garnered increasing interest as a strategy for producing distillate fuels via olefin oligomerization. In this work, we present Cu/Ta x O y /SiO 2 as a highly efficient and stable catalyst system for the direct conversion of ethanol into butene‐rich olefins. The synergy between Cu and Ta x O y species supported on SiO 2 provides a favorable balance of metallic and acidic functions, yielding high carbon efficiency and sustained catalytic performance. A 7.5%Cu/26%Ta 2 O 5 /SiO 2 catalyst exhibited olefins selectivity of 90%–92% at ethanol conversions of 98%–99%, maintained over 140 h on stream. This was achieved by systematically examining catalyst design variables—including preparation method (sequential vs. co‐impregnation), Cu and Ta 2 O 5 loadings, and choice of SiO 2 support. Lifetime studies revealed an initial induction period during which alkane selectivity declined while olefin selectivity increased, indicative of alkane dehydrogenation. Structural and spectroscopic characterization (XRD, TEM, CO‐FTIR, pyridine‐FTIR) enabled us to attribute this behavior to evolving surface properties of the Ta x O y species under reaction conditions.

ABSTRACT Thioester and amide are versatile functional groups commonly found in synthetic compounds, natural products, and functional materials, and they function as a crucial intermediate in organic transformations. The development of mild and efficient synthetic approaches provides a straightforward route to structurally diverse thioesters and amides, thereby enhancing the synthetic potential of carboxylic acid derivatives. This work presents a photochemical strategy for thioester and amide synthesis that employs thiobenzoic S‐acids as one‐electron reductants and sulfur‐centred radical precursors, utilizing Bi 2 S 3 nanostructures as the photocatalyst. The Bi 2 S 3 nanostructures were prepared through a solvothermal method employing a choline chloride/thiourea deep eutectic solvent, which plays a multifaceted role as the solvent, soft template, and in situ sulfur source. These nanostructures were subsequently employed in visible light‐induced thioesterification, enabling oxidative radical coupling of aromatic and aliphatic thioic acids with thiols under visible light. Mechanistic investigations, including TEMPO‐based radical trapping experiments, confirm the involvement of free radical intermediates. Additional control experiments were conducted to elucidate the reaction mechanism and define the catalytic pathway. This protocol offers several advantages, including excellent catalytic efficiency, broad substrate applicability, high selectivity, good functional group tolerance, and catalyst recyclability, establishing it as a sustainable and practical one‐pot route for thioesterification and amidation reactions.

ABSTRACT Rh(II) porphyrin complexes have been used to realize remarkable stoichiometric transformations, which include C─H activation in methane as well as C─H and O─H activation in methanol at room temperature. However, their catalytic application is often hindered by the formation of strong Rh─C and Rh─X bonds over the course of the catalytic cycle, in addition to a tendency to form dimeric species. In this Concept article, we highlight the unusual transition states and reaction steps observed with Rh(II) porphyrins, as well as the challenges associated with the regeneration of Rh(II) during catalytic cycles. We discuss how photochemistry, electrochemistry paired with spatial confinement, and remote metal–metal collaboration in solid matrices can be used to leverage the latent potential of Rh(II) porphyrin reactivity in catalysis.

ABSTRACT Pulsed laser excitation offers a compelling approach for accessing nonequilibrium conditions in catalysis by delivering energy to surfaces in a highly localized and time‐controlled manner. In contrast to continuous‐wave irradiation, pulsed lasers concentrate energy into extremely short bursts—ranging from femtoseconds to nanoseconds—which can induce steep thermal gradients, localized heating, and even partial decoupling between electronic and lattice subsystems. These effects often lead to surface restructuring, altered binding of intermediates, or activation of otherwise inaccessible pathways. Such transient photothermal environments have shown considerable promise in driving reactions like CO 2 reduction, hydrogen evolution, and ammonia synthesis, where heat and charge localization strongly influence product selectivity. This review examines the growing field of pulsed photothermal catalysis, highlighting the fundamental mechanisms of laser–matter interactions, the distinction between thermal and nonthermal regimes, and how key laser parameters affect surface reactivity. We also survey selected reaction systems and discuss how recent developments in time‐resolved spectroscopy and computational modeling are helping to unravel the underlying dynamics and inform the rational design of next‐generation catalytic platforms.

ABSTRACT Highly dispersed palladium nanoparticles (Pd NPs) embedded within a hierarchical UiO‐66 structure, referred to as Pd@U‐12, have been successfully synthesized via a green, straightforward of solid‐solid thermal (SST) method. This innovative SST technique enables uniform dispersion of Pd NPs, allowing their encapsulation within the hierarchical framework of UiO‐66. The unsaturated sites in the host UiO‐66 facilitate the coordination of Pd, which are subsequently reduced to nanoparticles during the SST process, forming Pd@U‐12. The Pd NPs are highly dispersed on the hierarchical support (U‐12) and serve effectively as catalytic sites for hydrogenation reactions. The optimally synthesized 20%Pd@U‐12 demonstrated exceptional performance as a heterogeneous catalyst for the hydrogenation of cyclohexene, achieving 99% conversion with stable activity over five consecutive cycles. Notably, the SST method for encapsulating Pd NPs (Pd@U‐12) offers several advantages, including rapid incorporation of metal nanoparticles within a short time, a green, solvent‐free synthesis process, high dispersion and stability of the metal content within the host material. These features could significantly enhance the effectiveness of Pd@U‐12 as a robust heterogeneous catalyst in various catalysis applications.

ABSTRACT Plastic waste can be converted into smaller hydrocarbons through hydrothermal conversion using supercritical water. It would be advantageous to introduce suitable catalyst materials under hydrothermal processing conditions to steer product selectivity. In this study, a series of commonly used solid catalysts were evaluated to identify those with the highest potential to tune the product portfolio and increase the overall performance of the hydrothermal conversion of polyethylene. Various metal oxides (i.e., TiO 2 , ZrO 2 , CeO 2 , SiO 2 and γ‐Al 2 O 3 ) and aluminosilicates (i.e., zeolites H‐Y and H‐ZSM‐5, as well as different amorphous aluminosilicates) improve the polyethylene conversion rate compared to non‐catalytic hydrothermal reaction conditions. CeO 2 is a promising material because it produces a naphtha‐like product stream, thereby achieving full conversion, high liquid yield, high alkane/alkene selectivity, and good hydrothermal stability. To steer the conversion toward aromatics, aluminosilicates were the most effective catalyst materials, with amorphous aluminosilicates outperforming their crystalline counterparts in terms of liquid yield (40 wt%), aromatic selectivity (16 wt%) as well as stability. Crystalline aluminosilicates, such as zeolites H‐Y and H‐ZSM‐5, also enhanced activity, but lost their structural integrity under hydrothermal reaction conditions. However, despite significant structural changes, catalysts could be reused, as reactivity of spent materials only decreased slightly.

ABSTRACT Developing high‐performance Ni‐based catalysts is critical for the practical application of dry reforming of methane (DRM). Herein, the 10wt%Ni/CeO 2 catalyst was mediated by CeAlO 3 formed by interfacial reaction between impregnated Al species and the CeO 2 support. The resultant CeAlO 3 has a significant influence on the structural properties and the catalytic performance. CeAlO 3 can enhance the dispersion of Ni, introduce more oxygen ion vacancies and medium basic sites, which contribute to the high activity and high coking resistance. Furthermore, the enhanced interaction between Ni and the support impedes the sintering of Ni nanoparticles, leading to improved stability. The sample with Al:Ce molar ratio of 0.1 demonstrates impressive performance, at 800°C and 120,000 mL/(h·g cat ), the CH 4 , CO 2 conversion and H 2 /CO ratio are 94.3%, 90.7%, and 0.92, respectively. The activity decreases by <5% over 200 h test at 750°C with a carbon accumulation rate of only 0.54 mg C/(g cat ·h).

ABSTRACT Fe‐based bimetallic catalysts have emerged as promising materials for peroxymonosulfate (PMS) activation toward antibiotic degradation in water, offering enhanced electron transfer, improved active site regeneration, and tunable reaction pathways over monometallic counterparts. This review systematically summarizes recent advances in their design and application, with a focus on synergistic mechanisms and the precise regulation of radical and non‐radical pathways. We classify these catalysts into four synergistic types—endogenous electron donors, coupled redox cycles, electronic structure modifiers, and anionic coordination—and outline mainstream synthesis strategies including coprecipitation, solvothermal, pyrolysis, impregnation, and electrochemical deposition. The core of this review elucidates how bimetallic centers act as regulatory hubs to steer PMS activation toward radical routes (SO 4 • − and •OH) and non‐radical routes ( 1 O 2 , high‐valent metal‐oxo species, and direct electron transfer). Using fluoroquinolones, sulfonamides, tetracyclines, and β‐lactams as model antibiotics, we further demonstrate how catalyst design governs specific degradation pathways and influences the evolution of environmental toxicity. Finally, we address key practical challenges including complex water matrix interference and catalyst deactivation, and outline future directions toward atomic‐level design, in situ characterization, and engineering integration for sustainable water purification.