Electron-Delocalization Across High Surface Entropy Sub-1 nm Nanobelts Toward Enhanced Electrocatalytic Urea Oxidation.

Integration of inherently incompatible elements into a single sublattice, resulting in the formation of monophasic metal oxide, holds great scientific promise; it unveils that the overlooked surface entropy in subnanometer materials can thermodynamically facilitate the formation of homogeneous single-phase structures. Here a facile approach is proposed for synthesizing multimetallic oxide subnanometer nanobelts (MMO-PMA SNBs) by harnessing the potential of phosphomolybdic acid (PMA) clusters to capture inorganic nuclei and inhibiting their subsequent growth in solvothermal reactions. Experimental and theoretical analyses show that PMA in MMO-PMA SNBs not only aids subnanometer structure formation but also induces in situ modifications to catalytic sites. The electron transfer from PMA, coupled with the loss of elemental identity of transition metals, leads to electron delocalization, jointly activating the reaction sites. The unique structure makes pentametallic oxide (PMO-PMA SNBs) achieve a current density of 10 mA cm-2 at a low potential of 1.34 V and remain stable for 24 h at 10 mA cm-2 on urea oxidation reaction (UOR). The exceptional UOR catalytic activity suggests a potential for utilizing multimetallic subnanometer nanostructures in energy conversion and environmental remediation.

Electron-Delocalization-Stabilized Photoelectrocatalytic Coupling of Methane by NiO-Polyoxometalate Sub-1 nm Heterostructures.

The oxidative coupling of methane to C2 oxygenates merits great scientific and technological potential yet remains a challenge due to its inferior selectivity. Subnanomaterials (SNMs) with "p-n-p-n"-type heteroconstructions feature enhanced external field coupling properties and tunable electronic structures, serving as promising catalysts for the selective partial oxidation of methane. Here we develop NiO-polyoxometalate (POM) subnanocoils with a thickness of 1.8 nm, showing excellent catalytic activity toward photoelectrochemical coupling of methane into a C2 product under mild conditions (1 bar, 25 °C) with a notable productivity (up to 4.48 mmol gcat-1 h-1) and a high selectivity (>99%). Under photoelectrochemical coupling, C-H bonds can be activated by NiO, and the resulted *COOH intermediates are stabilized by the delocalized electrons in POM clusters. The contiguous active sites of NiO and POM at the molecular level allow the in situ coupling of *COOH into oxalate. This work points out an economic way for the oxidation of methane under mild conditions and may enlighten the design of functional SNMs from fundamental standpoints.

Circumventing the activity-selectivity trade-off via the confinement effect from induced potential barriers on the Pd nanoparticle surface.

The request for both high catalytic selectivity and high catalytic activity is rather challenging, particularly for catalysis systems with the primary and side reactions having comparable energy barriers. Here in this study, we simultaneously optimized the selectivity and activity for acetylene semi-hydrogenation by rationally and continuously varying the doping ratio of Zn atoms on the surface of Pd particles in Pd/ZnO catalysts. In the reaction temperature range of 40-200 °C, the conversion of acetylene was close to ∼100%, and the selectivity for ethylene exceeded 90% (the highest ethylene selectivity, ∼98%). Experimental characterization and density functional theory calculations revealed that the Zn promoter could alter the catalyst's potential energy surface, resulting in a "confinement" effect, which effectively improves the selectivity yet without significantly impairing the catalytic activity. The mismatched impacts on activity and selectivity resulting from continuous and controllable alteration in the catalyst structure provide a promising parameter space within which the two aspects could both be optimized.

Microwave-assisted synthesis of polyoxometalate-Dy2O3 monolayer nanosheets and nanotubes.

Two-dimensional (2D) materials have shown unique chemical and physical properties; however, their synthesis is highly dependent on the layered structure of building blocks. Herein, we developed monolayer Dy2O3-phosphomolybdic acid (PMA) nanosheets and nanotubes based on microwave synthesis. Microwave-assisted synthesis with high-energy input gives a faster and dynamically driven growth of nanomaterials, resulting in high-purity nanostructures with a narrow size distribution. The reaction times of the nanosheets and nanotubes under microwave synthesis are significantly reduced compared with oven-synthesis. Dy2O3-PMA nanosheets and nanotubes exhibit enhanced activity and stability in photoconductance, with higher sensitivities (0.308 µA cm-2 for nanosheets and 0.271 µA cm-2 for nanotubes) compared to the individual PMA (0.12 µA cm-2) and Dy2O3 (0.025 µA cm-2) building blocks. This work demonstrates the promising application potential of microwave-synthesized 2D heterostructures in superconductors and photoelectronic devices.

Electron Delocalization and Transfer Across Polyoxometalates-Based Subnanomaterials in Catalytic Reactions.

Due to their identical building blocks and high surface-to-volume ratio, subnanomaterials exhibit significant properties compared to their bulk nanomaterial counterparts. The interactions between these building blocks can result in either equal or unequal sharing of electrons, leading to electron transfer in heterojunctions or electron delocalization within symmetric structures. Clusters, possessing electronic properties akin to atoms, can serve as reservoirs of electrons to stabilize crucial intermediates in catalytic reactions. This perspective provides a novel understanding of well-defined subnanomaterials with distinct architectures, such as cluster-based constructions and co-assembled heterojunctions, emphasizing the relationship between electronic structures and catalytic properties. The objective is to provide novel perspectives on the realm of subnanomaterials and cluster-based architectures.

Porous, Ultrathin PtAgBiTe Nanosheets for Direct Hydrazine Hydrate Fuel Cell Devices.

Ultrathin 2D nanomaterials have attracted extensive attention due to their fascinating applications in sustainable and clean-energy-related devices, but obtaining ultrathin 2D multimetallic polycrystalline structures with large lateral dimensions remains a challenge. In this study, ultrathin 2D porous PtAgBiTe and PtBiTe polycrystalline nanosheets (PNSs) are obtained via a visible-light-photoinduced Bi2 Te3 -nanosheet-mediated route. The PtAgBiTe PNSs are assembled by sub-5 nm grains with widths beyond 700 nm. Strain and ligand effects originating from the porous, curly polycrystalline structure endow the PtAgBiTe PNSs with robust hydrazine hydrate oxidation reaction activity. Theoretical research demonstrates that the modified Pt activates the N-H bonds in N2 H4 during the reaction, and strong hybridization between Pt-5d and N-2p facilitates dehydrogenation while reducing energy consumption. The peak power densities of the PtAgBiTe PNSs in actual hydrazine-O2 /air fuel cell devices are boosted to 532.9/315.9 mW cm-2 , while those of the commercial Pt/C are 394.7/157.9 mW cm-2 . This work provides a strategy not only for preparing ultrathin multimetallic PNSs but also for finding promising electrocatalysts for actual hydrazine fuel cells.